Method for Forming Anti-Glare Layer and Anti-Glare Film, and Ink-Jet Apparatus for Forming Anti-Glar

专利摘要:
Forming an anti-glare layer comprising the step of discharging an ink droplet containing an anti-glare imparting composition for forming a fine concavo-convex structure by an inkjet method, to form an anti-glare layer having a fine concavo-convex structure on the surface of the substrate. A method is disclosed.
公开号:KR20040038764A
申请号:KR1020030075733
申请日:2003-10-29
公开日:2004-05-08
发明作者:다까시 무라까미；소따 가와까미
申请人:코니카가부시끼가이샤；
IPC主号:

专利说明:

Method for forming anti-glare layer, anti-glare film, method for manufacturing same and inkjet device for anti-glare layer formation {Method for Forming Anti-Glare Layer and Anti-Glare Film, and Ink-Jet Apparatus for Forming Anti-Glare Layer}
[31] The present invention relates to a method for forming an antiglare layer having excellent antiglare function, an antiglare film, a method for producing the same, and an inkjet device for forming an antiglare layer.
[32] In recent years, development of a thin and lightweight notebook computer is progressing. Therefore, the protective film of the polarizing plate used by display apparatuses, such as a liquid crystal display device, is also becoming increasingly thin and high performance. In addition, a liquid crystal image display device such as a computer or a word processor which has an antireflection layer for improving visibility, prevents reflection, or provides an antiglare layer for scattering the reflected light to prevent unevenness and obtain a low sparkling display performance. Also called liquid crystal displays).
[33] The antireflection layer and the antiglare layer can be improved in various kinds and performances according to the use, and by providing various films having such a function in front of the liquid crystal display, the antireflection function or antiglare function can be given to the display for improved visibility. The method is used. The optical film used as these front plates is provided with an antireflection layer or an antiglare layer formed by coating or sputtering or the like.
[34] The anti-glare layer reduces the visibility of the reflective image by blurring the outline of the image reflected on the surface so that the projection of the reflective image is not bothered in use of image display devices such as liquid crystal displays, organic EL displays, and plasma displays.
[35] Proper irregularities can be provided on the surface to achieve this property. Conventionally, as a method of forming such an unevenness | corrugation, the method of adding microparticles | fine-particles to a coating liquid is disclosed (for example, refer Unexamined-Japanese-Patent No. 59-58036 (claim)). In addition, the embossing processing method disclosed in Unexamined-Japanese-Patent No. 6-234175, the method of transferring the mold previously disclosed by Unexamined-Japanese-Patent No. 63-298201, etc. are known. However, the method of forming the unevenness by embossing or transfer is inferior in productivity, and in particular, it is very difficult to form a fine uneven structure.
[36] On the other hand, as a method of forming irregularities using fine particles, a method of producing and applying a coating liquid obtained by dispersing fine particles, for example, inorganic fine particles or organic fine particles in a binder such as resin, is used to form the uneven structure on the surface. In this method, it is a pattern in which the fine particles forming the unevenness are present in the binder layer, and since it is necessary to disperse the fine particles properly, it is difficult to effectively form the desired uneven structure, which is a major obstacle to obtaining a sufficient anti-glare effect as the antiglare film. Had. In addition, when changing the shape of the unevenness, it is necessary to modify the particle size, the compounding amount, the film thickness, etc. of the fine particles, which makes the exchange of varieties very complicated. Moreover, in order to achieve a desired uneven structure, it is necessary to use fine particle with a comparatively large particle size, and as a result, it brought about the fall of the sharpness. Moreover, in the method of forming an anti-glare layer by the above-mentioned application | coating, it has the drawback that the occurrence of a coating | coating stain | stain and adhesiveness with a support body or a lower layer often fall, and also productivity falls, and development of a rapid improvement means is It is requested.
[37] On the other hand, as one of the methods of forming a functional layer, after apply | coating the coating liquid containing actinic-ray-curable resin or thermosetting resin and various microparticles | fine-particles on a base material, the method of hardening | curing by performing actinic irradiation or heat processing is known. (See, for example, Japanese Patent Application Laid-Open No. 2001-310912 (claims), Japanese Patent Application Laid-Open No. 2002-114928 (claims), and Japanese Patent Application Laid-Open No. 2002-120311 (claims). ). However, in the case of forming the antiglare layer using the actinic radiation curable resin or the thermosetting resin according to the coating method, it is necessary to appropriately control the coating liquid or the coating conditions in order to effectively form the desired uneven structure as described above. The amount of work at the time of exchanging is increasing, and it becomes a factor which reduces productivity in production of various products.
[38] In addition, in order to improve visibility, an anti-glare layer or an anti-reflection layer is conventionally provided on the surface of the display device, but an anti-glare film that is more excellent in visibility is required due to colorization and high precision of the display device.
[39] SUMMARY OF THE INVENTION An object of the present invention is a method of forming an antiglare layer having excellent film properties (film uniformity, adhesiveness) and excellent black finish when displaying an anti-glare effect, sharpness, visibility, and moving image, an anti-glare film, and a manufacturing method thereof And an inkjet device for forming an antiglare layer.
[1] BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which shows an example in which the anti-glare layer which consists of an uneven structure by the inkjet system was provided on the transparent base material.
[2] 2 is a cross-sectional view showing an example of another uneven structure constituting the antiglare layer according to the present invention.
[3] 3 is a cross-sectional view showing an example of an ink jet head which can be used in the ink jet method according to the present invention.
[4] 4 is a schematic view showing an example of an inkjet head portion and a nozzle plate which can be used in the present invention.
[5] Fig. 5 is a schematic diagram showing an example of an inkjet method which can be preferably used in the present invention.
[6] 6 is a schematic view showing an example of a preferred manufacturing apparatus used for producing a cellulose ester film according to the present invention.
[7] Fig. 7 is a schematic diagram showing an example in which a fine structure is formed with an ink droplet having a larger particle size by an inkjet method, and then a finer uneven structure is formed with an ink droplet having a smaller particle size.
[8] The schematic diagram which shows an example of the flow which produces an anti-glare film by providing an anti-glare layer by the inkjet system on a transparent base material.
[9] <Brief description of symbols for the main parts of the drawings>
[10] 1, 102 transparent substrate
[11] 2 hard coating layer
[12] 3, 31 ink drops
[13] 10 inkjet head
[14] 12 Piezoelectric Elements
[15] 29, 106 A to E active light irradiation
[16] 35 back rolls
[17] 51 stainless steel circulation belt
[18] 52 die
[19] 53 drying zones
[20] 55 flexible part
[21] 56 Peel Off
[22] 101 Lamination Roll
[23] 103 first coater
[24] 104 A to D back roll
[25] 105 A to D dry zone
[26] 107 plasma processing unit
[27] 108 ink supply tank
[28] 109 Inkjet Discharge Part
[29] 110 heating parts
[30] 113 winding roll
[40] The above object of the present invention is achieved by the following configuration.
[41] 1. An antiglare layer characterized by discharging ink droplets containing an antiglare imparting composition for forming a fine concavo-convex structure by an inkjet method on a transparent substrate to form an antiglare layer having a fine concavo-convex structure on the surface of the substrate. Method of formation.
[42] 2. The method for forming an antiglare layer according to item 1, wherein the center line average roughness Ra of the fine uneven structure is 0.05 to 5.0 µm.
[43] 3. The fine concavo-convex structure according to the above 1 or 2, wherein the fine uneven structure has 1 to 50 convex portions per 100 μm ² having a height of 0.5 to 10 μm based on the bottom of the recess. Formation method of antiglare layer to do.
[44] 4. The method for forming an antiglare layer according to any one of items 1 to 3, wherein the antiglare imparting composition is an active light curable resin.
[45] 5. The method for forming an antiglare layer according to item 4, wherein the actinic light is irradiated immediately after the ink droplets are landed on the transparent substrate.
[46] 6. The method for forming an antiglare layer according to any one of items 1 to 3, wherein the antiglare imparting composition is a thermosetting resin.
[47] 7. The method for forming an antiglare layer according to item 6, wherein heat curing is performed immediately after the ink droplets are landed on the transparent substrate.
[48] 8. The method for forming an antiglare layer according to any one of items 1 to 7, wherein two or more kinds of compositions are ejected with different ink droplets to form irregularities having different refractive indices.
[49] 9. The method for forming an antiglare layer according to any one of items 1 to 8, wherein the two or more kinds of particle diameters are formed by ejecting ink droplets.
[50] 10. The ink droplet according to item 9, wherein after forming a fine concavo-convex structure (first concave-convex structure) on the transparent substrate with an ink droplet having a large particle size (first ink droplet), 2 ink droplets) to form a finer uneven structure (second uneven structure).
[51] 11. The method for forming an antiglare layer according to any one of items 1 to 10, wherein the ink droplet contains fine particles having a particle diameter smaller than that of the ink droplet.
[52] 12. The method for forming an antiglare layer according to any one of items 1 to 10, wherein the ink droplets contain microdroplets having a particle diameter smaller than that of the ink droplets.
[53] 13. The method for forming an antiglare layer according to claim 12, wherein a difference in refractive index between the micro droplets and the ink droplet medium is 0.01 or more.
[54] 14. The method for forming an antiglare layer according to any one of items 1 to 13, wherein the ink jet method provides fine vibration to the ink jet head to eject ink droplets.
[55] 15. The antiglare imparting composition according to any one of items 1 to 14, wherein the transparent base material has a transparent support and at least one hard coating layer thereon, and the hard coating layer has a surface having an antiglare imparting composition. A method of forming an antiglare layer, comprising: discharging ink droplets to be formed to form an antiglare layer having a fine concavo-convex structure on the surface of the hard coating layer.
[56] 16. The method for forming an antiglare layer according to claim 15, wherein when the hard coating layer is in a semi-cured state, a fine concavo-convex structure is formed by ejecting the ink droplets on the hard coating layer surface.
[57] 17. The method for forming an antiglare layer according to the above 15 or 16, wherein after the plasma coating of the hard coating layer, the ink droplets are discharged on the surface of the hard coating layer to form a fine concavo-convex structure.
[58] 18. The method for forming an antiglare layer according to any one of items 15 to 17, wherein the hard coating layer contains a plasticizer.
[59] 19. The antiglare film is produced by forming an antiglare layer on a transparent substrate by the method for forming the antiglare layer according to any one of items 1 to 18.
[60] 20. The method for producing an antiglare film according to item 19, wherein after the antiglare layer is formed on the transparent substrate, an antireflection layer is provided on the antiglare layer.
[61] 21. It was manufactured by the manufacturing method of the anti-glare film of Claim 19 or 20, The anti-glare film characterized by the above-mentioned.
[62] 22. An inkjet device for forming an antiglare layer for producing an antiglare film according to item 21, comprising an active light ray irradiating portion or a heating portion disposed so that no direct acting light or heat acts on the ink jet head portion. Inkjet apparatus for anti-glare layer formation.
[63] 23. Polarizing plate containing anti-glare film of Claim 21.
[64] 24. A display device comprising the polarizing plate of item 23.
[65] MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in view of the said subject, the present inventors discharged the ink droplet which contains the anti-glare provision composition which forms a fine concavo-convex structure by the inkjet system on a transparent base material, and has a fine concavo-convex structure on the surface of this base material. The present invention has been found by forming an antiglare layer having an antiglare layer, which can realize the formation of an antiglare layer having excellent anti-glare effect, clarity and visibility.
[66] More specifically, as a fine concavo-convex structure, the centerline average roughness (Ra) is in the range of 0.05 to 5.0 μm, or the convex portion whose height a is 0.5 to 10.0 μm based on the bottom of the concave is 1 per 100 μm ² . It is preferable to set it as the range of 50-50, and the very fine uneven structure prescribed | regulated above can be implement | achieved by using actinic-ray-curable resin or thermosetting resin as an anti-glare provision composition. In addition, forming an uneven structure having a different refractive index by using ink droplets having two or more different compositions as the ink droplets by the inkjet method, or using ink droplets having two or more different particle sizes, or ink droplets having a large particle size. To form fine concavo-convex structures on the transparent substrate, and then form finer concavo-convex structures into ink droplets having a smaller particle size than the ink droplets, or the ink droplets contain fine particles or microdroplets having a particle size smaller than the ink droplets. By doing so, the present inventors have found that the object effect of the present invention can be further exhibited.
[67] The anti-glare film of this invention is a structure which forms the anti-glare layer prescribed | regulated above on a transparent base material, Although it is also possible to provide an anti-glare layer directly on a transparent base material directly, It is more preferable to provide on the transparent base material which has one or more hard-coat layers. Do. The hard coating layer at this time may be uncured when forming the uneven structure of the antiglare layer, but it is preferable to provide an antiglare layer when the hard coating layer is in a semi-cured state. It is more preferable to provide, or the hard coating layer contains a plasticizer, and by setting it as such a structure, the adhesiveness of a hard coating layer and an anti-glare layer can be improved.
[68] Moreover, in the anti-glare film of this invention, after providing a hard coating layer and an anti-glare layer on a transparent base material by the method mentioned above, it is preferable to further provide an anti-reflection layer on the surface. By setting it as such a structure, a very fine uneven structure can implement | achieve a preferable anti-glare effect and an anti-reflective effect, and can realize the anti-glare film excellent in visibility.
[69] Hereinafter, the present invention will be described in detail.
[70] In the present invention, an ink droplet containing an antiglare imparting composition for forming a fine concavo-convex structure by an inkjet method is ejected on a transparent substrate to form an antiglare layer having a fine concavo-convex structure on the surface of the substrate.
[71] One shape of the fine concavo-convex structure according to the present invention includes a concave-convex shape having a centerline average roughness Ra defined in JIS B 0601 of 0.05 to 5 μm, preferably Ra of 0.07 to 1 μm, and most preferably Ra It is an uneven shape which is 0.1-0.5 micrometer.
[72] Centerline average roughness Ra prescribed | regulated by this invention is what is defined by JIS-B-0601 of JIS surface roughness, and expressed the value calculated | required by following formula (1) in micrometer (micrometer).
[73]
[74] As a measuring method of center line average roughness (Ra), after 25-hour humidity control on 25 degreeC and 65% RH environment, on condition that a measurement sample does not overlap, it can measure and obtain | require in the said environment. The non-overlapping conditions as used herein include a method of winding in a state where the edge portion of a sample is raised, a method of interposing a paper between a sample and a sample, a thick paper, or the like, and forming the four corners. It is either way of fixing. As a measuring apparatus which can be used, RYPLUS non-contact three-dimensional micro surface shape measuring system by a WYKO company, etc. are mentioned, for example.
[75] Moreover, as another shape of the fine uneven structure which concerns on this invention, it is preferable to have 1-50 per 100 micrometers ² convex parts whose height a is 0.5-50.0 micrometers with respect to the bottom of a recessed part.
[76] BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example which provided the anti-glare layer containing an uneven structure on the transparent base material by the inkjet system.
[77] FIG. 1A is a perspective view of an antiglare layer including an uneven structure, and FIG. 1B is a sectional view.
[78] In FIG. 1B, an antiglare layer having a concave-convex structure formed by the ink droplets 3 by an inkjet method after providing a hard coating layer 2 composed of one layer or a plurality on the transparent substrate 1 is formed. Although an example is shown, the height a based on the concave bottom prescribed | regulated by this invention is defined as the height (micrometer) to the top part of an uneven structure by making the surface of the hard coating layer which is a bottom part into a bottom part.
[79] Fine irregularities on the surface of the antiglare layer can be measured by a commercially available foldable surface roughness measuring instrument, a commercially available optical interference surface roughness measuring instrument, or the like. For example, an unevenness is measured two-dimensionally in the range of about 4000 micrometer <^2> (55 micrometers x 75 micrometers) with an optical interference type surface roughness measuring instrument, and an unevenness is distinguished and displayed by color like a contour line from the bottom side.
[80] The number of the convex parts whose height is 0.5 micrometer-10 micrometers based on the adjacent bottom part is counted here, and is represented by the number per area of 100 micrometer <^2> . The measurement measures arbitrary ten points per 1 m <^2> of anti-glare films, and calculate | requires it as the average value.
[81] In the present invention, as the shape of the concave-convex structure constituting the anti-glare layer, an example in which convex portions of the coniferous (cone volcano) type is reached in Fig. 1B is shown, but the present invention is not limited to the concave-convex structure.
[82] It is sectional drawing which shows an example of the other uneven structure which comprises an anti-glare layer.
[83] Fig. 2A is an example of the concave-convex structure impacted in a spherical shape, and the concave-convex structure of such a shape can be formed by appropriately adjusting the viscosity of the ejected ink droplets and the contact angle between the ink droplets and the ink landing surface. . The method of forming the uneven structure by the inkjet method of the present invention is characterized in that the uneven structure of any shape can be formed as compared with the conventional antiglare layer forming method.
[84] FIG.2 (b) is sectional drawing which shows an example of the anti-glare layer containing semi-circular uneven structure.
[85] As the arrangement of the concave-convex structure, in the description of the drawings, an example in which the convex portions are landed at intervals is shown. However, as shown in FIG. 2C, the entire impact surface is covered with the convex portions without providing a gap. It may be.
[86] There is no restriction | limiting in particular as a structure of the anti-glare film of this invention, if an anti-glare layer is formed on a transparent base material, Preferably, after providing one or more hard coating layers on a transparent base material, the unevenness prescribed | regulated above by the inkjet system is preferable. It is preferable to provide an anti-glare layer containing a structure.
[87] Next, the inkjet system which concerns on this invention is demonstrated.
[88] 3 is a cross-sectional view showing an example of the ink jet head which can be used in the ink jet method according to the present invention.
[89] Fig. 3A is a sectional view of the inkjet head, and Fig. 3B is an enlarged view of the A-A line display in Fig. 3A. In the figure, 11 is a substrate, 12 is a piezoelectric element, 13 is a flow path plate, 13a is an ink flow path, 13b is a wall portion, 14 is a common liquid chamber constituent member, 14a is a common liquid chamber, 15 is an ink supply pipe, 16 is a nozzle plate, and 16a. Is a nozzle, 17 is a printed circuit board for driving, 18 is a lead portion, 19 is a driving electrode, 20 is a groove, 21 is a protection plate, 22 is a fluid resistance, 23 and 24 is an electrode, 25 is an upper partition, and 26 is a heater , 27 is a heater power supply, 28 is a heat transfer member, and 10 is an inkjet head.
[90] In the integrated inkjet head 10, the stacked piezoelectric elements 12 having the electrodes 23 and 24 are grooved in the direction of the flow path 13a corresponding to the flow path 13a, and the groove 20 ) And the driving piezoelectric element 12b and the non-driving piezoelectric element 12a. The filler 20 is sealed in the groove 20. The flow path plate 13 is joined to the piezoelectric element 12 in which the groove processing was performed through the upper partition 25. That is, the upper partition 25 is supported by the wall portion 13b sandwiching the non-driven piezoelectric element 12a and an adjacent flow path. The width of the drive piezoelectric element 12b is slightly narrower than the width of the flow path 13a. When the drive piezoelectric element 12b selected by the drive circuit on the driving circuit printed board PCB applies a pulsed signal voltage, this drive piezoelectric The element 12b changes in the thickness direction so that the volume of the flow passage 13a changes through the upper partition 25, and as a result, ink droplets are ejected from the nozzle 16a of the nozzle plate 16.
[91] The heaters 26 are adhered to the flow path plate 13 via the heat transfer members 28, respectively. The heat transfer member 28 is provided around the nozzle surface. The heat transfer member 28 efficiently transfers heat from the heater 26 to the flow path plate 13, and also transfers heat from the heater 26 to the vicinity of the nozzle surface to warm the air near the nozzle surface. Therefore, a material having good thermal conductivity is used. For example, metals, such as aluminum, iron, nickel, copper, stainless, or ceramics, such as SiC, BeO, AlN, etc. are mentioned as a preferable material.
[92] When the piezoelectric element is driven, it is displaced in a direction perpendicular to the longitudinal direction of the flow path and the volume of the flow path is changed, and ink droplets are ejected from the nozzle as the volume changes. The piezoelectric element is provided with a signal that always keeps the flow path volume small, displaces it in the direction of increasing the flow volume volume with respect to the selected flow path, and then applies a pulse signal that provides a displacement that reduces the flow volume of the flow path. Ink is ejected as ink droplets from a nozzle to be used.
[93] 4 is a schematic view showing an example of an inkjet head portion and a nozzle plate which can be used in the present invention.
[94] In FIG. 4, FIG. 4A is a sectional view of the head portion and FIG. 4B is a plan view of the nozzle plate. In the figure, 1 is a transparent base material, 31 is an ink droplet, 32 is a nozzle, and 29 is an active light irradiation part. The ink droplets 31 ejected from the nozzle 32 are adheringly attached in the direction of the transparent substrate 1. The ink droplets landed on the transparent substrate 1 are immediately irradiated with the active light from the active light irradiation unit 29 disposed in the upstream portion thereof and cured. In addition, 35 is a back roll holding the transparent base material 1.
[95] In the present invention, as shown in Fig. 4B, the nozzles of the inkjet head portion are preferably arranged in a zigzag shape, and are preferably provided in multiple stages in parallel in the conveying direction of the transparent base material 1. In addition, it is desirable to provide a fine vibration to the inkjet head portion at the time of ink ejection and to allow ink droplets to land on the transparent substrate randomly. As a result, the generation of interference fringes can be suppressed. Fine vibrations can be provided by high frequency voltage, sound waves, ultrasonic waves, and the like, but are not particularly limited thereto.
[96] As the method for forming the antiglare layer used in the present invention, it is preferable to use an inkjet method in which ink droplets are ejected from the multi-nozzle and formed.
[97] In FIG. 5, FIG. 5A shows the method of arranging the inkjet head 10 in the width direction of the transparent base material 1, and forming an anti-glare layer on the surface while conveying the transparent base material 1 (line head method). 5B is a method of forming an antiglare layer on the surface of the inkjet head 10 while moving in the sub-scanning direction (flat head method), and in FIG. 5C, the inkjet head 10 is transparent. It is a method (capstan method) which forms an anti-glare layer on the surface, scanning the width direction on the base material 1, and can use either method, but in this invention, a line head system is preferable from a productivity viewpoint. In addition, 29 in FIGS. 5A-C) is an active light irradiation part used when using actinic-rays curable resin mentioned later as ink.
[98] In addition, in this invention, another active light irradiation part can also be provided in the downstream of the conveyance direction of the transparent base material of FIG. 5 a), b), c).
[99] In the present invention, in order to form fine unevenness, 0.1 to 100 pl is preferable as the ink droplet, more preferably 0.1 to 50 pl, and particularly preferably 0.1 to 10 pl. By discharging ink droplets under the above conditions, an antiglare film having fine irregularities having excellent visibility can be obtained.
[100] The viscosity of the ink droplets is preferably 0.1 to 100 mPa · s at 25 ° C., more preferably 0.1 to 50 mPa · s.
[101] Next, the transparent base material which can be used by this invention is demonstrated.
[102] As a transparent base material which concerns on this invention, an easy thing, a thing with favorable adhesiveness with an anti-glare layer or an antireflection layer, etc., an optically isotropic thing, an optically transparent thing, etc. are mentioned as a preferable requirement.
[103] In this invention, transparent means that the transmittance | permeability of visible light is 60% or more, Preferably it is 80% or more, Especially preferably, it is 90% or more.
[104] Although it does not specifically limit if it has the said property, For example, a cellulose ester film, a polyester film, a polycarbonate film, a polyallylate film, a polysulfone (including polyether sulfone) type film, a polyethylene terephthalate Polyester films such as polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, cellulose diacetate films, cellulose triacetates, cellulose acetate butyrate films, polyvinylidene chloride films, polyvinyl alcohol films, ethylene vinyl alcohol films, Syndiotactic polystyrene film, polycarbonate film, norbornene resin film (Aton (manufactured by JSR), Xeonex, Zeonea (above, manufactured by Nihon Xeon)), polymethylpentene film, polyetherketone film, Polyether ketone imide film, polyamide film, fluorine water It may be a film, a nylon film, polymethyl methacrylate film, an acrylic film or a glass plate or the like. Among them, cellulose triacetate film, polycarbonate film and polysulfone (including polyether sulfone) are preferable, and in the present invention, in particular, a cellulose ester film (e.g., Konica-Tak product name KC8UX2MW, KC4UX2MW, KC50UN, KC12VR (Konica ( Note) Manufacture)) is preferably used from the viewpoint of production, cost, transparency, isotropy, adhesiveness and the like.
[105] Retardation value of the transparent film in the direction of the optical characteristics as retardation value R _t is 0 nm to 300 nm, the thickness direction of the surface of the base R _O is used preferably in the 0 nm to 1000 nm.
[106] In this invention, it is preferable to use a cellulose ester film as a transparent base material. As cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable, and cellulose acetate butyrate and cellulose acetate propionate are used especially preferably.
[107] In particular, when the degree of substitution of the acetyl group is X, the propionyl group or the butyryl group, Y, the antiglare layer and the antireflection layer are formed on a transparent substrate having a mixed fatty acid ester of cellulose in which X and Y are in the following range. The anti-glare film provided is preferably used.
[108] 2.3≤X + Y≤3.0
[109] 0.1≤Y≤1.2
[110] Specifically, 2.5≤X + Y≤2.85
[111] It is preferable that 0.3 <= Y <= 1.2.
[112] When using a cellulose ester as a transparent base material which concerns on this invention, although it does not specifically limit as a raw material cellulose of a cellulose ester, Cotton linter, a wood pulp (derived from softwood, derived from a hardwood), Kenaf etc. are mentioned. In addition, the cellulose ester obtained from these can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), the cellulose ester is reacted with a cellulose raw material using an organic solvent such as acetic acid or methylene chloride, and a protic catalyst such as sulfuric acid. You can get it by
[113] When the acylating agent is an acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can synthesize | combine with reference to the method of Unexamined-Japanese-Patent No. 10-45804, etc. In addition, the cellulose ester used for this invention mixes and reacts the said acylating agent amount according to each substitution degree, and, in the cellulose ester, these acylating agents react with the hydroxyl group of a cellulose molecule. Cellulose molecules include those in which a plurality of glucose units are linked and there are three hydroxyl groups in the glucose unit. The number which the acyl group derived from these three hydroxyl groups is called substitution degree (mol%). For example, cellulose triacetate has an acetyl group bonded to all three hydroxyl groups in the glucose unit (actually 2.6 to 3.0).
[114] The cellulose ester used in the present invention is particularly preferably a mixed fatty acid ester of cellulose having a propionate group or a butylate group bonded thereto in addition to an acetyl group such as cellulose acetate propionate, cellulose acetate butyrate or cellulose acetate propionate butyrate. Used. The butyryl group forming the butyrate may be linear or branched.
[115] The cellulose acetate propionate containing a propionate group as a substituent is excellent in water resistance and is useful as a film for liquid crystal image display devices.
[116] The measuring method of substitution degree of an acyl group can be measured according to the prescription | regulation of ASTM-D 817-96.
[117] The number average molecular weight of the cellulose ester is preferably 70,000 to 250,000 when the molded product has a high mechanical strength and a suitable doping viscosity, more preferably 80,000 to 150,000.
[118] Hereinafter, the manufacturing method of the support body by a casting film forming method is demonstrated.
[119] These cellulose esters are pressurized dies on an endless metal belt or rotating support of a rotating metal drum, for example, which transfers a cellulose ester solution (doping liquid) generally called a solution casting film forming method, as described later. It is preferably produced by a method of casting (casting) the doping liquid from the film.
[120] As an organic solvent used for manufacture of these dope liquids, a cellulose ester can be melt | dissolved and it is preferable that it is a suitable boiling point, for example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1 , 3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3 -Difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2 Propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone, and the like; organic halogen compounds such as methylene chloride, Dioxolane derivative, methyl acetate, ethyl acetate, acetone, etc. are mentioned as a preferable organic solvent (namely, a good solvent).
[121] In addition, as shown in the following film forming step, in the solvent evaporation step, when drying the solvent from the web (doped film) formed on the support for casting, as a boiling point of the organic solvent used from the viewpoint of preventing foaming in the web 30-80 degreeC is preferable, For example, the boiling point of the above-mentioned good solvent is methylene chloride (boiling point 40.4 degreeC), methyl acetate (boiling point 56.32 degreeC), acetone (boiling point 56.3 degreeC), ethyl acetate (boiling point 76.82 degreeC), etc. .
[122] Among the above good solvents, methylene chloride and methyl acetate excellent in solubility are preferably used, and it is particularly preferable that methylene chloride is contained in an amount of 50% by weight or more based on the total organic solvents.
[123] In addition to the organic solvent, it is preferable to contain 0.1 to 30% by weight of an alcohol having 1 to 4 carbon atoms. It is particularly preferable that the alcohol is included at 5 to 30% by weight. They soften the above-mentioned dope solution to the casting support, and then, when the solvent starts to evaporate and the proportion of the alcohol increases, the gel (gelling) is gelled, and the web is made strong to facilitate peeling from the casting support. When used as a solvent or when these ratios are small, it also has a role which accelerate | stimulates the dissolution of the cellulose ester of a non-chlorine organic solvent.
[124] Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, and the like.
[125] Among these solvents, ethanol is preferable from the viewpoint of good doping stability, relatively low boiling point, good dryness and no toxicity. Preference is given to using a solvent comprising 5% to 30% by weight of ethanol relative to 70% to 95% by weight of methylene chloride. Methyl acetate may be used instead of methylene chloride. At this time, a dope liquid can be manufactured by a cooling solution method.
[126] It is preferable that the cellulose-ester film used in this invention is extended | stretched at least in the width direction, and it is especially preferable to be drawn by 1.01 times-1.5 times in the width direction when peeling residual volume is 3 weight%-40 weight% in a solution casting process. . More preferably, the film is biaxially stretched in the width direction and the longitudinal direction, and is preferably stretched at 1.01 times to 1.5 times in the width direction and the length direction, respectively, when the peeling residual capacity is 3% by weight to 40% by weight. By doing in this way, the anti-glare low reflection film excellent in visibility can be obtained. Moreover, deterioration of the shape which dries when storing an elongate anti-glare film in roll shape can be remarkably improved by carrying out biaxial stretching and naring process mentioned later.
[127] As draw ratio at this time, 1.01 times-1.5 times are preferable, Especially preferably, they are 1.03 times-1.45 times.
[128] More preferably, the improvement effect of the storage stability of a roll-shaped anti-glare film is obtained by adjusting the number of the processus | protrusion on the back surface side mentioned later in a predetermined range.
[129] In this invention, it is preferable that a biaxially stretched cellulose-ester film is 90% or more of light transmittance, More preferably, it is 93% or more of a transparent support body.
[130] It is preferable that the thickness of the cellulose-ester film support body which concerns on this invention is 10 micrometers-100 micrometers, It is preferable that moisture permeability is 200 g / m <^{2> *} 24 hours or less, More preferably, it is 10-180 g / m <^2>. It is 24 hours or less, Especially preferably, it is 160 g / m <^{2> *} 24 hours or less. It is preferable that water vapor permeability in the film thickness of 10 micrometers-60 micrometers exists in the said range especially.
[131] Here, the moisture permeability of the support body can measure the moisture permeability of each sample according to the method described in JIS Z 0208.
[132] In this invention, a long film can be used, Specifically, it is a thing of the form which shows about 100 m-5000 m, and is normally provided in roll shape. Moreover, it is preferable to perform the naring process of the said long film described below. Here, naring processing is demonstrated.
[133] In the present invention, it is preferable that a so-called naring process is performed to impart unevenness to both ends in the width direction of the elongated film to make the end portion bulky. Here, the naring height is defined as in Equation 2 below.
[134] Ratio X (%) to film thickness (d: μm) of naring height (a: μm) = (a / d) × 100
[135] In this invention, it is preferable that it is the range of X = 1 to 25%, 5%-20% are more preferable, 10%-15% are especially preferable.
[136] Moreover, in this invention, it is preferable to provide said naring process before winding up after completion | finish of drying in the film forming process of a film.
[137] When using a cellulose-ester film for the support body of the anti-glare film of this invention, it is preferable to contain the same plasticizer as used for the hard-coat layer mentioned later.
[138] It is preferable to use these plasticizers individually or in combination.
[139] As for the usage-amount of these plasticizers, 1 weight%-20 weight% are preferable with respect to a cellulose ester from a film performance, workability, etc., Especially preferably, they are 3 weight%-13 weight%.
[140] The ultraviolet absorber used for the support body which concerns on this invention is demonstrated. A ultraviolet absorber is used suitably for the support body for anti-glare low reflection film.
[141] As the support for an antiglare film of the present invention, the same ultraviolet absorber as described above in the ink to be described later is preferably used.
[142] As an ultraviolet absorber, the thing excellent in the absorption ability of the ultraviolet-ray of wavelength 370 nm or less, and the absorption of visible light of wavelength 400 nm or more from a viewpoint of favorable liquid crystal display property is used preferably.
[143] In addition, the same fine particle as what was described in ink can be used for the cellulose-ester film used for this invention in order to provide lubricity.
[144] As a primary average particle diameter of the microparticles | fine-particles added to the cellulose-ester film used for this invention from a viewpoint of suppressing haze low, 20 nm or less is preferable, More preferably, it is 5-16 nm, Especially preferably, it is 5-12 nm. to be. It is preferable that these microparticles | fine-particles form the secondary particle of the particle size of 0.1-5 micrometers, and are contained in a cellulose-ester film, A preferable average particle diameter is 0.1-2 micrometers, More preferably, it is 0.2-0.6 micrometer. As a result, irregularities having a height of about 0.1 μm to 1.0 μm may be formed on the surface of the film, thereby providing appropriate lubricity to the surface of the film.
[145] The measurement of the primary average particle diameter of the microparticles | fine-particles used for this invention observes particle | grains with a transmission electron microscope (500,000-2 million times magnification), observes 100 particle | grains, and makes the average value into a primary average particle diameter.
[146] As apparent specific gravity of microparticles | fine-particles, 70 g / liter or more is preferable, More preferably, it is 90-200 g / liter, Especially preferably, it is 100-200 g / liter. The higher the specific specific gravity, the higher the concentration of the dispersion liquid can be produced, the haze and the aggregates are good, which is preferable, and is also particularly preferably used when preparing a high solid concentration dope as in the present invention.
[147] Silicon dioxide fine particles having an average particle diameter of primary particles of 20 nm or less and an apparent specific gravity of 70 g / liter or more can be obtained by, for example, burning a mixture of vaporized silicon tetrachloride and hydrogen in air at 1000 to 1200 ° C. Moreover, it is marketed under the brand names of Aerosil 200V and Aerosil R972V (above Nippon Aerosil Co., Ltd. make), for example, and can use these.
[148] The apparent specific gravity described above is calculated by the following equation 3 by taking silicon dioxide fine particles into a certain amount of a measuring cylinder and measuring the weight at this time.
[149] Apparent specific gravity (g / liter) = mass of silicon dioxide (g) ÷ volume of silicon dioxide (liter)
[150] As a method of manufacturing the dispersion liquid of microparticles | fine-particles used for this invention, three types as shown below are mentioned, for example.
[151] <Manufacturing method A>
[152] The solvent and the fine particles are stirred and mixed, and then dispersed with a disperser. This is called particulate dispersion. The fine particle dispersion is added to the dope and stirred.
[153] <Manufacturing method B>
[154] The solvent and the fine particles are stirred and mixed, and then dispersed with a disperser. Let this be a fine particle dispersion. Separately, a small amount of cellulose triacetate is added to the solvent and dissolved by stirring. The fine particle dispersion is added thereto and stirred. This is called fine particle addition liquid. The particulate additive liquid is sufficiently mixed with the dope liquid with an inline mixer.
[155] <Manufacturing method C>
[156] A small amount of cellulose triacetate is added to the solvent and dissolved by stirring. The fine particles are added thereto and dispersed in a disperser. Let this be a fine particle addition liquid. The particulate additive is sufficiently mixed with the dope in an inline mixer.
[157] The manufacturing method A is excellent in the dispersibility of silicon dioxide microparticles | fine-particles, and the manufacturing method C is excellent in the silicon dioxide microparticles | fine-particles being difficult to reaggregate. Especially, the manufacturing method B mentioned above is a preferable manufacturing method which was excellent in both dispersibility of silicon dioxide microparticles | fine-particles, and silicon dioxide microparticles | fine-particles being difficult to reaggregate.
[158] <Dispersion method>
[159] As for the density | concentration of silicon dioxide at the time of mixing and disperse | distributing silicon dioxide microparticles | fine-particles to a solvent etc., 5 weight%-30 weight% are preferable, 10 weight%-25 weight% are more preferable, and 15-20 weight% is the most preferable. The higher the dispersion concentration, the more preferable the liquid turbidity with respect to the added amount, and the haze and the aggregate become good.
[160] The solvent used may preferably include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvent other than lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.
[161] The amount of the silicon dioxide fine particles added to the cellulose ester is preferably 0.01 to 0.3 parts by weight, more preferably 0.05 to 0.2 parts by weight, more preferably 0.08 to 0.12 parts by weight based on 100 parts by weight of the cellulose ester. desirable. The amount of addition is excellent in the dynamic friction coefficient, and the amount of addition is excellent in the low haze and less aggregates.
[162] The disperser can use a conventional disperser. The disperser is largely divided into a media disperser and a medialess disperser. Dispersion of silicon dioxide fine particles is preferable because the medialess disperser has a low haze.
[163] A ball mill, a sand mill, a dyno mill etc. are mentioned as a media disperser.
[164] As the medialess disperser, there are an ultrasonic type, a centrifugal type, a high pressure type and the like, but in the present invention, a high pressure dispersion device is preferable. The high pressure dispersing device is a device that creates special conditions such as high shear and high pressure by passing a mixture of fine particles and a solvent at high speed through customs. When treating with a high pressure dispersing apparatus, it is preferable that the maximum pressure condition inside the apparatus is, for example, 9.807 MPa or more in the tubule having a tube diameter of 1 to 2000 µm. More preferably, it is 19.613 MPa or more. Moreover, at that time, it is preferable that the highest achieved speed reaches 100 m / sec or more and the heat transfer speed reaches 420 kJ / hour or more.
[165] Such a high pressure dispersion device includes an ultra high pressure homogenizer manufactured by Microfluidics Corporation (trade name Microfluidizer) or a nanomizer manufactured by Nanomizer Inc., in addition, a manton gorin type high pressure dispersion device, for example Izumi hood machine manufacture homogenizer, Sangwa Co., Ltd. UHN-01, etc. are mentioned.
[166] Moreover, it is preferable to cast the doping liquid containing fine particles so as to be in direct contact with the flexible support because a high lubricity and a low haze film are obtained.
[167] In addition, packaging is usually performed in order to protect the product from contamination or adhesion of dust by static electricity until it is shipped in rolls. This packaging material is not particularly limited as long as the above object is achieved, but it is preferable not to disturb volatilization of residual solvent from the film. Specifically, polyethylene, polyester, polypropylene, nylon, polystyrene, paper, various nonwoven fabrics, etc. are mentioned. It is more preferably used that the fiber has become a reticulated cross.
[168] The cellulose-ester film which concerns on this invention may have a multilayered constitution by the covalent smoke method etc. which used several doping liquid.
[169] Covalent lead is a sequential multilayer flexible method of two- or three-layer configuration through another die, a simultaneous multilayer flexible method of two- or three-layer configuration by joining in a die having two or three slits, and a sequential multilayer flexible method. Any of the multilayer casting methods in which simultaneous multilayer casting is combined may be used.
[170] An example of the preferable manufacturing apparatus used for manufacture of the cellulose-ester film which concerns on this invention is demonstrated using FIG.
[171] In FIG. 6, the stainless circulation belt 51 is circulated between the drying zone 53 and the drying zone 54. The doping composition is cast from the die 52 on the stainless endless belt 51 in the flexible part 55 and conveyed in the direction of the arrow to be dried in the drying zone 53 and the drying zone 54 to be removed at the peeling part 56. It peels from the stainless steel circulation belt 51 by the peeling roll 57. The peeled film also passes through the first drying zone 58 and is transported from the second drying zone 60 to the third drying zone 61 and wound up in the windings 62 as a product. In addition, the 1st drying zone 58 and the 3rd drying zone 61 are conveyed by the conveyance roll 59 in order to hold a path long.
[172] In the 2nd drying zone, it extends in the width | variety or both directions of width | variety and length by extending | stretching means, such as a tenter.
[173] In addition, the cellulose ester used by this invention is used suitably as a support body with little thing of a bright point foreign material at the time of using a film. In the present invention, a bright spot foreign material is two polarizers orthogonally arranged (cross nicol), a cellulose ester film is disposed between them, and the light of the light source is observed from one side to observe the cellulose ester film from the other side. When the light from the light source leaks.
[174] At this time, it is preferable that the polarizing plate used for evaluation is comprised from the protective film without a bright spot foreign material, and the thing using the glass plate for the protection of a polarizer is used preferably. The occurrence of bright spot foreign matter is considered to be one of the causes of the unacetized cellulose contained in the cellulose ester, and the countermeasure is to use a cellulose ester having a small amount of acetylated cellulose which is not acetylated, or to filter the doping solution in which the cellulose ester is dissolved. Removal and reduction are possible. Further, the thinner the film thickness, the smaller the number of bright spot foreign matters per unit area, and the smaller the content of the cellulose ester contained in the film, the smaller the bright spot foreign matters tends to be.
[175] It is preferable that the bright spot foreign material has a diameter of 0.01 mm or more at 200 or less / cm ² or less, and more preferably 100 or less cm / cm ² , 50 or less cm ² or less, 30 or less cm ² or less, or 10 or less cm ^2. Although it is preferable that it is the following, Especially preferably, it is zero.
[176] In addition, it is preferable that it is 200 pieces / cm <^2> or less also about the bright point of 0.005 mm-0.01 mm, More preferably, it is 100 pieces / cm <^2> or less, 50 pieces / cm <^2> or less, 30 pieces / cm <^2> or less, 10 pieces / cm ^Although it is preferable that it is ² or less, Especially preferable thing is a case where a bright point is zero. The smaller ones are also preferred for bright spots of 0.005 mm or less.
[177] In the case where the bright spot foreign matter is removed by filtration, it is preferable to filter the composition to which the plasticizer is added and mixed rather than to filter the cellulose ester dissolved alone, since the removal efficiency of the bright spot foreign matter is high. As a filter medium, although conventionally well-known things, such as fluororesins, such as glass fiber, a cellulose fiber, a filter paper, and ethylene tetrafluoride resin, are used preferably, a ceramic, a metal, etc. are also used preferably. As absolute filtration precision, 50 micrometers or less are preferable, More preferably, it is 30 micrometers or less and 10 micrometers or less, Especially preferably, it is 5 micrometers or less.
[178] These can be used in combination suitably. The filter medium may be either a surface type or a dips type, but the dip type is preferably used because it is relatively hard to block.
[179] Then, the ink used by the inkjet system which concerns on this invention is demonstrated. Although the ink which concerns on this invention contains the anti-glare provision composition which forms a fine uneven structure by the inkjet system, it is preferable that it is actinic-ray curable resin or a thermosetting resin as this anti-glare provision composition.
[180] First, the actinic-rays curable resin which concerns on this invention is demonstrated.
[181] Actinic-ray-curable resin is resin which hardens | cures via crosslinking reaction etc. by actinic light irradiation, such as an ultraviolet-ray or an electron beam. Examples of the actinic ray curable resins include ultraviolet curable resins and electron beam curable resins, but may be resins cured by actinic ray irradiation other than ultraviolet rays or electron beams.
[182] Examples of the ultraviolet curable resin include ultraviolet curable acrylic urethane resins, ultraviolet curable polyester acrylate resins, ultraviolet curable epoxy acrylate resins, ultraviolet curable polyol acrylate resins or ultraviolet curable epoxy resins.
[183] UV-curable acrylurethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as methacrylate) to products obtained by reacting an isocyanate monomer or a prepolymer with a polyester polyol. It can be obtained easily by making the acrylate-type monomer which has hydroxyl groups, such as an acrylate and 2-hydroxypropyl acrylate, react as containing. For example, a mixture of 100 parts of Unidiq 17-806 (manufactured by Dainippon Ink Co., Ltd.) and one part of colonate L (manufactured by Nippon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferable. Is used.
[184] UV-curable polyester acrylate resins can generally be easily obtained by reacting monomers such as 2-hydroxyethyl acrylate, glycidyl acrylate, and acrylic acid with hydroxyl or carboxyl groups at the polyester end (eg, Japan). Patent Publication No. 59-151112).
[185] An ultraviolet curing epoxy acrylate type resin is obtained by making monomers, such as acrylic acid, an acrylic acid chloride, and glycidyl acrylate, react with the hydroxyl group of the terminal of an epoxy resin.
[186] As ultraviolet curing polyol acrylic resin type, ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythrate Lithitol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl modified dipentaerythritol pentaacrylate, etc. are mentioned.
[187] The epoxy type actinic-ray reactive compound useful as an example of an ultraviolet curing epoxy acrylate resin and an ultraviolet curing epoxy resin is shown.
[188] (a) Glycidyl ether of bisphenol A (this compound is obtained as a mixture of different degrees of polymerization by reaction of epichlorohydrin and bisphenol A)
[189] (b) A compound having a glycidyl ether group at its terminal by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OH such as bisphenol A.
[190] (c) glycidyl ether of 4,4'-methylenebisphenol
[191] (d) Epoxy compound of phenol formaldehyde resin of novolak resin or resol resin
[192] (e) Compounds having alicyclic epoxides such as bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy- 6-cyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl pimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1 -Methylcyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3', 4'-epoxy-1'-methylcyclohexanecarboxylate , 3,4-epoxy-6-methyl-cyclohexylmethyl-3 ', 4'-epoxy-6'-methyl-1'-cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5' , 5'-spiro-3 ", 4" -epoxy) cyclohexane-meta-dioxane
[193] (f) Diglycidyl ethers of dibasic acids, for example glycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl phthalate
[194] (g) diglycidyl ethers of glycols, for example ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, copoly (ethylene glycol-propylene glycol) diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether
[195] (h) glycidyl esters of polymeric acids, for example polyacrylic acid polyglycidyl esters, polyester diglycidyl esters
[196] (i) glycidyl ethers of polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropanetriglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether Cyl ether, glucotriglycidyl ether
[197] (j) Diglycidyl ether of 2-fluoroalkyl-1,2-diol is the same as the example of the compound exemplified in the fluorine-containing epoxy compound of the fluorine-containing resin of the low refractive index material
[198] (k) As a fluorine-containing alkane terminal diol glycidyl ether, the fluorine-containing epoxy compound etc. of the fluorine-containing resin of the said low refractive index substance are mentioned.
[199] The molecular weight of the said epoxy compound is 2000 or less as an average molecular weight, Preferably it is 1000 or less.
[200] When hardening the said epoxy compound by actinic light, in order to raise hardness, it is effective to mix and use the compound which has a polyfunctional epoxy group of (h) or (i).
[201] A photoinitiator or a photosensitizer for cationic polymerization of an epoxy-based active light reactive compound is a compound capable of releasing a cationic polymerization initiation material by active light irradiation, and particularly preferably a Lewis acid having a cationic polymerization initiation property by irradiation. It is double salt of group 1 of onium salt releasing.
[202] The actinic light-reactive compound epoxy resin is not formed by radical polymerization but forms a polymerization, a crosslinked structure or a network structure by cationic polymerization. Unlike radical polymerization, it is a preferred actinic light reactive resin because it is not affected by oxygen in the reaction system.
[203] The actinic light-reactive epoxy resin useful in the present invention is polymerized by a photoinitiator or a photosensitizer which releases a substance which initiates cationic polymerization by actinic light irradiation. As a photoinitiator, the 1st group of the double salt of the onium salt which releases the Lewis acid which starts cationic polymerization by light irradiation is especially preferable.
[204] Representative of these is a compound represented by the following formula (3).
[205] [(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{w +} [MeX _v ] ^w-
[206] Wherein the cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg I, Br, Cl), or N = N (diazo), R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are integers of 0 to 3, respectively, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid that is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is halogen, w is the actual charge of the halogenated complex ions, and v is the number of halogen atoms in the halogenated complex ions.
[207] Anions of the formula 3 [MeX _v] ^w- Specific examples of tetrafluoroborate (BF ₄ ^-), phosphate, tetrafluoroborate (PF ₄ ^-), antimonate tetrafluoroethylene (SbF ₄ ^-), are tetrafluoroethylene Senate (AsF ₄ ^-), tetrachloro antimonate (SbCl ₄ ^-) and the like.
[208] In addition, other anions as perchloric acid ion (ClO ₄ ^-), and the like, toluenesulfonic acid ion, trinitro benzene acid anion, methyl sulfite ion (CF ₃ SO ₃ ^{- -)} trifluoroacetic acid ion fluoro (FSO ₃₎ .
[209] Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator, and among them, the aromatic halonium salts described in Japanese Patent Application Laid-open Nos. 50-151996, 50-158680, etc., Japanese Patent Publication No. 50-151997, VIA aromatic onium salts described in Japanese Patent Application Laid-Open Nos. 52-30899, 59-55420, 55-125105, Japanese Patent Laid-Open No. 56-8428, 56-149402, 57-192429 and the like. Aluminium salts, aromatic diazonium salts described in Japanese Patent Publication No. 49-17040 and the like, thiophyllilium salts described in US Patent No. 4,139,655 and the like are preferable. Moreover, an aluminum complex, a photodegradable silicon compound type polymerization initiator, etc. are mentioned. The said cationic polymerization initiator and photosensitizers, such as benzophenone, benzoin isopropyl ether, and thioxanthone, can be used together.
[210] In the case of an active light reactive compound having an epoxy acrylate group, a photosensitizer such as n-butylamine, triethylamine and tri-n-butylphosphine can be used. The photosensitizer and photoinitiator used for this actinic light-reactive compound are enough to start a photoreaction at 0.1 weight part-15 weight part with respect to 100 weight part of ultraviolet-ray reactive compounds, Preferably they are 1 weight part-10 weight part. It is preferable that this sensitizer has an absorption maximum in the visible light region from the near ultraviolet region.
[211] In the actinic ray-curable resin composition useful in the present invention, the polymerization initiator is preferably used in an amount of 0.1 to 15 parts by weight, more preferably 1 part by weight, based on 100 parts by weight of the actinic ray-curable epoxy resin (prepolymer). Addition in the range of 10 parts by weight to 10 parts by weight is preferred.
[212] Moreover, an epoxy resin can also be used together with the said urethane acrylate type resin, polyether acrylate type resin, etc. In this case, it is preferable to use an active light radical polymerization initiator and an active light cationic polymerization initiator together.
[213] Moreover, an oxetane compound can also be used for the anti-glare layer which concerns on this invention. The oxetane compound to be used is a compound having a three-membered ring oxetane ring containing oxygen or sulfur. Especially, the compound which has an oxetane ring containing oxygen is preferable. The oxetane ring may be substituted with a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxyl group, an allyloxy group, an acetoxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodinemethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) Oxetane, 3-methyl-3chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) jade Cetane, 3, 3- dimethyl oxetane, etc. are mentioned. Moreover, in this invention, any of a monomer, an oligomer, and a polymer may be sufficient.
[214] Specific examples of ultraviolet curable resins that can be used in the present invention include, for example, KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B of the adekaoptomer KR, BY series ( Asahi Denka Kogyo Co., Ltd.), Koei hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T -102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (above, manufactured by Koei Kagaku Kogyo Co., Ltd.), PHC 2210 of Seika Beam ( S), PHCX-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, Daiichi Seika High School ( Manufacturing), KRM7033, KRM7039, KRM7130, KRM713l, UVECRYL29201, UVECRYL29202 (above, Daicel Ushibi Co., Ltd.), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC -5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (above, manufactured by Dainippon Ink Chemical Co., Ltd.), Orex No.340 Kriya Koo Paint Co., Ltd.), Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 ( Sangyo Sankyo Co., Ltd.), SP-1509, SP-1507 (above, Showa Kobunshi Co., Ltd.), RCC-15C (Grace Japan Co., Ltd.), Alonics M-6100 , M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.), or other commercially available ones, can be appropriately selected and used.
[215] In the ink according to the present invention, a binder such as a known thermoplastic resin or hydrophilic resin such as gelatin can be mixed with the above-mentioned actinic curable resin and used. It is preferable that these resins have a polar group in the molecule. As the polar group, -COOM, -OH, -NR ₂ , -NR ₃ X, -SO ₃ M, -OSO ₃ M, -PO ₃ M ₂ , -OPO ₃ M (wherein M represents a hydrogen atom, an alkali metal or an ammonium group) , X represents an acid forming an amine salt, R represents a hydrogen atom, an alkyl group), and the like.
[216] In order to initiate the photopolymerization or photocrosslinking reaction of the actinic light-reactive compound used in the present invention, the actinic light-reactive compound is initiated only by the actinic light-reactive compound alone, but it is preferable to use a photosensitizer or a photoinitiator because the induction group of the polymerization is long or the initiation of polymerization is slow. Thus, the polymerization can be speeded up.
[217] When the ink concerning this invention contains actinic-rays curable resin, a photoreaction initiator and a photosensitizer can be used at the time of irradiation of actinic light.
[218] Specific examples thereof include acetophenone, benzophenone, hydroxybenzophenone, mihiraketone, α-amyl oxime ester, thioxanthone and the like and derivatives thereof. Moreover, when using a photoreactive agent for the synthesis | combination of epoxy acrylate type resin, sensitizers, such as n-butylamine, triethylamine, and tri-n-butylphosphine, can be used.
[219] Moreover, when using ultraviolet curable resin as actinic radiation curable resin, a ultraviolet absorber can also be included in an ultraviolet curable resin composition to the extent which does not prevent the photocuring of the said ultraviolet curable resin.
[220] As an ultraviolet absorber, the thing excellent in the absorption ability of the ultraviolet-ray of wavelength 370 nm or less, and the absorption of visible light of wavelength 400 nm or more from a viewpoint of favorable liquid crystal display property is used preferably.
[221] As a specific example of the ultraviolet absorber used preferably for this invention, an oxybenzophenone type compound, a benzotriazole type compound, a salicylic acid ester type compound, a benzophenone type compound, a cyanoacrylate type compound, a nickel complex salt type compound, etc. are mentioned, for example. Can be, but is not limited to these.
[222] As a benzotriazole type ultraviolet absorber, the compound represented by following formula (1) is used preferably.
[223]
[224] In formula, R <_1> , R <_2> , R <_3> , R <_4> and R <_5> may be same or different, and a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxyl group, an acyl An oxy group, an aryloxy group, an alkylthio group, an arylthio group, a mono or dialkylamino group, an acylamino group or a 5 to 6 membered heterocyclic group, and R ₄ and R ₅ are ring-closed to form a 5 to 6 membered carbocyclic ring You may.
[225] In addition, these groups described above may have any substituent.
[226] Although the specific example of the ultraviolet absorber which concerns on this invention is given to the following, this invention is not limited to these.
[227] UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole
[228] UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole
[229] UV-3: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole
[230] UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole
[231] UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidemethyl) -5'-methylphenyl) benzotriazole
[232] UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
[233] UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole
[234] UV-8: 2- (2H-benzotriazol-2-yl) -6- (straight and branched dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
[235] UV-9: octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3 A mixture of -tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
[236] Moreover, as a benzophenone type ultraviolet absorber, the compound represented by following formula (2) is used preferably.
[237]
[238] In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group and a phenyl group, and these alkyl groups, alkenyl groups and phenyl groups may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a -CO (NH) _n - ₁ -D group, and D represents a phenyl group which may have an alkyl group, an alkenyl group or a substituent . m and n represent 1 or 2.
[239] In the above, the alkyl group is, for example, a straight chain or branched aliphatic group having up to 24 carbon atoms, and the alkoxyl group is, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group is, for example, up to 16 carbon atoms. Allyl group, 2-butenyl group, etc. are shown as group. Examples of the substituent for the alkyl group, the alkenyl group, and the phenyl group include a halogen atom, for example, a chlorine atom, a bromine atom, a fluorine atom, a hydroxyl group, and a phenyl group (the phenyl group may be substituted with an alkyl group or a halogen atom). have.
[240] Although the specific example of the benzophenone type compound represented by General formula (2) below is shown, this invention is not limited to these.
[241] UV-10: 2,4-dihydroxybenzophenone
[242] UV-11: 2,2'-dihydroxy-4-methoxybenzophenone
[243] UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone
[244] UV-13: bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane)
[245] As the ultraviolet absorber which is preferably used in the present invention, a benzotriazole ultraviolet absorber or a benzophenone ultraviolet absorber, which has high transparency and is excellent in preventing the deterioration of a polarizing plate or a liquid crystal, is preferable, and a benzotriazole ultraviolet absorber having less unnecessary coloring is required. Is particularly preferably used.
[246] Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a support body, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorbent having a distribution coefficient of 10.1 or more.
[247] In addition, the polymeric ultraviolet absorber (or ultraviolet absorbent polymer) described in the general formula (1) or the general formula (2) of Japanese Patent Laid-Open No. 6-148430, and the general formulas (3), (6) and (7) of Japanese Patent Application 2000-156039 is also preferably used. As a polymer ultraviolet absorber, PUVA-30M (made by Otsuka Chemical Co., Ltd.) etc. is marketed.
[248] Moreover, in order to improve the heat resistance of the anti-glare layer formed by the inkjet system, antioxidant, such as not suppressing a photocuring reaction, can be selected and used. For example, a hindered phenol derivative, a thiopropionic acid derivative, a phosphite derivative, etc. are mentioned. Specifically, for example, 4,4'-thiobis (6-tert-3-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 1,3, 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesh Thylene, di-octadecyl-4-hydroxy-3,5-di-tert-butylbenzylphosphate, and the like.
[249] The ink according to the present invention, it is preferable to contain an antistatic agent such as conductive fine particles and cross-linked cationic polymer particles such as SnO _2, ITO, ZnO. In addition, these compounds can also be added to the hard coat layer mentioned later provided on a transparent base material.
[250] In this invention, when the anti-glare layer formed by the inkjet system contains actinic-rays curable resin, as an irradiation method of actinic light, it is preferable to irradiate an actinic light immediately after making an ink droplet land on a transparent base material.
[251] Immediately after the ink droplets referred to in the present invention are impacted on the transparent substrate, the ink droplets are preferably between 0.001 and 2.0 seconds after the impact of the ink droplets, more preferably between 0.001 and 1.0 seconds. If the irradiation interval of the irradiation light source is shorter than 0.001 second, the distance between the nozzle portion and the irradiation light source is too close and the curing reaction causes contamination of the head by sublimation material or curing of the nozzle portion by return of the irradiation light to the ink ejection portion. It is not preferable because the nozzles are clogged. Moreover, when the irradiation interval of an irradiation light source exceeds 2.0 second, it is difficult to obtain the desired uneven structure prescribed | regulated by this invention by the flow, deformation, etc. of an impacted ink droplet.
[252] In order to prevent the return of light to the nozzle portion at the time of the irradiation, in the inkjet method of the present invention, it is preferable to arrange the active light source irradiating portion at a position not directly acting on the nozzle portion of the inkjet head, and the active light to be irradiated is inkjet It is preferable to provide a light shield plate therebetween so as not to act on the nozzle part of a head.
[253] In addition, the irradiation of the actinic light immediately after the ink droplets land can be irradiated to such an extent that the fluidity of the landed ink droplets can be reduced and a desired uneven structure can be formed, and it may be in a semi-hardened state. In this case, the active light source separately installed downstream can be irradiated and hardened completely. In this way, actinic light acts on the nozzle portion of the inkjet head to prevent blocking.
[254] Examples of the active light that can be used in the present invention include ultraviolet rays, electron beams, gamma rays, and the like, and any light source that activates the active light curable resin, which is an anti-glare composition, can be used without limitation. Ultraviolet light is preferable in that energy can be easily obtained. As a light source of the ultraviolet-ray which photopolymerizes an ultraviolet-ray reactive compound, any light source which generate | occur | produces an ultraviolet-ray can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, and a xenon lamp can be used. ArF excimer lasers, KrF excimer lasers, excimer lamps or synchrotron radiation can also be used. The irradiation conditions vary depending on the respective lamps, but the amount of irradiation light is preferably 1 mJ / cm ² or more, more preferably 20 mJ / cm ² to 100 m0 / cm ² , particularly preferably 50 mJ / cm ² to ²⁰⁰ O mJ / cm ² .
[255] Moreover, an electron beam can also be used similarly. Examples of the electron beam include 50 to 1000 keV, preferably 100 to 300 keV, emitted from various electron beam accelerators such as cockloft walton type, vandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamtron type and high frequency type. The electron beam which has energy is mentioned.
[256] In this invention, it is more preferable that the oxygen concentration in the atmosphere at the time of actinic light irradiation is 1% or less.
[257] In addition, in this invention, in order to advance hardening reaction of actinic light efficiently, a transparent base material etc. can also be heated. Although there is no restriction | limiting in particular as a heating method, It is preferable to use methods, such as spraying hot air, on a heat plate, a heat roll, a thermal head, or an impacted ink surface. Moreover, the back roll used on the opposite side can be continuously heated as a heat roll between the transparent support body of an inkjet discharge part.
[258] Although it cannot be prescribed | regulated uniformly according to the kind of actinic-ray-curable resin to be used as heating temperature, it is preferable that it is the temperature range which does not affect thermal deformation, etc. to a transparent base material, and 30-200 degreeC is preferable, and 50-120 More preferably, it is 70-100 degreeC.
[259] Next, the thermosetting resin which concerns on this invention is demonstrated.
[260] Examples of the thermosetting resin that can be used in the present invention include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, thermosetting polyimide resins, and thermosetting polyamide imides.
[261] Examples of the unsaturated polyester resin include orthophthalic acid resins, isophthalic acid resins, terephthalic acid resins, bisphenol resins, propylene glycol-maleic acid resins, dicyclopentadiene and derivatives thereof, which are introduced into the unsaturated polyester composition. Low-shrinkable volatile resins having a molecular weight or a film-forming wax compound, low-shrinkable resins having a thermoplastic resin (polyvinyl acetate resin, styrene-butadiene copolymer, polystyrene, saturated polyester, etc.) and unsaturated polyester Directly brominated with Br ₂ , or a reactive type obtained by copolymerizing het acid and dibrom neopentyl glycol, or a combination of an halide such as chlorinated paraffin, tetrabrombisphenol, antimony trioxide, phosphorus compound, aluminum hydroxide, etc. as an additive Flame retardant resin, polyurethane Or there is a resin such as toughness of the silicon and the hybridization or IPN hwahan toughness (high strength, high elastic modulus, high elongation).
[262] As the epoxy resin, for example, a glycidyl ether epoxy resin containing a bisphenol A type, a novolac phenol type, a bisphenol F type, a brominated bisphenol A type, a glycidylamine type, a glycidyl ester type, a cyclic aliphatic type, The special epoxy resin containing a heterocyclic epoxy type etc. are mentioned.
[263] As vinyl ester resin, the oligomer obtained by ring-opening addition reaction of unsaturated monobasic acids, such as an epoxy resin and methacrylic acid, is usually melt | dissolved in monomers, such as styrene. There are also special types such as having a vinyl group at the terminal or side chain of the molecule and containing a vinyl monomer. Examples of the vinyl ester resins of the glycidyl ether epoxy resins include bisphenols, novolacs, and brominated bisphenols. Examples of the special vinyl ester resins include vinyl ester urethanes, isocyanuric acid vinyls, and side chain vinyl esters. Etc.
[264] A phenol resin is obtained by polycondensing phenols and formaldehydes as raw materials, and there are a resol type and a novolak type.
[265] Examples of the thermosetting polyimide resin include maleic acid-based polyimides such as polymaleimideamine, polyaminobismaleimide, bismaleimide, 0,0'-diallylbisphenol-A resin, and bismaleimide and triazine. Resins and the like, and also nadic acid-modified polyimide and acetylene-terminated polyimide.
[266] In addition, a part of the above-mentioned actinic radiation curable resin can also be used as the thermosetting resin.
[267] In addition, the ink containing the thermosetting resin which concerns on this invention can use suitably the antioxidant and ultraviolet absorber described in the ink containing actinic-rays curable resin.
[268] In this invention, when the anti-glare layer formed by the inkjet system contains a thermosetting resin, it is preferable to heat-process immediately after making the ink droplets land on a transparent base material as a heating method.
[269] It is preferable that the ink droplet referred to in the present invention immediately after the ink droplets are impregnated onto the transparent substrate, specifically, the ink droplets start heating simultaneously or within 5 seconds, more preferably between 0.001 and 2.0 seconds. If the heating interval is shorter than 0.001 seconds, it is necessary to pay attention because the distance between the nozzle portion and the heating portion is too close and heat is transferred to the head portion, thereby clogging the nozzle by curing at the nozzle portion. In addition, when the heating interval exceeds 5.0 seconds, it is difficult to obtain the desired concave-convex structure defined in the present invention due to flow, deformation, or the like of the impacted ink droplets.
[270] In order to prevent the heat transfer to the nozzle part at the time of the said heating, in the inkjet system of this invention, it is preferable to arrange | position a heating part in the position which does not directly act as the nozzle part of an inkjet head.
[271] Although there is no restriction | limiting in particular as a heating method, It is preferable to use methods, such as spraying hot air, on a heat plate, a heat roll, a thermal head, or the surface of an impacted ink. In addition, the back roll provided on the opposite side by sandwiching the transparent support of the inkjet discharge portion can be continuously heated as a heat roll. As heating temperature, although it cannot be prescribed | regulated uniformly according to the kind of thermosetting resin to be used, it is preferable that it is the temperature range which does not affect thermal deformation, etc. to a transparent base material, It is preferable that it is 30-200 degreeC, and also it is 50-120 degreeC More preferably, it is 70-100 degreeC.
[272] In the ink according to the present invention, any of the above-mentioned actinic ray curable resins and thermosetting resins can be used as the antiglare composition, but actinic ray curable resins are preferably used.
[273] The said ink which concerns on this invention can be made to contain a solvent as needed. For example, the above-mentioned actinic radiation-curable resin monomer component or thermosetting resin monomer component can be dissolved or dispersed in an aqueous solvent, or an organic solvent can be used. The organic solvent can be appropriately selected even if it is a low boiling point or a high boiling point, and it is preferable that the amount, type, and composition of these solvents are appropriately adjusted in order to adjust the viscosity of the ink.
[274] As a solvent which can be used for the ink which concerns on this invention, For example, Alcohol, such as methanol, ethanol, 1-propanol, 2-propanol, butanol; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as benzene, toluene and xylene; Glycols such as ethylene glycol, propylene glycol and hexylene glycol; Glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, and propylene glycol monomethyl ether; Esters such as N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate and amyl acetate; Ethers, such as diethyl ether, water, etc. are mentioned, These can be used individually or in mixture of 2 or more types. Moreover, what has an ether bond in a molecule | numerator is especially preferable, and glycol ethers are also used preferably.
[275] Specific examples of the glycol ethers include, but are not particularly limited to, the following solvents. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether Ac, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene Glycol monoethyl ether Ac, ethylene glycol diethyl ether, and the like, wherein Ac represents acetate. In the ink concerning this invention, the solvent whose boiling point is less than 100 degreeC among the said solvents is preferable.
[276] Next, the preferable aspect which forms an uneven structure by the inkjet system in this invention is demonstrated.
[277] One of the preferable formation methods of the anti-glare layer which has an uneven structure in this invention is the method of ejecting and forming the ink droplet from which two or more types of refractive index differ. In detail, since the anti-glare layer which is excellent in visibility can be formed by using 2 or more types of ink droplets in which the refractive index in 550 nm after hardening differs 0.01 or more, it is preferable. Preferably, it is preferable to combine other ink liquids having a refractive index difference of 0.01 to 2.0, particularly 0.03 to 1.0. In the ink according to the present invention, the method for satisfying the above conditions is not particularly limited. For example, the type or amount of the actinic ray curable resin or the thermosetting resin, or the type or amount of the nonvolatile organic solvent, or other additives It can achieve by adjusting a kind and addition amount suitably.
[278] As another preferable formation method of the anti-glare layer which has an uneven structure in this invention, it is preferable to form by ejecting and forming ink droplets in which 2 or more types of particle diameters differ, More preferably, fine unevenness | corrugation on a transparent base material is a large droplet size ink droplet. After forming the structure, a finer uneven structure is formed into ink droplets having a smaller particle size than the ink droplets.
[279] FIG. 7: is a schematic diagram which shows an example in which the fine structure 71 was formed with the ink droplet with the large particle size on the transparent base material by the ink droplet, and again formed the fine uneven structure 72 with the ink droplet with the smaller particle diameter.
[280] Fig. 7A is an example in which the condensed convex portion 71 of the condensation type is provided using ink of relatively low viscosity, and then the convex portions 72 are formed by the surface and the unattached portion. 7 (b) is an example in which the contact angle between the ink droplets and the substrate surface is controlled and the convex portions 71 'of the spherical shape are provided, and then the convex portions 72 are formed by the surface and the unattached portions. to be.
[281] In the present invention, by forming ink using an ink droplet having a different particle size as an ink for forming an uneven structure, it is possible to form fine unevenness which makes it difficult to form interference fringes and also has excellent visibility of the display device. Each ink droplet is preferably 0.1 to 100 pl, more preferably 0.1 to 50 pl, and particularly preferably 0.1 to 10 pl. When two or more kinds of ink droplets having different sizes are used, the volume of the ink droplets having the smallest average particle diameter with respect to the ink droplets having the largest average particle diameter is 0.1 to 80% by volume, more preferably 1 to 60% by volume. Especially preferably, it is 3-50 volume%. Moreover, it is a more preferable aspect to combine the ink droplets from which 3 or more types of capacity differ.
[282] Moreover, when using 2 or more types of ink droplets, each ink droplet from which solid content concentration differs can be used. For example, it is preferable that the smaller droplets mainly discharged later have a lower solid content concentration than the larger ink droplets. Thus, by adjusting the solid content concentration of each ink droplet suitably, formation and shape of a fine uneven structure can be controlled easily.
[283] In the present invention, in the case of forming an uneven structure by combining ink droplets of different capacities, it is preferable that the larger ink droplets are impacted on the transparent substrate, and then the finer ink droplets are impacted thereon. Although larger ink droplets may be impacted to reach the finer ink droplets thereon in an uncured state, in the present invention, after the large ink droplets have been impacted, irradiated with actinic rays or by heat treatment to harden them more completely After or in a semi-cured state, finer ink droplets are preferably landed thereon.
[284] As another preferable formation method of the anti-glare layer which has an uneven structure in this invention, it is preferable that ink droplet contains microparticles | fine-particles which have a particle size smaller than this ink droplet.
[285] In the present invention, examples of the fine particles that can be contained in the ink droplets include inorganic fine particles and organic fine particles.
[286] Examples of the inorganic fine particles include silicon-containing compounds, silicon dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and the like. Preferably, more preferably, an inorganic compound containing zirconium or zirconium oxide, but silicon dioxide is particularly preferably used.
[287] As microparticles | fine-particles of silicon dioxide, commercial items, such as aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd. product) can be used, for example. have.
[288] As microparticles | fine-particles of a zirconium oxide, commercial items, such as aerosil R976 and R811 (above Nippon Aerosil Co., Ltd. product), can be used, for example.
[289] As organic fine particles, polymethyl methacrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicone resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, Melamine resin microparticles | fine-particles, polyolefin resin microparticles | fine-particles, polyester resin microparticles | fine-particles, polyamide-type resin microparticles | fine-particles, polyimide-type resin microparticles | fine-particles, or polyfluoroethylene resin microparticles | fine-particles etc. are mentioned.
[290] As for the average particle diameter of the microparticles | fine-particles used by this invention, 0.01-1 micrometer is preferable, More preferably, it is 0.005-3 micrometers, Especially preferably, it is 0.01-1 micrometer. It is also possible to contain two or more kinds of fine particles having different particle diameters and refractive indices.
[291] As another preferable formation method of the anti-glare layer which has an uneven structure in this invention, it is preferable that an ink droplet contains microdroplets which have a particle diameter smaller than this ink droplet.
[292] The microdroplets referred to in the present invention have a particle diameter smaller than that of the ink droplets, preferably in a phase separation state or in the liquid phase in the form of an emulsion, and preferably not mixed with the main components of the ink completely. After the ink has cured, it is preferable that the refractive index at 550 nm differs from the ink droplet medium by 0.01 or more. Preferably, the refractive index is different from 0.01 to 2.0, in particular, the refractive index is different from 0.03 to 1.0.
[293] In the case where fine particles are used in the above-described ink droplets, the possibility of causing blocking of the inkjet head remains, but it is particularly preferable because of the fact that it is difficult to cause blocking if it is a liquid substance. Moreover, it is preferable that the microdroplet itself also contains a curable component, and it is preferable to harden after impacting. By using these, the effect of finer unevenness and light scattering can be obtained, and the improvement of visibility can be expected.
[294] It is particularly preferable to use a metal alkoxide or its hydrolyzate or partial polymerization product as the microdroplets according to the present invention.
[295] Examples of the metal atom include Si, Ti, Zr, and the like, and specific examples of the metal alkoxide that can be used in the present invention include silanes such as tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, and dimethyldiethoxysilane. Although a coupling agent, tetraisopropyl titanium, tetrabutyl titanium, tetrabutyl zirconium, tetraisopropyl zirconium, tetraethoxy titanium, etc. are mentioned, It is not limited to these. Such an metal alkoxide lands on the transparent substrate, and the ink alkoxide can be cured by a hardening treatment with actinic light or the like, thereby forming a concave-convex structure having a different refractive index.
[296] Next, the other component of the anti-glare film of this invention is demonstrated.
[297] In the anti-glare film of the present invention, the anti-glare layer can be formed directly on the transparent substrate by an inkjet method. More preferably, after forming one or more hard coating layers, the anti-glare layer having an uneven structure on the surface of the hard coating layer. It is preferable to form
[298] Although the thermosetting resin or actinic-ray-curable resin similar to what was used for the ink can be used suitably for a hard coating layer, UV curable resin is especially preferable. In addition, in formation of a hard coating layer, in addition to each said resin, the same photoreaction initiator, photosensitizer, antioxidant, ultraviolet absorber, antistatic agent, inorganic microparticles | fine-particles, organic microparticles | fine-particles, etc. similar to what was described with ink can be added suitably. .
[299] In addition, in the present invention, the hard coating layer may be composed of a plurality of layers, but it is preferable that the outermost layer of the hard coating layer for impacting ink droplets contains a plasticizer.
[300] Examples of the plasticizer that can be used in the hard coating layer include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citric acid ester plasticizers, and polyester plasticizers. It can be used preferably.
[301] As a phosphate ester plasticizer, For example, as a phthalic ester plasticizer, such as a triphenyl phosphate, a tricresyl phosphate, a cresyl diphenyl phosphate, an octyl diphenyl phosphate, a diphenyl biphenyl phosphate, a trioctyl phosphate, a tributyl phosphate, Examples of trimellitic acid-based plasticizers such as ethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butylbenzyl phthalate, diphenyl phthalate and dicyclohexyl phthalate As pyromellitic acid ester plasticizers, such as a melitate, a triphenyl trimellitate, and a triethyl trimellitate, such as tetrabutyl pilomellitate, tetraphenyl pyromellitate, and tetraethyl pyromellitate, triacetin, Tributyrin, ethyl Examples of citric acid ester plasticizers such as yl ethyl glycolate, methyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate include triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, and acetyl tri-n-butyl Citrate, acetyltri-n- (2-ethylhexyl) citrate, etc. can be used preferably. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacinate, and various trimellitic acid esters.
[302] As a polyester plasticizer, the copolymer of dibasic acids and glycols, such as aliphatic dibasic acid, alicyclic dibasic acid, and aromatic dibasic acid, can be used. Although it does not specifically limit as aliphatic dibasic acid, Adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1, 4- cyclohexyl dicarboxylic acid, etc. can be used. Ethylene glycol, diethylene glycol, 1, 3-propylene glycol, 1,2-propylene glycol, 1, 4- butylene glycol, 1, 3- butylene glycol, 1, 2- butylene glycol etc. can be used as glycol. have. These dibasic acids and glycols can be used individually or in mixture of 2 or more types, respectively.
[303] In particular, the cellulose ester which has additives, such as the epoxy type compound, rosin type compound, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, ketone resin, toluene sulfonamide resin, etc. which were described in Japanese Patent Application 2000-338883 is also used preferably. .
[304] As said compound, KE-604 and KE-610 are marketed by Arakawa Chemical Industries, Ltd. by acid value 237 and 170, respectively. Similarly, KE-100 and KE-356 are commercially available from Arakawa Kagaku Kogyo Co., Ltd. as acid values of 8 and 0, respectively, as esters of a mixture of three kinds of abietinic acid, dihydroabietinic acid, and palatinic acid. . In addition, a mixture of three kinds of abietinic acid, dihydroabietinic acid, and paladrinic acid is commercially available from Harima Kasei Co., Ltd. at G-7 and Hatol R-X having acid values 167 and 168, respectively.
[305] In addition, as an epoxy resin, alaldide EPN 1179 and alaldide AER 260 are commercially available from Asahi Chiba.
[306] As a ketone resin, Hi-Lock 110 and Hi-Lock 110H are marketed from Hitachi Kasei.
[307] As paratoluene sulfonamide resin, it is marketed by Fuji Amide Chemical Co., Ltd. as a topler.
[308] It is preferable that the hard-coat layer outermost surface which touches the ink droplet which forms an anti-glare layer contains 0.1-10 weight% of plasticizers. For example, it is preferable to add a plasticizer to the coating composition of the said hard coating layer previously, and you may apply or apply a plasticizer to the surface of a base material before apply | coating a hard coating layer. Thereby, the adhesiveness of the ink droplet after hardening improves.
[309] The solvent at the time of apply | coating the hard coat layer which concerns on this invention can be used suitably, for example, can be used, or mixed among hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents. Preferably a solvent containing at least 5% by weight, more preferably at least 5% by weight and at least 80% by weight of propylene glycol mono (C1 to C4) alkyl ether or propylene glycol mono (C1 to C4) alkyl ether ester is used.
[310] As a method of applying the hard coating layer composition coating liquid which consists of the composition mentioned above on a transparent base material, well-known methods, such as gravure coating, spinner coating, wire bar coating, roll coating, reverse coating, extrusion coating, air doctor coating, can be used. . The coating amount is suitably 5 µm to 30 µm in terms of the wet film thickness, and preferably 10 µm to 20 µm. The application rate is preferably 10 m / min to 60 m / min. Moreover, as dry film thickness, 1-10 micrometers is preferable.
[311] The hard coating layer composition is preferably applied and dried, and then irradiated with active rays such as ultraviolet rays or electron beams or cured by heat treatment in the same manner as the curing of the ink, but the irradiation time of the active rays is preferably 0.1 seconds to 5 minutes. More preferably, it is 0.1 to 10 second according to the curing efficiency, work efficiency, etc. of an ultraviolet curable resin.
[312] In the present invention, any of the hard coating layers coated on the transparent substrate by the above method is in an uncured state, or after curing is completely completed, and the ink droplets forming the antiglare layer by the inkjet method may be impacted. Preferably, after the hard coating layer is cured, the ink droplets are impregnated to form an uneven structure by an inkjet method, and particularly preferably, the ink droplets are impregnated when the hard coating layer is in a semi-cured state to form the uneven structure. Since it is easy to form fine unevenness | corrugation and excellent in productivity, it is preferable to make it, and also the adhesiveness of the uneven structure part and the surface of a hard coating layer can be improved.
[313] Furthermore, before the ink droplet which forms an anti-glare layer is reached on the hard-coat layer surface apply | coated on the transparent base material by the said method, it is preferable because plasma treatment can form finer uneven | corrugated structure. In particular, it is preferable to perform an atmospheric plasma treatment, and rare gases such as helium and argon or discharge gases such as nitrogen and air, and oxygen, hydrogen, nitrogen, carbon monoxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, water vapor, methane, 4 as necessary. The surface can be modified by a reaction gas containing one or more kinds of methane fluoride and the like, and with reference to the method described in, for example, Japanese Patent Laid-Open No. 2000-356714, the surface of the hard coating layer can be subjected to plasma treatment. .
[314] In the anti-glare film of the present invention, after coating and drying a hard coating layer on a transparent substrate, an anti-glare layer having an uneven structure is formed by the inkjet method according to the present invention, and an anti-reflection layer or an anti-fouling layer is provided on the anti-glare layer. It is preferable.
[315] As for the anti-reflection layer which concerns on this invention, it is preferable to provide a some refractive index layer on the glare-proof layer side, and it is preferable to laminate | stack a high refractive index layer and a low refractive index layer in order. The height of the refractive index is almost determined depending on the metal or compound included therein, for example, Ti is high, Si is low, and the compound containing F is lower, and the refractive index is set according to this combination. The refractive index and the film thickness can be calculated and calculated according to the measurement of the spectral reflectance.
[316] It is preferable that the anti-glare film of this invention has an anti-glare layer on a transparent base material (support), and is laminated | stacked in consideration of refractive index, film thickness, number of layers, layer order, etc. so that reflectance may reduce by optical interference. The antireflection layer is configured by combining a high refractive index layer having a higher refractive index than a support and a low refractive index layer having a lower refractive index than the support. Particularly preferably, it is an antireflection layer composed of three or more refractive index layers, and three layers having different refractive indices from the support side are formed of a medium refractive index layer (a layer having a higher refractive index than the support or the antiglare layer and having a lower refractive index than the high refractive index layer) / What is laminated | stacked in order of the high refractive index layer / low refractive index layer is used preferably. Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.
[317] Moreover, it is also preferable to provide an antifouling layer on the low refractive index layer of the outermost surface so that contamination and fingerprint wiping become easy as needed. As the antifouling layer, a fluorine-containing organosilane compound is preferably used.
[318] The antireflection layer according to the present invention may be formed by the coating method described above, and may be formed by a metal oxide layer (SiO ₂ , TiO ₂ , Ta ₂ O ₅ , ZrO ₂ , ZnO) by a dry process such as atmospheric pressure plasma treatment or CVD. , SnO ₂ , ITO, etc.) may be provided.
[319] As the high refractive index layer according to the present invention, preferably, titanium oxide is contained. Although these can be added as microparticles | fine-particles, More preferably, they are the layer of refractive index 1.55-2.5 formed by apply | coating and drying the coating liquid containing the monomer, oligomer, or these hydrolyzate of an organic titanium compound.
[320] As monomers and oligomers of the organic titanium compound used in the present invention, Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OnC ₃ H ₇ ) ₄ , Ti (OiC ₃ H ₇ ) ₄ , Ti (OnC _{4 H 9) 4, Ti (} OnC 3 H 7) 2 and 10-mer of _{4, Ti (OiC 3 H 7} ) 2 and 10-mer of _{4, Ti (OnC 4 H 9} ) preferably include ₄₂ to 10-mer of It is mentioned as an example. These can be used individually or in combination of 2 or more types. Among them, 2 to 10 dimers of Ti (OnC ₃ H ₇ ) ₄ , Ti (OiC ₃ H ₇ ) ₄ , Ti (OnC ₄ H ₉ ) ₄ , Ti (OnC ₃ H ₇ ) ₄ , Ti (OnC ₄ H ₉ ) 2-10 tetramer of ₄ is particularly preferred.
[321] It is preferable that the monomer, oligomer, or these hydrolyzate of the organic titanium compound used for this invention occupies 50.0 weight%-98.0 weight% in solid content contained in a coating liquid. 50 weight%-90 weight% are more preferable, and, as for solid content ratio, 55 weight%-90 weight% are more preferable. In addition, it is also preferable to add the polymer of an organic titanium compound (what was previously bridge | crosslinked by hydrolyzing an organic titanium compound) or titanium oxide microparticles | fine-particles.
[322] In addition, in this invention, although the monomer and oligomer of the said organic titanium compound and the partial hydrolyzate are included in the coating liquid, the monomer and oligomer of the organic titanium compound are self-condensed, crosslinked, and reticularly bonded. In order to accelerate the reaction, a catalyst or a curing agent can be used, and organic metal compounds such as metal chelate compounds and organic carboxylates, organosilicon compounds having amino groups, acid generators (photoacid generators), etc. There is this. Particularly preferred among such catalysts or curing agents are aluminum chelate compounds and photoacid generators. Examples of the aluminum chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum trisethyl acetoacetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethyl acetoacetate, aluminum triacetylacetylacetonate and the like. As an example, the benzyl triphenyl phosphonium hexafluoro phosphate, another phosphonium salt, the salt of a triphenyl phosphonium hexafluoro phosphate, etc. are mentioned.
[323] It is preferable to contain 0.5 weight%-20 weight% of a binder as solid content ratio in the coating liquid of an antireflection layer.
[324] As a binder, it has a polymerizable group, such as a vinyl group, an allyl group, acryloyl group, a methacryloyl group, isopropenyl group, an epoxy group, and an oxetane ring, which can superpose | polymerize, and forms a crosslinked structure or a network structure by actinic light irradiation. Acrylic or methacrylic active energy ray reactive compounds, epoxy active energy ray reactive compounds or oxetane active energy ray reactive compounds similar to those used for the ink can be used. These compounds include monomers, oligomers, and polymers. From the viewpoint of polymerization rate and reactivity, an acryloyl group, methacryloyl group or an epoxy group is preferable among these active groups, and a polyfunctional monomer or oligomer is more preferable. Moreover, the actinic-rays curable resin used for the above-mentioned ink and hard coating layer can also be used preferably. Alcohol soluble acrylic resins are also preferably used.
[325] In the medium to high refractive index layer containing the titanium compound, an alcohol soluble acrylic resin is also preferably used as the binder, whereby the high refractive index layer can be obtained while the film thickness unevenness is small. Specifically, alkyl (meth) acrylate polymer or alkyl (meth) acrylate copolymer, for example n-butyl methacrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate Although copolymers, such as these, are used preferably, it is not limited to these as a copolymerization component. Commercially available products include diamond BR-50, BR-51, BR-52, BR-60, BR-64, BR-65, BR-70, BR-73, BR-75, BR-76, BR-77, BR- 79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-89, BR-90, BR-93, BR-95, BR-96, BR-100, BR-101, BR-102, BR-105, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118 (above Mitsubishi Rayon Co., Ltd.) Production) can be used. Such monomer components can also be added as a binder for the medium to high refractive index layer. The refractive index can be adjusted by changing the addition ratio of the binder.
[326] It is preferable to add a lubricant to the low refractive index layer, and the scratch resistance can be improved by providing lubricity. As the lubricant, silicone oils or waxy substances are also preferably used.
[327] Specifically, higher fatty acids such as behenic acid, stearic acid amide and pentacoic acid or derivatives thereof, and carnava wax, beeswax and montan wax containing many of these components as natural products can also be preferably used. Polyorganosiloxanes as disclosed in Japanese Patent Publication No. 53-292, higher fatty acid amides as disclosed in US Patent No. 4,275,146, Japanese Patent Publication No. 58-33541, British Patent No. 927,446 or Japan Higher fatty acid esters (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms), such as those disclosed in Patent Publications Nos. 55-126238 and 58-90633, and US Pat. No. 3,933,516. Higher fatty acid metal salts as described above, polyester compounds consisting of dicarboxylic acids having up to 10 carbon atoms and aliphatic or cyclic aliphatic diols as disclosed in Japanese Patent Laid-Open No. 51-37217, and Japanese Patent Laid-Open No. 7-13292. Oligopolyester from dicarboxylic acid and diol which were disclosed, etc. are mentioned.
[328] The amount of the lubricant used in the low refractive index layer is preferably from 0.1 mg / m ² to 10 mg / m ² . As needed, you may add to a medium refractive index layer and a high refractive index layer.
[329] It is preferable to add surfactant, a softening agent, a softening smoothing agent, etc. to the low refractive index layer of this invention, and abrasion resistance improves by this. Especially, anionic or nonionic surfactant is preferable, for example, the dialkyl sodium sulfosuccinate salt, the nonionic surfactant emulsion of a polyhydric alcohol fatty acid ester, etc. are preferable. For example, reboils NT-6, NT-12, NT-33, TC-1, TC-68, TC-78, CW-6, TCF-208, TCF-608, NK oil CS-11, AW-9 , AW-10, AW-20, Polysoft N-606, paint additive PC-700 (manufactured by Nikka Chemical Industries, Ltd.), and the like.
[330] The low refractive index layer according to the present invention is preferably formed by applying silicon compound fine particles such as silicon oxide or fluorine-containing compound fine particles. Preferred organosilicon compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and the like. Oligomers are obtained. The hydrolysis reaction can be carried out according to a known method. For example, a predetermined amount of water is added to the tetraalkoxysilane, and the reaction product is usually reacted at room temperature to 100 ° C while distilling off the byproduct alcohol in the presence of an acid catalyst. By this reaction, the alkoxysilane is hydrolyzed, and then a condensation reaction occurs to obtain a liquid silicate oligomer (usually average degree of polymerization of 2 to 8, preferably 3 to 6) having two or more hydroxyl groups as a hydrolyzate. Can be.
[331] Examples of the curing catalyst include acids, alkalis, organic metals, metal alkoxides, and the like. In the present invention, an acid, in particular an organic acid having a sulfonyl group or a carboxyl group, is preferably used. For example, acetic acid, polyacrylic acid, benzenesulfonic acid, paratoluenesulfonic acid, methylsulfonic acid and the like are used. The organic acid is more preferably a compound having a hydroxyl group and a carboxyl group in one molecule, and for example, hydroxydicarboxylic acid such as citric acid or tartaric acid is used. In addition, the organic acid is more preferably a water-soluble acid. For example, in addition to citric acid and tartaric acid, for example, revric acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaroacetic acid, pyruvic acid, 2-oxoglutaric acid, Glycolic acid, D-glyceric acid, D-gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are preferably used. In addition, benzoic acid, hydroxy benzoic acid, atroic acid and the like can also be suitably used.
[332] By using the organic acid, it is possible to solve the corrosion of pipes and safety during production by the use of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid and boric acid, as well as without causing gelation during hydrolysis. Decomposition can be obtained. The amount of addition is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight based on 100 parts by weight of the partial hydrolyzate. In addition, with respect to the amount of water added, the partial hydrolyzate may be at least an amount capable of hydrolyzing 100% in theory, and an amount corresponding to 100 to 300%, preferably 100 to 200%, may be added.
[333] The coating composition for the low refractive index layer thus obtained is very stable.
[334] (Aging process)
[335] Moreover, in this invention, the crosslinking by hydrolysis and condensation of an organosilicon compound fully advances by the aging process, and it becomes the thing excellent in the characteristic of the film obtained. Aging can leave the oligomer liquid, and the leaving time is a time when the above-mentioned crosslinking proceeds to a degree sufficient to obtain desired membrane properties. Although it depends specifically on the kind of catalyst to be used, hydrochloric acid is enough for 1 hour or more at room temperature, for several hours or more for maleic acid, and 8 hours-1 week, and it is about 3 days normally. The aging temperature affects the aging time, and it may be better to use a means for heating to around 20 ° C in the extreme regions. Generally, at high temperatures, aging proceeds rapidly, but gelation occurs when heated to 100 ° C or higher, so heating to 50 to 60 ° C is appropriate at most. The silicate oligomer used in the present invention may be a modified product modified by an organic compound (monomer, oligomer, polymer) or the like having functional groups such as, for example, an epoxy group, an amino group, an isocyanate group, and a carboxyl group, in addition to the above. It can also be used together with a silicate oligomer.
[336] Moreover, in this invention, the said low refractive index layer can contain a silicon oxide fine particle. It is preferable to contain silicon oxide fine particles having a particle diameter of 0.1 m or less. For example, aerosil 200V (made by Nippon Aerosil Co., Ltd.) etc. can be added. In particular, silicon oxide fine particles whose surface is modified with an alkyl group are preferably used. For example, silicon oxide fine particles whose surface is commercially available as aerosil R972 and R972 V (manufactured by Nippon Aerosil Co., Ltd.) is modified with a methyl group. Can be preferably added. In addition, the silicon oxide microparticles | fine-particles whose surface described in Unexamined-Japanese-Patent No. 2001-2799 substituted by the alkyl group can also be used, and it can also be easily obtained by treating with the alkylsilane coupling agent after hydrolysis of the above-mentioned silicate oligomer. As addition amount, it is preferable to add so that it may become 0.1 to 40weight% of a range in solid content ratio in a low refractive index layer.
[337] To each refractive index layer of the present invention, a silane compound may be further added for adjusting the refractive index or improving the film quality.
[338] The solvent used for the coating liquid at the time of apply | coating the high to low refractive index layer (also called optical interference layer) which concerns on this invention is alcohol, such as methanol, ethanol, 1-propanol, 2-propanol, butanol; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as benzene, toluene and xylene; Glycols such as ethylene glycol, propylene glycol and hexylene glycol; Glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, and propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, water, etc. are mentioned, These can be used individually or in mixture of 2 or more types.
[339] Moreover, it is especially preferable to have an ether bond in a molecule | numerator, and glycol ethers are more preferable.
[340] Glycol ethers are propylene glycol mono (C1 to C4) alkyl ethers and propylene glycol mono (C1 to C4) alkyl ether esters. Specifically, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, and propylene glycol mono- n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, etc. are mentioned. In addition, examples of the propylene glycol mono (C1 to C4) alkyl ether ester include propylene glycol monoalkyl ether acetate, and propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. It is preferable that these solvents are added 1 to 90 weight% of all the organic solvents in a coating liquid.
[341] Moreover, it is preferable to add low surface tension substances, such as various leveling agents, surfactant, silicone oil, to the coating liquid of each layer of the high to low refractive index layer which concerns on this invention.
[342] It is preferable to irradiate actinic light in order to accelerate the hydrolysis or hardening of the composition containing a metal alkoxide after application | coating of the medium to high refractive index layer and low refractive index layer which concern on this invention. More preferably, the active energy ray is irradiated each time the respective layers are applied.
[343] The actinic light used in the present invention can use the same light source as used in curing of the ink. Irradiation conditions vary with each lamp, but the amount of irradiation light is preferably 20 mJ / cm ² to 10,000 mJ / cm ² , more preferably 100 mJ / cm ² to 2,000 mJ / cm ² , particularly preferably 400 mJ / cm ² to 2,0 0 mJ / cm ² .
[344] When ultraviolet rays are used, the multilayered antireflection layer can be irradiated one by one and irradiated after lamination, but it is particularly preferable to irradiate ultraviolet rays after laminating the multilayers.
[345] Moreover, in this invention, the method of providing an antireflection layer by a dry process can also be used preferably, For example, Unexamined-Japanese-Patent No. 7-333404, 11-133205, 11-61406, Japan Patent Publication 2002 Although the antireflection layer or antifouling layer can be formed according to the method described in each of -228803, in this invention, it is especially preferable to form an antireflection layer by the atmospheric pressure plasma processing method.
[346] Next, the manufacturing method of the anti-glare film of this invention is demonstrated.
[347] It is a schematic diagram which shows an example of the flow which produces an anti-glare film by providing an anti-glare layer by the inkjet system on a transparent base material. In detail, after apply | coating a hard coating layer on a transparent base material by the apply | coating system, the anti-glare layer which has an uneven structure is formed by the inkjet method, and the several anti-reflective layer is then provided by the apply | coating system, and the flow which manufactures an anti-glare film is shown.
[348] In FIG. 8, the transparent base material 102 which came out of the lamination roll 101 is conveyed, and a hard coat layer is apply | coated by the 1st coater 103 of an extrusion system in 1st coating station A. FIG. At this time, the hard coating layer may be a single layer structure or may be a layer composed of a plurality. The transparent base material 102 coated with the hard coating layer is subsequently dried in the drying zone 105A. Drying is performed by warm air whose temperature-humidity was controlled rather than both surfaces of the transparent base material 102. In the case where an active light curable resin is used as a binder for the hard coating layer after drying, the active light irradiation unit 106A irradiates and hardens the active light, for example, ultraviolet rays, or controls the irradiation amount or irradiation conditions to form a semi-cured state. You can also do
[349] Subsequently, it is conveyed to the 2nd coating station B which installs the anti-glare layer using the inkjet system, but it is preferable that a hard coating layer is a semi-hardened state. Or it is preferable to perform surface treatment in the plasma processing part 107 before forming an anti-glare layer. An ink supply tank 108 is connected to the inkjet discharge part 109, from which ink liquid is supplied. The inkjet ejecting section 109 arranges a plurality of inkjet nozzles as shown in FIG. 4B in a zigzag form over the entire width of the transparent substrate to eject ink droplets onto the hard coating layer to form an uneven structure on the surface thereof. . In addition, when discharging two or more types of ink droplets, the respective ink droplets can be discharged from the inkjet nozzles arranged in two or more rows, and ink droplets can be discharged randomly from any inkjet nozzles. It is also possible to arrange a plurality of inkjet ejecting portions and eject different ink droplets from each ink ejecting portion. In the present invention, since the droplets are discharged from 0.1 to 100 pl, and in some cases, from 0.1 to 10 pl, the second coating station B is entirely partitioned because it is easy to be influenced by outside air flow due to the incompatibility of the ink droplets. It is preferable to cover with a windshield and to perform a windbreak process. In addition, in order to accurately fly very fine droplets of 1 pl or less with high precision, a voltage is applied between the inkjet ejecting portion 109 and the transparent substrate 102 or the back roll 104B, and an electric charge is supplied to the ink droplets to electrically discharge the ink droplets. A method of assisting stability is also preferred. It is also preferable to use a method of cooling the transparent substrate to quickly reduce the flow of the ink droplets after impacting in order to prevent deformation of the ink droplets which have reached the impact. Alternatively, it is preferable to form a finer uneven structure by volatilizing the solvent contained in the emergency until the landing of the ink droplets after ejection of the ink droplets, thereby reducing the amount of the solvent contained in the ink droplets. Therefore, a method of increasing the temperature of the ink emergency space or controlling the air pressure to 1 atm or less, for example, 20 to 100 kPa is also preferable.
[350] The ink droplets impacted on the surface of the hard coating layer are cured by irradiating actinic rays, for example, ultraviolet rays, in the actinic ray irradiating portion 106B disposed immediately after the inkjet ejecting portion 109 when using an actinic ray curable resin. Let's do it. In addition, when ink droplets use a thermosetting resin, they are heated and cured by the heating unit 110, for example, a heat plate. Moreover, the method of heating the back roll 104B with a heat roll is also preferable.
[351] In the second coating station B, the active light irradiation unit 106B and the inkjet discharge unit 109 are properly spaced so that the irradiation light of the active light irradiation unit 106B does not directly affect the inkjet nozzles of the inkjet discharge unit 109. Or a light shielding wall or the like is provided between the active light irradiation unit 106B and the inkjet discharge unit 109. In addition, in order that the heat of the heating part 110 does not directly affect the inkjet nozzle of the inkjet discharge part 109, the inkjet discharge part 109 is covered with a thermal insulation cover, or as shown in FIG. It is preferable to arrange | position 110 to the back surface side of the transparent base material 102 so that it may not affect the inkjet discharge part 109. FIG.
[352] The transparent base material 102, which has been cured to such an extent that the uneven structure formed by the impacted ink droplets can be maintained, is further evaporated by the active light irradiation part 106C after evaporating unnecessary organic solvents or the like in the drying zone 105B. Irradiate to complete curing.
[353] The transparent substrate 102 provided with the antiglare layer is the first coating station by the third coating station C or the fourth coating station D and the fifth coating station (not shown) when the plurality of antireflection layers are provided. In the same manner as in A, coating, drying, and curing treatment are performed to produce an antiglare film, which is then laminated on the take-up roll 113.
[354] In FIG. 8, although the coating method was illustrated as a method of forming an antireflection layer, an antireflection layer or an antifouling layer may be formed by a known atmospheric pressure plasma treatment method instead of the coating method.
[355] The anti-glare film produced as mentioned above can be used suitably as a polarizing plate protective film, can be laminated | stacked and bonded to at least one of a polarizer, and can be used as a polarizing plate, and also various display apparatuses, such as an organic electroluminescent display, an inorganic electroluminescent display, and a plasma display, It is also useful as a front panel.
[356] The polarizing plate using the antiglare film of this invention and the display apparatus using the same are demonstrated.
[357] As a polarizer used for a polarizing plate, a conventionally well-known thing can be used. A polarizer is an element which makes only the light of a polarization plane of a predetermined direction pass, and the representative polarizer currently known is a polyvinyl alcohol-type polarizing film, which has dyed iodine to a polyvinyl alcohol-type film and dyed dichroic dye. . These membranes are prepared using a polyvinyl alcohol aqueous solution, uniaxially stretched, dyed or dyed, uniaxially stretched, and preferably subjected to durability treatment with a boron compound.
[358] A polarizing plate is obtained by bonding together the polarizer obtained in this way and the anti-glare film of this invention. Or you may provide a polarizer by application | coating to the back surface side of an anti-glare film.
[359] The polarizing plate which concerns on this invention can be manufactured by a general method. For example, there exists a method of bonding using the fully saponified polyvinyl alcohol aqueous solution to both surfaces of the polarizing film manufactured by alkali-processing the anti-glare film of this invention and immersing and stretching in an iodine solution. The above-described alkali saponification treatment refers to a treatment in which the cellulose ester film is immersed in a high temperature strong alkaline liquid in order to improve the wetting of the aqueous adhesive at this time and to improve the adhesiveness. At this time, it is possible to protect from alkali and dirt by providing a repeelable protective film (made of a polyolefin resin such as polyethylene or a polyester resin such as polyethylene terephthalate) on the surface of the antireflection layer.
[360] When using the anti-glare film of this invention as one polarizing plate protective film, the other polarizing plate protective film can be made to have an optical compensation function. For example, an optically anisotropic layer (for example, a layer immobilized in a hybrid orientation) formed by applying liquid crystals directly or through an alignment layer is provided and used as a polarizing plate protective film to provide a polarizing plate having a viewing angle enlargement effect. It can manufacture.
[361] If necessary, the surface of the antireflection layer may have antifouling properties or an antifouling layer may be provided. As the antifouling layer, a layer having a thickness of 1 to 30 nm using a known compound of silicon or fluorine is preferably used.
[362] The structure of a typical polarizing plate is shown below.
[363] Antifouling layer / antireflection layer / antiglare layer / cellulose ester film / polarizer / cellulose ester film / alignment layer / optical anisotropic layer (liquid crystal cell side)
[364] The polarizing plate thus obtained can be provided on one surface or both surfaces of the liquid crystal cell. The anti-glare film of this invention sticks to a liquid crystal cell so that an antireflection layer may face outward, and a display apparatus is obtained. By using the anti-glare film of the present invention, it is possible to provide a display device having high precision and excellent visibility.
[365] <Example>
[366] Hereinafter, although an Example is shown and the structure and effect of this invention are demonstrated concretely, this invention is not limited to these.
[367] <Example 1>
[368] Preparation of Transparent Substrate
[369] Various additive liquids and various dope liquids were prepared as follows, and the cellulose-ester film which is a transparent base material was manufactured.
[370] (Production of Cellulose Ester Film)
[371] Preparation of Silicon Oxide Dispersion A
[372] Aerosil R972V (made by Nippon Aerosil Co., Ltd.) 1 kg
[373] 9 kg of ethanol
[374] The above was stirred and mixed for 30 minutes with a dissol bar, and then dispersed using a Mantongorin-type high pressure dispersion device to prepare a silicon oxide dispersion A.
[375] <Production of Additive B>
[376] 6 kg of cellulose triacetate (acetyl substitution degree 2.88)
[377] Methylene chloride 140 kg
[378] The above was put into an airtight container, and it melt | dissolved and filtered, heating and stirring. 10 kg of the silicon oxide dispersion A was added thereto while stirring, followed by further stirring for 30 minutes, followed by filtration to prepare an additive solution B.
[379] Preparation of Doping C
[380] Methylene chloride440 kg
[381] Ethanol 35 kg
[382] 100 kg of cellulose triacetate (acetyl substitution degree 2.88)
[383] 10 kg of triphenylphosphate
[384] 2 kg of ethyl phthalyl ethyl glycolate
[385] Tinuvin 326 (product of Chiba Specialty Chemicals) 0.3 kg
[386] Tinuvin 109 (product of Chiba Specialty Chemicals) 0.5 kg
[387] Tinuvin 171 (product of Chiba Specialty Chemicals) 0.5 kg
[388] The solvent was added to a sealed container, and the remaining material was added while stirring, followed by heating and stirring to completely dissolve and mix. After the dope was lowered to the temperature at which it was cast, it was allowed to stand overnight and subjected to defoaming, and then the solution was added to Azumi Rossi No. It was filtered using 244. To the solution was further added 3 kg of the addition solution B, mixed for 10 minutes with an in-line mixer (Toray Co., Ltd. static tube mixer Hi-Mixer, SWJ) for 10 minutes, and filtered to prepare a doping solution C.
[389] After filtering the dope C, a 35 degreeC dope liquid was cast uniformly on the 35 degreeC stainless band support body using the belt casting apparatus. Thereafter, after drying on the support, the film was peeled off on the stainless band support. The amount of residual solvent of the film at this time was 80%. After peeling from the stainless band support, after drying for 1 minute in a drying zone maintained at 80 ℃, using a biaxially stretched tenter 1.03 times in the longitudinal direction under an atmosphere of 100 ℃ when the residual solvent amount is 3 to 10% by weight, Stretched 1.1 times in the width direction to release the width grips and transported them to a large number of rolls while finishing drying in a drying zone at 125 ° C. A 10 mm wide and 10 μm high naring was applied to both ends of the film to form a cellulose film having a thickness of 80 μm. Was prepared.
[390] << production of anti-glare film 1 >>
[391] [Application of Hard Coating Layer]
[392] On one side of the cellulose ester film, the following hard coat layer coating composition was applied with a slit die, gradually strengthened the temperature and wind speed of hot air and finally dried at 85 ° C., and then irradiated with 115 mJ / cm ² in an active light irradiation part. It was irradiated with ultraviolet rays, and a hard coating layer having a dry film thickness of 5 μm and a centerline average surface roughness (Ra) of 12 nm was provided.
[393] <Hard Coating Layer Coating Composition>
[394] 60 parts by weight of dipentaerythritol hexaacrylate monomer
[395] 20 parts by weight of dipentaerythritol hexaacrylate dimer
[396] 20 parts by weight of a component of dipentaerythritol hexaacrylate or higher
[397] 4 parts by weight of dimethoxybenzophenone photoreaction initiator
[398] Propylene glycol monomethyl ether 75 parts by weight
[399] Methyl ethyl ketone 75 parts by weight
[400] [Formation of Antireflection Layer]
[401] On the hard coating layer formed as mentioned above, the anti-reflection layer was apply | coated in order of the medium refractive index layer, the high refractive index layer, and then the low refractive index layer as follows, and the anti-glare film 1 was manufactured.
[402] (Application of Medium Refractive Index Layer)
[403] On the hard coat layer of the cellulose ester film, the following medium refractive index layer composition was applied with an extrusion coater and dried at 80 ° C. for 5 minutes, and then irradiated with ultraviolet light at 175 mJ / cm ² using a high pressure mercury lamp (80 W) and cured. The medium refractive index layer was provided so that thickness might be 78 nm. Moreover, the refractive index of this medium refractive index layer was 1.70.
[404] <Medium refractive index layer composition>
[405] Isopropyl alcohol510 parts by weight
[406] 2 parts by weight of water
[407] Propylene glycol monomethyl ether 227 parts by weight
[408] Methyl ethyl ketone 84 parts by weight
[409] 39 parts by weight of tetra (n) butoxytitanium
[410] γ-methacryloxypropyl trimethoxysilane (KBM 503 by Shin-Etsu Chemical Co., Ltd.)
[411] 6 parts by weight
[412] 31% by weight of 5% acrylic resin solution (manufactured by Mitsubishi Rayon Co., Ltd., dissolved in diamond BR-102, solvent propylene glycol monomethyl ether)
[413] 1.5 weight part of 10% silicone oil (KF-96-1,000 CS by Shin-Etsu Chemical Co., Ltd., solvent: methyl ethyl ketone)
[414] (Formation of high refractive index layer)
[415] On the medium refractive index layer, the following high refractive index layer composition was applied with an extrusion coater and dried at 80 ° C. for 5 minutes, and then cured by irradiating UV light at 175 mJ / cm ² using a high pressure mercury lamp (80 W). The high refractive index layer was provided so that it might be set to 66 nm. Moreover, the refractive index of this high refractive index layer was 1.85.
[416] <High refractive index layer composition>
[417] Isopropyl alcohol 445 parts by weight
[418] 1.5 parts by weight of water
[419] Propylene glycol monomethyl ether 223 parts by weight
[420] Methyl ethyl ketone 73 parts by weight
[421] 545 parts by weight of tetra (n) butoxytitanium
[422] γ-methacryloxypropyl trimethoxysilane (KBM 503 by Shin-Etsu Chemical Co., Ltd.)
[423] 0.8 parts by weight
[424] 10% silicone oil (KF-96-1,000 CS manufactured by Shin-Etsu Chemical Co., Ltd., solvent: methyl ethyl ketone) 1.4 parts by weight
[425] <Formation of Low Refractive Index Layer>
[426] On the high refractive index layer, the following low refractive index layer composition was applied with an extrusion coater, dried at 80 ° C. for 5 minutes, and further thermally cured at 120 ° C. for 5 minutes, and further cured by irradiation with ultraviolet rays at 175 mJ / cm ^2. The low refractive index layer was provided so that it might be set to 95 nm in thickness. Moreover, the refractive index of this low refractive index layer was 1.45.
[427] <Production of Tetraethoxysilane Hydrolyzate A>
[428] After mixing 580 g of tetraethoxysilane and 1144 g of ethanol, an aqueous citric acid solution (which dissolved 5.4 g of citric acid monohydrate in 272 g of water) was added thereto, followed by stirring at room temperature (25 ° C.) for 1 hour. Silane Hydrolyzate A was prepared.
[429] <Low Refractive Index Layer Composition>
[430] Propylene glycol monomethyl ether 303 parts by weight
[431] Isopropyl alcohol305 parts by weight
[432] Tetraethoxysilane hydrolyzate A 139 parts by weight
[433] γ-methacryloxypropyl trimethoxysilane (KBM503 by Shin-Etsu Chemical Co., Ltd.)
[434] 1.6 parts by weight
[435] 10% FZ-2207, propylene glycol monomethyl ether solution (manufactured by Nippon Unicar Co., Ltd.)
[436] 1.3 parts by weight
[437] << production of anti-glare film 2 >>
[438] In the anti-glare film 1 prepared above, after applying the hard coating layer, the anti-glare film 2 was produced in the same manner except that the following anti-glare layer was formed using a coating method and subsequently the anti-reflection layer was provided.
[439] [Application of Anti-glare Layer]
[440] On the hard coat layer, the following anti-glare layer coating composition was applied with a slit die so as to have a wet film thickness of 10 μm, and the temperature of the hot air and the wind speed were gradually strengthened and finally dried at 85 ° C., followed by 115 mJ from the active light irradiation part. Ultraviolet irradiation was carried out at an irradiation intensity of / cm ² to provide an anti-glare layer having a thickness of 5 m with a dry film thickness.
[441] <Antiglare Layer Coating Composition>
[442] 60 parts by weight of dipentaerythritol hexaacrylate monomer
[443] 20 parts by weight of dipentaerythritol hexaacrylate dimer
[444] 20 parts by weight of a component of dipentaerythritol hexaacrylate or higher
[445] 8 parts by weight of synthetic silica particles (average particle size 1.8 μm)
[446] 4 parts by weight of dimethoxybenzophenone photoreaction initiator
[447] Propylene glycol monomethyl ether 75 parts by weight
[448] Methyl ethyl ketone 75 parts by weight
[449] << production of anti-glare film 3 >>
[450] In the anti-glare film 1 prepared above, after applying the hard coating layer, the anti-glare film 3 was produced in the same manner except that the following anti-glare layer was formed by an inkjet method, and then the anti-reflection layer was subsequently provided.
[451] [Formation of Anti-glare Layer]
[452] On the hard coating layer, the following antiglare layer ink liquid 1 was discharged at 1 pl as ink droplets by the inkjet method, and after 0.2 seconds, it was irradiated with ultraviolet radiation with an irradiation intensity of 100 mJ / cm ² from the active light irradiation part and cured, followed by hot air. The temperature and wind speed were gradually strengthened, and finally dried at 85 ° C., and irradiated with ultraviolet rays at an irradiation intensity of 100 mJ / cm ² , the center line surface roughness was 2 μm and the height a based on the bottom of the recess was 0.5 to 10.0 μm. The anti-glare layer which has one phosphorus convex part per 100 micrometer <^2> was formed.
[453] <Inkjet Discharge Method>
[454] The inkjet discharge apparatus used the line head system (FIG. 4 (a)), and prepared ten inkjet heads which have predetermined number of nozzles whose nozzle diameter is 3.5 micrometers. The inkjet head used the thing of the structure shown in FIG.
[455] The ink supply system is composed of an ink supply tank, a filter, a piezo-type inkjet head and a pipe, and the ink supply head is insulated and heated (40 ° C.) from the ink supply tank to a discharge temperature of 40 ° C. and a driving frequency of 20 kHz. It was done.
[456] <The composition of the antiglare layer ink liquid 1>
[457] 100 parts by weight of dipentaerythritol hexaacrylate
[458] (Includes dimers and terpolymers or more)
[459] 4 parts by weight of a photoreaction initiator (dimethoxybenzophenone)
[460] Propylene glycol monomethyl ether 30 parts by weight
[461] 100 parts by weight of methyl ethyl ketone
[462] << production of anti-glare films 4-9 >>
[463] In the production of the antiglare film 3, the type of the antiglare layer ink liquid (the above antiglare layer ink liquid 1 and the following antiglare layer ink liquids 2 and 3) and the ink droplet amount were changed as shown in Table 1 below. In the same manner, antiglare films 4 to 9 were prepared.
[464] <Composition of Anti-glare Layer Ink Liquid 2>
[465] 100 parts by weight of dipentaerythritol hexaacrylate
[466] (Includes dimers and terpolymers or more)
[467] 4 parts by weight of a photoreaction initiator (dimethoxybenzophenone)
[468] Acetone 900 parts by weight
[469] 10 parts by weight of isopropyl alcohol
[470] 10 parts by weight of ethyl acetate
[471] <Composition of Anti-glare Layer Ink Liquid 3>
[472] 100 parts by weight of dipentaerythritol hexaacrylate
[473] (Includes dimers and terpolymers or more)
[474] 4 parts by weight of a photoreaction initiator (dimethoxybenzophenone)
[475] Acetone 10000 parts by weight
[476] 5 parts by weight of isopropyl alcohol
[477] 5 parts by weight of ethyl acetate
[478] << production of anti-glare film 10 >>
[479] In the production of the antiglare film 9, the antiglare layer ink liquid 3 was discharged under the condition of 0.1 pl of the ink droplet amount, and irradiated and cured with ultraviolet rays in the same manner, except that fine irregularities were formed. Thereby to prepare an anti-glare film 10.
[480] << production of anti-glare film 11 >>
[481] In the production of the antiglare film 8, an antiglare film 11 was produced in the same manner as the hard coat layer in the semi-cured state except that the antiglare layer was formed by the inkjet method.
[482] << production of anti-glare film 12 >>
[483] In manufacture of the said anti-glare film 8, the anti-glare film 12 was produced similarly except having added 1 weight part of triphenyl phosphates as a plasticizer to the hard-coat layer coating liquid.
[484] << production of anti-glare film 13 >>
[485] In the production of the anti-glare film 8, the surface of the hard coating layer is surface-treated by plasma discharge at a high frequency voltage of 100 kHz under an atmospheric pressure in a nitrogen atmosphere containing 1% oxygen before forming the anti-glare layer by the inkjet method, followed by inkjet An antiglare film 13 was produced in the same manner except that an antiglare layer was formed by the anticorrosion method.
[486] << production of anti-glare film 14 >>
[487] In the production of the antiglare film 11, an antiglare film 14 was prepared in the same manner except that 1 part by weight of vapor-phase silica (Tokuyama Co., Ltd .: Reolosil QS-20) was added to the antiglare layer ink solution 1. It was.
[488] << production of anti-glare film 15 >>
[489] In the production of the antiglare film 11, an antiglare film 15 was produced in the same manner except that 20 parts by weight of the following tetraethoxysilane hydrolyzate was added to the antiglare layer ink solution 1.
[490] Tetraethoxysilane hydrolyzate: contained in ink as microdroplets
[491] 580 parts by weight of tetraethoxysilane and 1100 parts by weight of ethanol were mixed, and 5.4 parts by weight of citric acid monohydrate dissolved in 300 parts by weight of water was added, followed by stirring at room temperature for 1 hour to prepare a tetraethoxysilane hydrolyzate.
[492] << production of anti-glare film 16 >>
[493] In the production of the antiglare film 11, an antiglare film 16 was produced in the same manner except that at the same time, 0.5 pl and 0.3 pl of ink droplets were ejected at the time of forming the antiglare layer.
[494] << production of anti-glare film 17 >>
[495] In the production of the anti-glare film 11, the anti-glare film 17 was produced in the same manner except that 0.5 pl of the ink droplets were discharged and 0.3 pl of the ink droplets were ejected and then cured in the same manner after 1 second of irradiation with the actinic light.
[496] << production of anti-glare film 18 >>
[497] In manufacture of the said anti-glare film 11, the anti-glare film 18 was produced similarly except having changed the irradiation time of the actinic light at the time of forming an anti-glare layer into 4 second after an ink reached.
[498]
[499] * 1: Number per 100 µm ² of convex portions having a height of 0.5 to 10.0 µm based on the bottom of the concave portion (the number of the convex portions was measured by an optical interference surface roughness meter)
[500] << evaluation of anti-glare film >>
[501] The following angle evaluation was performed about the anti-glare films 1-18 which have the anti-reflective layer manufactured above.
[502] (Evaluation of adhesiveness)
[503] The board scale test based on JISK5400 was done. Specifically, by using the sample of the step of forming the anti-glare layer of the anti-glare film obtained by inserting one perforation line vertically and horizontally at intervals of 1 mm, 100 checkerboard eyes of 1 mm angle are made, and the cellophane adhesive tape is adhered thereon. It peeled rapidly at 90 degrees, and the number of the board | substrate eyes which remained without peeling was counted, and grade evaluation as shown below was performed.
[504] A: 100
[505] B: 95 to 99
[506] C: 90 to 94
[507] D: 70 to 89
[508] E: 69 or less
[509] C grade or more is practical.
[510] (Evaluation of reflectivity)
[511] The color unevenness of the reflected light of each produced anti-glare film was grasped as follows by visually confirming about 1 m <^2> .
[512] A: The change in the color tone of the reflected light is not confirmed.
[513] B: The hue change of reflected light is barely recognized (less than 5% of area).
[514] C: Only a small part of the color tone change of the reflected light is confirmed (5% or more of the area and less than 10%).
[515] D: The change of the color tone of reflected light is confirmed partially (10% or more and less than 30% of an area). E: The hue change of reflected light is confirmed as a whole.
[516] (Evaluation of visibility)
[517] About the visibility of each antiglare film, polarizing plates 1-18 were manufactured using the antiglare films 1-18 as follows, these polarizing plates were assembled to the liquid crystal display panel, and the visibility was evaluated.
[518] According to the following method, the polarizing plate was produced using each of an anti-glare film and the cellulose-ester film used as a support body for this film as a polarizing plate protective film.
[519] a) Preparation of polarizing film
[520] The long polyvinyl alcohol film of 120 micrometers in thickness was uniaxially stretched (temperature 110 degreeC, draw ratio 5 times). This was immersed for 60 seconds in the aqueous solution which consists of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water, and then immersed in the aqueous solution of 68 degreeC which consists of a ratio of 6 g of potassium iodide, 7.5 g of boric acid, and 100 g of water. This was washed with water and dried to obtain a long polarizing film.
[521] b) production of polarizing plate
[522] Next, the polarizing film and the protective film for polarizing plates were bonded together according to the following processes 1-5, and the polarizing plate was manufactured.
[523] Process 1: The long cellulose-ester film and the anti-glare film 1 were immersed in 2 mol / L sodium hydroxide solution at 60 degreeC for 90 second, and then washed with water and dried. A peelable protective film (made of polyethylene) was pasted and protected on the surface on which the antireflection layer of the antiglare film was provided.
[524] Similarly, the long cellulose-ester film was immersed in 2 mol / L sodium hydroxide solution at 60 degreeC for 90 second, and then washed with water and dried.
[525] Process 2: The above-mentioned long polarizing film was immersed for 1-2 second in the polyvinyl alcohol adhesive tank of 2 weight% of solid content.
[526] Process 3: The excess adhesive adhering to the polarizing film in the process 2 was lightly removed, and it laminated | stacked and sandwiched the cellulose-ester film and anti-glare film 1 which were alkali-treated in the process 1, and was laminated | stacked.
[527] Step 4: Bonding at a speed of about 2 m / min with two rotating rollers at a pressure of 20-30 N / cm ² . At this time, care was taken so that bubbles did not enter.
[528] Process 5: The sample manufactured by the process 4 was dried for 2 minutes in 80 degreeC dryer, and the polarizing plate 1 of this invention was manufactured.
[529] Except having used the anti-glare film 1 as one polarizing plate protective film instead of the anti-glare films 2-18, it carried out similarly and manufactured the polarizing plates 2-18, respectively.
[530] The polarizing plate of the outermost surface of a commercially available liquid crystal display panel (NEC color liquid crystal display Multi Sync LCD 1525 J: model name LA-1529HM) was carefully peeled, and the polarizing plates 1-18 which matched the polarization direction were stuck here.
[531] The liquid crystal panel obtained as mentioned above is arrange | positioned on the desk of 80 cm high from the floor, and the linear fluorescent lamp of primary color light is made to the ceiling of 3 m from the floor (FLR40S / D / MX Matsushita Denki Sangyo Co., Ltd. make) 40 10 sets of Wx2 were arranged at 1.5 m intervals as 1 set. At this time, when the evaluator is in front of the liquid crystal panel display surface, the fluorescent lamp is disposed in the ceiling portion toward the rear side of the evaluator's head. The liquid crystal panel was tilted 25 ° in the vertical direction with respect to the desk so that the fluorescent lamps reflected, and the easiness of view (visibility) of the screen was evaluated as follows.
[532] A: The reflection of the nearest fluorescent lamp is not worried at all, and the letter of size 8 or less of the font can be clearly read.
[533] B: The reflection of the nearest fluorescent lamp is hardly noticed, and characters of size 8 or less of the font can be read.
[534] C: I'm a bit worried about the reflections of nearby fluorescent lights, but I don't care from afar, and I can barely read characters under 8 in font size.
[535] D: I am worried about the reflection of a distant fluorescent lamp, and it is difficult to read the characters of the font size 8 or less.
[536] E: The reflection of the fluorescent lamp is very concerned, and the reflection portion cannot read characters of size 8 or less of the font.
[537] (Evaluation of image quality and clarity)
[538] The test chart image for moving picture and sharpness evaluation was output to each liquid crystal panel manufactured by the said visibility evaluation, and image finishing and sharpness were evaluated according to the following criteria.
[539] A: The black finish of the moving picture is very good, and the test pattern is projected very clearly.
[540] B: The black finish of the moving picture is satisfactory, and a slight decrease in the sharpness is observed in the high frequency test pattern, but there is no problem at all.
[541] C: The black finish of the moving picture is weak, and the weak acid sharpness is confirmed by a test pattern of high frequency and high frequency, but there is no problem in practical use.
[542] D: The black finish of a moving picture is weak, and the fall of sharpness is confirmed by the test pattern of all frequencies, and there exists a problem practically.
[543] E: The black finish of the moving picture is poor, and a clear deterioration of sharpness is confirmed in the test pattern of all frequencies, and there is a problem in practical use.
[544] The results obtained from the above are shown in Table 2 below.
[545]
[546] As is apparent from Table 2, the anti-glare film of the present invention in which the anti-glare layer was formed by the inkjet method has good adhesion and film uniformity to the comparative example, and does not mind the reflection when used in the liquid crystal panel. It can be seen that the black finish at the time of displaying the moving image is good and the sharpness is excellent. Especially, antiglare films 6-17 showed the more favorable result.
[547] According to the present invention, the film formation properties (film uniformity, adhesiveness) are good, and the antiglare layer forming method, the antiglare film, and the production thereof having excellent black finish when displaying the anti-glare effect, sharpness, visibility, and moving image A method and an inkjet apparatus for antiglare layer formation can be provided.

权利要求:
Claims (24)
[1" claim-type="Currently amended] Discharging ink droplets containing an antiglare imparting composition for forming a fine concavo-convex structure by an inkjet method on a transparent substrate, thereby forming an antiglare layer having a fine concavo-convex structure on the surface of the transparent substrate. Forming method.
[2" claim-type="Currently amended] The method for forming an antiglare layer according to claim 1, wherein the centerline average roughness Ra of the fine uneven structure is 0.05 to 5.0 µm.
[3" claim-type="Currently amended] The method for forming an antiglare layer according to claim 1, wherein the fine uneven structure has 1 to 50 convex portions per 100 µm ² having a height of 0.5 to 10 .mu.m based on the bottom of the recess. .
[4" claim-type="Currently amended] The method of forming an antiglare layer according to claim 1, wherein the antiglare composition is an active light curable resin.
[5" claim-type="Currently amended] The method of claim 1, further comprising irradiating actinic rays after the ink droplets have been impacted on the transparent substrate.
[6" claim-type="Currently amended] The anti-glare composition is a thermosetting resin, The formation method of the anti-glare layer according to claim 1.
[7" claim-type="Currently amended] The method of forming an antiglare layer according to claim 6, further comprising heat-curing the ink droplets which have been landed on the transparent substrate.
[8" claim-type="Currently amended] The method of forming an antiglare layer according to claim 1, wherein the ink droplets having different refractive indices are ejected to form irregularities having different refractive indices.
[9" claim-type="Currently amended] The method of forming an anti-glare layer according to claim 1, wherein ink of two or more kinds of compositions is discharged, and droplets of inks of different compositions differ in particle size.
[10" claim-type="Currently amended] The method of claim 9, wherein after forming the first fine concavo-convex structure on the transparent substrate using the first ink droplet, the second fine concave-convex structure is formed by using the second ink droplet having a particle diameter smaller than the first ink droplet. Formation method of the anti-glare layer characterized in that.
[11" claim-type="Currently amended] The method of forming an antiglare layer according to claim 1, wherein the ink droplet contains fine particles having a particle diameter smaller than that of the ink droplet.
[12" claim-type="Currently amended] 12. The method of forming an antiglare layer according to claim 11, wherein the fine particles in the ink droplets are microdroplets.
[13" claim-type="Currently amended] The method of forming an antiglare layer according to claim 12, wherein a difference in refractive index between the microdroplets and the ink droplet medium is 0.01 or more.
[14" claim-type="Currently amended] The method of claim 1, wherein the inkjet method provides fine vibration to the inkjet head portion so that ink droplets are randomly ejected onto the transparent substrate during the ejecting step.
[15" claim-type="Currently amended] The method of forming an antiglare layer according to claim 1, wherein the transparent substrate has at least one hard coating layer thereon, and ink droplets are ejected onto the surface of the hard coating layer.
[16" claim-type="Currently amended] The method of forming an antiglare layer according to claim 15, wherein when the hard coating layer is in a semi-cured state, the ink droplet is ejected onto the surface of the hard coating layer.
[17" claim-type="Currently amended] The method of forming an antiglare layer according to claim 15, wherein after the plasma treatment of the surface of the hard coating layer, the ink droplet is ejected onto the surface of the hard coating layer.
[18" claim-type="Currently amended] The method for forming an antiglare layer according to claim 15, wherein the hard coating layer contains a plasticizer.
[19" claim-type="Currently amended] A method for producing an antiglare film comprising forming an antiglare layer on a transparent substrate by producing the antiglare layer according to claim 1 to produce an antiglare film.
[20" claim-type="Currently amended] The anti-glare film production method according to claim 19, further comprising an anti-reflection layer on the anti-glare layer.
[21" claim-type="Currently amended] It produced by the manufacturing method of the anti-glare film of Claim 19, The anti-glare film characterized by the above-mentioned.
[22" claim-type="Currently amended] An inkjet device for forming an antiglare layer for producing the antiglare film according to claim 21, comprising an active light ray irradiating portion or a heating portion disposed so that actinic light or heat does not directly act on the inkjet head portion. Formation inkjet apparatus.
[23" claim-type="Currently amended] The polarizing plate containing the anti-glare film of Claim 21.
[24" claim-type="Currently amended] The display device containing the polarizing plate of Claim 23.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2002-11-01|Priority to JP2002319665A

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2002-11-01|Priority to JPJP-P-2002-00319665

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2003-10-29|Application filed by 코니카가부시끼가이샤

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2004-05-08|Publication of KR20040038764A

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2011-12-08|Application granted

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2011-12-08|Publication of KR101090580B1

优先权:

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申请号 | 申请日 | 专利标题

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JP2002319665A|JP4506070B2|2002-11-01|2002-11-01|Method for forming antiglare layer, method for producing antiglare film, and ink jet device for forming antiglare layer|

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JPJP-P-2002-00319665|2002-11-01|