JP5700283B2 - Nanofiber reinforced transparent composite - Google Patents

Description

  The present invention relates to a fiber-reinforced transparent composite material composed of chitin or chitosan nanofibers and silicon resin.

  As a substrate for a display device such as LCD, PDP, organic EL, electronic paper, and touch panel, glass is generally used from the viewpoints of transparency, heat resistance, low water absorption, surface hardness, reliability, and the like. In recent years, however, LCDs and other display devices are required to be thinner, lighter, and more flexible, and there is a challenge to reduce the weight of glass substrates that occupy a large weight among the devices. .

  In response to such demands, measures by thin processing of glass have been studied, but there is a limit from the viewpoint of maintaining a certain strength. In addition, in order to manufacture thin, light, and hard-to-break display devices at a lower cost, we are also considering a roll-to-roll manufacturing process based on a technology called “printed electronics” that applies printing technology to form electronic circuits. There is a high demand for a lightweight substrate that combines flexibility and strength in addition to the reliability of glass.

  Accordingly, various transparent resins have been developed as lightweight materials for glass replacement that can satisfy such requirements. There is a growing demand for such transparent resin as a substitute for glass not only in electronic materials such as display devices, but also in the automobile industry, for example, in weight reduction by using resin for automobile glass.

  Examples of the resin used for the substrate of the display device include a thermosetting composition comprising an alicyclic epoxy resin, an acid anhydride curing agent, and a curing catalyst (see, for example, Patent Document 1) and a thermoplastic resin film ( For example, see Patent Document 2). In addition, a resin composition comprising an amorphous thermoplastic resin and bis (meth) acrylate that can be cured with active energy rays has been studied (for example, see Patent Document 3). However, in general, organic resins have a larger coefficient of linear expansion than glass and poor dimensional stability, which often causes problems in the manufacturing process of display devices that require a high degree of alignment. There is a problem that warpage due to expansion, disconnection of aluminum wiring, and the like occur.

  As means for solving such a problem, a fiber reinforced composite material obtained by impregnating a resin into a glass filler or glass fiber (glass cloth) and molding it into a sheet has been studied (for example, Patent Document 4, 5). However, in such a composite material of glass fiber and resin, in order to obtain a high degree of transparency, it is necessary to strictly match the refractive index and Abbe number of the glass fiber and the resin. Since the refractive index fluctuates due to a slight difference in the composition of silicate, it is extremely difficult to produce a transparent substrate with a stable quality in a composite material with a resin. In such a composite material, it is common to use a glass cloth. However, due to the undulation of the glass cloth, it is difficult to ensure surface smoothness, and high surface smoothness is required. Problems often arise as a display device substrate material.

  An acrylic resin film using chitin nanofibers instead of glass fibers has been proposed as a transparent material that can suppress thermal expansion (for example, see Non-Patent Document 1). This document shows that the 600 nm light transmittance of a film obtained by impregnating chitin nanofibers with about 60% of an acrylic monomer and polymerized by ultraviolet irradiation was 89.8%. This indicates that the transparency is only 1.5% lower than the light transmittance of the resin alone. Further, as a relationship between the light transmittance of the chitin nanofiber reinforced resin film and the refractive index of the resin to be used, when the resin refractive index is about 1.49, the light transmittance is about 72%, and the resin refractive index is 1 The light transmittance of the chitin nanofiber reinforced resin film rises as it goes up from .49, the resin refractive index is about 1.50, about 80%, the resin refractive index is about 1.52, about 86%, The resin refractive index reaches a plateau of about 89% over about 1.53 to 1.54, and as the resin refractive index further increases, the light transmittance decreases rapidly, and the resin refractive index is about 1.56. The light transmittance of the chitin nanofiber reinforced resin film is observed to be about 83%. Interpreting this observation, the document points out that high transparency could be maintained even when using resins having various refractive indexes. Certainly, the light transmittance was maintained at about 89% regardless of the change in the refractive index difference between the nanofiber and the resin in the range of the resin refractive index from 1.53 to 1.54, and high transparency was achieved. It is shown. From this, it is pointed out that various types of resins can be selected in accordance with applications in the production of transparent materials. However, this document does not describe that high transparency can be secured even when the resin refractive index is outside the range of 1.53 to 1.54 using chitin nanofibers, and glass fibers were used. There is no disclosure or suggestion as to whether a high degree of transparency can be achieved even with a resin refractive index in a wider range than the above, even if the refractive index matching is not strictly required.

Japanese Patent Laid-Open No. 06-337408 Japanese Patent Laid-Open No. 07-120740 JP 10-77321 A JP 2004-231934 A JP 2007-217673 A

Shinsuke Ifuku, Monthly Display, Techno Times, March 2010, pages 54-61

  The present invention is a transparent composite material using chitin or chitosan nanofibers as a reinforcing fiber, can exhibit high transparency in a wide range of resin refractive index, is flexible, has mechanical strength, light weight, and smooth surface. It aims at providing the novel composite material which exhibits the property, heat resistance, UV resistance, chemical resistance, etc.

In the present invention, a silicon resin mixture comprising a reaction mixture obtained by hydrolyzing and condensing an alkoxysilane containing at least trifunctional or a chlorosilane containing at least trifunctional under acidic or alkaline conditions is obtained as chitin nanofibers. And a nanofiber-reinforced transparent composite material impregnated with at least one nanofiber selected from chitosan nanofibers.
The present invention is also a display device substrate using the composite material.
The present invention is also a structural material using the composite material.

With the above-described configuration, the composite material of the present invention is such that the silicon resin mixture has good impregnation and adhesion to the nanofibers of chitin or chitosan, and has high transparency (that is, high light transmission) in a wide range of resin refractive indexes. And a composite material having a low coefficient of linear expansion and excellent heat resistance and mechanical strength.
In the composite material of the present invention, the refractive index of the silicon resin mixture can be easily adjusted in a wide range, and the refractive index of the chitin or chitosan nanofiber is stable. It is possible to stably produce a composite material having a high degree of transparency.
Therefore, according to the present invention, it can be suitably used as a resin substrate that replaces a glass substrate such as for display devices and a transparent resin that replaces a glass for automobiles.

  The silicon resin mixture in the present invention is a reaction mixture obtained by hydrolyzing and condensing alkoxysilane containing at least trifunctional or chlorosilane containing at least trifunctional under acidic or alkaline conditions. Silicon compounds obtained by hydrolyzing and condensing only trifunctional silanes are called silsesquioxane compounds, and those having structures such as a cage type, a ladder type, and a random type are known. The silicon resin mixture in the present invention is mainly composed of a resin having a ladder type structure or a random type structure. Such a silicone resin mixture in the present invention is obtained by simultaneously hydrolyzing and condensing alkoxysilane or chlorosilane under acidic or alkaline conditions, or after hydrolyzing alkoxysilane or chlorosilane under acidic or alkaline conditions. It can be obtained by further condensation without isolating an intermediate containing silanol. Therefore, a silicon resin containing only a compound having a specific structure, such as a double-decker type silicon resin described in JP2009-167390A, produced by a multi-step synthesis process is not included.

  As the above alkoxysilane, an alkoxysilane containing three alkoxysilyl groups in one molecule (also referred to as trifunctional alkoxysilane in the present specification. 1-4 functional alkoxysilane is also based on this). For example, methyltrimethoxysilane, methyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, i-propyltrimethoxysilane, n -Butyltrimethoxysilane, s-butyltrimethoxysilane, t-butyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyl Trimetoki Silane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, allyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Examples thereof include methoxysilane and 3-mercaptopropyltriethoxysilane.

  The trifunctional alkoxysilane is preferably used in an amount of 10 to 100% by weight in the raw material alkoxysilane compound. More preferably, it is 30 to 95% by weight.

  In addition to the trifunctional alkoxysilane, a silane compound having 90% by weight or less, 50% by weight or less, or 10% by weight or less, 1, 2 or 4 functionals in the starting alkoxysilane compound may be used. Examples of the alkoxysilane compound other than the above trifunctional compounds include, for example, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane. , Tetramethoxylane, tetraethoxysilane and the like.

  Examples of the chlorosilane include chlorosilane containing three chloro groups in one molecule (also referred to as trifunctional chlorosilane in the present specification. 1-4 functional chlorosilane is also based on this), for example, trichlorosilane, Examples thereof include methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, isobutyltrichlorosilane, cyclohexyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, phenyltrichlorosilane, allyltrichlorosilane, and vinyltrichlorosilane.

  The trifunctional chlorosilane is preferably used in an amount of 10 to 100% by weight in the raw material chlorosilane compound. More preferably, it is 30 to 95% by weight.

  In addition to the trifunctional chlorosilane, a 1, 2 or tetrafunctional silane compound, preferably 90% by weight or less, more preferably 5 to 75% by weight, in the raw material chlorosilane compound may be used. Examples of chlorosilane compounds other than the above trifunctional compounds include dimethyldichlorosilane, diphenyldichlorosilane, dibutyldichlorosilane, diethyldichlorosilane, dihexyldichlorosilane, and diisopropyldichlorosilane.

  The silicon resin preferably has a functional group imparting curability (hereinafter also simply referred to as a curing group). Examples of the curing group include cyclic ether groups such as an epoxy group, a 3,4-epoxycyclohexyl group, and an oxetanyl group, a methacryl group, an acrylic group, and a vinyl group. As a method for introducing the curing group into the silicon resin, a method of using the curing group-containing silane compound as all or part of the raw material silane compound, a method of introducing the curing group-containing compound into the silicon resin by a method such as hydrosilylation reaction, etc. Etc. Any of these methods can be a known method. As the hydrosilylation reaction technique, for example, the technique described in JP-A-2009-173910 can be used.

  The method for curing the silicon resin is not particularly limited, and may be thermal curing, UV curing, or a composite method thereof.

  Examples of the curing group-containing silane compound include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Mention may be made of 3-acryloxypropyltrimethoxysilane.

  10-100 weight% is preferable and, as for the mixture ratio in the raw material silane compound of the said hardening group containing silane compound, 30-95 weight% is more preferable.

  The silicone resin mixture preferably has a weight average molecular weight of 1500 to 30000 because the resin viscosity at room temperature (for example, 25 ° C.) is excellent in impregnation into nanofibers. The weight average molecular weight is measured by GPC method.

  In the production of the silicon resin mixture, the reaction temperature is preferably 20 to 120 ° C, more preferably 40 to 80 ° C. The reaction time is preferably 30 to 300 minutes, more preferably 60 to 180 minutes. In order to carry out hydrolysis and condensation under acidic or alkaline conditions, a catalyst may be used in the reaction.

  Examples of the catalyst include organic acids, inorganic acids, organic bases, and inorganic bases.

  Organic acids include formic acid, maleic acid, fumaric acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, adipic acid, sebacic acid, butyric acid, Examples include oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, phthalic acid, sulfonic acid, tartaric acid, trifluoromethanesulfonic acid and the like. Examples of the inorganic acid include hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid, and hydrofluoric acid. Among these, formic acid, acetic acid, hydrochloric acid, and nitric acid are preferable from the viewpoint of catalytic activity.

  Examples of organic bases include quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide, and amines such as ammonia, triethylamine, and pyridine. Can be mentioned. Examples of the inorganic base include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide. Among these, tetramethylammonium hydroxide, sodium hydroxide, and potassium hydroxide are preferable from the viewpoint of catalytic activity.

  As a compounding quantity of a catalyst, 0.05-5 weight part is preferable with respect to 100 weight part of raw material silane compounds.

  Moreover, you may use a solvent as needed, for example, alcohols, such as methanol, ethanol, isopropyl alcohol, aromatic hydrocarbons, such as toluene, xylene, benzene, chlorobenzene, methylene chloride, chloroform, dichloroethylene, trichloroethylene. , Halogenated hydrocarbons such as trichloroethane, ethers such as tetrahydrofuran, 1,4-dioxane, diethyl ether, dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, Examples include esters such as ethyl acetate and butyl acetate, and other solvents such as dimethylformamide and dimethyl sulfoxide. These solvents can be used alone or in admixture of two or more.

  After the hydrolysis and condensation, the reaction mixture is appropriately diluted with a solvent, and then the reaction catalyst is removed from the reaction system by conventional methods such as washing with water, adsorbent treatment, and filtration to obtain a solution of the desired resin mixture. I can do it. Further, by removing the solvent from the solution of the resin mixture, a desired resin mixture from a semi-liquid state to a solid state can be obtained.

  The structure obtained mainly by this reaction (for example, 80% by weight or more in the resin mixture, preferably 90% or more, more preferably 95% or more) is a ladder type or a random type. Secondary or incompletely-shaped silicon resin may be contained in the resin mixture.

  The nanofiber in the present invention is chitin or chitosan nanofiber. The chitosan nanofiber is preferably a nanofiber in which the surface of the chitin nanofiber is converted to chitosan (referred to herein as a surface chitosanized chitin nanofiber). Nanofibers are expressed in nanometers in diameter and are 1 micron or thinner, but generally have a thickness of about 1 nm to 100 nm and an aspect ratio of 100 or more. It is understood by those skilled in the art that it indicates. In the present specification, the term “nanofiber” means a fiber having a diameter of 1 to 100 nm and an aspect ratio of 100 or more. Although the chitin or chitosan nanofiber in the present invention depends on the production method, the diameter is preferably 5 to 50 nm, more preferably 10 to 20 nm. The aspect ratio is preferably 100 to 1000, and the lower limit is more preferably 500 or more.

  Chitin is an amino polysaccharide mainly composed of N-acetyl-D-glucosamine, and chitin nanofibers are formed by forming extended chain crystals in which dozens to hundreds of chitin chains are arranged in parallel. . Chitosan contains D-glucosamine as a main constituent, and can be generally obtained by treating chitin with an alkali to remove acetyl groups in N-acetyl-D-glucosamine units. Surface chitosanized chitin nanofibers are prepared by subjecting chitin to alkali treatment and then defibration. The surface of surface chitosanized chitin nanofibers is converted to chitosan, but the inside retains the crystal structure of chitin nanofibers.

  Specifically as a manufacturing method of chitin nanofiber, the method described below can be mentioned, for example. That is, a chitin-containing material that exists in nature is prepared as a raw material, and chitin nanofibers are isolated. As the chitin-containing material, materials derived from the animal kingdom, fungal kingdom, and plant kingdom can be used, and examples thereof include outer shells or shells of crabs, shrimps, insects, molds, mushrooms, algae and the like. Crab and shrimp shells are often handled as industrial waste, and are preferred as starting materials from the viewpoint of easy availability and effective use. In the case of using crab shell as a raw material, chitin is first purified by sequentially treating with 1N hydrochloric acid, 2N sodium hydroxide, and ethanol. Next, acetic acid is added to the purified crab shell (chitin), and the fiber is defibrated with a grinder or homogenizer. Specifically, for example, purified chitin is dispersed in water, acetic acid is added, and then defibrated using, for example, a super mascolloider (manufactured by Masuko Sangyo) to obtain chitin nanofibers. The acid is not limited to acetic acid, and various organic and inorganic acids may be used. In addition, since it is important to apply a physical load to the defibrating process, not only the super mass collider but various homogenizers such as an ultrasonic homogenizer and a high-speed blender can be used. Thus, chitin nanofibers having a diameter of 10 to 20 nm can be obtained. In the treatment using such naturally-derived chitin-containing material, a method of performing a series of treatments in an undried state without drying the chitin in the production process may be used, or the chitin is dried at the stage of purification and acquisition. It is good also as a target of defibration processing. By once drying chitin after purification, it is advantageous in terms of storage and transportation, and production costs can be reduced. Moreover, even if dry chitin is defibrated, sufficiently high quality chitin nanofibers can be obtained according to the method using acetic acid.

  Examples of the method for producing chitosan nanofibers include a method in which purified chitin is heated in a sodium hydroxide aqueous solution. When the concentration of sodium hydroxide is 40% or more, it does not stop on the chitin surface, but deacetylation proceeds to the inside, which is disadvantageous because chitin is dissolved, crystallinity is lowered, various physical properties are lowered, and the like. Therefore, the concentration of sodium hydroxide is preferably about 5 to 30%, more preferably about 20 to 30%. After deacetylation-treated chitin is dispersed in water and acetic acid is added, for example, super-mass colloider (manufactured by Masuko Sangyo) is used for defibration to prepare surface chitosanized chitin nanofibers.

  Examples of the form of chitin or chitosan nanofibers include non-woven fabrics, flakes, and powders.

  In the composite material of the present invention, the blending ratio of the silicon resin mixture to the nanofiber is preferably 10:90 to 90:10, more preferably 30:70 to 80:20, by weight. If the nanofiber is less than 10 in weight ratio, the linear expansion coefficient becomes large, and if it exceeds 90 in weight ratio, the mechanical strength of the composite material of the present invention decreases.

  In the present invention, the silicon resin mixture may not contain a curing group, but may contain a curing group. When it contains a curing group, a curing catalyst and, if necessary, a curing catalyst can be used, or a polymerization initiator can be blended without using a curing agent. In the case of a composition containing a polymerization initiator and not containing a curing agent, the proportion of the silicone resin mixture in the composition can be made higher than the composition containing the curing agent component, and no curing agent is contained. Therefore, there is an advantage that the characteristics of the silicon resin are easily exhibited. On the other hand, in the case of a composition containing a curing agent and not containing a polymerization initiator, the type of the curing agent is selected to improve the curability of the composition. There is an advantage that it is easy to adjust.

  The polymerization initiator may be a compound that acts as an initiator for ring-opening polymerization of a cyclic ether group or radical polymerization of an unsaturated bond. For example, there is a cationic polymerization initiator of a cyclic ether group, specifically, Quaternary ammonium salts, tertiary amine salts, phosphonium salts, sulfonium salts, diazonium salts, iodonium salts, and the like. Examples of unsaturated bond radical polymerization initiators include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, xanthone compounds, α-aminoalkylphenone compounds, and the like.

  Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, and the like.

  Examples of the tertiary amine salt include N, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-dimethyl-N-benzyl. Anilinium tetrafluoroborate, N, N-diethyl-N-benzyltrifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl-N- (4- And methoxybenzyl) toluidinium hexafluoroantimonate.

  Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the sulfonium salt include Optomer SP150, Optomer SP170, Optomer SP172, Adeka Opton CP-66, Adeka Opton CP-77, Sunshine SI-80L, Sanade Chemical SI manufactured by Asahi Denka Kogyo Co., Ltd. -100L, CYRACURE made by Union Carbide Corporation
UVI-6974 etc. are mentioned.

  Examples of the diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate, and the like.

  Examples of the iodonium salt include diphenyliodonium hexafluoroarsinate, bis (4-chlorophenyl) iodonium hexafluoroarsinate, bis (4-bromophenyl) iodonium hexafluoroarsinate, phenyl (4-methoxyphenyl) iodonium hexafluoro. Examples include alginate.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Specific examples of the acetophenone compound include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxy-cyclohexyl-phenyl- Examples include ketones.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.

  Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

  Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide. Etc.

  Specific examples of the α-aminoalkylphenone compound include, for example, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1 and the like.

  The said polymerization initiator may be used independently or may use 2 or more types together.

  Among these, a sulfonium salt is preferable as the polymerization initiator.

  The amount of the polymerization initiator is usually 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight per 100 parts by weight of the silicon resin mixture, although it depends on the amount of the cyclic ether group of the silicone resin mixture. Part by weight is more preferred.

  The said hardening | curing agent says the compound containing the functional group which can react with a cyclic ether group. As such a compound, various compounds known as an epoxy resin curing agent can be used. For example, acid anhydrides (for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydro Phthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or a mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, anhydrous Nadic acid, methyl nadic acid anhydride, etc.), phenol compounds (for example, bisphenol compounds such as bisphenol A and bisphenol F, novolac resins such as phenol novolac, cresol novolac and bisphenol A type novolac resins, 2- (4- (1,1- Scan (4-hydroxyphenyl) ethyl) phenyl) -2- (4-hydroxyphenyl) tris phenolic compounds such as propane) and the like.

  The compounding amount of the curing agent is an epoxy group 0.5 to 1 mol per 1 mol of a reactive functional group of the curing agent (for example, an acid anhydride group for an acid anhydride, a phenolic hydroxyl group for a phenol compound). 2.0 mol is preferable, and more preferably 0.8 to 1.3 mol.

  Examples of the curing catalyst include imidazole compounds, tertiary amines, organic phosphine compounds, or salts thereof. Specifically, for example, as imidazole compounds, 2-methylimidazole, 2-ethylimidazole, 4-methylimidazole, 4-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4 -Hydroxymethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. Can be mentioned. Organic phosphorus compounds can also be used, and specific examples thereof include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, tri (p-toluyl) phosphine, tri Triorganophosphine compounds such as (p-methoxyphenyl) phosphine, tri (p-ethoxyphenyl) phosphine, triphenylphosphine / triphenylborane, tetraphenylphosphonium bromide (TPP-PB), tetraphenylphosphonium / tetraphenylborate, etc. And organophosphines such as quaternary phosphonium salts and derivatives thereof. Examples of tertiary amines include triethylamine, dimethylethanolamine, dimethylbenzylamine, 2,4,6-tris (dimethylamino) phenol, 1,8-diazabicyclo [5,4,0] undecene. These compounds can be used alone or in combination of two or more.

  The addition amount of the curing catalyst is, for example, preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the compound containing a cyclic ether group in the curable resin composition. preferable.

  The composites of the present invention do not exclude the presence of a class of materials that do not adversely affect the effects of the present invention or amounts of other materials that do not adversely affect the effects of the present invention.

  Examples of the types of substances that do not adversely affect the effects of the present invention include, for example, adjusting the crosslinking density of a cured product obtained from the curable composition, and reactivity such as epoxy groups and unsaturated bonds in the curable composition. Examples thereof include an epoxy resin and a (meth) acrylate compound for achieving the purpose of adjusting the content of the functional group.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy. Examples thereof include resins and fluorene skeleton-containing epoxy resins. The blending amount is generally 5 to 50 parts by weight per 100 parts by weight of the resin component.

  The (meth) acrylate compound is not particularly limited, and examples thereof include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. 1,4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, poly (butanediol) di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, triisopropylene glycol di (meth) acrylate, poly Ethylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, di (meth) acrylate of bisphenol A ethylene oxide adduct, trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, trimethylol Propanetriethoxytri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol (monohydroxy) penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, urethane (meth) acrylate, and the like. These (meth) acrylic compounds may be used alone or in combination of two or more. As a compounding quantity of such a (meth) acrylate compound, it is 5-200 weight part per 100 weight part of silicon resin mixtures.

  As said urethane acrylate, the compound obtained by making hydroxy group containing (meth) acrylate and polyisocyanate react can be mentioned, for example. Here, examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and pentaerythritol tris. Examples include acrylate, dipentaerythritol pentaacrylate, and trimethylolpropane diacrylate. These hydroxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The polyisocyanate may be any of aliphatic, aromatic and alicyclic polyisocyanates, such as methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate. , Isophorone diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, methylenebisphenyl diisocyanate, and the like. These polyisocyanates may be used alone or in combination of two or more. Of these polyisocyanates, those that are non-yellowing urethanes are preferred.

  As the urethane (meth) acrylate, various commercially available products can be used. As a commercial item of urethane (meth) acrylate, for example, EBECRYL series (manufactured by Daicel Cytec Co., Ltd.), purple light series (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), New Frontier R-1000 series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ), UA-306H, UF-8001 (manufactured by Kyoeisha Chemical Co., Ltd.), NK oligo U series, NK oligo UA series (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

  The composite material of the present invention can be produced by impregnating nanofibers with a resin component obtained by mixing the above-described components. The viscosity of the curable resin composition is preferably 1000 to 5000 cP at 25 ° C. Moreover, as hardening conditions, 120-180 degreeC and 1 to 5 hours are preferable. Moreover, in the case of resin which does not have a hardening group, it is preferable to heat-process for 150-200 degreeC and 3 to 12 hours.

  The composite material of the present invention contains nanofibers in a silicone resin mixture, which is a transparent resin, and chitin or chitosan nanofibers are extended chains as described above, so there are few structural defects as fibers, Since it is excellent in strength, expansion, and heat resistance, the composite material is excellent in mechanical strength, heat resistance, expansion, weather resistance, UV resistance, and the like. In addition, since the diameter of the nanofiber is sufficiently smaller than the wavelength of visible light, light scattering hardly occurs at the fiber interface, and high transparency can be achieved without strictly matching the refractive index with the resin. Very high transparency can be achieved in a much wider range of refractive indices than chitin-containing transparent materials. Moreover, it is excellent in the surface smoothness of a composite material by mix | blending nanofiber.

  The composite material of the present invention can have an appropriate shape such as a plate shape or a film shape. Preferably, it is a sheet having a thickness of 0.02 to 2.0 mm. In the composite material of the present invention, the haze value of a sheet having a thickness of 0.05 to 1.2 mm is preferably 5% or less, more preferably 2.5% or less. In the composite material of the present invention, the total visible light transmittance of a sheet having a thickness of 0.05 to 1.2 mm is preferably 90% or more. The haze value is the ratio of the scattered light component to the total transmitted light. These values are values obtained by an integrating sphere light transmittance measuring device according to JIS K 7105 when the values differ depending on the measurement method.

  Applications of the composite material of the present invention include various transparent resin substrates and transparent resin sheets, such as display element transparent substrates, color filter substrates, touch panels and electronic paper transparent resin sheets used for LCD, PDP, organic EL, etc. And a solar cell module plate material and a solar cell element encapsulating resin sheet. Moreover, it is used suitably for uses, such as a structural material, for example, the window material or ceiling material for vehicles.

Hereinafter, the present invention will be described more specifically by way of examples. The abbreviations in the table are as follows.
SQ epoxy 1: silsesquioxane derivative (SQ-1) obtained in Synthesis Example 1
SQ epoxy 2: Silsesquioxane derivative (SQ-2) obtained in Synthesis Example 2
SQ epoxy 3: Silsesquioxane derivative (SQ-3) obtained in Synthesis Example 3
SQ epoxy 4: Silsesquioxane derivative (SQ-4) obtained in Synthesis Example 4
SQ epoxy 5: Silsesquioxane derivative (SQ-5) obtained in Synthesis Example 5
SQ epoxy 6: Silsesquioxane derivative (SQ-6) obtained in Synthesis Example 6
SQ epoxy 7: Silsesquioxane derivative (SQ-7) obtained in Synthesis Example 7
SQ acrylic 1: silsesquioxane derivative (SQ-8) obtained in Synthesis Example 8
AER-260: Bisphenol A type epoxy resin (Asahi Kasei Corporation)
YX-8000: Hydrogenated bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)
DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
EBCRYL 9270: Urethane acrylate resin (manufactured by Daicel Cytec Co., Ltd.)
MH-700: alicyclic acid free product (manufactured by Shin Nippon Rika Co., Ltd.)
TPP-PB: Tetraphenylphosphonium bromide (Hokuko Chemical Co., Ltd.)
TrisP-PA: Trisphenol methane resin (Honshu Chemical Industry Co., Ltd.)
TPP: Triphenylphosphine (Hokuko Chemical Co., Ltd.)
SI-100L: Aromatic sulfonium salt (manufactured by Sanshin Chemical Industry Co., Ltd.)
CP-66: Trialkylsulfonium salt (manufactured by ADEKA Corporation)
Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Japan Co., Ltd.)
Irgacure 907: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Japan Co., Ltd.)
Nanofiber: Non-woven fabric E glass cloth with a thickness of 100 μm prepared by suction filtration of a chitin nanofiber suspension obtained by the above-described production method with a 0.5 μm membrane: manufactured by Nittobo Co., Ltd., woven fabric, thickness 100 μm
NE glass cloth: Nitto Boseki Co., Ltd., woven fabric, thickness 100 μm
T glass cloth: manufactured by Nitto Boseki Co., Ltd.
E glass filler: Asahi Kasei E-materials, powder, average particle size 0.8μm
EPCy: 2- (3,4-epoxycyclohexyl) ethyl group Gly: glycidoxypropyl group Ph: phenyl group Hexyl: hexyl group i-Butyl: isobutyl group Mac: 3-methacryloyloxypropyl group

Synthesis Example 1: Synthesis of Silsesquioxane Derivative (SQ-1) In a reaction vessel equipped with a stirrer and a thermometer, 200 g of methyl isobutyl ketone (MIBK) and 13.4 g of a 20% aqueous solution of tetramethylammonium hydroxide (water After adding tetramethylammonium oxide 0.03 mol) and distilled water 37.8 g (2.7 mol), 110.8 g (0.46 mol) 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, phenyltrimethoxy 89.2 g (0.45 mol) of silane was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 200 g of MIBK was added to the system, and further washed with 100 g of distilled water until the pH of the aqueous layer became neutral. Next, the MIBK layer was washed twice with 100 g of distilled water, and then MIBK was distilled off under reduced pressure to obtain 137 g of a silsesquioxane derivative (SQ-1).

Synthesis Example 2: Synthesis of silsesquioxane derivative (SQ-2) In a reaction vessel equipped with a stirrer and a thermometer, 200 g of methyl isobutyl ketone (MIBK) and 13.3 g of 20% aqueous solution of tetramethylammonium hydroxide (water After charging tetramethylammonium oxide (0.03 mol) and distilled water (37.4 g, 2.7 mol), 3-glycidoxypropyltrimethoxysilane (147.1 g, 0.62 mol), phenyltrimethoxysilane (52.9 g) 0.27 mol) was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 200 g of MIBK was added to the system, and further washed with 100 g of distilled water until the pH of the aqueous layer became neutral. Next, the MIBK layer was washed twice with 100 g of distilled water, and then MIBK was distilled off under reduced pressure to obtain 138 g of a silsesquioxane derivative (SQ-2).

Synthesis Example 3 Synthesis of Silsesquioxane Derivative (SQ-3) In a reaction vessel equipped with a stirrer and a thermometer, 200 g of methyl isobutyl ketone (MIBK) and 15.0 g of 20% aqueous solution of tetramethylammonium hydroxide (water After charging tetramethylammonium oxide (0.03 mol) and distilled water (42.3 g, 3.0 mol), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (74.4 g, 0.30 mol), isobutyltrimethoxy 125.6 g (0.70 mol) of silane was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 200 g of MIBK was added to the system, and further washed with 100 g of distilled water until the pH of the aqueous layer became neutral. Next, the MIBK layer was washed twice with 100 g of distilled water, and then MIBK was distilled off under reduced pressure to obtain 141 g of a silsesquioxane derivative (SQ-3).

Synthesis Example 4: Synthesis of Silsesquioxane Derivative (SQ-4) In a reaction vessel equipped with a stirrer and a thermometer, 200 g of methyl isobutyl ketone (MIBK) and 13.5 g of 20% aqueous solution of tetramethylammonium hydroxide (water After charging tetramethylammonium oxide (0.03 mol) and distilled water (38.1 g, 2.7 mol), 3-glycidoxypropyltrimethoxysilane (108.3 g, 0.46 mol), phenyltrimethoxysilane (71.8 g, 0.36 mol) was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 200 g of MIBK was added to the system, and further washed with 100 g of distilled water until the pH of the aqueous layer became neutral. Next, the MIBK layer was washed twice with 100 g of distilled water, and then MIBK was distilled off under reduced pressure to obtain 138 g of a silsesquioxane derivative (SQ-4).

Synthesis Example 5: Synthesis of silsesquioxane derivative (SQ-5) In a reaction vessel equipped with a stirrer and a thermometer, 200 g of methyl isobutyl ketone (MIBK) and 12.5 g of a 20% aqueous solution of tetramethylammonium hydroxide (water Tetramethylammonium oxide (0.03 mol) and distilled water (35.3 g, 2.5 mol) were charged, then 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (165.4 g, 0.67 mol), hexyltrimethoxy 34.6 g (0.17 mol) of silane was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 200 g of MIBK was added to the system, and further washed with 100 g of distilled water until the pH of the aqueous layer became neutral. Next, the MIBK layer was washed twice with 100 g of distilled water, and then MIBK was distilled off under reduced pressure to obtain 141 g of a silsesquioxane derivative (SQ-5).

Synthesis Example 6 Synthesis of Silsesquioxane Derivative (SQ-6) In a reaction vessel equipped with a stirrer and a thermometer, 200 g of methyl isobutyl ketone (MIBK) and 14.3 g of 20% aqueous solution of tetramethylammonium hydroxide (water Tetramethylammonium oxide (0.03 mol) and distilled water (40.5 g, 2.9 mol) were charged, then 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (108.3 g, 0.19 mol), phenyltrimethoxy 152.6 g (0.77 mol) of silane was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 200 g of MIBK was added to the system, and further washed with 100 g of distilled water until the pH of the aqueous layer became neutral. Next, the MIBK layer was washed twice with 100 g of distilled water, and then MIBK was distilled off under reduced pressure to obtain 131 g of a silsesquioxane derivative (SQ-6).

Synthesis Example 7: Synthesis of Silsesquioxane Derivative (SQ-7) In a reaction vessel equipped with a stirrer and a thermometer, 200 g of methyl isobutyl ketone (MIBK) and 14.7 g of a 20% aqueous solution of tetramethylammonium hydroxide (water) After charging tetramethylammonium oxide (0.03 mol) and distilled water (41.6 g, 3.0 mol), 3-glycidoxypropyltrimethoxysilane (23.4 g, 0.10 mol) and phenyltrimethoxysilane (176.6 g, 0.89 mol) was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 200 g of MIBK was added to the system, and further washed with 100 g of distilled water until the pH of the aqueous layer became neutral. Next, the MIBK layer was washed twice with 100 g of distilled water, and then MIBK was distilled off under reduced pressure to obtain 130 g of a silsesquioxane derivative (SQ-7).

Synthesis Example 8: Synthesis of Silsesquioxane Derivative (SQ-8) In a reaction vessel equipped with a stirrer and a thermometer, 200 g of methyl isobutyl ketone (MIBK) and 12.6 g of 20% aqueous solution of tetramethylammonium hydroxide (water) After charging tetramethylammonium oxide (0.028 mol) and distilled water (41.6 g, 3.0 mol), 3-methacryloyloxypropyltrimethoxysilane (158.0 g, 0.64 mol), phenyltrimethoxysilane (42.0 g) ( 0.21
mol) was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 200 g of MIBK was added to the system, and further washed with 100 g of distilled water until the pH of the aqueous layer became neutral. Next, the MIBK layer was washed twice with 100 g of distilled water, and then MIBK was distilled off under reduced pressure to obtain 132 g of a silsesquioxane derivative (SQ-8).

Production Example: Preparation of Nanofiber Distilled water was added to chitin powder derived from crab shell (manufactured by Nacalai Tesque) to make a 1 wt% chitin suspension, and the pH was adjusted to 3 by adding acetic acid while stirring. Next, nanofibers with a concentration of 1% are obtained by defibrating the suspension using a stone mill grinder MKCA6-3 (manufactured by Masuko Sangyo Co., Ltd.) (rotation speed of grinding wheel: 1500 rpm, number of passes: 1 to 2 times). Got. When SEM measurement was performed, the fiber width of the nanofiber was 10-20 nm. Furthermore, the obtained nanofiber suspension was subjected to suction filtration under reduced pressure with a 0.5 μm hydrophilic PTFE membrane filter (manufactured by Toyo Roshi Kaisha, Ltd., product name: T050A047A) to obtain sheet-like nanofibers. Furthermore, the obtained sheet-like nanofiber was dried with a 60 ° C. dryer for 12 hours to obtain a nanofiber sheet having a thickness of 100 μm.

Examples 1-5, Comparative Examples 1-4
Each component was mixed by the mixing | blending of Table 1, and the resin composition was obtained. This is a nanofiber (obtained in the above production example. In Table 1, for convenience, expressed as a nanofiber) or glass fiber, at a temperature of 25 ° C., 10 parts by weight of the nanofiber or glass fiber is a resin composition 10. A transparent composite material having a thickness of 0.1 mm was obtained by impregnation at a weight ratio and curing at 150 ° C. for 3 hours.

Comparative Example 5
Each component was mixed by the mixing | blending of Table 1, and the resin composition was obtained. A transparent composite material having a thickness of 0.1 mm is obtained by impregnating 10 parts by weight of the nanofiber with 10 parts by weight of the resin composition and curing it with an exposure amount of 1000 mJ / cm ² (UVH-1500M; manufactured by USHIO). Got.

  About each transparent composite material, refractive index, total light transmittance, haze value, linear expansion coefficient, plane roughness, and bending resistance were measured by the following methods. The results are shown in Table 1.

Evaluation method Total light transmittance: Measured with a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.) in accordance with JIS K 7105, measurement method A.
Haze value: Measured with a haze meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K 7105.
Linear expansion coefficient: Using an SS120C type thermal stress strain measuring device (manufactured by Seiko Electronics Co., Ltd.), the temperature is raised from 30 ° C. to 400 ° C. at a rate of 5 ° C. per minute and held for 20 minutes, and 30 to 150 ° C. The value at the time of was measured.
Refractive index, Abbe number: Based on JIS K 7105, measured with an Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.).
Planar roughness: Measured with a stylus type surface shape measuring device Dektak 6M (manufactured by ULVAC, Inc.).
Bending resistance: An operation of holding both ends of a test piece (width 10 mm × length 70 mm) by hand and bending the test piece to return to the original state was repeated 30 times. It was verified whether a crease or a tear occurred in the test piece. Evaluation was made according to the following criteria.
○: When the appearance was not changed at all after 30 repeated operations ×: When a tear occurred during the 30 repeated operations

Examples 6-9
Each component was mixed by the mixing | blending of Table 2, and the resin composition was obtained. This was impregnated with 10 parts by weight of a nanofiber (obtained in the above-mentioned production example. In Table 2, for convenience, it was indicated as nanofiber) at a ratio of 10 parts by weight of the resin composition, and then this was coated with a smooth glass plate. By sandwiching and curing with a UV irradiation device (20 J / cm 2, device name; Spot Cure SP-7, manufactured by USHIO), a transparent composite material having a thickness of 0.1 mm was obtained.

Comparative Example 6
Each component was mixed by the mixing | blending of Table 2, and the resin composition was obtained. This is sandwiched between smooth glass plates provided with spacers, and cured with a UV irradiation device (20 J / cm 2, device name; Spot Cure SP-7, manufactured by USHIO) to obtain a transparent resin cured product having a thickness of 0.1 mm. Obtained.

  About each composite material of Examples 6-9 and transparent resin hardened | cured material of the comparative example 6, the measurement of the refractive index, 600 nm spectral transmittance, thermal decomposition temperature, tensile strength, Young's modulus, and a linear expansion coefficient was measured with the following method. . The results are shown in Table 2.

Evaluation method Refractive index: Measured with an Abbe refractometer DR-A2 (manufactured by Atago Co., Ltd.) at room temperature.
600 nm spectral transmittance: The transparency of the sample was evaluated with 600 nm light using an ultraviolet-visible spectrophotometer V-550 (manufactured by JASCO).
Thermal decomposition temperature: The thermal decomposition temperature of the sample was evaluated using a differential thermobalance TG 8120 (manufactured by Rigaku) in an argon gas atmosphere. The weight of the sample to be measured is 5 mg, and the heating rate is 10 ° C./min.
Tensile strength and Young's modulus: The breaking strength (tensile strength MPa) and Young's modulus (elastic modulus GPa) of the sample were measured using a precision universal testing machine Autograph AG-X (manufactured by Shimadzu Corporation). The capacity of the load cell is 50 kN, the test speed is 1 mm / min, and the size of the test piece is 1 cm × 5 cm.
Linear expansion coefficient (ppm): The thermal expansion coefficient of the sample was evaluated under an argon gas atmosphere using a thermomechanical measurement apparatus (TMA) Q400 (manufactured by TA Instruments). The measurement temperature range is 30 to 160 ° C., the temperature raising rate is 5 ° C./min, and the size of the test piece is 3 mm × 30 mm.

From the result of the said table | surface, it was clear that the composite material of this invention has excellent transparency, mechanical strength, and a low linear expansion coefficient in the wide range whose resin refractive index is 1.512-1.547. And from the result with a high light transmittance and a haze value significantly lower than that of the comparative example, it was proved that Rayleigh scattering can be suppressed and the transparency is high. Further, from the experimental results (Table 2) of the transparent composite material using the (meth) acrylic compound, the transparent composite material of the present invention is excellent in transparency, tensile strength and Young's modulus are improved, and the strength is excellent. The rate was low and proved to be excellent in dimensional stability.

Claims (12)

Hydrolysis and condensation of alkoxysilane containing at least trifunctional or chlorosilane containing at least trifunctional under acidic or alkaline conditions, and a silicone resin mixture comprising the resulting reaction mixture is converted into chitin nanofiber and chitosan nanofiber. A nanofiber reinforced transparent composite material impregnated with at least one nanofiber selected from the above, wherein the silicone resin mixture is selected from the group consisting of epoxy groups, 3,4-epoxycyclohexyl groups and oxetanyl groups A trifunctional alkoxysilane or a trifunctional chlorosilane having at least one unsaturated bond-containing group selected from the group consisting of at least one cyclic ether group or methacryl group, acrylic group and vinyl group 1 in alkoxysilane compounds At least one cyclic ether group selected from the group consisting of an epoxy group, a 3,4-epoxycyclohexyl group, and an oxetanyl group, or methacrylic acid, obtained by using ~ 100% by weight or 10% to 100% by weight in the raw material chlorosilane compound A polysiloxane mixture having a ladder-type or random-type structure having a weight average molecular weight of 1500 to 30000 having at least one unsaturated bond-containing group selected from the group consisting of a group, an acrylic group and a vinyl group, and further curing The composite material comprising an agent or a polymerization initiator.
The polysiloxane mixture has a ladder-type or random-type structure having a weight average molecular weight of 1500 to 30000 having at least one cyclic ether group selected from the group consisting of an epoxy group, a 3,4-epoxycyclohexyl group, and an oxetanyl group. The composite of claim 1 which is a polysiloxane mixture.
The polysiloxane mixture is a polysiloxane mixture having a ladder-type or random-type structure having a weight average molecular weight of 1500 to 30000 having at least one unsaturated bond-containing group selected from the group consisting of methacrylic group, acrylic group and vinyl group The composite material according to claim 1.
Nanofibers composite according to any one of claims 1-3 chitin nanofibers. The composite material according to any one of claims 1 to 3 , wherein the nanofiber is chitosan nanofiber. The composite material according to any one of claims 1 to 5 , wherein the nanofiber has a diameter of 5 to 50 nm and an aspect ratio of 100 to 1000. The composite material according to any one of claims 1 to 6 , wherein the nanofiber is a nanofiber derived from dried chitin. The composite material according to any one of claims 1 to 7 , wherein a mixing ratio of the silicon resin mixture to the nanofiber is 10:90 to 90:10 by weight ratio. It is plate shape or film shape, The composite material in any one of Claims 1-8 . Display element transparent substrate using the composite material according to any one of claims 1-9. Structure material using the composite material according to any one of claims 1-9. The structural material according to claim 11, which is a window material or a ceiling material for a vehicle.