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    • 专利摘要:
    The present invention is capable of producing a transparent cured product having a high refractive index, high hardness, and excellent wear resistance, and to prepare a liquid curable resin composition that can be suitably used as a coating material, in order to prepare at least three (meth) molecules in (A) molecules. A reaction product obtained by the reaction of a polyfunctional (meth) acrylic compound having an acryloyl group, a compound having a polymerizable unsaturated group and an alkoxysilyl group in the molecule and a metal oxide particle (wherein the metal is zirconium, antimony, Selected from the group consisting of zinc, tin, cerium and titanium), and (C) a radiation curable resin composition.
    公开号:KR20010100989A
    申请号:KR1020017005705
    申请日:1999-11-04
    公开日:2001-11-14
    发明作者:야시로다카오；에리야마유이치；니시와키이사오；우카치다카시
    申请人:윌리암 로엘프 드 보에르；디에스엠 엔.브이；마쯔모또 에이찌；제이에스알 가부시끼가이샤；이이다 이사오；재팬파인코팅스 가부시키가이샤；
    IPC主号:
    专利说明:

    Radiation-Curable Metal Particles and Curable Resin Compositions Comprising the Same
    [2] Conventionally, hard coat treatment has been applied as a means for protecting not only the surfaces of prefabricated plastic materials, such as plastic optical parts, contact panels, and liquid crystal devices, but also coating surfaces, such as floors and walls in buildings. UV curable acrylic hard coat materials such as polyester acrylates, urethane acrylates and epoxy acrylates have been used as such hard coat materials. However, when used alone, the hard coat material could not sufficiently improve the mar resistance, slip characteristics, and stain resistance of the plastic surface and the coating surface.
    [3] The addition of inorganic fillers such as silica or organic fillers such as polyethylene powder and polycarbonate powder, and the addition of additives such as silicon, are well suited as methods for improving the damage resistance, slip properties and contamination resistance of the prefabricated plastic surface. Known.
    [4] However, the method of adding the inorganic filler or the organic filler has disadvantages such as increasing haze value and damaging the appearance of the resulting coating film. The method of adding silicon can improve the sliding characteristics of the coated surface, but cannot improve the damage resistance due to the grinding wheel difference. And, the hard coat applied to the contact panel or the like requires a post-treatment step by alkali etching. These include hydrolysis of commonly used silicon additives with alkali, resulting in damage to the appearance of the coating from the prefabricated plastic material, or peeling of the coating.
    [5] Regarding a thermoplastic resin material having a high refractive index, Japanese Patent Publication No. 12489/1990 discloses a high refractive index resin used for a lens. The resin includes a polymer obtained by the reaction of a urethane (meth) acrylic monomer and a vinyl compound obtained by the reaction of a (meth) acrylic monomer having a halogen-substituted aromatic ring with a polyfunctional isocyanate compound. Although the resin has a high refractive index, its wear resistance is insufficient.
    [6] On the other hand, regarding the photopolymerizable crosslinking coating material, Japanese Patent Application No. 169833/1987 discloses a photocurable monomer containing a polyacrylate of dipentaerythritol. Coatings with sufficient hardness can be obtained in a short time using the monomers. However, since the coating has a refractive index of 1.55 or less, if the monomer is coated on a substrate having a high refractive index, such as polycarbonate, polyester carbonate, polyethylene terephthalate, or poly-1,4-cyclohexane dimethylene terephthalate, Interference stripes can be formed. Thus, the material is not suitable for use in optical products requiring high resolution.
    [7] Problem solved by the present invention
    [8] An object of the present invention is to provide a liquid curable resin composition which can produce a transparent cured product having high refractive index, high hardness and excellent wear resistance, and can be suitably used as a coating material.
    [9] Another object of the present invention is to provide a liquid curable resin composition suitable for forming a hard coat on the surface of a prefabricated plastic material.
    [10] Other objects and features of the present invention will become apparent from the following detailed description of the invention.
    [11] Summary of the Invention
    [12] The present invention provides a radiation-curable metal particle comprising a radiation-curable group in which a silyl group is bonded to a metal, in particular the metal does not include a silicon metal. Also provided are methods of making the particles.
    [13] In addition, the present invention provides a composition comprising the particles. Preferred compositions provided by the present invention are compositions which, after radiation curing, provide products with high transparency, low haze and a refractive index of at least 1.55.
    [14] The present invention also provides an article made by curing the composition, including an article comprising a film and a coating formed from the composition. In particular, an article having antireflection characteristics is provided.
    [1] The present invention relates to a radiation-curable metal particle composed of a radiation-curable group in which a silyl group is bonded to a metal, and a liquid curable resin composition composed of a polyfunctional (meth) acryl compound and the metal oxide particles. In particular, the present invention relates to a liquid curable resin composition capable of producing a cured product having a high refractive index for use in a prefabricated plastic article or film, and also capable of producing an antireflection film.
    [15] The terminology used herein is used to define certain chemical aspects. The terms are defined below.
    [16] A (meth) acryl compound is a compound containing a (meth) acryloyl group, where a (meth) acryloyl group contains an unsaturated bond.
    [17] For references in the Periodic Table of the Elements, see "CRC Handbook of Chemistry and Physics", 78th ed. See the periodic table on the inner front cover of 1997-1998 and "New Notation".
    [18] Therefore, the group is numbered in Arabic notation, for example, group 11 is a group consisting of copper, silver and gold, and group 2 is a group containing magnesium, calcium, barium and the like. In the present invention, group 3 is considered to include elements 57-71 and elements 89-103, that is, lanthanum series and actinium series.
    [19] The present invention provides a radiation-curable metal particle comprising a radiation-curable group in which a silyl group is bonded to a metal, which will be referred to as "component B" below. Those skilled in the art will appreciate that "component B" means a single particle, a multiparticulate or a particle mixture.
    [20] The present invention also provides a composition comprising the particles. The radiation-curable composition is a suitable radiation-curable composition and may further comprise a (meth) acryl compound (hereinafter referred to as "component (A)"). The composition is independent of the presence of component (A) and may also comprise a radiation polymerization initiator (hereinafter referred to as "component (C)").
    [21] Component (A) may be a suitable (meth) acrylic compound. Preferably, component (A) has at least three (meth) acryloyl groups in the molecule, more preferably 3 to 10 (meth) acryloyl groups, more preferably 4 to 10 (meth) acryloyl groups And most preferably 4 to 8 (meth) acryloyl groups.
    [22] Examples of the (meth) acryl compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
    [23] Examples of commercially available products of (meth) acrylic compounds having at least three (meth) acryloyl groups in the molecule include Kayarrad DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 , D-310, D-330, PET-30, GPO-303, TMPTA, THE-330, TPA-330 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M -315, M-325 (made by Toagosei Co., Ltd.), etc. are mentioned.
    [24] The proportion of the (meth) acryl compound having at least three (meth) acryloyl groups in the molecule, used as component (A) in the composition of the present invention, is preferably 1 to 99 wt%, more preferably 10 to 90 wt % And particularly preferably 30 to 70 wt%. The number of intramolecular (meth) acryloyl groups is preferably 4-10, and more preferably 4-8.
    [25] Particles of component (B) comprise radiation-curable groups in which silyl groups are bonded to the metal. The metal may be a suitable metal, preferably a metal selected from Group 2-16 metals of the Periodic Table of the Elements except silicon metal. Preferably, the metal is selected from metals 3-4 and 12-15 of the Periodic Table of the Elements (except silicon metal). In particular, the metal is selected from the group consisting of zirconium, titanium, antimony, zinc, tin, indium, cerium and aluminum, and most preferably the metal is selected from the group consisting of zirconium, antimony, zinc and cerium.
    [26] The silyl group is preferably a substituted silyl group. Substituted silyl groups may be suitable silyl groups. Preferably, substituted silyl groups include urethane groups, thiourethane groups and / or alkoxy groups. Preferably, the silyl group contains at least a urethane group.
    [27] The silyl group is derived from a compound having at least one alkoxysilyl group and mercapto group in the molecule, and as described below, the compound is reacted with the following isocyanate.
    [28] In a composition comprising both component (A) and component (B), the proportion of component (B) is preferably 1 to 99 wt%, more preferably 10 to 90 wt% and particularly preferably based on the total weight of the composition 30 to 70 wt%.
    [29] When component (B) is a mixture of particles 5, preferably at least 90 wt%, more preferably at least 95 wt% and most preferably at least 99 wt% of the total metal (excluding silicon in the silyl group) is zirconium, titanium , Antimony, zinc, tin, indium, cerium and aluminum.
    [30] Component (B) is the reaction product.
    [31] The reaction product used as component (B) is obtained by reaction of a metal oxide particle with an organosilicon compound having a polymerizable unsaturated group and an alkoxysilyl group in a molecule, and the main components of the metal oxide particle are zirconium, titanium, antimony, Oxide of a metal selected from the group consisting of zinc, tin, indium, cerium and aluminum. The proportion of the reaction product contained in the composition of the present invention as component (B) is preferably 1 to 99 wt%, more preferably 10 to 90 wt% and particularly preferably 30 to 70 wt%. The reaction is preferably carried out in the presence of water.
    [32] The reaction product used as component (B) in the present invention can be produced by a method comprising at least the operation of mixing the organosilicon compound and the metal particles. The amount of remaining organosilicon compound immobilized on the metal oxide particles is preferably at least 0.01 wt%, more preferably at least 0.1 wt% and most preferably at least 1 wt%. If the amount of the remaining organosilicon compound fixed on the metal oxide particles is less than 0.01 wt%, the dispersion degree of the reaction product containing the metal oxide particles in the composition of the present invention is insufficient, thereby resulting in a lack of transparency and wear resistance of the composition. The proportion of the organosilicon compound in the raw material compound for preparing component (B) is preferably at least 10 wt%, and more preferably at least 30 wt%. If the ratio of the organosilicon compound is less than 10 wt%, the film forming ability of the resultant composition is insufficient. The proportion of metal oxide particles in the starting compound for component (B) is preferably 50 wt% or less, and more preferably 20 wt% or less. If the amount of metal oxide particles in the raw material compound for preparing component (B) is 50 wt% or more, the dispersion, transparency and wear resistance of the resulting composition are insufficient.
    [33] Preferably, the organosilicon compound contains a polymerizable unsaturated group and an alkoxysilyl group in the molecule. As a preferable example of the polymerizable unsaturated group, an acryl group, a vinyl group and a styryl group may be provided. As the alkoxysilyl group, groups which can be hydrolyzed in the presence of water or a hydrolysis catalyst are preferred. The organosilicon compound contains at least one bond selected from ester groups, ether groups, urethane groups, sulfide groups, and thiourethane groups in the molecule. The organosilicon compound preferably contains at least one polymerizable unsaturated group, urethane bond group and alkoxysilyl group as its components. The alkoxysilyl group is a component combined with an absorbent present on the surface of the metal oxide particles by hydrolysis-condensation reaction. The polymerizable unsaturated group is a component in which molecules are chemically crosslinked with each other by adding to a polymerization reaction in the presence of a reactive radical. A urethane bond group is a structural unit which couple | bonds the molecule | numerator which has an alkoxysilyl group, and the molecule | numerator which has a polymerizable unsaturated group directly or through another molecule. At the same time, the urethane bonder forms a moderate adhesion force between molecules due to hydrogen bonding, thereby providing a cured product made from the composition of the present invention having excellent mechanical strength, good adhesion to a substrate, high coldness, and the like.
    [34] As an example of the preferred organosilicon compound, the compound of formula 1 may be provided.
    [35]
    [36] (In Formula 1, R 1 is a monovalent organic group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, phenyl group or octyl group or hydrogen atom; R 2 has 1 to 3 carbon atoms. An alkyl group or a hydrogen atom, and m is 1, 2 or 3. Examples of the trimethoxysilyl group represented by the general formula (RO 1 ) m R 2 3-m Si include triethoxysilyl group and triphenoxysilyl group. , Methyldimethoxysilyl group, dimethylmethoxysilyl group, etc. may be provided, and preferred groups are trimethoxysilyl group and triethoxysilyl group General formula-(C = O) NH-R 4 -NH (C = O) OXO] p -is a structural unit introduced to expand the molecular chain to the structure represented by Formula 1. R 3 is a divalent organic group having 1 to 3 carbon atoms, or is the same as R 3 , or the other R 4 is a divalent organic group and a molecular weight of 14 to 10,000, preferably from 78 to 1,000 Divalent organic groups having, for example, linear polyalkylene groups such as methylene groups, ethylene groups, propylene groups, hexamethylene groups, octamethylene groups and dodecamethylene groups; aliphatic or polycyclic divalent organic groups such as cyclohexylene groups And a norbornylene group, a divalent aromatic group such as a phenylene group, a naphthylene group, a biphenylene group and a polyphenylene group, and an alkyl or aryl group substitution product of the group. It may further comprise an aromatic group containing the elements of p and q in the formula 1 is 0 or 1. X is an active hydrogen atom capable of reacting divalent organic groups, in particular isocyanate groups in the molecule by addition reaction Divalent organic groups originating from a compound having, for example, polyalkylene glycol, polyalkylene thioglycol, polyester, polyamide, polycarbo There is a divalent organic group obtained by removing two active hydrogen atoms from a compound such as a nate, polyalkylene diamine, polyalkylene dicarboxylic acid, polyalkylene diol, or polyalkylene dimercaptan R 5 is (n + 1) It is an organic group having a valence of The organic group is preferably selected from linear, branched or cyclic saturated hydrocarbon groups, unsaturated hydrocarbon groups and aliphatic ring groups. In Formula 1, Y is a monovalent organic group having a polymerizable unsaturated group which causes crosslinking reaction between molecules in the presence of a reactive radical, for example, an acryloxy group, methacryloxy group, vinyl group, propenyl group, butadienyl group, Styryl group, ethynyl group, cinnamoyl group, maleate group, acrylamide group and the like. Among the above, an acryloxy group is preferable. n is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 3 to 5 positive numbers.
    [37] The organosilicon compounds used in the present invention are, for example, (1) a mercapto group (ie, mercaptoalkoxysilane), a polyisocyanate compound, and an active hydrogen group-containing polymerizable containing active hydrogen capable of causing an addition reaction. Addition reaction of an alkoxysilane having an unsaturated compound with an isocyanate group; (2) direct reaction between an isocyanate compound having an isocyanate group and an alkoxysilyl group in the molecule and an active hydrogen-containing polymerizable unsaturated compound; Or (3) addition reaction between a compound having a polymerizable unsaturated group and an isocyanate group in a molecule and a mercaptoalkoxysilane or aminosilane compound.
    [38] The following methods can be provided as an example of the method using mercaptoalkoxysilane as a raw material.
    [39] Method (a):
    [40] Mercaptoalkoxysilane reacts with a polyisocyanate compound to produce an intermediate containing an alkoxysilyl group, a -S (C = O) NH- bond group and an isocyanate group in the molecule, and isocyanate and active hydrogen-containing polymerization in the intermediate compound. Reacting the unsaturated unsaturated compound to combine the unsaturated compound via a urethane group.
    [41] Method (b):
    [42] The polyisocyanate compound is reacted with an active hydrogen-containing polymerizable unsaturated compound to produce an intermediate containing a polymerizable unsaturated group, a urethane bond group, and an isocyanate group in the molecule, and the intermediate is reacted with a mercaptoalkoxysilane to give -S ( Combining with mercaptoalkoxysilane via a C═O) NH— group.
    [43] In the above methods (a) or (b), linear, cyclic, or branched compounds having two or more active hydrogen atoms reactive with isocyanates by intramolecular addition reactions may further be used. The compound can extend the chain length of the alkoxysilane compound obtained by reacting with the polyisocyanate compound through a urethane bond.
    [44] Compounds having at least one alkoxysilyl group and a mercapto group in the molecule are examples of alkoxysilanes which can form -S (C═O) NH— bonds by reaction with isocyanate groups in the preparation of the compound of Formula 1 Can be provided.
    [45] Examples of the compound include mercaptoalkoxysilanes such as mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane , Mercaptopropyltriethoxysilane, mercaptopropyltriphenoxysilane and mercaptopropyltributoxysilane. Among the above, preferred compounds are mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane. An example of a commercially available mercaptoalkoxysilane can be provided with Do606 Corning Toray Silicone Co., Ltd. SH6062. The mercaptoalkoxysilanes may be used alone or in combination of two or more. As other mercaptoalkoxysilanes, addition products of amino-substituted alkoxysilanes and epoxy group-substituted mercaptans, addition products of epoxy silanes and α, ω-dimercapto compounds may be provided.
    [46] The isocyanate compound used to prepare the organosilicon compound may be selected from compounds having a linear saturated hydrocarbon, cyclic saturated hydrocarbon or aromatic hydrocarbon structure. The isocyanate compounds may be used alone or in combination of two or more. The number of isocyanate groups in the molecule is usually 1 to 30, preferably 2 to 10. If it is 30 or more, the viscosity of the product is increased to reduce workability.
    [47] Examples of such isocyanate compounds include linear hydrocarbon isocyanate compounds such as 3-trimethoxysilylpropane isocyanate, 3-triethoxysilylpropane isocyanate, 3-methacryloxypropyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Cyclic saturated hydrocarbon isocyanate compounds such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate and 1,3 -Bis (isocyanate methyl) cyclohexane; And aromatic hydrocarbon isocyanate compounds such as 2,4-tolylene diisocyanate of polydiphenylmethane, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, p- Phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-biphenylene diisocyanate, 6-isopropyl -1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, 1,5-naphthalene diisocyanate and polyisocyanate.
    [48] In the above, a preferable compound is a cyclic saturated hydrocarbon polyisocyanate compound, an aromatic hydrocarbon polyisocyanate compound, and a more preferable compound is a cyclic saturated hydrocarbon polyisocyanate compound. Particular examples of particularly preferred polyisocyanate compounds are 3-trimethoxysilylpropane isocyanate, 3-triethoxysilylpropane isocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate and hydrogenated toluene diisocyanate. Examples of commercially available polyisocyanate compounds include A-1310 and Y-5187 from Nippon Unicar Co., Ltd .; Calenz MOI, produced by Showa Denko Co., Ltd .; TDI-80 / 20, TDI-100, MDI-CR100, MDI-CR300, MDI-PH and NDI manufactured by Mitsui-Nisso Urethan Co., Ltd .; Coronate T, Millionate MT, Millionate MR, and HDI from Nippon Polyurethan Industry Co., Ltd .; And Takenate 600 manufactured by Takeda Chemical Industries Co., Ltd.
    [49] The amount of the polyisocyanate compound used in the method (a) is 0.1 to 100 equivalents, preferably 0.5 to 10 equivalents, and more preferably 0.9 to 10 equivalents of the isocyanate group to 1 equivalent of the mercapto group in the mercaptoalkoxysilane. 1.2 equivalents is determined. If the amount of the polyisocyanate compound is less than 0.1 in view of the equivalent of isocyanate groups, 0.9 equivalent of mercaptosilane remains unreacted, resulting in insufficient wear resistance of the coating film. When the polyisocyanate compound is used in an isocyanate group of 100 equivalents or more, a large amount of unreacted isocyanate groups remain, resulting in a composition having poor weather resistance.
    [50] On the other hand, in the method (b), the amount of the polyisocyanate compound in terms of the equivalent of the isocyanate group is 0.1 to 100, preferably 0.5 to 10, relative to the equivalent of the active hydrogen contained in the active hydrogen-containing polymerizable unsaturated compound, and More preferably, it exists in the range of 0.9-1.2.
    [51] In method (a) or method (b), a catalyst can be added to shorten the reaction time. Basic catalysts or acidic catalysts can be used as catalysts. Examples of basic catalysts include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia; Phosphines such as tributyl phosphine and triphenyl phosphine and the like can be provided. Of these, tertiary amines such as pyridine and triethylamine are preferred. As the acid catalyst, metal alkoxides such as copper naphthenate, cobalt naphthenate, zinc naphthenate, 1,4-diazabicyclo [2.2.2] octane (DABCO), methyl DABCO, tributoxy aluminum, tri Titanium tetrabooxide, and zirconium tetrabooxide; Lewis acids such as trifluoroboron diethyl etherate and aluminum chloride; Tin compounds such as tin 2-ethylhexanoate, octyl tin trilaurate, dibutyl tin dilaurate, octyl tin diacetate and the like can be provided. Among the above, an acid catalyst is preferable and a tin compound is especially preferable. Examples of particularly preferred tin compounds are octyl tin trilaurate, dibutyl tin dilaurate, octyl tin diacetate and the like. The amount of the catalyst added is 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of the polyisocyanate. The effect of reducing the reaction time is weak if the amount of added catalyst is 0.01 parts by weight. On the other hand, if the amount of the catalyst is 5 parts by weight or more, the storage stability of the product may be impaired.
    [52] An example of an active hydrogen-containing polymerizable unsaturated compound capable of bonding with the polyisocyanate compound through a urethane bond by an addition reaction in preparing an organosilicon compound is a urethane bond formed by addition reaction with an isocyanate group in a molecule. Compounds having at least one active hydrogen and at least one polymerizable unsaturated group can be provided. The compounds may be used alone or in combination of two or more. The carboxylic acid group-containing polymerizable unsaturated compound and the hydroxyl group-containing polymerizable unsaturated compound are provided as the compound. Specific examples of the polymerizable unsaturated compound having a carboxylic acid group include unsaturated aliphatic carboxylic acids such as (meth) acrylic acid, itaconic acid, cinnamic acid, maleic acid, fumaric acid, 2- (meth) acryloxypropyl hexahydrogenphthalate, and 2- (meth) acryloxyethyl hexahydrophthalphthalate; And unsaturated aromatic carboxylic acids such as 2- (meth) acryloxypropyl phthalate and 2- (meth) acryloxypropylethyl phthalate. Examples of hydroxyl group-containing polymerizable unsaturated compounds include hydroxyl group-containing acrylates, hydroxyl group-containing methacrylates, and hydroxyl group-containing styrenes, such as 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2 -Hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, poly (pentamethyleneoxycarboxylate) ethoxy (meth) acrylate , Hydroxy styrene, hydroxy α-methylstyrene, hydroxyethyl styrene, hydroxy-terminated polyethylene glycol styryl ether, hydroxy-terminated polypropylene glycol styryl ether, hydroxy-terminated polytetrame Ethylene glycol styryl ether, end-hydroxy polyethylene glycol (meth) acrylate, end-hydroxy polypropylene glycol (meth) acrylate, end-hydroxy poly (tetraethylene glycol (meth) acrylate), trimethylolpropane Di (meth) acrylate, trimethylolpropane mono (meth) acrylate, ethylene oxide (EO) -modified trimethylolpropane tri (meth) acrylate, propylene oxide (PO) -modified trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra ( Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate and dipentaerythritol No (meth) acrylates.
    [53] Among the above, unsaturated aliphatic carboxylic acid and hydroxyl group-containing acrylate compound are preferable, and hydroxyl group-containing acrylate compound such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, Pentaerythritol triacrylate and dipentaerythritol pentacrylate are particularly preferred. In view of the equivalent of active hydrogen, the amount of the active hydrogen-containing polymerizable unsaturated compound is at least 1 equivalent to 1 equivalent of the isocyanate group remaining in the intermediate compound produced by the addition reaction of mercapto alkoxysilane and polyisocyanate compound. If less than 1 equivalent, the resultant composition may exhibit undesirable effects such as foaming, increasing viscosity and coloring due to the reaction of the reactive isocyanate groups with water remaining in the alkoxysilyl compound.
    [54] In preparing an organosilicon compound for the purpose of improving the flexibility of the coating film and increasing the adhesion to the substrate, the divalent organic group can be introduced by the addition reaction of an alkoxysilyl group and a polyunsaturated polyisocyanate compound of a polymerizable unsaturated nitrile. . As the organic compound reacting with the isocyanate group by the addition reaction, a linear, cyclic or branched organic compound having two or more active hydrogen atoms in the molecule may be used. Here, as an example of a group having an active hydrogen atom, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, a sulfone group, a phosphoric acid group, a silanol group and the like can be provided. The organic compound contains at least two, preferably 2 to 10, more preferably two active hydrogen atoms in the molecule. The molecular weight of the compound having an active hydrogen atom is preferably 50 to 100,000, more preferably 100 to 50,000 and particularly preferably 500 to 10,000. Examples of the divalent organic compound include polyalkylene glycol, polyalkylene thioglycol, polyester diol, polyamide, polycarbonate diol, polyalkylene diamine, polyalkylene dicarboxylic acid, polyalkylene diol and polyalkyl Lene dimercaptans may be provided. As examples of commercially available polyalkylene glycols, copolymers of two or more of polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyhexamethylene glycol, and polyalkylene glycols may be provided. Commercially available products are UNISAFE DC1100, UNISAFE DC1800, UNISAFE DCB1100, UNISAFE DCB 1800, and PPTG 4000, PPTG 2000, manufactured by Hodogaya Chemical Co., Ltd., manufactured by Nippon Oil and Fats Co., Ltd. PPTG 1000, PTG 2000, PTG 3000, PTG 650, PTGL 2000, PTGL 1000 and EXCENOL 1020, Daiichi Kogyo Seiyaku Co., Ltd., manufactured by Asahi Glass Co., Ltd. PBG 3000, PBG 2000, PBG 1000, and Z3001. The process for preparing the polymerizable unsaturated group-containing alkoxysilane containing a divalent organic group as a constituent will be described with polyalkylene glycol as an example of the divalent organic group.
    [55] Method (c):
    [56] A polyalkylene glycol is added to the addition compound of the mercapto alkoxysilane having a reactive isocyanate group at the terminal and the polyisocyanate compound to convert the terminal hydroxyl group into an alkoxysilane group, and a polymerizable unsaturated compound having a hydroxyl group at the terminal and polyisocyanate A method of reacting separately prepared addition compounds of the compounds with the resulting compounds to combine them via urethane bonds.
    [57] Method (d):
    [58] The addition compound of the mercapto alkoxysilane which has a reactive isocyanate group at the terminal, and the polyisocyanate compound are prepared, The polyalkylene glycol polyisocyanate compound which has a reactive hydroxyl group at the terminal, and the hydroxyl group containing polymerizable unsaturated compound are the said addition compound. Reacting with each other to combine the compounds via a urethane bond.
    [59] The conditions for forming the urethane bond in the method (c) or the method (d) are the same as those used in the method (a) or (b). The equivalent ratio of the compound having a hydroxyl group at the terminal to the compound having a reactive isocyanate group at the terminal participating in the bond is preferably 1.0 to 1.2. If it is less than 1.0, coloring and viscosity increase due to unreacted isocyanate groups tend to occur.
    [60] And the co-hydrolyzate with other organic alkoxysilanes is used as a hydrolyzate of the polymerizable unsaturated group-modified alkoxysilane in producing an alkoxysilane compound. For example, co-condensation products with other organic alkoxysilanes, such as alkyl alkoxysilanes, for example tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Dimethyldimethoxysilane, phenyltrimethoxysilane and the like can be used. In the case of producing the hydrolyzate, the amount of water used for the hydrolysis is usually 0.5 to 1.5 equivalents relative to the amount of the total alkoxy group. The hydrolysis-condensation polymer may be obtained by stirring the reaction mixture for 5 minutes to 24 hours in the presence or absence of a solvent while heating at a temperature of 0 ° C. to the boiling point of the component. In this case, acid catalysts or base catalysts can be used to shorten the reaction time. The metal oxide particles used to prepare component (B) are in the form of fine particles or solvent dispersed sol. As the metal oxide, antimony oxide, zinc oxide, tin oxide, indium-tin mixed oxide, cerium oxide, aluminum oxide, titanium dioxide and zirconium oxide may be provided as an example. These may be used alone or in combination of two or more. And, in view of the solubility and dispersity with component A and the solubility with photoinitiators and photosensitizers, sol or cellosolve in polar solvents such as alcohols, dimethylformamide, dimethylacetamide is used more than sol. As a particularly preferred sol, sols of antimony oxide, zinc oxide, cerium oxide and zirconium oxide can be provided.
    [61] The average diameter of the metal oxide particles is, for example, 0.001 to 2 µm. The metal oxide particles may be manufactured under trade names, such as Alumina Sol-100, Alumina Sol-200, Alumina Sol-520 (alumina powder dispersed in water, manufactured by Nissan Chemical Industries., Ltd.) Celnax (antimonic acid zinc dispersed in water, Nissan Chemical Industries., Ltd.), Nanotek (alumina, titanium oxide, tin oxide, indium oxide, and zinc oxide powder dispersed in solvent, manufactured by CI Chemical Co., Ltd.), Titania Sol, SN-100D (in water Sol of dispersed antimony dope tin oxide powder, manufactured by Ishihara Sangyo Kaisha, Ltd., ITO powder (manufactured by Mitsubishi Material Co., Ltd.), Needral (cerium oxide powder dispersed in water, manufactured by Taki Chemical Co., Ltd. ) Can be used for commercial purposes. In order to produce a transparent film using the composition of the present invention, the preferred particle diameter is 0.001 to 2 µm, more preferably 0.001 to 0.05 µm. The shape of the metal oxide particles is spherical, hollow, porous, rod-shaped, plate-shaped, fibrous or crystalline and preferably spherical. The specific surface area of the metal oxide particles is preferably 10 to 3,000 m 2 / g, and more preferably 20 to 1,500 m 2 / g. The metal oxide particles may be used as a dispersion or a dry powder in water or an organic solvent. As the solvent dispersing sol of the metal oxide, dispersion of fine particles of the metal oxide well known in the art may be used. It is particularly preferable to use a solvent dispersing sol of a metal oxide to ensure transparency. Organic solvents that can be used as the dispersion medium for the metal oxides include methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dimethylformamide and the organic solvent. And other solvents that are intersoluble with the above, as well as mixtures of the organic solvents and water.
    [62] Preferred solvents are methanol, isopropyl alcohol, methyl ethyl ketone, xylene and toluene.
    [63] When the fine dry particles are completely burned in air by thermogravimetric analysis at room temperature to 800 ° C., the amount of the alkoxysilane compound immobilized on component (B) can be determined by measuring the percentage of weight loss of the compound.
    [64] The amount of water consumed by hydrolyzing the alkoxysilane compound in preparing component (B) is equivalent to the amount of water for hydrolyzing at least one alkoxy group on silicon atoms in the molecule. The amount of water added or present during the hydrolysis reaction is preferably at least 1/3, and more preferably 1/2 to 3 times the moles of the total alkoxy groups on the silicon atom. Only products having an alkoxysilane compound physically absorbed on the surface of the metal oxide particles may be obtained by mainly mixing the metal oxide particles with the alkoxysilane compound of the formula (1) under conditions that are completely free of water. The effect of improving wear resistance, which is one of the objects of the composition of the present invention, cannot be exhibited using the above materials as component (B).
    [65] The following methods can be used to prepare component (B) of the present invention: hydrolyzing an alkoxysilane compound of Formula 1, mixing fine particles of metal oxides and the hydrolyzate in the form of a solvent dispersion sol or powder And stirring the mixture by heating; Hydrolyzing the alkoxysilane compound of Formula 1 in the presence of metal oxide particles; Other components such as multi-functional unsaturated organic compounds, single-functional unsaturated organic compounds and methods of treating the surface of metal oxide particles in the presence of a photopolymerization initiator. Among the above methods, a method of hydrolyzing the alkoxysilane compound of formula 1 in the presence of metal oxide particles is preferred. In preparing component (B), a temperature of 20 to 150 ° C. and a treatment time of 5 minutes to 24 hours are applied.
    [66] Metal oxide particles are known to contain water on the surface of the particles as water absorbed during normal storage conditions. Therefore, by mixing the alkoxysilane compound and the metal oxide particles and stirring the mixture while heating, water contained in the raw material in the preparation of the component (B) can be used.
    [67] When a powder of fine metal oxide particles is used to prepare component (B) of the present invention, an organic solvent intersoluble with water may be added to react the powder of fine metal oxide particles homogeneously and gently with the alkoxysilane compound. Preferred examples of such organic solvents include alcohols, ketones, ethers and amides. Specific examples include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone and the like. The amount of the solvent added is not particularly limited because it is an amount suitable for the purpose of carrying out the reaction smoothly and homogeneously.
    [68] In addition, acids or bases may be added as catalysts for accelerating the reaction for preparing component (B). Examples of acids include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; Organic acids such as methane sulfonic acid, toluene sulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid and oxalic acid; Unsaturated organic acids such as methacrylic acid, acrylic acid and itaconic acid; And ammonium salts such as tetramethyl ammonium chloride and tetrabutyl ammonium chloride. Examples of bases include aqueous ammonia; Primary, secondary or tertiary aliphatic amines such as diethylamine, triethylamine, dibutylamine and cyclohexylamine; Aromatic amines such as pyridine; Sodium hydroxide, potassium hydroxide and quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Among these, preferred examples are tertiary amines or tertiary ammonium hydroxides in organic acids and unsaturated organic acids and bases in acids. The amount of the acid or base added is preferably 0.001 to 1.0 parts by weight, more preferably 0.01 to 0.1 parts by weight based on 100 parts by weight of the alkoxysilane compound. Compounds that decompose upon irradiation and initiate polymerization can be used as radiation polymerization initiators of component (C) in the present invention. A photosensitizer can be added as needed. As used herein, the term "radiation" includes infrared rays, visible rays, ultraviolet rays, deep ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays, and the like.
    [69] Specific examples of the above-mentioned radiation polymerization initiators include acetophenone, acetophenone benzyl ketal, anthraquinone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone compound, triphenyl Amine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, xanthone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl- 4-methoxybenzophenone, thioxanthone compound, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 1- (4-dodecylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylforce Pinoxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bisacylphosph Oxide, benzyl dimethyl ketal, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butan-1-one, 3-methylacetophenone and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB). Combinations of BTTB and coloring material photosensitizers, such as xanthene, thioxanthene, coumarin or ketocoumarin, may also be given as special examples of initiators. Among the above, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Especially preferred are phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like.
    [70] Examples of commercially available products of the photoinitiator include Irgacure 184, 651, 500, 907, 369, 784, 2959, Darocur 1116, 1173 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucirin (Lucirine) TPO (made by BASF), Ubecryl P36 (made by UCB), Escacure KIP150, and KIP100F (made by Lamberti) are mentioned.
    [71] Examples of photosensitizers include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate and isoamyl 4-dimethylamino Not only benzoate but also commercially available products, such as ubecryl P102, 103, 104, 105 (made by UCB), etc. are mentioned.
    [72] The proportion of photoinitiators used as component (C) in the compositions of the invention is preferably in the range of 0.01 to 10 wt%, more preferably 0.5 to 7 wt% and particularly preferably 1 to 5 wt%. If more than 10wt%, the storage stability of the composition and the properties of the cured product may be adversely affected. If the amount is 0.01 parts by weight or less, the curing rate is slow.
    [73] Polymerizable monomers having vinyl groups or (meth) acryloyl groups in addition to the above-mentioned component (A) may be used as optional components in the present invention. The polymerizable monomer may be a single-functional monomer or a multi-functional monomer.
    [74] Examples of single-functional monomers include vinyl group-containing monomers such as N-vinyl caprolactam, N-vinyl pyrrolidone, N-vinylcarbazole and vinylpyridine; Acrylamide, acryloyl morpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth ) Acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) Acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) Acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate and methyltriethylene diglycol (meth) acrylate There is.
    [75] Among the above, N-vinyl caprolactam, N-vinyl pyrrolidone, acryloyl morpholine, N-vinylcarbazole, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. are preferable, Particular preference is given to N-vinyl caprolactam, N-vinyl pyrrolidone and acryloyl morpholine. Most preferred monofunctional polymerizable monomer is acryloyl morpholine.
    [76] Examples of commercially available products of such single-acting monomers include Aronix M-111, M-113, M-117 (manufactured by Toagosei Co., Ltd.), Gayarad TC110S, R-629, R-644 (Nippon Kayaku Co ., Ltd.), Viscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.
    [77] Examples of multi-functional monomers include (meth) acryloyl group-containing monomers such as ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) ) Acrylate, tricyclodecanediyldimethylene di (meth) acrylate, tripropylene diacrylate, neopentyl glycol di (meth) acrylate, both ends of (meth) acrylate of ethylene oxide addition bisphenol A, propylene oxide addition Both ends of (meth) acrylate of bisphenol A, Both ends of (meth) acrylate of ethylene oxide-added tetrabromobisphenol A, Both ends of (meth) acrylate of propylene oxide-added tetrabromobisphenol A, Bisphenol A diglyci Dyl ether, (meth) acrylate both ends of tetrabromobisphenol A diglycidyl ether, 1,4-butane Ol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyester di (meth) acrylate and polyethylene glycol di (meth) acrylate. Among the above, both ends of the (meth) acrylate of ethylene oxide-added bisphenol A, both ends of the (meth) acrylate of propylene oxide-added bisphenol A, tricyclodecanediyldimethylene di (meth) acrylate, and tetraethylene glycol di (meth ) Acrylates, tripropylene glycol di (meth) acrylates, neopentyl glycol di (meth) acrylates and polyethylene glycol di (meth) acrylates are preferred.
    [78] Commercially available products of the multi-functional monomers include Yupimer UV, SA1002 (manufactured by Mitsubishi Chemical Corp.), Biscot 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and Gayarad R-604 (Nippon Kayaku Co.). , Ltd.), Aronix M-210 (manufactured by Toagosei Co., Ltd.) and the like can be used.
    [79] In addition to the above-described components, various additives may be optionally added to the compositions of the present invention. Examples of the additives include antioxidants, UV absorbers, light stabilizers, silane binders, antioxidants, thermal polymerization inhibitors, colorants, leveling agents, surfactants, preservatives, plasticizers, lubricants, solvents, inorganic fillers, organic fillers, wetting enhancers. And coating surface improvers. Commercially available products of antioxidants include Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals Co.). Commercially available products for UV absorbers include Tinuvin P, 234, 320, 326, 327, 328, 213, 400 (manufactured by Ciba Specialty Chemicals Co.), Sumisorb 110, 130, 140, 220 , 250, 300, 320, 340, 350, 400 (manufactured by Sumitomo Chemical Industries Co., Ltd.), and the like. Commercially available products of light stabilizers include Tinuvin 292, 144, 622LD (manufactured by Ciba Specialty Chemicals Co.), Sanol LS-770, 765, 292, 2626, 1114, 744 (manufactured by Sankyo Chemical Co.) There is this. Silane binders include γ-aminopropyl triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and commercially available products such as SH6062, SZ6030 (Dow Corning Toray Silicone Co., Ltd.), KBE903, and KBM803 (manufactured by Shin-Etsu Silicone Co., Ltd.). Commercially available products of anti-aging agents include Antigene W, S, P, 3C, 6C, RD-G, FR, AW (manufactured by Sumitomo Chemical Industries Co., Ltd.). Polymers or oligomers such as epoxy resins, polymerizable compounds (eg urethane (meth) acrylates, vinyl ethers, propenyl ethers, maleic acid derivatives), polyamides, polyimides, polyamideimides, polyurethanes, polybutadiene, chloroprene, poly Ethers, polyesters, pentadiene derivatives, styrene / butadiene / styrene block copolymers, styrene / ethylene / butene / styrene block copolymers, styrene / isoprene / styrene block copolymers, petroleum resins, xylene resins, Ketone resins, fluorine-containing oligomers, silicon-containing oligomers, polysulfide-type oligomers may be incorporated into the compositions of the present invention as another additive.
    [80] The radiation curable resin composition of the present invention can produce a cured product having excellent properties such as high refractive index, good wear resistance, transparency, chemical resistance, etc. Thus, the composition can be used in plastic optical parts, contact panels and film-type liquid crystals. It is suitable for use as hard coatings for devices and prefabricated plastic materials and also for use as color-test or defect-test coating materials for floors and walls inside buildings. In addition, the composition can be suitably used for optical applications because the composition does not produce interference fringes when applied to substrates having similar refractive indices by high refractive indices. When the radiation curable resin composition of the present invention is cured, a cured product of pencil hardness of 23 to H to 9H can be obtained. The shrinkage rate at the time of curing is usually 10% or less, and preferably 6% or less. As mentioned above, the resulting cured product has high refractive index, good wear resistance, transparency, chemical resistance and the like. The cured product preferably has a refractive index of at least 1.55 and a light transmittance of at least 98%. Further, preferably about 5 μm thick composition layer after curing will have a light transmittance of at least 90%, and after abrasion test of Taber set for this purpose, it will have a haze value of 40% or less. Therefore, the composition can suitably be used as a plastic sheet, a plastic film and the required transparency, and especially as an optical material. Other uses of the composition include cathode ray tubes and front panels such as flat panel displays, laser displays, photocromic displays, electrochromic displays, liquid crystal displays, plasma displays, light emitting diode displays and electroluminescence As well as the panel, as well as components for the input device of the front panel. Other uses include front covers such as encapsulation containers, lenses for optics, eye glasses lenses, window shields, light covers, helmet shields, and the like. In addition, when a high refractive index coating is used as the optical material, it is desirable to provide a coating having a low refractive index to prevent reflection.
    [81] The invention will be described in more detail by way of example which is not to be understood as limiting the invention. In the following examples, unless otherwise indicated, "parts" and "%" mean "parts by weight" and "wt%", respectively.
    [82] Preparation Example of Alkoxysilane Compound
    [83] Reference Example 1
    [84] To a solution containing 7.8 parts by weight of mercaptopropyl trimethoxysilane and 0.2 parts by weight of dibutyl tin dilaurate was added dropwise 20.6 parts by weight of isophorone diisocyanate for 1 hour with stirring in dry air at 50 ° C. After further stirring at 60 ° C. for 3 hours, 71.4 parts by weight of pentaerythritol triacylate was added dropwise at 30 ° C. for 1 hour. The mixture was heated at 60 ° C. and stirred for an additional 3 hours to give a compound having a polymerizable unsaturated group and an alkoxysilane group in the molecule. The compound is referred to herein as "silane compound X". The amount of isocyanate groups remaining in the product was analyzed. It was confirmed that the amount of remaining isocyanate groups was 0.1% or less, and it was found that the reaction was almost completed in quantity.
    [85] Preparation Example of Component (B)
    [86] Reference Example 2
    [87] 8.1 parts by weight of silane compound X prepared in Reference Example 1, 90.5 parts by weight of zirconium oxide sol (number average particle diameter: 0.01 mu m, zirconium oxide concentration: 30%) in methyl ethyl ketone solvent and 0.1 weight of ion-exchanged water The mixture of parts was stirred at 60 ° C. for 3 hours. After addition of 1.3 parts by weight of methyl orthoformate and 41.2 parts by weight of methyl ethyl ketone, the mixture was stirred for a further 1 hour while heating at the same temperature to compound and zirconium particles having a polymerizable unsaturated group and an alkoxysilane group in the molecule. A dispersion of the reaction product with was obtained. The dispersion is represented here as "dispersion b1".
    [88] Reference Example 3
    [89] 8.1 parts by weight of the silane compound X prepared in Reference Example 1, 90.5 parts by weight of an antimony pentoxide sol (number average particle diameter: 0.05 mu m, antimony pentoxide concentration: 30%) in a methyl ethyl ketone solvent, and ion exchanged water 0.1 parts by weight of the mixture was stirred at 60 ° C. for 3 hours. After addition of 1.3 parts by weight of methyl ortho-formate and 41.2 parts by weight of methyl ethyl ketone, the mixture was stirred for a further 1 hour while heating at the same temperature to polymerize unsaturated groups and alkoxysilane groups and antimony pentoxide in the molecule. A dispersion of the reaction product of the compound with the particles was obtained. The dispersion is represented here as "dispersion b2". The solids content (%) of the dispersion was 25%.
    [90] Reference Example 4
    [91] 8.1 parts by weight of silane compound X prepared in Reference Example 1, 100 parts by weight of alumina sol (number average particle diameter: 0.0075 μm, solids content: 30%, water content: 5.6%) in methanol and p-methoxy phenol 0.01 parts by weight of the mixture was stirred at 60 ° C. for 3 hours. After addition of 1.3 parts by weight of methyl orthoformate and 41.2 parts by weight of methanol, the mixture was stirred for an additional 1 hour while heating at the same temperature to induce a compound of alumina particles with a compound having an intramolecularly polymerizable unsaturated group and an alkoxysilane group. A dispersion of the reaction product was obtained. The dispersion is represented here as "dispersion b3". The solids content (%) of the dispersion was 25%.
    [92] Preparation of Composition
    [93] Examples of preparation of the compositions used in the present invention will now be described. The weight ratio of each component is shown in Table 1.
    [94] Example 1
    [95] 80 parts by weight of the dispersion b1 prepared in Reference Example 2 as component (B), 20 parts by weight of dipentaerythritol hexaacrylate as component (A), and 1-hydroxycyclohexyl phenyl ketone as component (C). 1.2 parts by weight and 0.8 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one are placed in a UV-blocked container and the mixture is allowed to stand at room temperature for 30 minutes. It stirred and obtained the composition shown in Table 1 as a homogeneous solution. The compositions of Examples 2-5 and 1-3 described in Table 1 were prepared in the same manner. The compositions of Examples 1 and 3 correspond to the compositions of Comparative Examples 2 and 3, respectively. The compositions of Examples 2 and 4 and Comparative Example 1 contain large amounts of component (B) which increase the refractive index.
    [96] Some (part of solid components)ExampleComparative exampleOne2345One23Component (A) Unsaturated organic compound (Dipentaerythritol hexaacrylate)208201212 2020 Metal Oxide Sol Solution without Silane Treatment Zirconia Sol Antimony Oxide Sol 80 (20)80 (20)Component (B) Silane-treated metal oxide sol solution b1b2b380 (20)92 (32)80 (20)88 (28)80 (20)100 (40) Component (C) * 1-hydroxycyclohexyl phenyl ketone * 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one1.20.81.20.81.20.81.20.81.20.81.20.81.20.81.20.8 all10210210210294102102102 Solids content (%)4141414136414141 Metal oxides in solid components (wt%)3861385346765050
    [97] Test Example
    [98] Test specimens were prepared using the resin compositions prepared in Examples and Comparative Examples to evaluate pencil hardness, damage resistance, abrasion resistance, adhesion to substrate, transmittance and refractive index of the cured film according to the following method. The results are shown in Table 2.
    [99] Preparation of Test Specimens :
    [100] The resin compositions prepared in Examples and Comparative Examples were added to a thickness of about 5 μm on a commercially available PET film (thickness: 188 μm) using a wire bar coater (No. 10). The coating was held in a 40 ° C. UV drying oven for 1 minute and exposed to 0.3 J / cm 2 UV in air to yield a cured coating film. The cured film was then maintained at 23 ° C. and relative humidity 50% for 24 hours to obtain test specimens.
    [101] Outward appearance :
    [102] The appearance was evaluated by visual observation.
    [103] Light transmittance :
    [104] The light transmittance at a wavelength of 500 nm was measured using a spectrophotometer and the reflectance and transmittance of the substrate were corrected.
    [105] Refractive Index :
    [106] The refractive index was measured with an Abbe's refractometer.
    [107] Pencil Hardness :
    [108] Pencil hardness was measured according to JIS K5400 using a pencil scratch test system.
    [109] Abrasion Resistance :
    [110] After the taber abrasion test (wear wheel CS-10F, load 500g, rotation 100), turbidity (H) was measured using a taber abrasion test system according to JIS R3221.
    [111] Substrate Adhesion :
    [112] JIS K5400 was performed. 100 squares (1 mm × 1 mm) were produced by 11 × 11 crossing lines on the surface of the cured test specimen. Commercial cellophane tape adhered and quickly peeled off. Substrate adhesion is expressed as X / 100, where X is the number of squares remaining on the substrate without being separated.
    [113] ExampleComparative exampleOne2345One23 AppearanceTransparencyTransparencyTransparencyTransparencyTransparencyTransparencyTranslucentopacity Light transmittance (/%)9999100100971008963 Refractive index1.5951.6451.5551.5661.5601.5851.641- Pencil hardness3H2H3H2H3HH3H3H Turbidity of Coating Film (%)0.50.60.50.50.60.64.46.8 Burn test *282228318492746 Adhesion **100100100100100100100100
    [114] Turbidity (%)
    [115] ** Number of cross squares (%) after peeling off cellophane tape
    [116] Effects of the Invention
    [117] The radiation curable resin composition of the present invention can produce a cured product having excellent properties such as high refractive index, good wear resistance, transparency, chemical resistance and the like. The composition is therefore suitable for use as a hard coating for plastic optical components, contact panels and film-type liquid crystal devices and prefabricated plastic materials, and is also a color-test or tamper-test coating material for floors and walls inside buildings. It is suitable to use. In addition, because of the high refractive index, the composition does not produce interference fringes when applied to a substrate having a similar refractive index, so that the composition can be suitably used for optical purposes.
    权利要求:
    Claims (13)
    [1" claim-type="Currently amended] A radiation-curable metal particle comprising a radiation-curable group in which a silyl group is bonded to a metal.
    [2" claim-type="Currently amended] The method of claim 1,
    And said metal is selected from the group consisting of zirconium, titanium, antimony, zinc, tin, indium, cerium and aluminum.
    [3" claim-type="Currently amended] The method according to claim 1 or 2,
    Wherein said silyl group is a substituted silyl group comprising an alkoxy group, a urethane group and / or a thiourethane group.
    [4" claim-type="Currently amended] The method according to any one of claims 1 to 3,
    And said particles are obtained by reacting an organosilicon compound with a metal oxide.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4,
    The particles are radiation-curable metal particles, characterized in that having a diameter of 0.001 to 2㎛.
    [6" claim-type="Currently amended] A method for producing a radiation-curable metal particle according to any one of claims 1 to 5, which comprises reacting a metal oxide with an organosilicon compound.
    [7" claim-type="Currently amended] The method of claim 6,
    The metal oxide is a method of producing a radiation-curable metal particles, characterized in that the reaction with the organosilicon compound in the presence of an acid or a base.
    [8" claim-type="Currently amended] (a) a (meth) acryl compound;
    (b) the metal particles of any one of claims 1 to 6; And
    (c) a radiation-curable composition consisting of a radiation polymerized photoinitiator.
    [9" claim-type="Currently amended] The method of claim 8,
    The (meth) acryl compound comprises at least three (meth) acryloyl groups.
    [10" claim-type="Currently amended] The method according to claim 8 or 9,
    The composition of about 5 μm thick layer has a light transmittance of at least 90% after curing and a haze of less than 40% after the burn wear test.
    [11" claim-type="Currently amended] A product made by curing the radiation-curable composition according to claim 8, having a refractive index of at least 1.55 and a light transmittance of at least 95%.
    [12" claim-type="Currently amended] The method of claim 11,
    The product is a product characterized in that the coating material.
    [13" claim-type="Currently amended] An antireflective article comprising the product according to claim 11.
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    同族专利:
    公开号 | 公开日
    KR100649293B1|2006-11-24|
    JP3900506B2|2007-04-04|
    TWI290570B|2007-12-01|
    CN1240787C|2006-02-08|
    US20020019461A1|2002-02-14|
    JP2000143924A|2000-05-26|
    US20030105189A1|2003-06-05|
    EP1137720A1|2001-10-04|
    WO2000027931A1|2000-05-18|
    US6521677B2|2003-02-18|
    EP1137720B1|2007-08-22|
    CN1333803A|2002-01-30|
    DE69936932D1|2007-10-04|
    AT370995T|2007-09-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-11-06|Priority to JP10/316144
    1998-11-06|Priority to JP31614498A
    1999-11-04|Application filed by 윌리암 로엘프 드 보에르, 디에스엠 엔.브이, 마쯔모또 에이찌, 제이에스알 가부시끼가이샤, 이이다 이사오, 재팬파인코팅스 가부시키가이샤
    2001-11-14|Publication of KR20010100989A
    2006-11-24|Application granted
    2006-11-24|Publication of KR100649293B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP10/316144|1998-11-06|
    JP31614498A|JP3900506B2|1998-11-06|1998-11-06|Liquid curable resin composition, cured product thereof and antireflection film|
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