method for producing a prepreg

专利摘要:
MATRIX RESIN COMPOSITION, PRE-IMPREGNATED AND METHOD TO PRODUCE THE SAME, AND FIBER REINFORCED COMPOSITE MATERIAL The present invention relates to a method for producing a prepreg that contains reinforced fibers and a matrix resin composition with weight per square meter of reinforced fibers being 250-2,000 g / mA 2Λ. The production method comprising the following steps (1) - (3): (1) a matrix resin composition mixing step to obtain a matrix resin composition by mixing an epoxy resin, an unsaturated compound radically polymerizable, an epoxy resin curing agent and a polymerization initiator that generates radicals, in that stage the content of the radically polymerizable unsaturated compound in relation to 100% by mass of the total epoxy resin and the radically polymerizable unsaturated compound being 10 -25% by mass, (2) a step of impregnating the matrix resin composition, and (3) a step of increasing the surface viscosity.
公开号:BR112013022040B1
申请号:R112013022040-6
申请日:2012-03-02
公开日:2020-12-01
发明作者:Masahiro Ichino；Manabu Kaneko；Kazuki Koga；Teppei MIURA；Takuya Teranishi；Kiharu Numata；Kazutami Mitani；Tadao Samejima
申请人:Mitsubishi Chemical Corporation；
IPC主号:

专利说明:

TECHNICAL FIELD
[0001] The present invention relates to a matrix resin composition suitable for a fiber reinforced composite material and a prepreg with it, as well as a fiber reinforced composite material.
[0002] This application is based on and claims the priority benefit of Japanese Patent Application No 2011-046576 filed on March 3, 2011 and Japanese Patent Application No 2012-010,429 filed on January 20, 2012, the content of which is incorporated herein by reference. TECHNICAL FUNDAMENTALS
[0003] The fiber-reinforced composite material consisting of a fiber-reinforced matrix matrix is lightweight and has superior mechanical characteristics. For this reason, fiber-reinforced composite material is widely used as a structural material for airplanes, ships, automobiles, construction and the like, as well as for sports equipment, such as golf axes, fishing rods, tennis rackets. and the like.
[0004] Various methods are used to produce the material with fiber-reinforced composite. Among these, a method of impregnating a set of fibers reinforced with a matrix resin in order to obtain a prepreg type sheet, tape, or a sequence that is used as an intermediate base material is widely practiced. A thermally curable resin and a thermoplastic resin can be used as the matrix resin used for the prepreg, and the thermally curable resin is used more often.
[0005] A molded product (fiber-reinforced composite material) is obtained by laminating the prepreg in multiple layers, placing a mold material, and then heating. Here, the proper viscosity (adhesion property) of a surface of the prepreg can facilitate its placement on the mold material and joining of the prepregs. In addition, if the prepreg position placed on the mold material is inadequate, position correction is necessary. Therefore, the property of excessive adhesion is undesirable on the surface of the prepreg.
[0006] If a molded product to be obtained has a curved shape, a curve mold material is used. Here, a rigid prepreg does not follow the shape of the mold material in which the prepreg is placed. Therefore, adequate flexibility is required for a prepreg.
[0007] For the molding of a fiber reinforced composite material using a prepreg, in general, a plurality of prepregs of a certain thickness is laminated to obtain the fiber reinforced composite material of a desired thickness. Here, in the case of using the material as a structural material for vehicles, such as ships, rail vehicles, and automobiles, as well as for windmills and the like, the components are large in size and thick. Given this, for such purposes, it is advantageous to use a prepreg of high thickness. A thick prepreg can be obtained by increasing the thickness of the set of reinforced fibers.
[0008] In the production of fiber-reinforced composite material, it is important to reduce voids generated due to the portions, which are not impregnated with a matrix resin, inside the material. If the prepreg has empty spaces, the voids persist in the fiber-reinforced composite material, which is a molded product, and cause failure leading to a reduction in the strength of the fiber-reinforced composite material. Therefore, it is necessary that the prepreg has no voids.
[0009] After impregnating the set of fibers reinforced with the matrix resin, the excessively high viscosity of the matrix resin makes it difficult to impregnate the set of fibers reinforced with the matrix resin inside it. In order to solve this problem, a so-called lacquer method and a varnish method have been proposed. In these methods, a thermally curable resin and a solvent are mixed, the set of reinforced fibers is impregnated with the mixture, and then the solvent is removed by drying, thus obtaining a prepreg.
[00010] However, in these methods, if the drying temperature for solvent removal is too high, the thermally curable resin cures in a prepreg phase. In addition, this can dissolve or modify the curing agent in the thermally curable resin and a shorter life problem of the prepreg is likely. This problem is particularly noticeable when using a thermally curable resin with a low curing temperature. In other words, in these methods, it is difficult to completely remove the solvent in the prepreg. If the solvent remains, the solvent is aerated during molding and causes voids in the fiber-reinforced composite material.
[00011] In order to solve this problem, a so-called hot melt film method has been proposed. In this method, a film of a thermally curable resin (resin film) is formed without the use of a solvent, the resin film is bonded to a surface of, for example, a set of sheet-like reinforced fibers in which bundles of reinforced fibers they are aligned, the sheet is heated to reduce viscosity and then it was pressurized to impregnate the set of reinforced fibers with the thermally curable resin, in order to obtain a prepreg. However, in the hot melt film method, a thick reinforced fiber bundle, more specifically, a reinforced fiber bundle weighing 300 g / m2 or more, cannot be completely impregnated with the surface's thermally curable resin. inland.
[00012] Furthermore, the high viscosity of the matrix resin can inhibit the movement of the set of reinforced fibers during impregnation with the resin. Therefore, a sheet-like reinforced fiber set in which fiber bundles are aligned, if the reinforced fiber bundles are not evenly distributed, the surface smoothness of the prepreg after impregnation with the matrix resin is likely to be insufficient and color spots are likely to appear in appearance. In order to avoid these problems, impregnation must be carried out under high pressure.
[00013] However, in a case of causing the matrix resin to enter the monofilaments of the set of reinforced fibers under high pressure, the so-called elastic recovery is likely to occur. Elastic recovery is a phenomenon in which the bundles of reinforced fibers, which have been compacted, gradually return to their original shape after the pressure on the production of the prepreg is removed, as if the bundles of optical fibers resemble the shape before impregnation. . Therefore, the hot melt film method is not suitable for the production of thick prepreg.
[00014] Low viscosity of the matrix resin facilitates the impregnation of the set of fibers reinforced with it. Therefore, high temperature is not necessary during impregnation. In addition, since the bundles of reinforced fibers are easily distributed by impregnation, high external pressure is not necessary. This can prevent elastic recovery. In addition, since resin impregnation can preferably be carried out, the speed of a production line can be increased and productivity can be improved. In addition, fiber bundles reinforced with a high number of monofilaments can be used. In general, fiber bundles reinforced with a higher number of monofilaments are less expensive and advantageous in terms of cost. This can also reduce the number of bundles of reinforced fiber needed, thereby improving the productivity of the prepreg.
[00015] In a case where the viscosity of the matrix resin is low enough, methods other than the hot melt film method of, for example, a method of impregnating the set of fibers reinforced with the matrix resin by a method contact roller, dipping method, dyeing method, dispenser method and the like can be used. In these methods, it is not necessary to prepare a thermally curable resin film in a separate step. In addition, the mold release paper, which is necessary in a case where the viscosity of the matrix resin is high, is not necessarily required. These methods are cost effective, since there is no need for: processing cost of an additional step, the mold release paper to support the thermally curable resin film, a protective film to protect the thermally curable resin film, and similar. In addition, in these methods, pre-impregnated of a great thickness, which is difficult to produce, by a method using the mold release paper, can be easily produced.
[00016] However, in the case of using a low viscosity matrix resin, the viscosity of the matrix resin in the prepreg to be obtained is also low, which caused the following problems.
[00017] The adhesion property of the surface of the prepreg is too high and treatment of the prepreg is difficult. In addition, the matrix resin can easily adhere to an operator and a work area. In addition, the prepreg with the bundles of reinforced fibers aligned in one direction is accessible at the limit of elasticity against a force applied in one direction intersecting the alignment direction of the bundles of reinforced fibers. This causes sinuosity of the reinforced fiber bundles and rupture of the prepreg. In addition, it is difficult to correct an improper position of the laminated prepregs.
[00018] In other words, there is no equilibrium relationship between the viscosity of the matrix resin and the handling property of the prepreg.
[00019] As a resin composition that can solve the trade-off problem, for example, Patent Document 1 describes a resin composition that comprises a thermally curable resin, such as epoxy resin, radically polymerizable unsaturated compound, and a polymerization initiator that generates radicals in response to heating. In Patent Document 1, after impregnating the fiber reinforced with the resin composition, the polymerization initiator is reacted with it to generate radicals. Here, the resin composition with which the reinforced fiber is impregnated is a heat treatment at a temperature below the curing temperature of the thermally curable resin, in order to increase the viscosity of the resin composition in the prepreg.
[00020] However, in the method described in Patent Document 1, a curing reaction of the thermally curable resin progresses in one part being heated. Therefore, viscosity is increased not only on the surface, but also in the central part of the prepreg. As a result, especially in a heavy prepreg, stiffness is extraordinarily increased due to the increased viscosity of the matrix resin, leading to a decrease in the flexibility of the prepreg.
[00021] Polymerization initiator reactivity to heat processing after impregnation can be controlled by the addition of a polymerization inhibitor or a polymerization accelerator in the resin composition. However, the polymerization inhibitor or polymerization accelerator makes the reaction complex. In addition, the addition of the polymerization accelerator can initiate a polymerization reaction of the thermally curable resin and can shorten the life of a prepreg. Prior Art Reference
[00022] Patent Document 1: Unexamined Japanese Patent Application, Publication No. 208838-H9 DESCRIPTION OF THE INVENTION Problem to be solved by the invention
[00023] The present invention was made considering the situation mentioned above. A first objective of the present invention is to provide a method for producing a prepreg that contains reinforced fibers and a matrix resin composition with the weight per square meter of the reinforced fibers, being 250-2,000 g / m2, in which the set of Reinforced fibers can be impregnated with the matrix resin, without generating voids, and a prepreg with superior flexibility and an adhesion property can be obtained.
[00024] A second objective of the present invention is to provide a prepreg containing reinforced fibers and a matrix resin composition with the weight per square meter of reinforced fibers being 250-2,000 g / m2, prepreg with flexibility upper and a grip property.
[00025] A third objective of the present invention is to provide a matrix resin composition, which can preferably be used in the production of a prepreg with the weight per square meter of reinforced fibers being 250-2,000 g / m2.
[00026] A fourth objective of the present invention is to provide a fiber reinforced composite material obtained by curing the prepreg described above. Means to Solve Problems
[00027] A first aspect of the present invention has the following modes. (1) A method for the production of a prepreg that contains reinforced fibers and a matrix resin composition with the weight per square meter of reinforced fibers being 250-2,000 g / m2, the production method comprising the following steps ( 1) - (3): (2) a matrix resin composition mixing step to obtain a matrix resin composition by mixing an epoxy resin, a radically polymerizable unsaturated compound, a resin curing agent epoxy and a polymerization initiator that generates radicals, in that stage the content of the radically polymerizable unsaturated compound in relation to 100% by mass of the total epoxy resin and the radically polymerizable unsaturated compound being 10-25% by mass ; (3) a step of impregnating the matrix resin composition to obtain a prepreg precursor by impregnating a set of reinforced fibers being 250-2,000 g / m2, by weight, with the resin composition of matrix, and (4) a step of increasing the surface viscosity to obtain a prepreg in which the viscosity of the matrix resin composition is increased more in a surface part than in the central part, stimulating the precursor of the pre- impregnated to allow the polymerization initiator present in the superficial part of the prepreg precursor to generate a radical, although not allowing the polymerization initiator present in the central part to generate a radical. [2] The method for producing a prepreg as described in [1], in which the matrix resin composition used for impregnation in step (2) has a viscosity of 12 Pa.sa 40,000 Pa.sa 30 ° C. The method for producing a prepreg as described in [1] or [2], in which a means for allowing the polymerization initiator to generate a radical in the step described above (3) is the following method (3-i ): (3-i) a method of irradiating the prepreg precursor with an energy wave selected from a group consisting of: ultraviolet, infrared; visible light, and electron beam, with an incident intensity not exceeding such an incident intensity that the transmittance is 0% to a depth of 40% from a surface of the prepreg precursor with respect to the thickness of the precursor of the prepreg as being 100%. [4] The method for producing a prepreg as described in [3], wherein the polymerization initiator is α-aminoalkyl phenone or α-hydroxyalkyl phenone. [5] The process for producing a prepreg as described in [1] or [2], in which a means for allowing the polymerization initiator to generate a radical in the step described above (3) is the following method (3- ii): (3-ii) a method of heating the prepreg precursor from the outside in a non-contact state, for example a period of time in which a rate of temperature change is 0% at a depth of 40% from a surface of the prepreg with the precursor with respect to a thickness of the prepreg precursor as being 100%. [6] The method for producing a prepreg as described in [5], in which method (3-ii) is carried out by means of high frequency heating. [7] The method for producing a prepreg as described in [1] or [2], where step (2) includes the following steps (2- i) to (iii-2): (2- i) a matrix resin composition application step to apply the matrix resin composition to a first face of a first reinforced fiber sheet A1 composed of consecutive reinforced fiber bundles; (2-ii) a reinforced fiber matrix lamination step to laminate a second reinforced fiber sheet A2 composed of consecutive reinforced fiber bundles on face A1 to which the matrix resin composition has been applied, and (2-iii ) a pressurization step to obtain the prepreg precursor by impregnating A1 and A2 with the matrix resin composition by pressurizing A1 and A2. [8] The method for producing a prepreg according to [1] or [2], where step (2) includes the following steps (2-iv) to (2-vi): (2- iv) a matrix resin composition application step to apply the matrix resin composition to a first reinforced fiber sheet A1 composed of consecutive reinforced fiber bundles; (2-v), a fiber reinforced matrix lamination step to laminate a second fiber reinforced sheet A2 and a third fiber reinforced sheet A3 composed of consecutive reinforced fiber bundles on a first face A1 and a second face A1 respectively, and (2-vi) a pressurization step to obtain the precursor of the prepreg by impregnating A1, A2, and A3 with the matrix resin composition by pressurizing A1, A2, and A3.
[00028] A second aspect of the present invention has the following mode. [9] A prepreg which comprises a reinforced fiber and a matrix resin composition with the weight per square meter of reinforced fibers being 250-2,000 g / m2, where the prepreg is flexible to such an extent that the prepreg can follow a curve when placed on a mold material, which is curved, and has an adhesion property of a degree such that the prepreg can be redisposed after laminating the prepregs.
[00029] A third aspect of the present invention has the following mode. [10] A fiber reinforced composite material, where the fiber reinforced composite material is obtained by curing the prepreg as described in [9].
[00030] A fourth aspect of the present invention has the following mode. [11] The matrix resin composition for a fiber-reinforced composite material, comprising: an epoxy resin, a radically polymerizable unsaturated compound, the curing agent of an epoxy resin, and a polymerization initiator that generates radicals, where the epoxy resin contains at least one epoxy resin having an oxazolidone ring in the molecule, and the content of the radically polymerizable unsaturated compound in relation to 100% by weight of the total epoxy resin and the radically polymerizable unsaturated compound is 10 to 25% in pasta. Effects of the Invention
[00031] According to the method for producing a prepreg of the present invention, even in the prepreg with the weight per square meter of reinforced fibers being 250-2,000 g / m2, the set of reinforced fibers can be impregnated with the matrix resin composition without generating voids, and a prepreg with superior flexibility and an adhesion property can be obtained. In addition, the prepreg obtained by the method for producing a prepreg of the present invention is free of elastic recovery.
[00032] According to the prepreg of the present invention, even a prepreg, the weight per square meter of reinforced fibers, being 250-2,000 g / m2 has superior flexibility and an adhesion property. The prepreg is suitable for the production of large structural materials for vehicles, mills and the like.
[00033] According to the matrix resin composition of the present invention, in the production of a prepreg with the weight per square meter of the reinforced fibers being 250-2,000 g / m2, a superior flexibility and a cold property can be obtained; and, when in use as the fiber-reinforced composite material after curing, superior physical properties can be obtained.
[00034] According to the fiber-reinforced composite material of the present invention, even in a fiber-reinforced composite material with the weight per square meter of the reinforced fibers being 2502,000 g / m2, a gap formed between a mold and a pre- impregnated in the production of a large molded product having a non-linear shape can be suppressed by superior followability to a mold due to superior flexibility and cold property; and generation of voids can be prevented by the appropriate cold property by eliminating overhead pockets between the mold and the prepreg. BRIEF DESCRIPTION OF THE DRAWINGS
[00035] FIG. 1 is a schematic view illustrating an example of the method for producing a prepreg of the present invention;
[00036] FIG. 2 is a schematic view illustrating a pre-impregnated production machine of the present invention;
[00037] FIG. 3 is a front view, illustrating a measurement method for assessing a cold property;
[00038] FIG. 4 is a sectional sectional view illustrating a measurement method for evaluating a cold property; and
[00039] FIG. 5 is a sectional cross-sectional view illustrating a measurement method for assessing a bending property. REFERENCE LISTING 11a Fiber reinforced sheet A1 11b Fiber reinforced sheet A2 11c Fiber reinforced sheet A3 12 Application Unit 12a Matrix 12b Batch of resin 12c Touch roll 13 Pressurizing unit 13a, b Pressurizing rollers 14 Sheet supplier roll protection sheet 14a, b Protection sheet 15 Protection sheet winding roll 16 Surface viscosity increase step 17 Protective film 18 Actuator roll 19 Winding elements 20 Prepreg PREFERRED MODE FOR CARRYING OUT THE INVENTION
[00040] The present invention is described in detail hereinafter. The present invention relates to a prepreg with the weight per square meter of the reinforced fibers being 250-2,000 g / m2 and a method for producing it, a matrix resin composition, and a composite material reinforced with fiber. The present invention is most preferably used for a prepreg with the weight per square meter of the reinforced fibers being at least 400 g / m2. The present invention is even more preferably used for a prepreg with the weight per square meter of the reinforced fibers being at least 500 g / m2. The present invention is particularly preferably used for a prepreg with the weight per square meter of the reinforced fibers being at least 600 g / m2. (Matrix Resin Composition)
[00041] The matrix resin composition of the present invention is for a fiber-reinforced composite material and comprises: an epoxy resin; a radically polymerizable unsaturated compound; an epoxy resin curing agent; and a polymerization initiator that generates radicals. [Epoxy Resin]
[00042] As the epoxy resin used for a prepreg and a method for producing the prepreg according to the present invention, for example, a glycidyl ether epoxy resin, glycidyl amine epoxy resin, glycidyl epoxy resin ester, and alicyclic epoxy resin, as well as an epoxy resin with radicals of at least two types selected from the aforementioned resins being present in a molecule, can be exemplified.
[00043] Specific examples of the glycidyl ether epoxy resin include bisphenol type A epoxy resins, bisphenol type F epoxy resins, resorcinol epoxy resins, phenolated novolac epoxy resins, polyethylene glycol epoxy resins, resins of epoxy type polypropylene glycol, epoxy resins type naphthalene, epoxy resins type dicyclopentadiene, and regioisomers thereof and those obtained by replacing them with an alkyl or halogen group.
[00044] Specific examples of the glycidyl amine epoxy resin include tetraglycidyl diaminodiphenyl methanes, aminophenol and aminocresol glycidyl compounds, glycidyl anilines, and xylene diamine glycidyl compounds, and the like.
[00045] Specific examples of the glycidyl ester type epoxy resins include glycidyl phthalic ester, diglycidyl hexahydrophthalic ester, diglycidyl isophthalic ester, diglycidyl ester of dimer acid, and various isomers thereof.
[00046] Epoxy resins can be used alone or in combination of two or more. Among these epoxy resins, it is preferable to include a bisphenol type A epoxy resin, from the point of view of heat resistant properties and toughness.
[00047] By including an epoxy resin having an oxazolidone ring in the molecule like the epoxy resin, high Tg is obtained and toughness is increased. Such an epoxy resin can provide superior physical properties when used in a fiber-reinforced composite material, and is therefore more preferable. More specifically, a 0 ° compression force, a 0 ° bending force, a 90 ° bending force, an interlayer shear force, and the Tg are improved. Especially the flexural strength of 90 ° and Tg are noticeably improved. This may be due to the fact that the oxazolidone ring has a rigid main structure that gives a high Tg even at a crosslink density and can provide high toughness and high Tg simultaneously, and because a large number of oxygen atoms that make up the ring of oxazolidone have polarities, thus realizing the superior adhesion between the epoxy resin having the oxazolidone ring in the molecule and a carbon fiber surface.
[00048] The content of the epoxy resin having an oxazolidone ring in the molecule is preferably 2 to 95% by weight and more preferably 5 to 60% by weight, relative to the entire epoxy resin being 100% by weight. The content specified above can simultaneously perceive a heat resistant and high tenacity property of the cured resin.
[00049] An upper limit of the content of the epoxy resin having an oxazolidone ring in the molecule is more preferably 80% by weight, and even more preferably 40% by weight, with respect to the entire epoxy resin as being 100% by mass.
[00050] A lower limit of the content of the epoxy resin having an oxazolidone ring in the molecule is more preferably 4% by weight, and even more preferably 10% by weight, with respect to the entire epoxy resin as being 100% by weight.
[00051] A preferred example of the epoxy resin having an oxazolidone ring in the molecule is AER4152. An oxazoidone ring structure is represented by the following general formula (1). The oxazolidone ring structure can be obtained, for example, by a reaction between an epoxy ring and an isocyanate.

[00052] Here, R represents a hydrogen atom, a halogen atom or an alkyl group.
[00053] Just like the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be exemplified.
[00054] Like the alkyl group, a straight or branched alkyl group having a number of carbons from 1 to 10 can be exemplified. More specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and the like, can be exemplified.
[00055] As the epoxy resin having an oxazolidone ring in the molecule, an isocyanate modified epoxy resin can be exemplified. As a commercially available epoxy resin having an oxazolidone ring in the molecule, AER4152, XAC4151, LSA4311, LSA4311, LSA7001 (manufactured by ASAHI KASEI E-MATERIALS) can be exemplified. [Radically Polymerizable Unsaturated Compound]
[00056] The radically polymerizable unsaturated compound used in the prepreg and the method for producing the prepreg of the present invention is a compound including a radically polymerizable unsaturated bond, in other words a double bond or a triple bond, in the molecule. The radically polymerizable unsaturated compound used in the present invention can be used alone or in combination of two or more being mixed. As the radically polymerizable unsaturated compound, an accessible molecular compound having at least one, for example 1 to 6, radically polymerizable unsaturated bonds in a molecule can be exemplified. Examples of such an accessible molecular compound include a (meth) acrylate compound, a (meth) acrylic acid adduct, an allyl phthalate, an allyl isophthalate compound, an allyl terephthalate compound, a compound of allyl cyanurate, and the like. An acrylate compound and a methacrylate compound are preferable.
[00057] As the radically polymerizable unsaturated compound, a high molecular compound or an oligomer having a radically polymerizable unsaturated bond can be exemplified. As such a compound, a compound having a radically polymerizable unsaturated bond at a terminal, a side chain, and a main chain can be used. For example, a compound in which a terminal hydroxyl group of polyethylene glycol or polypropylene glycol is esterified with acrylic acid or methacrylic acid; polyester including maleic acid or fumaric acid as an acidic component; polyimide in which an amino terminus is capped with anhydrous naic acid or ethynyl phthalic anhydride having a radically polymerizable unsaturated bond; and the like, can be exemplified.
[00058] As the unsaturated radically polymerizable compound, a high molecular or inferred molecular compound having a partial reactive structure with the epoxy resin, as well as a radically polymerizable unsaturated bond can also be used. When using such a compound, a chemical bond is formed between the epoxy resin and a compound having the radically polymerizable unsaturated bond in the cured product, thereby improving morphology and physical properties.
[00059] As the partial structure reactive with the epoxy resin, an epoxy group, a carboxyl group, a hydroxyl group, a methyl alkoxy group, the primary or secondary amine, amide, 1,2-dicarboxylic acid anhydride structure, heterocycle containing nitrogen and the like can be exemplified.
[00060] In a case of using a single compound it is preferable to use a compound having a plurality of radically polymerizable unsaturated bonds in the molecule, since the high molecular weight component generated by radical polymerization on the surface of the prepreg has a structure cross-linked and a remarkable effect of increasing viscosity can be obtained on the surface of the prepreg, as described later. As a compound having a plurality of radically polymerizable unsaturated bonds, a compound having an epoxy group and a carboxyl group; a compound having an epoxy group and a hydroxyl group; and a compound having a carboxyl group and a hydroxyl group are more preferable. The aforementioned compounds are compatible with epoxy resin when used together.
[00061] On the other hand, defined in the case of using two or more compounds when mixing, a compound having a plurality of radically polymerizable unsaturated bonds in the molecule is preferably included in an amount of 50 to 99% by mass, and more preferably , 60 to 90% by mass, with respect to the radically polymerizable unsaturated compound as being 100% by mass.
[00062] This content of the radically polymerizable unsaturated compound is 5 to 25% by weight, with respect to a total of the epoxy resin and the radically polymerizable unsaturated compound as being 100% by weight. If the content of the radically polymerizable unsaturated compound is less than 5% by mass, the cold property of the surface of the prepreg becomes excessive after passing through a step of increasing the surface viscosity (described later).
[00063] On the other hand, if the content of the radically polymerizable unsaturated compound is greater than 25% by mass, the cold property of the surface of the prepreg becomes insufficient. This action can reduce a curing property, strength, heat resistance, and interlayer bonding strength when a cured product (fiber reinforced composite material) in which a plurality of prepregs is laminated and cured is obtained.
[00064] The content of the radically polymerizable unsaturated compound is preferably 5 to 20% by weight, and more preferably 5 to 15% by weight, with respect to a total of epoxy resin and the radically unsaturated compound polymerizable as being 100% by mass. [Epoxy Resin Curing Agent]
[00065] Amine, anhydrous acid (eg, anhydrous carboxylic acid), phenol (eg, novolak resin), mercaptan, Lewis acid amine complex, onium salts, imidazole and the like, are used as a curing agent for the epoxy resin used in the prepreg and the method for producing the prepreg of the present invention, but those having any structure can be used just as they can cure the epoxy resin. Among these, the amine curing agent is preferable. Curing agents can be used alone or in combination of two or more.
[00066] The amine type curing agent includes: aromatic amine such as methane diaminodiphenyl and diaminodiphenyl sulfone; aliphatic amine; imidazole derivatives; dicyandiamide; tetramethylguanidine; and amine added to thiourea, as well as isomers and modified forms thereof. Among these, dicyandiamide, which provides a superior preservative property for the prepreg, is particularly preferable.
[00067] The content of the curing agent for the epoxy resin is preferably such that an equivalent active hydrogen ratio of the curing agent is 0.3 to 1 with respect to 1 epoxy equivalent of the epoxy resin. If the equivalent active hydrogen ratio is at least 0.3, the curing agent can cure the epoxy resin. If the ratio of equivalent active hydrogen is none greater than 1, the toughness of a cured product of the matrix resin composition can be increased. The ratio of equivalent active hydrogen is most preferably 0.4 to 0.8. In this range, an uncontrolled reaction due to heat generation and heat build-up during curing can be suppressed by producing a large molded product.
[00068] A healing aid can also be used to increase healing activity. The curing aid can be any agent having an effect of increasing the curing activity of the curing agent. For example, in a case in which the curing agent is dicyandiamide, the curing aid is preferably a urea derivative such as 3-phenyl-1, 1-dimethylurea, 3 - (3,4-dichlorophenyl) - 1,1-dimethylurea (DCMU), 3 - (3-chloro-4-methylphenyl) -1,1-dimethylurea, 2,4-bis (3,3-dimethylureido) toluene and the like.
[00069] In a case in which the curing agent is a carboxylic acid anhydride or a novolak resin, the curing aid is preferably one of tertiary amine. In a case where the curing agent is diaminodiphenyl sulfone, the curing aid is preferably: an imidazole compound; a urea compound, such as phenyldimethylurea (PDMU); and an amine complex such as monoethylamine trifluoride and an amine trichloride complex.
[00070] Among these, a combination of dicyandiamide and DCMU is particularly preferable.
[00071] The content of the curing aid is preferably 1 to 20% by weight, and more preferably 2 to 6% by weight, with respect to 100% by weight of the entire epoxy resin. A content of at least 1% by weight can provide an effect of lowering the curing reaction temperature of the epoxy resin by the curing agent. On the other hand, a content of no greater than 20% by mass, can suppress the reduction in the heat resistance property due to a curing reaction at an accessible temperature and an uncontrolled reaction due to heat generation and heat accumulation during cure when producing a large sized molded product. [Polymerization Initiator Generation Radicals]
[00072] A polymerization initiator used for the prepreg and the method for producing the prepreg is a polymerization initiator that generates radicals. As used herein, a stimulus is one that can cause a composition to have low-binding energy generation radicals under relatively mild reaction conditions, and that can control the generation of radicals as an industrial process. Such a stimulus includes energy wave radiation, heating, vibration preparation, and the like.
[00073] In a case in which energy wave radiation is used as the stimulus for the generation of radicals, the polymerization initiator can be a compound that develops a reaction, such as cleavage, hydrogen abstraction, electron transfer and the like in response to the radiation of the energy wave. Such a compound includes a dihalogen compound, a nitrogen compound, an alkylphenone compound and the like. The compounds can be used alone or in combination of two or more.
[00074] The energy wave is not particularly limited in that it can cause the polymerization initiator to develop the above reactions; however, at least one energy wave selected from a group consisting of: ultraviolet, infrared, visible light, and electron beam, is preferable. The amount of energy in the energy wave can be selected as appropriate to progress the above reactions. Among them, so-called light mode is more preferable.
[00075] In a case of using light according to the stimulus, the polymerization initiator is preferably an alkylphenone compound. An alkylphenone compound is easily cured by light of relatively accessible intensity (eg, ultraviolet) and in a relatively short period of irradiation. Among the alkyl phenone compounds, α-aminoalkyl phenone compound or α-hydroxyalkyl phenone compound is more preferable.
[00076] The α-aminoalkyl phenone compound includes: 2-methyl-1- [4 (methylthio) phenyl] -2-morpholino-propan-1-one (for example, Irgacure907 manufactured by BASF); 2-benzyl-2-dimethylamino-1- (4-morpholino phenyl) -1- butanone (for example, Irgacure369 or 1300 manufactured by BASF); 2- dimethylamino-2- (4-methylbenzyl) -1 - (4-morpholino phenyl) -1-butanone (for example, Irgacure379 manufactured by BASF); 3,6-di-bis (2-methyl-2-morpholinopropionyl) -9-octylcarbazole (for example, Adekaoptomer N-1414 manufactured by ADEKA Corporation); and the like.
[00077] The α-hydroxyalkyl phenone compound includes: 1-hydroxy-cyclohexyl-phenyl-keton (for example, Irgacure184 manufactured by BASF); 2-hydroxy-2-methyl-1-phenyl-propan-1-one (for example, DAROCURE1173 manufactured by BASF); 1 - [4 - (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (for example, IRGACURE2959 manufactured by BASF); 2- hydroxy-1- {4 - [4 - (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (for example, IRGACURE127 manufactured by BASF); and the like.
[00078] In a case using the alkylphenone compound, the content thereof is preferably 0.5 to 4 parts by weight with respect to a total of the epoxy resin, the radically polymerizable unsaturated compound, and the curing agent being 100 parts by mass. If the content of the polymerization initiator is at least 0.5 parts close to mass, the curing time when producing the fiber-reinforced composite material can be shortened. On the other hand, if the content of the polymerization initiator is no greater than 4 parts by mass, the heat resistance property of the cured product of the resin composition can be improved. In addition, the leakage of the remaining radical generating agent from the cured product of the matrix resin composition can be suppressed.
[00079] In a case where heating is used as the stimulus for generation radicals, the polymerization initiator can be a compound that develops a reaction, such as cleavage, hydrogen abstraction, electron transfer and the like in response to heat . Such a compound includes an azo compound, peroxide, and the like. The compounds can be used alone or in combination of two or more.
[00080] Such a polymerization initiator includes: 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azodiisobutyronitrile, 2,2'-azobis ( 2-methyl butyronitrile), 2,2'-azo-bis- (2-methylpropionic acid) -dimethyl; dibenzoyl peroxide; tert-butyl hydroperoxide; α, α-dimethylbenzyl hydroperoxide; tert-butylperoxide, and the like. [Other Components]
[00081] The matrix resin composition can include at least one resin selected from the group consisting of: a thermoplastic resin; thermoplastic elastomer, and elastomer, if necessary, in such a way that the effects of the present invention are not reduced. These resins have the function of improving the hardness and changing the viscoelasticity of the resin composition to make the viscosity, elasticity modulus of storage, and thixotropy of them suitable. These resins can be mixed with various components or dissolved in the epoxy resin in advance.
[00082] The thermoplastic resin preferably has a bond selected from the group consisting of: a carbon-carbon bond, an amide bond, an imide bond, an ester bond, an ether bond, a carbonate bond, an urethane bond , a urea bond, a thioether bond, a sulfone bond, an imidazole bond and a carbonyl bond, in a backbone. As such a thermoplastic resin, a group of thermoplastic resins falling under constructed plastics, such as polyacrylate, polyamide, polyamide, polyester, polycarbonate, polyphenylene sulfide, polybenzimidazole, polyimide, polyetherimide, polysulfone and polyethersulfone can be exemplified. Among these, polyimide, polyetherimide, polysulfone and polyethersulfone, which are superior in heat resistant properties, are particularly preferable.
[00083] From the point of view of increasing the toughness and maintaining an environment of properties resistant to cured resin, it is preferable that the thermoplastic resin has a functional group reactive with the thermally curable resin. Particularly preferable functional group includes a carboxylic group, an amino group, a hydroxyl group, and the like.
[00084] The matrix resin composition may include a solid additive, like other components, inasmuch as the solid additive is in a liquid state at the time of the impregnation of the reinforced fiber. As the additive, inorganic particles such as silica, alumina, titanium oxide, zirconia, clay minerals, talc, mica and ferrite, and carbonaceous components, such as carbon nanotubes and fullerene, can be exemplified. These additives provide an effect of: adding thixotropy to an uncured resin composition, improving the elasticity and heat resistant properties of a cured product of the resin composition, and improving the fatigue and abrasion resistant properties. In addition, particles of metal, carbon black, copper oxide, tin oxide and the like can be included in order to improve conductivity. The content of the solid additive is preferably not more than 50% by weight of the matrix resin composition. (Prepreg Production Method)
[00085] The method for producing a prepreg of the present invention is described below. The method for production according to the present invention comprises the following steps. (1) step of mixing matrix resin composition; (2) step of impregnating the matrix resin composition, and (3) step of increasing the surface viscosity. [(1) Stage of Mixing Matrix Resin Composition]
[00086] This is a step towards obtaining the matrix resin composition. The matrix resin composition can be obtained by mixing components simultaneously. Alternatively, the resin composition can be obtained by: firstly preparing a masterbatch of curing agent by mixing the epoxy resin, the curing agent, and if necessary the drying aid; separately preparing a polymerization initiator master batch by mixing the epoxy resin and polymerization initiator, and then mixing the curing agent master batch, the polymerization initiator master batch, the epoxy resin and the unsaturated compound radically polymerizable.
[00087] In the case of using a thermoplastic resin, thermoplastic elastomer, elastomer and the like as the other components, these components can be dissolved or dispersed in component (A) in advance.
[00088] As described above with respect to matrix resin, the types and content of the components are selected according to various requirements. As described above with respect to the matrix resin, the content of the radically polymerizable unsaturated compound is required to be 5 to 25% by weight relative to the total epoxy resin and the radically polymerizable unsaturated compound to be 100% by mass. By mixing, mixing machines such as a triple roller mill, planetary mixer, kneader, universal mixer, homogenizer, homo disperser and the like can be used. [(2) Matrix Resin Impregnation Step]
[00089] In this step, the precursor of the prepreg is obtained by impregnating the set of fibers reinforced with the matrix resin composition. The weight per square meter of the set of reinforced fibers used in this step is 250 to 2,000 g / m2.
[00090] As the fiber reinforced, several inorganic fibers and organic fibers can be used. For example, carbon fiber, graphite fiber, aramid fiber, nylon fibers, high strength polyester fibers, glass fiber, boron fiber, alumina fiber, silicon nitride fiber can be used. Among these, carbon fibers and graphite fibers are preferably used. Carbon fibers and graphite fibers are highly specific and have a specific modulus of elasticity. Like carbon fiber and graphite fiber, various carbon and graphite fibers can be used according to use. Highly resistant carbon fiber with a tensile elongation of at least 1.5% is preferably used. High strength carbon fiber, with a tensile strength of at least 4.4 GPa and a tensile elongation of at least 1.7% is preferable, and high strength carbon fibers with a tensile elongation of at least 1 , 9% is more suitable.
[00091] The set of reinforced fibers can be in the form of: a bundle of consecutive reinforced fibers; a plurality of bundles of consecutive reinforced fibers aligned in one direction, a fabric, a braid, a nonwoven fabric, and the like. A shape in which a plurality of consecutive reinforced fiber bundles are aligned in one direction is preferable, since such a shape can increase the strength of the fiber reinforced composite material. In addition, the array of reinforced fibers may be in a form in which a plurality of bundles of continuous fibers are aligned in one direction, without any gap, or with intervals. The set of reinforced fibers can be configured in the ways described above by the respective well-known methods.
[00092] Then, the set of reinforced fibers is impregnated with the matrix resin composition, thus obtained in the matrix resin composition mixing step, in order to obtain the precursor of the prepreg. Here, it is preferable to impregnate the reinforced fiber assembly with the matrix resin composition in such a way that the precursor of the prepreg comprises substantially no void. An impregnation method is not particularly limited and any well-known method can be employed, however, it is preferable to use the following method.
[00093] The viscosity of the matrix resin composition at 30 ° C is preferably from 12 Pa.s to 40,000 Pa.s, and more preferably from 40 Pa.s to 3000 Pa.s. If the lower viscosity limit is less than 12 Pa.s, handling properties are deteriorated and matrix resin composition becomes difficult to process. The lower limit of viscosity is more preferably 50 Pa.s, and even more preferably 60 Pa.s. An upper viscosity limit of more than 40,000 Pa.s is not preferable, since impregnation of the reinforced fiber with the matrix resin composition is inhibited and heating is necessary. The upper limit of viscosity is more preferably 20,000 Pa.s, even more preferably 10,000 Pa.s.
[00094] After impregnating the set of reinforced fibers with the matrix resin composition, it is preferable to first apply the matrix resin composition to the set of reinforced fibers and then in pressurization to impregnate the set of reinforced fibers with the matrix resin composition. A method of applying the matrix resin composition can be any known method, for example, a contact roll method, a dipping method, a dyeing method, a dispensing method and the like. An application amount of the matrix resin composition is adjusted according to the requirements of the fiber reinforced composite material. The amount is, for example, from 25 to 50% in relation to the weight of the prepreg. A pressurization method can be any known method, for example, a method of interposing the set of reinforced fibers between a pair of rollers and pressurizing, a method of wrapping a plurality of rollers and circular to impregnate and the like.
[00095] In a superficial layer of the prepreg, at least one resin selected from a group consisting of: a thermoplastic resin; thermoplastic elastomer, and elastomer can be arranged in a form of microparticles, long fibers, short fibers, fabric, a non-woven fabric, a mesh, cellulose and the like, as needed, such that the effects of the present invention are not reduced.
[00096] It is preferable that the impregnation step of the matrix resin composition includes the following steps (2-i) to (iii-2), in order to continuously and effectively impregnate the set of fibers reinforced with the composition of matrix resin. (2-i) a matrix resin composition application step to apply the matrix resin composition to a first face of a first fiber-reinforced base material A1, which is composed of consecutively reinforced fiber bundles leaf-like; (2-ii) a fiber-reinforced lamination step for lamination of a second fiber-reinforced A2 base material, which is composed of consecutive reinforced fiber bundles in a sheet-like manner, on face A1 on which the composition matrix resin has been applied; and (2-iii) a pressurization step of obtaining a prepreg precursor by impregnating A1 and A2 with the matrix resin composition by pressurizing A1 and A2.
[00097] FIG. 1 is a schematic view showing an example of a production flow, including these steps. The prepreg production device illustrated in FIG. 1 comprises the following components: an application unit 12 which applies the matrix resin composition to the reinforced fiber sheet A1 (11a); a pressurizing unit 13 impregnating A1 (11a) and the reinforced fiber sheet A2 (11b) with the matrix resin composition, which has been applied to A1 (11a), the pressurizing unit includes a pair of pressurization 13a, 13b which can be heated; and a protective foil supply roller 14, which provides a protective foil to A1 and A2, and a protective foil winding roller 15 which removes and coils the precursor precursor protective foil. [(2-i) Matrix Resin Composition Application Step]
[00098] In this step, the matrix resin composition is applied to a first face of the first reinforced fiber sheet A1 (11a), composed of consecutive reinforced fiber bundles. In an example shown in FIG. 1, A1 (11a) is driven by a roller and continuously transported to a rear side. The application unit 12 comprises a disk 12a and extrudes the matrix resin composition, which is supplied from a resin bath (not shown), from the mold 12a for applying A1 (11a). It should be noted that, although template 12a is used in this example, other methods can also be employed. [(2-ii) Reinforced Fiber Sheet Rolling Stage]
[00099] In this step, the second sheet of reinforced fiber A2 (11b), composed of bundles of consecutive reinforced fibers on the face of A1 (11a), to which the matrix resin composition has been applied. In an example shown in FIG. 1, A2 (11b) is arranged over the application unit 12, driven by a roller and continuously transported to a rear side. And then, on a front side of the pressurizing rollers 13a, 13b, the A2 (11b) is laminated on the face of the A1 (11a), to which the matrix resin composition has been applied. Here, A1 (11a) and A2 (11b) are in a state being laminated with the matrix resin composition being interposed between them. [(2-iii) Pressurization stage]
[000100] In this step, the precursor of the prepreg is obtained by impregnating the A1 and A2 with the matrix resin composition by pressurizing the A1 and A2. The weight per square meter of the set of reinforced fibers in the precursor of the prepreg thus obtained is 250 to 2,000 g / m2. In other words, the weight of A1 and A2 can be adjusted according to that weight. In addition, a compression force of the pressurizing rollers is preferably 6.7 x 103 N to 180.0 x 103 N and, more preferably, 20.0 x 103 N to 133.3 x 103 N for each 1 m of width, precursor of prepreg.
[000101] In the example of FIG. 1, A1 (11a) and A2 (11b), which are laminated, are interposed and pressurized between the pressurizing rollers 13a and 13b as the pressurizing unit 13, thereby impregnating the matrix resin composition. In the example of FIG. 1, three pairs of pressurizing rollers 13a and 13b are arranged, however, the present invention is not limited to them. If the pressurizing unit 13 is configured to allow temperature control, the conditions of impregnation of the matrix resin composition can be controlled with greater precision. A known configuration can be employed as such a configuration. For example, a configuration that allows a heating medium such as hot water to be introduced into it, a configuration with a heater provided on a surface thereof, and the like can be employed.
[000102] Thus, pressurizing A1 (11a) and A2 (11b), in a state of being laminated with the matrix resin composition being interposed between them, the matrix resin composition migrates outwards from the A1 (11a) and A2 (11b). This facilitates the evacuation of air from the space in the set of reinforced fibers. As a result, the precursor of the prepreg so obtained has substantially no void. On the other hand, in the hot melt film method described above, the direction of migration of the matrix resin composition is from outside to inside the set of reinforced fibers. This prevents air from evacuating from the spaces in the reinforced fiber set. In other words, by employing the steps described above (2- i) to (iii-2), impregnation with the matrix resin composition can be performed while substantially generating no void, at a lower pressure.
[000103] In the example of FIG. 1, the protective sheet supply orolo 14 and the protective sheet winding orolo 15 are arranged in front of and behind the pressurization unit 13. The use of the protective sheet is not mandatory, but optional. A sheet of a material that is conventionally used as mold release paper, for example, can be used as the protective sheet. The protective sheet protects A1 and A2, which are interposed between pressurizing rollers 13a and 13b, while preventing leakage of the matrix resin composition A1 and A2.
[000104] Alternatively, it is preferable that a matrix resin composition impregnation step includes the following steps (2-iv) to (2-vi), instead of the steps mentioned above (2-i) to (iii- 2), so as to continuously and effectively impregnate the set of reinforced fibers with the matrix resin composition. (2-iv) a matrix resin composition application step to apply the matrix resin composition to a first reinforced fiber sheet A1 composed of consecutive reinforced fiber bundles; (2-v) a fiber reinforced matrix lamination step to laminate a second reinforced fiber sheet A2 and a third fiber reinforced sheet A3 composed of consecutive reinforced fiber bundles on a first face of A1 and a second face of A1 respectively, and (2-vi) a pressurization step to obtain the precursor of the prepreg by impregnating A1, A2, and A3 with the matrix resin composition by pressurizing A1, A2, and A3. [(2-iv) Stage of Application of Matrix Resin Composition]
[000105] In this step, the matrix resin composition is applied to the first sheet of reinforced fiber A1 composed of bundles of consecutive reinforced fibers. Here, the matrix resin composition can be applied to either face or both sides of A1, however, it is preferable to apply the matrix resin composition to one face in order to facilitate the evacuation of air in the step pressurization. The application is executed, specifically in a similar way to the above step (2-i). [(2-v) Reinforced Fiber Sheet Lamination Stage]
[000106] In this step, a second sheet of reinforced fiber A2 and a third sheet of reinforced fiber A3 are composed of bundles of consecutive reinforced fibers, and the A2 is laminated on a first face of the A1 and A3 is laminated on a second face of the TO 1. This step is different from the step described above (II-2) in which A1 is interposed between two sheets of reinforced fibers, in other words, A2 and A3. Also in this configuration, the fiber reinforced assembly is obtained in a state of being laminated with the matrix resin composition being interposed between them, as in the case of carrying out the above-mentioned step (2-ii).
[000107] It is readily understood by those skilled in the art that the step described above (2-ii) can be applied as a method for laminating the reinforced fiber sheets. For example, A2 can be arranged above application unit 12 and A3, it can be arranged below A1, or vice versa. [(2-vi) Pressurization stage]
[000108] In this step, the precursor of the prepreg is obtained by impregnating A1, A2 and A3 with the matrix resin composition by pressurizing A1, A2 and A3. As in the case of carrying out the aforementioned step of pressurization (2-iii), pressurizing the A1, A2 and A3, which are laminated, the matrix resin composition migrates outward from the inside of the reinforced fiber set. This also facilitates the evacuation of air from the space in the set of reinforced fibers. It should be noted that it can be easily understood that a similar effect can be obtained, even if more than three sheets of reinforced fiber are being used. Therefore, the present invention also encompasses a configuration in which another fiber-reinforced sheet is laminated to A2 and A3.
[000109] The previously described method (2-iii) can be applied as a process to carry out this step.
[000110] As described above, the weight per square meter of the set of reinforced fibers in the precursor of the prepreg so obtained is 250 to 2,000 g / m2 and the weight of A1, A2 and A3 can be adjusted according to that weight . In addition, a compression force of the pressurizing rollers is preferably 6.7 x 103 N to 180.0 x 103 N and, more preferably, 20.0 x 103 N to 133.3 x 103 N for each 1 m of width, precursor of prepreg. [(3) Step to Increase Surface Viscosity]
[000111] In this step, a prepreg is obtained in which the viscosity of the matrix resin composition is increased more in a superficial part than in the central part, stimulating the precursor of the prepreg obtained by (1) step of matrix resin composition mixing (2) matrix resin composition impregnation step, allowing the polymerization initiator present in the surface part of the prepreg precursor to generate a radical, while not leaving the polymerization initiator present in the central part generate a radical.
[000112] Here, the "central part" indicates a region at a depth of at least 40%, with respect to the thickness of the prepreg precursor as being 100%, from the surface of the prepreg precursor.
[000113] Here, the "surface part" indicates a region more outer than the fibers closest to a surface layer.
[000114] After the generation of radicals, a viscosity of the central part of the prepreg at 30 ° C is preferably 12 Pa.s, at 40,000 Pa.s, and a viscosity of the surface part of the prepreg is preferably 3,000 Pa.sa 4000,000 Pa.s. The viscosity of the central part of the prepreg is more preferably 40 Pa.s to 3000 Pa.s, and a viscosity of the surface part of the prepreg is preferably 9,000 Pa.s to 1500,000 Pa.s. A prepreg that is superior in adhesion properties and therefore flexibility can be achieved.
[000115] In a case where the irradiation of the energy wave is used as the stimulus for the generation of free radicals, a degree of viscosity increase is determined by a synergy of: an amount of radiated energy; reactivity of a monomer and oligomer; reactivity of the resin composition, an absorption coefficient and the precursor thickness of the prepreg, and the like. Therefore, irradiation conditions can be defined according to these factors.
[000116] In a case where the light is used as the stimulus, the light is absorbed according to the so-called Beer-Lambert law. In other words, given Io being the light intensity before being incident and I being the light intensity after passing through a sample, a log (Io / I) = e.c.d ratio is satisfied. Therefore, by irradiating the light under a condition such that I in the relationship becomes substantially 0 at a certain depth, a degree of increase in surface viscosity can be controlled.
[000117] In this step, it is preferable to apply the stimulus referred to by the following method (3-i).
[000118] (3-i) a method of irradiating the prepreg precursor with at least one energy wave selected from a group consisting of: ultraviolet, infrared; visible light, and electron beam, with an incident intensity not exceeding an incident intensity that transmittance becomes 0% at a depth of 40% from a surface of the prepreg precursor with respect to the thickness of the prepreg precursor impregnated as being 100%.
[000119] It should be noted that carbon fiber and graphite fiber do not allow light to pass through it. Given this, these fibers are particularly suitable as the reinforced fiber for a case of using light as a stimulus, in order to increase viscosity only on the surface.
[000120] In a case where heating is used as the stimulus for the generation of radicals, a degree of viscosity increase is determined by a synergy of: an amount of thermal energy, reactivity of a monomer and oligomer; reactivity of the resin composition, with a heat conductivity and precursor thickness of the prepreg, and the like. Therefore, the heating conditions can be adjusted according to these factors.
[000121] At this stage, it is preferable to apply said stimulus by the following method (3-ii).
[000122] (3-ii) a method of heating the prepreg precursor from the outside in a non-contact state, for example a period of time in which a rate of temperature change is 0% at a depth of 40% from a surface of the prepreg precursor with respect to a thickness of the prepreg precursor as being 100%.
[000123] Here, the "contactless state" indicates a state in which no contact is made. It should be noted that carbon fiber and graphite fiber are relatively high in thermal conductivity. Therefore, in the case of an increase in viscosity only on the surface, it is preferable to perform instant heating in the shortest possible time, preferably by means of high frequency heating, such as laser heating, electromagnetic heating and the like. Here, high frequency heating indicates a method of heating using an exothermic phenomenon by high frequency electromagnetic waves. The frequency used is at least 100 Hz and a heating time can be adjusted in order to reach a temperature at which a desired initiator generates radicals.
[000124] In the prepreg obtained by performing the procedure described above (3) step of increasing surface viscosity, the viscosity of the matrix resin composition is more increased on the surface than on the central part. Therefore, even with a heavy prepreg with a weight per square meter of reinforced fibers, 250-2,000 g / m2 can be flexible, such that the prepreg can follow a curve when being placed in the mold of a material that is curved and can have an adhesion property of such a degree that the prepreg can be redisposed after laminating the prepregs.
[000125] The fiber-reinforced composite material obtained by curing the prepreg has superior mechanical properties and can thus be used preferably for large structures such as aircraft, automobile, shipbuilding, construction, mills and the like.
[000126] The flexibility of the prepreg is preferably defined in such a way that an arched angle θ of the prepreg under its own weight, which is measured using a method in the evaluation of a flexural property described later in FIG. 5 is at least 30 ° and more preferably at least 40 °. (Fiber Reinforced Composite Material)
[000127] The fiber reinforced composite material of the present invention can be obtained by curing the prepreg described above. As a method of curing the prepreg, autoclave molding, vacuum bag molding and the like can be exemplified. EXAMPLES
[000128] The present invention will be described in greater detail by way of examples, which are not intended, however, to limit the present invention.
[000129] The materials (resins and the like), reinforced fibers, as well as measurement and evaluation methods used in the following examples are listed below. (Materials) [Epoxy Resin (hereinafter referred to as component (A))]
[000130] A-1: Bisphenol type A liquid epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation)
[000131] A-2: Type A bisphenol solid epoxy resin (jER1001 manufactured by Mitsubishi Chemical Corporation)
[000132] A-3: isocyanate modified epoxy resin (AER4152 manufactured by Asahi Kasei KK epoxy) [Radically polymerizable unsaturated compound (hereinafter referred to as component (B))]
[000133] B-1: diglycidyl ether-bisphenol-A acrylic acid adduct (Epoxy Ester 3000A manufactured by Kyoeisha Chemical Co., Ltd.)
[000134] B-2: adduct of acrylic acid of glycidyl ether novolac type (DI-CLITE ES-8740 manufactured by DIC Corporation) [Curing Agent (hereinafter referred to as component (C))]
[000135] C-1: dicyandiamide (Dicy 15 manufactured by Mitsubishi Chemical Corporation) [Curing aid]
[000136] DCMU: diphenyl dimethylurea (DCMU99 manufactured by Hodogaya Chemical Co., Ltd.) [Radical polymerization initiator (hereinafter referred to as component (D))]
[000137] BASF) D-1: α-aminoalkyl phenone (Irgacure379 manufactured by
[000138] D-2: α-aminoalkyl phenone (Irgacure369 manufactured by BASF)
[000139] D-3: α-aminoalkyl phenone (Irgacure907 manufactured by BASF)
[000140] D-4: - α-hydroxyalkyl phenone (Irgacure184 manufactured by BASF) (fiber-reinforced bundle)
[000141] A bundle of carbon fibers: tensile strength 4.90 GPa, tensile modulus 240 GPa, number of filaments 15,000, weight per meter 1 g / m (manufactured by Mitsubishi Rayon Co., Ltd.)
[000142] Carbon fiber bundle 2: tensile strength 4.90 GPa, tensile modulus 250 GPa, number of filaments 60,000, weight per meter 3.2 g / m (manufactured by Mitsubishi Rayon Co., Ltd. )
[000143] Carbon fiber bundle 3: tensile strength 4.2 GPa, tensile modulus 235 GPa, number of filaments 50,000, weight per meter 3.8 g / m (manufactured by Mitsubishi Rayon Co., Ltd. ) (Measurement and Evaluation Methods) [Viscosity Measurement of Resin Composition under Ultraviolet Irradiation]
[000144] Change in viscosity of the resin composition by ultraviolet irradiation was measured under the following measurement conditions.
[000145] - Measuring device: VAR-100 (manufactured by Rheology Instruments AB) - Test mode: high speed oscillation - Measuring temperature: 30 ° C - Plate size: 8mm ^ - Range: 0.05 mm - Stress: 700 Pa - Frequency: 1.59 Hz - Intensity of ultraviolet rays (λ = 365nm): 53 mW / cm2 - Irradiation time: 6.0 s - Number of irradiations and interval between viscosity measurements: after measurement from the viscosity of the pre-irradiation resin, the ultraviolet rays were irradiated once and, after an interval of 120 seconds, the post-irradiation resin viscosity was measured. [Viscosity measurement of resin composition]
[000146] The viscosity of the resin composition was measured under the following measurement conditions.
[000147] Measuring device: Rheometer (DSR-200 manufactured by TA Instruments)
[000148] Plate: 40 ^ parallel plates
[000149] Plate range: 0.5 mm
[000150] Measurement frequency: 10 rad / s
[000151] Heating rate: 2 ° C / minute
[000152] Stress: 3000 dyne / cm2 [Prepreg Impregnation Property Assessment]
[000153] The obtained prepreg was visually observed and the impregnation with the resin composition was evaluated with the following two point scale.
[000154] Circle: part not impregnated was not observed.
[000155] Cross: part not impregnated was observed. [Cold Prepreg Property Assessment (Sensory Assessment)]
[000156] Cold property of the prepreg was evaluated on the following four-point scale based on a tactile sensation of the prepreg and a position correction property between the prepregs.
[000157] Double circle: cold property is moderate and the position can be easily corrected
[000158] Circle: light viscosity is observed, but position correction is possible
[000159] Cruz (Baixa): Substantially no stickiness is observed
[000160] Cross (high): Stickiness is extremely high and the resin sticks for one hand, or pre-impregnated position cannot be corrected maintaining shape [Cold Property Assessment]
[000161] The measurement was performed as follows: a polyethylene film was attached to the prepreg as shown in FIG. 3 such that a contact area is 50 mm wide and 50 mm long, a weight has been placed on it as shown in FIG. 4 in such a way that the load is evenly distributed in the area, and after 60 seconds, the weight was removed, so the polyethylene film and prepreg were gently lifted vertically, and the time for the polyethylene film to be detached was measured. The adhesion property of the prepreg was determined from the time thus measured. The test was repeated using nine weights of 5, 7, 15, 30, 60, 150, 300, 600 and 1,200 g sequentially in that order, until the polyethylene film was not separated within 10 seconds after being lifted vertically. When the polyethylene film was not separated in 10 seconds, the weight load used was used as an index for the adhesion property. If the polyethylene film was separated with the same weight of 1,200 g, this load was used as the index for the adhesion property. The measurement of the adhesion property was performed three times and an average was obtained.
[000162] Three of the 35 cm long and 20 cm wide prepregs were used in a state of being laminated. In addition, a stainless steel plate 1 mm thick, 35 cm long and 20 cm wide was placed below the prepreg in order to avoid distortion of the prepreg.
[000163] A polyethylene film: polylon film LD (trade name), produced by HiroSekikako K.K., 25 μm thick, 50 mm wide, 250 mm long. [Pleat Property Valuation]
[000164] Two parts of prepregs of 0 ° direction and 90 ° direction, 50 mm wide and 300 mm long were cut from the same prepreg, the 90 ° prepreg part, was laminated over the 0 ° pre-impregnated part to obtain a test part, and the test part was left for 60 minutes under conditions of 23 ° C and 50% humidity.
[000165] Using an apparatus as shown in FIG. 5, a weight of 300 g was placed on the test part in such a way that the load is evenly distributed over an area 50 mm long from one end of the test part and 50 mm wide, and the part test was left. Three minutes later, an angle of curvature of the test part was measured using a protractor as an index for the pleat property. An average of results from three measurements was used as an index for the fold property. [Liaison Property Assessment]
[000166] A binding property of the prepreg was evaluated in the following method. Two prepregs, which had been cut to a size of 150 mm in a longitudinal direction and 50 mm in a direction of the width of the reinforced fiber included in the prepregs, were left for at least 30 minutes at an ambient temperature of 23 ° C and 50% humidity, and the prepregs were laminated on top of each other with a mold release film interposed between them, in order to avoid sticking between them. The mold release film was removed from an area 50 mm long at one end and 50 mm wide (area hereinafter referred to as the bonding area) and the rest was defined as an unlinked area. Using a universal testing machine (Model 5565, manufactured by Instron), a pressure of 30 N / 25 cm2 was applied over the entire connection area for 1 minute for the pressure connection. A bonding state was assessed on the following two-point scale.
[000167] Circle: the prepregs maintained a state of being connected to each other by increasing the sample, maintaining the unconnected area of one of the prepregs.
[000168] Cross: the prepregs were separated in the bonding area. [Position Correction Property Assessment]
[000169] The unconnected area of the two prepregs connected by the same method as in the evaluation of the bonding properties was raised, the prepregs were separated in a vertical direction in relation to a contact surface at a rate of 10 mm / s, and a shape retention state of the prepregs was evaluated on the following two point scale.
[000170] Circle: the shape and condition of the surface of the prepreg have been retained.
[000171] Cross: the shape or surface condition of the prepreg has been deteriorated. [Prepreg Flexibility Assessment]
[000172] The prepreg was produced folded by the fingers and observed, and the flexibility of the prepreg was evaluated based on observation on the following two-point scale.
[000173] Circle: the prepreg was very flexible and easily followed by a curved mold material.
[000174] Cross: the prepreg was rigid and hard, and almost did not follow a curved mold material. [Fiber Reinforced Composite Material Production] [Autoclave Curing]
[000175] A predetermined number of unidirectional prepregs was layered in the same direction as the fiber, and bagged. The inside of the bag was depressurized by a vacuum pump and an autoclave was loaded with the bag. The temperature inside the autoclave was raised at a rate of 2 ° C / min and maintained at 80 ° C for 1 hour. Then, the temperature was increased at a rate of 2 ° C / min and maintained at 130 ° C for 1.5 hours, to cure and thus obtain the fiber-reinforced composite material. During this process, pressurization occurred after maintenance at 80 ° C for 1 hour, in order to make the pressure inside the autoclave of 6.0 kg / cm2. The vacuum pump was stopped when the pressure inside the autoclave was 1.4 kg / cm2, and the bag was opened to the atmosphere. [Vacuum Packaging Healing]
[000176] A predetermined number of unidirectional prepregs was layered in the same direction as the fiber, and bagged. The inside of the bag was depressurized by a vacuum pump and an oven was loaded with the bag. The temperature inside the oven was increased at a rate of 0.5 ° C / min and maintained at 90 ° C for 2 hours. Then, the temperature was increased at a rate of 0.17 ° C / min and maintained at 110 ° C for 4 hours to cure and thus obtain the fiber-reinforced composite material. [Fiber reinforced composite material evaluation] [0 ° Compression Property Evaluation]
[000177] 2 layers of the pre-impregnate were placed in bed and bagged. The interior of the bag was depressurized by a vacuum pump, and then the autoclave curing or vacuum bag curing was carried out to obtain the six parts of 12.7 mm wide fiber-reinforced composite material and 1 mm thick. Using INSTRON 5882 as a measuring device, which is compatible with the SACMA SRM 1R and supplied with a 100 kN load cell, the compression force and the compression elasticity module of the test parts thus obtained were measured in a ambient temperature of 23 ° C and 50% relative humidity, under the condition of 1.27 mm / min of top cross speed, and the measured values were converted with Vf (fraction of fiber volume) 60%. The six test parts were measured in the same way and an average of the values was obtained. It should be noted that the measurement was carried out by connecting a separator, which had been cut from the same plate, to each of the test parts. [Bending Property Assessment at 0 °]
[000178] 4 layers of the pre-impregnate were placed on bedding and bagged. The interior of the bag was depressurized by a vacuum pump, and then the autoclave curing or vacuum bag curing was carried out to obtain six parts of 12.7 mm wide fiber-reinforced composite material. , 120 mm long, and 2 mm thick.
[000179] Using INSTRON 4465 as a measuring device, which is compatible with the ASTM D790 standard and supplied with a 5 kN load cell, the flexural strength, the flexural modulus of elasticity, and the tensile strength at Bending of the test parts thus obtained was measured in an environment of 23 ° C of temperature and 50% relative humidity, under conditions of: cutter R = 5.0R, support R = 3.2R, and L / D = 40. The measured values for flexural strength and flexural modulus of elasticity were converted with 60% Vf. The six test parts were measured in the same way and an average of the values was obtained. [90 ° Bending Property Assessment]
[000180] 4 layers of the pre-impregnate were placed on bedding and bagged. The interior of the bag was depressurized by a vacuum pump, and then the autoclave curing or vacuum bag curing was carried out to obtain six parts of 25.4 mm fiber-reinforced composite material. wide, 60 mm long, and 2 mm thick.
[000181] Using INSTRON 4465 as a measuring device, which is compatible with the ASTM D790 standard and supplied with 500 kN load cell, the flexural strength, flexural elasticity modulus, and the flexural stress of the parts The test results thus obtained were measured in an environment of 23 ° C temperature and 50% relative humidity, under conditions of: cutter R = 5.0R, support R = 3.2R, and L / D = 16. The six parts test results were measured in the same way and an average of the values was obtained. [ILSS Property Valuation]
[000182] 4 layers of the pre-impregnate were placed on bedding and bagged. The interior of the bag was depressurized by a vacuum pump, and then the autoclave curing or vacuum bag curing was carried out to obtain six parts of 6.3 mm wide fiber-reinforced composite material. , 20 mm long, and 2.6 mm thick.
[000183] Using INSTRON 4465 as a measuring device, which is compatible with the ASTM D 2344 standard and equipped with a 5 kN load cell, the ILSS (interlayer shear force) of the test parts thus obtained it was measured in an environment of 23 ° C temperature and 50% relative humidity, under conditions of 1.27 mm / min at the top cross speed, cutter R = 3.2R; Support R = 1.6R and L / D = 4. [Evaluation of G'-Tg]
[000184] Four layers of prepreg were layered and bagged. The inside of the bag was depressurized by a vacuum pump, and then the autoclave curing or vacuum bag curing was carried out to obtain a 12.7 mm part of fiber-reinforced composite material. wide, 55 mm long, and 2 mm thick.
[000185] Using ARES-RDA (manufactured by TA Instruments), which is compatible with the ASTM D4065 standard, G'-Tg of the test parts thus obtained was measured under conditions of: heating rate of 5 ° C / min; frequency of 1 Hz; deformation 0.05%, and the temperature measurement range from room temperature to 180 ° C. [Thermal Curing Agent Masterbatch Preparation]
[000186] Component (A), component (C) and a curing aid were measured according to the composition shown in Table 1, stirred and mixed in a container. The mixture thus obtained was further mixed finely in a triple roller mill to obtain a master batch of thermal curing agent. [Table 1]

[000187] Component (A) and component (D) were measured according to the compositions shown in Table 2, stirred and mixed in containers. The mixtures thus obtained were then finely mixed by a triple roller mill to obtain master batches of polymerization initiator 1 to 3. [Table 2]
[Preparation of Masterbateladas of Mixed Initiator with Thermal Curing Agent and Polymerization 1 and 2]
[000188] Component (B), component (C), component (D) and a curing aid were measured according to the compositions shown in Table 3, agitated and mixed in containers. The mixtures thus obtained were more finely mixed by means of a triple roller mill to obtain master batches of initiator mixed with thermal curing agent and polymerization. [Table 3]
[EXAMPLE 1] [Preparation of Matrix Resin Composition]
[000189] 57.7 parts by mass of A-1 and 18 parts by mass of A-2 were measured, such as component (A), in a glass flask, heated to 130 ° C in an oil bath, mixed and then cooled to approximately 60 ° C. For the mixture thus obtained, 10 parts by mass of B-1 as component (B), 22.5 parts by mass of the thermal curing agent masterbatch prepared above (Table 1), and 4 parts by mass of the initiator masterbaked polymerization 1 prepared above (Table 2) were added, and stirred to mix using a hybrid mixer (trade name: HM-500 manufactured by KEYENCE CORPORATION), thus obtaining a matrix resin composition 1.
[000190] As a result of the measurement a change in viscosity by ultraviolet irradiation of the matrix resin composition 1 was thus obtained, the viscosity before ultraviolet irradiation was 5.5 x 101 Pa.se and a viscosity after a single ultraviolet irradiation was 2.5 x 103 Pa.sa 30 ° C. [Prepreg production]
[000191] A sheet of mold release paper was wrapped around a drum winding machine in which a drum with a circumference of 2 m was installed. Carbon fiber 1 was encased in it with a definition of 200 g / m2 FAW (fiber areal weight).
[000192] Meanwhile, the temperature of a resin in a resin bath was maintained at 40 ° C to 50 ° C and the matrix resin composition 1 was applied to a carbon fiber bundle cable 1, using a roller contact with a free space of a medical blade being defined as 200 to 400 mM. And then, around the bundle of carbon fibers 1 around the drum in advance, the cable on which the matrix resin composition 1 was applied was wound with the settings of 2 m / min, peripheral speed of the drum and 200 g / m2 FAW. After that, the bundle of carbon fibers 1 was wrapped in the 200 g / m2 FAW configuration, a sheet of mold release paper was attached to it, and all the elements described above were removed from the drum. These materials were processed, without heating, three times by a fusion press machine (trade name: JR-600S manufactured by Asahi Fiber Industry Corporation, processing length: 1340 mm, pressure: cylinder pressure), under pressure conditions of 0.2 MPa and 0.9 m / min feed speed, to obtain a prepreg 1.
[000193] An attempt to disassemble the prepreg 1 by the fingers failed and the prepreg 1 was not disassembled, since the matrix resin composition 1 fully functioned as a bond between the carbon fibers. In addition, an un-impregnated part of the matrix resin composition 1 was not visually observed, which means that a superior impregnation state was confirmed.
[000194] And then, the prepreg 1, thus obtained was irradiated with ultraviolet radiation of 240 mW / cm2 in illumination and 320 mJ / cm2 of irradiance, using a metal halide lamp (manufactured by EYE Graphics Co. , Ltd.).
[000195] The adhesion and flexibility properties of the pre-impregnated 1 thus irradiated with ultraviolet rays were evaluated. The results are shown in Table 4. [EXAMPLES 2] [Preparation of Matrix Resin Composition]
[000196] A matrix resin composition 2 was obtained in a similar manner to that of Example 1, except for the composition being changed to that indicated in Table 4.
[000197] As a result of the measurement a viscosity changed by ultraviolet irradiation of the matrix resin composition 2 thus obtained, the viscosity before ultraviolet irradiation was 8.7 x 101 Pa.sea viscosity after a single ultraviolet irradiation was 1.2 x 105 Pa.sa 30 ° C. [Prepreg production]
[000198] A prepreg 2 was produced in a similar manner to Example 1, except for the matrix resin composition 2 being used. The prepreg 2 thus obtained was irradiated with ultraviolet radiation in a similar manner to that of Example 1. The impregnation property of the matrix resin composition 2, as well as the adhesion and flexibility property of the prepreg 2, thus irradiated with ultraviolet rays were evaluated. The results are shown in Table 4.
[000199] The weight of the prepreg so obtained measured by a solvent method was 594 g / m2 FAW, and 34% resin content.
[000200] In addition, the prepreg so obtained was interleaved in a predetermined number of layers and then cured by autoclave curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Table 4. [Example 3]
[000201] A matrix resin composition 3 was obtained in a similar manner to Example 1, except for the composition being changed to that indicated in Table 4.
[000202] A prepreg 3 was produced in a similar manner to Example 1, except for the matrix resin composition 3 being used. The prepreg 3 thus obtained was irradiated with ultraviolet radiation in a similar manner to that of Example 1. The impregnation property of the matrix resin composition 3, as well as the adhesion and flexibility property of the prepreg 3 thus irradiated with the ultraviolet rays were evaluated. The results are shown in Table 4.
[000203] The weight of the prepreg so obtained measured by a solvent method was 592 g / m2 FAW, and 27% resin content.
[000204] In addition, the prepreg so obtained was interleaved in a predetermined number of layers and then cured by autoclave curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Table 4. [Example 4]
[000205] A matrix resin composition 4 was obtained in a similar manner to Example 1, except for the composition being changed to that indicated in Table 4.
[000206] A prepreg 4 was produced in a similar manner to Example 1, except for the matrix resin composition 4 being used. The prepreg 4 thus obtained was irradiated with ultraviolet radiation in a similar manner to that of Example 1. The impregnation property of the matrix resin composition 4, as well as the adhesion and flexibility property of the prepreg 4 thus irradiated with the ultraviolet rays were evaluated. The results are shown in Table 4. The weight of the prepreg thus obtained measured by a solvent method was 539 g / m2 FAW, and 36% resin content.
[000207] In addition, the prepreg so obtained was interleaved in a predetermined number of layers and then cured by autoclave curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Table 4. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6



* 1 all values converted with 56% vf * 1: impregnation O; cold property O; and flexibility The easily estimated from the data for resin component 6 (viscosity change by heating and UV irradiation) * 2: impregnation O; cold property x; and flexibility The easily estimated from the data for resin component 9 (viscosity change by heating and UV irradiation)
[000208] It should be noted that, in Table 4, "Component Content (B)" is a ratio of component (B) to a total of the amount of the entire component (A) and the amount of mixture of the component (B) being 100% by mass. [Example 5] [Preparation of the Resin Composition]
[000209] 50 parts by mass of A-1 and 40 parts by mass of A-3 were measured, as well as component (A), in a glass flask, heated to 130 ° C in an oil bath, mixed and , then air-cooled to approximately 60 ° C. The mixture was placed in a kneader, 19 parts by mass of the initiator master batch mixed with thermal curing agent and polymerization 1 (Table 3), prepared in advance was added to it, and stirred at 60 ° C to obtain a composition matrix resin 5.
[000210] As a result of the measurement a change in viscosity by ultraviolet irradiation of the matrix resin composition 5 was thus obtained, the viscosity before ultraviolet irradiation was 5.8 x 102 Pa.se a viscosity, after a single ultraviolet irradiation was from 9.3 to 103 Pa.sa 30 ° C. [Prepreg production]
[000211] A prepreg was produced as follows, using the prepreg production device illustrated in FIG. 1. Carbon fiber 3 was used as the reinforced fiber.
[000212] First, a resin bath from application unit 12 was loaded with the matrix resin composition 5 and a resin temperature in the resin bath was maintained at 60 ° C. A thickness of the matrix opening 12a was adjusted to 30 μm, a first continuous reinforced fiber sheet fiber A1 was formed using carbon fibers, and the matrix resin composition 5 was applied to a first face thereof. A second sheet of continuous reinforced fiber A2 was formed using carbon fibers, and laminated over the face of A1 to which the matrix resin composition 5 was applied. And then the A1 and A2 were removed under a condition of 5.0 m / min at the withdrawal rate, a protective sheet was fed from the protective sheet supply roll 14, and these fiber-based materials were interleaved between the protective sheets.
[000213] Then, using pressurization unit 13, A2 was impregnated with the matrix resin composition 5 that had been applied to A1 under a condition of 9.8 x 103 N as a compressive force of the pressurizing rollers 13a , 13b, in order to obtain a prepreg. And then, the prepreg so obtained was irradiated with ultraviolet rays of 240 mW / cm2 of illumination and 320 mJ / cm2 of irradiance, using a metal halide lamp (manufactured by EYE Graphics Co., Ltd.). The adhesion and flexibility properties of the prepreg thus irradiated with ultraviolet rays were evaluated. The results are shown in Table 5.
[000214] The weight of the prepreg 5 obtained in this way measured by a solvent method was 562 g / m2 FAW, and 35% resin content.
[000215] In addition, the prepreg so obtained was interleaved in a certain number of layers and then cured by vacuum bag curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Tables 4 and 5. [Example 6] [Prepreg production]
[000216] A prepreg 6 was obtained using the same method as in Example 1, using carbon fiber 3 and the matrix resin composition 5. The weight of the prepreg thus obtained measured by a solvent method was 313 g / m2 FAW, and 31% resin content.
[000217] In addition, the prepreg so obtained was interleaved in a predetermined number of layers and then cured by vacuum bag curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Tables 4 and 5. [Example 7] [Preparation of Matrix Resin Composition]
[000218] 50 parts by mass of A-1 and 40 parts by mass of A-3 were measured, as well as component (A), in a glass flask, heated to 130 ° C in an oil bath, mixed and , then air-cooled to approximately 60 ° C. The mixture was placed in a kneader, 19 parts by mass of the initiator masterbelt mixed with thermal curing agent and polymerization 2 (Table 3), prepared in advance was added to it, and stirred at 60 ° C to obtain a composition matrix resin 6.
[000219] As a result of the measurement a change in viscosity by ultraviolet irradiation of the matrix resin composition 6 was thus obtained, the viscosity before ultraviolet irradiation was 4.2 x 102 Pa.se a viscosity, after a single ultraviolet irradiation was 1.8 x 104 Pa.30 ° C. Assuming that a prepreg was produced using the matrix resin composition 6, its adhesion and flexibility property could be estimated to be within a suitable range (evaluation of the circle symbol in both units), based on in viscosity before and after irradiation by the ultraviolet ray, compared to the matrix resin composition 5. Consequently, the production of a prepreg was omitted. [Example 8] [Prepreg production]
[000220] A prepreg 10 was obtained using the same method as in Example 1, using carbon fiber 3 and the matrix resin composition 5. The weight of the prepreg thus obtained measured by a solvent method was 467 g / m2 FAW, and 29% resin content.
[000221] In addition, the prepreg so obtained was interleaved in a predetermined number of layers and then cured by vacuum bag curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Table 5. [Example 9] [Prepreg production]
[000222] A prepreg 11 was obtained using the same method as in Example 5, using carbon fiber 3 and the matrix resin composition 5. The weight of the prepreg thus obtained measured by a solvent method was 790 g / m2 FAW, and 30% resin content.
[000223] In addition, the prepreg so obtained was interleaved in a predetermined number of layers and then cured by vacuum bag curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Table 5. [Example 10] [Prepreg production]
[000224] A prepreg was produced with carbon fiber 3 and the matrix resin composition 5, as follows, using the prepreg production device 10 illustrated in FIG. two.
[000225] First, a resin bath 12b of the application elements 12 was loaded with resin composition 3 and a resin temperature in the resin bath was maintained at 50 ° C. In addition, the spacing of the medical blade (not shown) was adjusted to 530 mM. As reinforced fiber sheets A1 to A3, reinforced sheet-type fiber sheets, in which carbon fiber cables are aligned in a single direction, without gap, were used.
[000226] And then the reinforced fiber sheet A1, the reinforced fiber sheet A2 and the reinforced fiber sheet A3 were removed by a drive roller 19 under a condition of 6.0 m / min, at a rate of removed, the resin composition 3 was applied to the reinforced fiber sheet A3 by application elements 12, the reinforced fiber sheet A3 was interleaved between the reinforced fiber sheet A1 and the reinforced fiber sheet A2; protective sheets 14a, 14b have been fed with a food element 14, and these reinforced fiber sheets are further interspersed between protective sheets 14a, 14b.
[000227] Subsequently, the reinforced fiber sheet A1 and reinforced fiber sheet A2 were impregnated with the resin composition 3 that had been bonded to the reinforced fiber sheet A3 by an impregnation element 13, under a condition of 130.7 x 103 N in the form of a compressive force of the pressurizing rollers 13a and 13b (for a width of 1 m of a prepreg precursor), and a prepreg so obtained was encased by a winding means. Then, the prepreg so obtained was irradiated with ultraviolet rays of 240 mW / cm2 of illumination and 320 mJ / cm2 of irradiance, using a metal halide lamp (manufactured by EYE Graphics Co., Ltd.). The adherence and flexibility properties of the prepreg thus irradiated with ultraviolet rays were evaluated. The results are shown in Table 5.
[000228] The weight of the prepreg 12 thus obtained measured by a solvent method was 911 g / m2 FAW, and 34% resin content.
[000229] Furthermore, the prepreg so obtained was interleaved in a predetermined number of layers and then cured by vacuum bag curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Table 5. [EXAMPLE 11] [Prepreg production]
[000230] A prepreg 13 was obtained using the same method as in Example 10, using carbon fiber 3 and the matrix resin composition 5. The weight of the prepreg thus obtained measured by a solvent method was 1240 g / m2 FAW, and 29% resin content. The adhesion and flexibility properties of the prepreg were evaluated. The results are shown in Table 5. In addition, the prepreg so obtained was sandwiched in a predetermined number of layers and then cured by vacuum bag curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Table 5.

[Examples 12 to 14] [Prepreg production]
[000231] Ultraviolet rays were emitted by the same method as in Example 5, using a metal halide lamp (manufactured by EYE Graphics Co., Ltd.), with lighting of 240 mW / cm2 and irradiance of 80, 160 and 480 mJ / cm2, in order to obtain impregnates 14 to 16. The adhesion and flexibility properties of the prepregs thus obtained were evaluated. The results are shown in Table 6. In addition, the prepreg so obtained was sandwiched in a predetermined number of layers and then cured by vacuum bag curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Table 6.
Comparative Examples 5 to 7 and Example 15] [Preparation of Matrix Resin Composition]
[000232] Matrix resin compositions 11 through 14 were obtained by the same method as in Example 5, except by changing the compositions from those shown in Table 7. [Prepreg production]
[000233] Prepregs 17 to 20 were obtained by the same method as in Example 5, using matrix resin compositions 11 to 14. The adhesion and flexibility properties of the prepregs thus obtained were evaluated. The results are shown in Table 7. In addition, the prepreg so obtained was interspersed in a predetermined number of layers and then cured by vacuum bag curing to produce a fiber-reinforced composite material, which was evaluated for the various properties. The results are shown in Table 7.

[Preparation of Matrix Resin Composition]
[000234] 15 to 19 matrix resin compositions were obtained by the same method as in Example 5, except by changing the compositions from those shown in Table 8. [Prepreg production]
[000235] Prepregs 21 to 25 were obtained by the same method as in Example 5, using matrix resin compositions 15 to 19. In addition, the prepreg so obtained was sandwiched in a predetermined number of layers and, then cured by vacuum bag curing to produce a fiber-reinforced composite material, which was evaluated for its various properties. The results are shown in Table 8.


[Comparative Example 1] [Preparation of the Resin Composition]
[000236] 66.4 parts by mass of A-1 and 20 parts by mass of A-2 were measured, such as component (A), in a glass flask, heated to 130 ° C in an oil bath, mixed and then cooled to approximately 60 ° C. 25 parts by mass of the thermal curing mixer prepared above (Table 1) were added to it, and stirred and mixed in a water bath regulated at 60 ° C, in order to obtain the matrix resin composition 7 .
[000237] The viscosity measured by DSR-200 of the matrix resin composition 7 thus obtained was 6.0 x 101 Pa.s at 30 ° C. [Prepreg production]
[000238] A sheet of mold release paper was wrapped around a drum winding machine on which a drum with a circumference of 2 m was installed.
[000239] Meanwhile, the temperature of a resin in a resin bath was maintained at 40 ° C to 50 ° C, and the matrix resin composition 7 was applied to a fiber bundle of carbon fiber 2 using a roller contact with a free space of a medical blade being defined as 500 to 600 mM. And then, around the mold release paper wrapped around the drum in advance, the cable on which the matrix resin composition 7 was applied was wrapped with the settings of 2 m / min of circumferential speed of the drum and 600 g / m2 FAW, and it was removed from the drum.
[000240] These materials were processed, without heating, three times by a fusion press machine (trade name: JR-600S manufactured by Asahi Fiber Industry Corporation, processing length: 1340 mm, pressure: cylinder pressure), under conditions pressure of 0.2 MPa and 0.9 m / min of feeding speed, in order to obtain a prepreg 7.
[000241] As a result of visual observation of the prepreg thus obtained 7, an un-impregnated part of the matrix resin composition 7 has not been observed, which means that a superior impregnation state has been confirmed.
[000242] In addition, the adherence and flexibility properties of the pre-impregnated 7 were evaluated. The results are shown in Table 4. [Comparative Example 2]
[000243] A matrix resin composition 8 was obtained in a similar manner to Example 1, except for the composition being changed to that indicated in Table 4.
[000244] A prepreg 8 was then produced in a similar manner to Example 1, except for the matrix resin composition 8 being used. The prepreg 8 thus obtained was irradiated with ultraviolet radiation in a similar manner to that of Example 1. The impregnation property of the matrix resin composition 8, as well as the adhesion and flexibility property of the prepreg 8 thus irradiated with ultraviolet rays were evaluated. The results are shown in Table 4. [Comparative Example 3]
[000245] A resin composition 9 was obtained in a similar manner to that of Example 1, except for the composition being changed to that indicated in Table 4.
[000246] As a result of the measurement a change in viscosity by ultraviolet irradiation of the resin composition 9 was thus obtained, the viscosity before ultraviolet irradiation was 8.0 x 104 Pa.se a viscosity after single ultraviolet irradiation was 1, 3 x 106 Pa.sa 30 ° C.
[000247] From these results, it was confirmed that the viscosity of the resin composition 9 was markedly increased by the single ultraviolet irradiation. The adhesion property of the prepreg could thus be easily estimated to be weak (almost no adhesion). Therefore, the production of a prepreg has been omitted. [Comparative Example 4] [Preparation of Matrix Resin Composition]
[000248] A matrix resin composition 10 was obtained in a similar manner to Example 1, except that the composition was changed to that indicated in Table 4.
[000249] The viscosity measured by DSR-200 of the matrix resin composition 10 thus obtained was 7.2 x 103 Pa.s at 30 ° C. [Prepreg production]
[000250] The resin composition 10 thus obtained was applied to the mold release paper by a comma coater (M-500 manufactured by Hirano TECSEED Co., Ltd.), at 65 ° C, and a polyethylene film as well as protective film was interleaved in it, to thus produce a hot melt film of 40.4 g / m2 FAW.
[000251] The hot melt film was cut in 2 m, and wound around a drum winding machine in which a drum with a 2 m circumference was installed. Carbon fiber 1 was wrapped with a definition of 150 g / m2 FAW. Another 2 m hot melt film was attached to it to obtain a double film.
[000252] The double film was removed from the drum and processed three times by a melting press heated to 100 ° C (trade name: JR-600 manufactured by Asahi Fiber Industry Corporation, processing length: 1,340 mm, pressure: cylinder pressure ), under pressure conditions of 0.2 MPa and 0.9 m / min of feed speed, in order to obtain a prepreg. The prepreg so obtained was interleaved in four layers to obtain a prepreg of 9 600 g / m2 FAW.
[000253] The impregnation property of the resin composition 10, as well as the adhesion property and the flexibility of the prepreg 9 were evaluated. The results are shown in Table 4.
[000254] As is evident from Tables 4 and 5, the matrix resin compositions 1 to 5, of Examples 1 to 5 were superior in the fiber-reinforced impregnation property. In addition, as a result of bending prepregs 1 to 6 irradiated with ultraviolet rays, which were obtained in Examples 1 to 6, superior flexibility was observed. As for adhesion, slight viscosity was observed and position correction was possible, even after adding a prepreg with another prepreg.
[000255] On the other hand, the matrix resin composition 7 obtained in Comparative Example 1 was as superior as in the examples in the property of impregnation with the reinforced fiber and the prepreg 7 showed greater flexibility when being bent by the finger; however, the matrix resin composition 7 was extremely high in adhesion property and the resin held by hand, and therefore position correction was difficult after adding a prepreg with another prepreg.
[000256] The composition of matrix resin 8 obtained in Comparative Example 2 was as superior as in the examples in the property of impregnation with the reinforced fiber and the prepreg 8 irradiated with ultraviolet rays showed greater flexibility when being bent by the finger, in the However, the matrix resin composition 8 was low in adhesion properties, and the surface texture of the prepreg was almost dry.
[000257] The matrix resin composition 10 obtained in Comparative Example 4 was as superior as in the examples in the fiber reinforced impregnation property and the prepreg 9 had an adequate adhesion property and superior position correction properties, in the However, the prepreg 9 was rigid and inferior in flexibility being bent by the finger. INDUSTRIAL APPLICABILITY
[000258] According to the method for producing a prepreg of the present invention, even in the prepreg with the weight per square meter of the reinforced fibers being 250-2,000 g / m2, the set of reinforced fibers can be impregnated with the matrix resin composition without generating voids, and a prepreg with superior flexibility and an adhesion property can be obtained. In addition, the prepreg obtained by the method for producing a prepreg of the present invention is free of elastic recovery.
[000259] According to the prepreg of the present invention, even a prepreg with the weight per square meter of reinforced fibers being 250-2,000 g / m2 has superior flexibility and an adhesion property. The prepreg is suitable for the production of large structural materials for vehicles, mills and the like.
[000260] According to the matrix resin composition of the present invention, in the production of a prepreg with the weight per square meter of the reinforced fibers being 250-2,000 g / m2, superior flexibility and a cold property can be obtained; and, when in use as the fiber-reinforced composite material after curing, superior physical properties can be obtained.
[000261] According to the fiber-reinforced composite material of the present invention, even a fiber-reinforced composite material with the weight per square meter of the reinforced fibers being 2502,000 g / m2, a void formed between a mold and a prepreg. in the production of a large molded product having a non-linear shape it can be suppressed by superior accompaniment in a mold due to superior flexibility and cold property; and generation of voids can be prevented by the appropriate cold property by eliminating overhead pockets between the mold and the prepreg.

权利要求:
Claims (6)
[0001]
1. Method for producing a prepreg that contains reinforced fibers and a matrix resin composition with the weight per square meter of reinforced fibers being 250-2,000 g / m2, the production method comprising the following steps (1) - (3), characterized by the fact that it comprises the steps of: (1) a step of mixing matrix resin composition to obtain a matrix resin composition by mixing an epoxy resin, a radically unsaturated compound polymerizable, an epoxy resin curing agent and a polymerization initiator that generates radicals, in that stage the content of the radically polymerizable unsaturated compound in relation to 100% by mass of the total epoxy resin and the radically polymerizable unsaturated compound 10-25% by weight; and the viscosity at 30 ° C of the matrix resin composition is 12 Pa.sa 30,000 Pa.s, (2) a step of impregnation of the matrix resin composition to obtain a prepreg precursor by impregnation of a set of reinforced fibers being 250-2,000 g / m2 by weight, with the matrix resin composition, and (3) a step of increasing the surface viscosity to obtain a prepreg in which the viscosity of the matrix resin composition is increased more in a superficial part than in the central part, allowing the polymerization initiator present in the superficial part of the prepreg precursor to generate a radical by the method (3-i) below, although do not let the polymerization initiator present in the central part generate a radical, (3-i) a method of irradiating the prepreg precursor with an energy wave selected from a group consisting of: ultraviolet, infrared; visible light, and electron beam, with an incident intensity not exceeding an incident intensity that the transmittance is 0% at a depth of 40% from a prepreg precursor surface with respect to the pre precursor thickness -impregnated as being 100%.
[0002]
2. Method for producing a prepreg, according to claim 1, characterized in that the polymerization initiator is α-aminoalkyl phenone or α-hydroxyalkyl phenone.
[0003]
Method for producing a prepreg, according to claim 1 or 2, characterized in that a means for allowing the polymerization initiator to generate a radical in the step described above (3) is the following method (3- ii): (3-ii) a method of heating the prepreg precursor from the outside in a non-contact state, for example a period of time in which a rate of temperature change is 0% at a depth of 40% from a surface of the prepreg precursor in relation to the thickness of the prepreg precursor being 100%.
[0004]
4. Method for producing a prepreg, according to claim 3, characterized by the fact that method (3-ii) is carried out by means of high frequency heating.
[0005]
5. Method for producing a prepreg according to claim 1 or 2, characterized by the fact that step (2) includes the following steps (2-i) to (2-iii): (2-i) a matrix resin composition application step for applying the matrix resin composition to a first face of a first fiber reinforced sheet A1 composed of consecutive fiber reinforced bundles; (2-ii) a reinforced fiber matrix lamination step to laminate a second reinforced fiber sheet A2 composed of consecutive reinforced fiber bundles on face A1 to which the matrix resin composition was applied, and (2- iii) a pressurization step to obtain the pre-impregnated pre-cursor by impregnating A1 and A2 with the matrix resin composition by pressurizing A1 and A2.
[0006]
6. Method for producing a prepreg, according to claim 1 or 2, characterized by the fact that step (2) includes the following steps (2-iv) to (2-vi): (2-iv) a step of applying matrix resin composition to apply the matrix resin composition to a first reinforced fiber sheet A1 composed of consecutive reinforced fiber bundles; (2-v) a fiber reinforced matrix lamination step to laminate a second reinforced fiber sheet A2 and a third fiber reinforced sheet A3 composed of consecutive reinforced fiber bundles on a first face of A1 and a second face of A1 respectively, and (2-vi) a pressurization step to obtain the precursor of the prepreg by impregnating A1, A2, and A3 with the matrix resin composition by pressurizing A1, A2, and A3.

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法律状态:
2017-08-15| B25D| Requested change of name of applicant approved|Owner name: MITSUBISHI CHEMICAL CORPORATION (JP) |

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2017-08-29| B25G| Requested change of headquarter approved|Owner name: MITSUBISHI CHEMICAL CORPORATION (JP) |

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2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-04-07| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2020-08-18| B09A| Decision: intention to grant|

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2020-12-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2011046576|2011-03-03|

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JP2011-046576|2011-03-03|

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JP2012-010429|2012-01-20|

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JP2012010429|2012-01-20|

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PCT/JP2012/055473|WO2012118208A1|2011-03-03|2012-03-02|Matrix resin composition, prepreg, method for producing prepreg, and fiber-reinforced composite material|

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