KR20120083875A - Transparent composite sheet - Google Patents

Abstract

The present invention provides a transparent composite sheet with little deformation in perspective. The transparent composite sheet which concerns on this invention contains a transparent resin hardened | cured material and the glass cloth embedded in the said transparent resin hardened | cured material. In the transparent composite sheet according to the present invention, the image sharpness defined in JIS K7374 is 50% or more at an optical comb width of 0.125 mm.

Description

Transparent composite sheet {TRANSPARENT COMPOSITE SHEET}

TECHNICAL FIELD The present invention relates to a transparent composite sheet containing a cured transparent resin and a glass cloth embedded in the cured transparent resin, and more particularly, to a transparent composite sheet having less deformation in perspective.

Glass substrates are widely used for substrates for display elements such as liquid crystal display elements or organic EL display elements, and substrates for solar cells. However, there is a problem that the glass substrate is fragile, has low flexibility, and cannot be reduced in weight. For this reason, using a plastic substrate instead of a glass substrate is examined in recent years.

However, conventional plastic substrates may have a thermal expansion coefficient about 10 to 20 times larger than glass. When a display element or a solar cell is manufactured using a plastic substrate having a large coefficient of thermal expansion, in the heating and cooling step for forming a semiconductor layer, a color filter layer, or the like, the thermal expansion coefficient of the plastic substrate and the semiconductor inorganic film or the conductive inorganic film is determined. Due to the difference, cracks may occur in the inorganic film. In addition, when a display element is manufactured using a plastic substrate having a large coefficient of thermal expansion, the dimensions of the plastic substrate may change greatly in accordance with the temperature variation in the manufacturing process, which may make it difficult to align the mask in the photolithography process. .

In order to make a coefficient of thermal expansion low, the following patent document 1 discloses the plastic substrate obtained by apply | coating, impregnating, and drying a resin composition to glass cloth.

Japanese Patent Laid-Open No. 2004-151291

In the plastic substrate of patent document 1, when hardening a resin composition by impregnating and drying a resin composition in a glass cloth, the unevenness which reflected the fiber shape of the glass cloth on the surface of a plastic board | substrate easily arises by hardening shrinkage of a resin composition. . For this reason, there exists a problem that a deformation | transformation arises in the permeation | transmission phase visually recognized through a plastic substrate.

An object of the present invention is to provide a transparent composite sheet with little deformation in perspective.

According to a broad aspect of the present invention, there is provided a transparent composite sheet containing a cured transparent resin and a glass cloth embedded in the cured transparent resin, wherein the image sharpness defined in JIS K7374 is 50% or more at an optical comb width of 0.125 mm. do.

In a particular aspect of the transparent composite sheet according to the present invention, the glass cloth is formed by glass fiber single yarn having a filament diameter of 3 to 10 µm, a Tex number of 10 to 20, and a twist number of 2 / inch or less, The glass cloth is a glass cloth that has been opened to a woven fabric having a density of 40 to 70 pieces / inch of warp and weft so as to have an opening degree of the following formula (X) in a range of 2 to 4.

<Equation X>

Opening degree = diameter of the yarn width / glass fiber single yarn of the fiber bundle in the glass cloth after opening processing

It is preferable that the refractive index difference between the said transparent resin hardened | cured material and the said glass cloth is 0.01 or less. It is preferable that the Abbe number of the said transparent resin hardened | cured material exists in the range of 35-50.

In another specific situation of the transparent composite sheet which concerns on this invention, the said transparent resin cured material is hardened | cured material of transparent resin containing the hydrolysis-condensation product of the thiol group containing silane compound represented by following General formula (1).

&Lt; Formula 1 >

R1Si (OR2) ₃

In the formula (1), R 1 represents an organic group having 1 to 8 carbon atoms having a thiol group and no aromatic ring, or an organic group having a thiol group and having an aromatic ring, and R 2 represents a hydrogen atom or an aromatic ring having 1 to 8 carbon atoms. An organic group or the organic group which has an aromatic ring is shown.

In another particular aspect of the transparent composite sheet according to the invention, the transparent resin further comprises a compound having a carbon-carbon double bond.

In another specific situation of the transparent composite sheet which concerns on this invention, the said transparent resin hardened | cured material is hardened | cured material of transparent resin containing the compound which has a fluorene skeleton.

In another specific aspect of the transparent composite sheet according to the present invention, the compound having a fluorene skeleton is a compound having a fluorene skeleton represented by the following formula (2) or (3).

<Formula 2>

In said Formula (2), R <3> -R <8> represents a hydrogen atom or a methyl group, respectively, and m1 and m2 represent 1 or 2, respectively.

<Formula 3>

In said Formula (3), R9-R12 represent a hydrogen atom or a methyl group, respectively, n1 and n2 represent the integer of 0-2, respectively.

In another specific aspect of the transparent composite sheet according to the present invention, the transparent resin further includes at least one of a compound having an epoxy group and a compound having an isocyanate group.

In another particular aspect of the transparent composite sheet according to the present invention, the compound having an epoxy group has a fluorene skeleton.

It is preferable that the fiber of the said glass cloth is E glass fiber or T glass fiber.

Since the transparent composite sheet which concerns on this invention contains a transparent resin hardened | cured material and the glass cloth embedded in the said transparent resin hardened | cured material, and the image sharpness defined by JISK7374 is 50% or more at 0.125 mm of optical comb width, Less deformation

Therefore, when the transparent composite sheet according to the present invention is used, in particular, as a substrate for a substrate or a touch panel of a display element such as a liquid crystal display element or an EL display element, good display with reduced deformation of an image can be obtained.

Hereinafter, the present invention will be described in detail.

MEANS TO SOLVE THE PROBLEM The present inventors examined reducing the unevenness | corrugation of the transparent composite sheet surface in order to reduce the deformation | transformation of the transparent image in the transparent composite sheet in which glass cloth is embedded in the transparent resin hardened | cured material. As a result, it was found that the deformation of the perspective image in the transparent composite sheet is not merely a lens effect due to irregularities on the surface. In addition, it was found that there is a distribution in the refractive index of the cured transparent resin in the vicinity of the glass fiber, and deformation of the transparent image occurs even when the transmitted light is distorted in accordance with the refractive index change of the cured transparent resin.

That is, the present inventors have found that the deformation of the transparent image in the transparent composite sheet is not improved only by flattening the surface of the sheet, but it is necessary to control the refractive index distribution of the cured transparent resin in the vicinity of the glass fiber. .

In addition, the present inventors found that in the transparent composite sheet having an image clarity defined in JIS K7374 having 50% or more at an optical comb width of 0.125 mm, the deformation of the transparent image is sufficiently small, and the transparent composite sheet is particularly displayed such as a liquid crystal display element or an EL display element. When used as a board | substrate of a device or a sheet | seat for touch panels, it discovered that the favorable display by which image distortion was reduced was obtained.

The transparent composite sheet concerning this invention contains the transparent resin hardened | cured material (A) and the glass cloth (b) embedded in the said transparent resin hardened | cured material (A). The transparent composite sheet which concerns on this invention can be formed using the transparent resin material which becomes a transparent resin hardened | cured material (A), and the transparent composite material containing a glass cloth (b). For example, a transparent composite sheet can be obtained by hardening a transparent composite material with at least 1 sort (s) of heating and irradiation of an actinic light. The transparent composite material can be obtained by, for example, impregnating the transparent resin (a) into the glass cloth (b).

Hereinafter, the detail of each component contained in the transparent composite sheet which concerns on this invention, and each component contained in the transparent composite material for obtaining the said transparent composite sheet is demonstrated.

(Transparent Resin (a) and Cured Resin (A))

The transparent resin (a) contained in the transparent composite material is not particularly limited as long as it is a transparent resin. Only 1 type may be used for transparent resin (a), and 2 or more types may be used together.

As said transparent resin (a), polyester resin, polyethylene resin, poly (meth) acrylic resin, polystyrene resin, polycarbonate resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, (meth) acrylic resin, epoxy resin And phenol resins, vinyl ester resins, polyimide resins, melamine resins, urea resins, silsesquioxane resins and allyl group-containing resins.

It is preferable that transparent resin (a) is liquid curable resin at room temperature (25 degreeC) before hardening. It is preferable that transparent resin (a) is at least 1 sort (s) chosen from the group which consists of a (meth) acrylic resin, an epoxy resin, a silsesquioxane resin, and an allyl group containing resin.

A (meth) acryl oligomer is mentioned as said (meth) acrylic resin which is liquid curable resin at room temperature before hardening. The (meth) acrylic resin is crosslinked and cured by heating and irradiation with active light. The hardened | cured material of the said (meth) acrylic resin has high transparency with respect to visible light. It is preferable that the said (meth) acrylic resin has two or more (meth) acryloyl groups.

As for the said (meth) acrylic resin, it is more preferable that it is (meth) acrylate which has alicyclic (meth) acrylate or cyclic ether structure. It is preferable that the said alicyclic (meth) acrylate resin is at least 1 sort (s) of norbornane dimethylol diacrylate and dicyclopentadienyl diacrylate. It is preferable that the (meth) acrylate which has the said cyclic ether structure is neopentyl glycol modified trimethylol propane diacrylate. By use of these preferable (meth) acrylic resins, transparency and heat resistance of a transparent composite sheet can be improved further. Only 1 type may be used for the said (meth) acrylic resin, and 2 or more types may be used together.

Said (meth) acryl represents acryl and methacryl. The said (meth) acrylate represents an acrylate and a methacrylate. The (meth) acryloyl represents acryloyl and methacryloyl.

As a method of crosslinking and hardening transparent resin (a), the method of heating, the method of irradiating an actinic light, and the method of heating and irradiating an active energy ray are mentioned. It is preferable that transparent resin (a) is resin hardened | cured by at least one of heating and irradiation of an actinic light.

When transparent resin (a) is (meth) acrylic resin or allyl-group containing resin, the method of irradiating actinic light is preferable. From the viewpoint of completing the curing reaction, a method of further heating after irradiation with actinic light is more preferable.

It is preferable that the said actinic light is an ultraviolet-ray. As a light source for irradiating this ultraviolet-ray, a metal halide type, a high pressure mercury lamp, etc. are mentioned, for example.

In order to crosslink and harden transparent resin (a) by irradiation of an actinic light, it is preferable that the said transparent composite material contains a photoinitiator. When transparent resin (a) is said (meth) acrylic resin or allyl-group containing resin, it is preferable that a photoinitiator is used. It is preferable that this photoinitiator is a photoinitiator which generate | occur | produces a radical. It is preferable that the said photoinitiator is added in transparent resin (a).

The photoinitiator is not particularly limited. As said photoinitiator, a benzophenone, N, N'- tetraethyl-4,4'- diamino benzophenone, 4-methoxy-4'- dimethylamino benzophenone, 2, 2- diethoxy aceto, are mentioned, for example. Phenone, benzoin, benzoin methyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl Phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1,2,6-dimethylbenzoyldiphenylphosphineoxide, 2,4,6-trimethylbenzoyldiphenylphosphineoxide, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone , 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2 -Phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenyl Imidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine and the like Can be mentioned. Only 1 type may be used for the said photoinitiator, and 2 or more types may be used together.

The minimum with preferable content of the said photoinitiator is 0.01 weight part, a more preferable minimum is 0.1 weight part, a preferable upper limit is 2 weight part, and a more preferable upper limit is 1 weight part with respect to 100 weight part of transparent resin (a). The more content of the said photoinitiator, the higher the sensitivity of a transparent composite material. When content of the said photoinitiator satisfy | fills the said preferable minimum, a transparent composite material can fully be hardened. When content of the said photoinitiator satisfy | fills the said preferable upper limit, hardening reaction will become difficult to advance rapidly, and it will become difficult to produce problems, such as the crack at the time of hardening, coloring of the hardened | cured resin transparent (A), etc ..

It is preferable to further heat-process at high temperature after crosslinking and hardening a transparent composite material by at least one of heating and irradiation of an actinic light. By heat processing, the linear expansion coefficient of a transparent composite sheet can be made low. It is preferable that the conditions of the said heat processing are conditions of 150-250 degreeC and 1 to 24 hours in nitrogen atmosphere or a vacuum state.

An epoxy resin can also be used as transparent resin (a). As said epoxy resin, a conventionally well-known epoxy resin can be used, for example, It is not specifically limited. As said epoxy resin, For example, epoxy resins, such as bisphenol A type, bisphenol F type, or bisphenol S type, novolak-type epoxy resins, such as a phenol novolak-type or cresol novolak-type, a triglycidyl isocyanurate type, or Dicyclo-types, such as nitrogen-containing cyclic epoxy resins, such as a hydantoin type, an alicyclic type epoxy resin, an aliphatic type epoxy resin, a naphthalene type epoxy resin, a glycidyl ether type epoxy resin, a biphenyl type epoxy resin, and a dicyclopentadiene type Epoxy resin, ester type epoxy resin, ether ester type epoxy resin, etc. are mentioned. Modified products of these epoxy resins can also be used. From the viewpoint of preventing discoloration of the transparent composite sheet, the epoxy resin is at least selected from the group consisting of bisphenol A epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate type epoxy resin and dicyclopentadiene type epoxy resin It is preferable that it is 1 type. Only 1 type may be used for the said epoxy resin, and 2 or more types may be used together.

In order to harden transparent resin (a), the said transparent composite material may contain the hardening | curing agent. It is preferable that a hardening | curing agent is used especially when transparent resin (a) is an epoxy resin. Only 1 type may be used for the said hardening | curing agent, and 2 or more types may be used together. It is preferable that the said transparent composite material contains at least 1 sort (s) of a photoinitiator and a hardening | curing agent.

As said hardening | curing agent, an organic acid compound, an amine compound, etc. are mentioned, for example. Tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc. are mentioned as said organic acid compound. Ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, metaphenylenediamine, diaminediphenylmethane, diaminodiphenylsulfonic acid, etc. are mentioned as said amine compound. Amine adducts of these amine compounds can also be used.

Moreover, as another hardening | curing agent, an amide compound, a hydrazide compound, an imidazole compound, an imidazoline compound, a phenol compound, a urea compound, a polysulfide compound, etc. are mentioned, for example.

Dicyandiamide, a polyamide, etc. are mentioned as said amide compound. Dihydrazet etc. are mentioned as said hydrazide compound. As said imidazole compound, methyl imidazole, 2-ethyl-4- methyl imidazole, ethyl di imidazole, isopropyl imidazole, 2, 4- dimethyl imidazole, phenyl imidazole, undecyl imida Sol, heptadecylimidazole, 2-phenyl-4-methylimidazole, and the like. As said imidazoline compound, methyl imidazoline, 2-ethyl-4-methyl imidazoline, ethyl imidazoline, isopropyl imidazoline, 2,4-dimethyl imidazoline, phenyl imidazoline, and undecyl are Midazoline, heptadecylimidazoline, 2-phenyl-4-methylimidazoline, and the like.

As said hardening | curing agent, an acid anhydride compound can also be used. By use of the said acid anhydride compound, discoloration of a transparent composite sheet can be prevented further. Examples of the acid anhydride compounds include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, nadic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methyltetrahydro. Phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnasic anhydride, dodecenyl succinic anhydride, dichlorosuccinic anhydride, benzophenonetetracarboxylic anhydride, chloric anhydride, and the like.

When using together the said epoxy resin and the said acid anhydride compound, content of an epoxy resin and a hardening | curing agent is not specifically limited. The minimum with equivalent equivalent of the acid anhydride of an acid anhydride compound is 0.5 equivalent with respect to 1 equivalent of epoxy groups of an epoxy resin, More preferably, 0.7 equivalent is preferable, an upper limit is 1.5 equivalent, and a more preferable upper limit is 1.2 equivalent. When the equivalent of the said hardening | curing agent satisfy | fills the said preferable minimum, coloring of a transparent composite sheet can fully be suppressed. If the equivalent of the said hardening | curing agent satisfy | fills the said preferable upper limit, moisture resistance of a transparent composite sheet will become favorable.

The transparent composite material may contain a curing accelerator. The said hardening accelerator is not specifically limited. As said hardening accelerator, tertiary amine, imidazole, quaternary ammonium salt, quaternary phosphonium salt, organometallic salt, phosphorus compound, urea compound, etc. are mentioned, for example. It is preferable that the said hardening accelerator is at least 1 sort (s) chosen from the group which consists of a tertiary amine, an imidazole, and a quaternary phosphonium salt. Only 1 type may be used for the said hardening accelerator, and 2 or more types may be used together.

Content of the said hardening accelerator is not specifically limited. The minimum with preferable content of the said hardening accelerator is 0.05 weight part, a more preferable minimum is 0.2 weight part, a preferable upper limit is 7.0 weight part, and a more preferable upper limit is 3.0 weight part with respect to 100 weight part of transparent resin (a). When content of the said hardening accelerator meets the said preferable minimum, a transparent composite material can be fully hardened. When content of the said hardening accelerator satisfy | fills the said preferable upper limit, coloring of a transparent composite sheet can be suppressed further.

It is preferable that transparent resin (a) contains the hydrolysis-condensation product (henceforth a hydrolysis-condensation product (a1)) of the thiol group containing silane compound represented by following General formula (1). It is preferable that a transparent resin hardened | cured material (A) is hardened | cured material of transparent resin containing a hydrolysis-condensation product. The hydrolysis condensate (a1) is a silsesquioxane resin. By use of a hydrolysis-condensation product (a1), transparency and heat resistance of a transparent composite material can be improved further.

&Lt; Formula 1 >

R1Si (OR2) ₃

In the formula (1), R 1 represents an organic group having 1 to 8 carbon atoms having a thiol group and no aromatic ring, or an organic group having a thiol group and having an aromatic ring, and R 2 represents a hydrogen atom or an aromatic ring having 1 to 8 carbon atoms. An organic group or the organic group which has an aromatic ring is shown.

Specifically as said R1, the C1-C8 aliphatic hydrocarbon group which has a thiol group, the C1-C8 alicyclic hydrocarbon group which has a thiol group, the aromatic hydrocarbon group which has a thiol group, etc. are mentioned. Specific examples of R2 include a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 1 to 8 carbon atoms, an aromatic hydrocarbon group, and the like. The "hydrocarbon group" in the case of having a thiol group is a group containing not only a carbon atom and a hydrogen atom, but also the sulfur atom derived from a thiol group. A plurality of said R2 may be the same and may differ.

Hydrolysis-condensation product (a1) can be obtained by hydrolyzing and condensing the component (henceforth a component (a11)) containing the thiol group containing silane compound represented by the said Formula (1). That is, a hydrolysis condensate (a1) can be obtained by a hydrolysis reaction and a condensation reaction.

As the thiol group-containing silane compound represented by the formula (1), 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltributoxy Silane, 1,4-dimercapto-2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl ) Butane, 1,4-dimercapto-2- (tributoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxy Silane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2-mercaptomethyl-3-mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2- Dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-dimercaptoethyltributoxysilane, and the like. Especially, since the reactivity of a hydrolysis reaction is high and it is easy to acquire, 3-mercaptopropyl trimethoxysilane is preferable. Only 1 type may be used for the thiol group containing silane compound represented by the said Formula (1), and 2 or more types may be used together.

When obtaining a hydrolysis-condensation product (a1), only 1 type may be used for the thiol group containing silane compound represented by the said Formula (1), and 2 or more types may be used together. In addition, when obtaining a hydrolysis-condensation product (a1), crosslinkable compounds other than the said thiol group containing silane compound can also be used. The hydrolysis-condensation product (a1) includes not only the thiol group-containing silane compound but also a thiol group-containing silane compound and a crosslinkable compound other than the thiol group-containing silane compound. The said component (a11) contains the thiol group containing silane compound represented by the said General formula (1), and the said crosslinkable compound used as needed.

Examples of the crosslinkable compound include trialkylalkoxysilane, dialkyldialkoxysilane, alkyltrialkoxysilane, tetraalkoxysilane, tetraalkoxytitanium and tetraalkoxyzirconium. Especially, a trialkyl alkoxysilane, a dialkyl dialkoxysilane, or tetraalkoxysilane is preferable. By use of these preferable crosslinkable compounds, the crosslinking density of a hydrolysis-condensation product (a1) can be easily adjusted. By use of the said alkyltrialkoxysilane, the number of the thiol groups contained in a hydrolysis-condensation product (a1) can be adjusted easily. By using tetraalkoxy titanium or tetraalkoxy zirconium, the refractive index of the hardened | cured material of a hydrolysis-condensation product (a1) becomes high. Only 1 type may be used for the said crosslinkable compound, and 2 or more types may be used together.

Examples of the trialkoxysilane include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane and triphenylethoxysilane. Examples of the dialkyl dialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane. And 3-mercaptopropylmethyldimethoxysilane. Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane. Examples of the tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like. Examples of the tetraalkoxy titanium include tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium and tetrabutoxytitanium. Examples of the tetraalkoxy zirconium include tetraethoxy zirconium, tetrapropoxy zirconium, tetrabutoxy zirconium and the like. Metal alkoxides other than these can also be used.

The catalyst used for the hydrolysis reaction at the time of obtaining a hydrolysis-condensation product (a1) can use a conventionally well-known catalyst, It does not specifically limit. Since the catalyst activity is high and also functions as a catalyst for the condensation reaction, the catalyst is preferably formic acid.

The lower limit of the content of the catalyst is preferably 0.1 parts by weight, more preferably 1 part by weight, more preferably 25 parts by weight, and more preferably 10 parts by weight based on 100 parts by weight of the component (a11). When the said preferable minimum of content of the said catalyst is satisfied, the said hydrolysis reaction fully advances and reaction time can be shortened. When content of the said catalyst satisfy | fills the said preferable upper limit, there exists a tendency for the storage stability of a transparent resin (a) to become high. In addition, the catalyst can be easily removed in subsequent processes.

The reaction temperature and reaction time of the said hydrolysis reaction can be arbitrarily set according to the reactivity of the said silane compound. The reaction temperature is usually 0 to 100 ° C, preferably 20 to 60 ° C. The reaction time is about 1 minute to 2 hours.

At the time of the said hydrolysis reaction, a solvent may be used and a solvent may not be used. The kind of the said solvent is not specifically limited. Only 1 type of solvents may be used, and 2 or more types may be used together. It is preferable that the said solvent used at the time of the said hydrolysis reaction is the same as the solvent used for a condensation reaction. When the reactivity of the said silane compound is low, it is preferable not to use a solvent at the time of the said hydrolysis reaction.

It is preferable to advance the said hydrolysis reaction so that [the number-of-moles of the hydroxyl group produced by the hydrolysis reaction] / [the total number-of-moles of the alkoxy group contained in component (a11)] (henceforth molar ratio A) is 0.5 or more. As for the said molar ratio A, it is more preferable that it is 0.8 or more. The condensation reaction proceeds not only between the hydroxyl groups produced by hydrolysis, but also between the hydroxyl groups and the remaining alkoxy groups. For this reason, it is preferable that the said molar ratio A is 0.5 or more.

In the said condensation reaction, water is produced | generated between the hydroxyl groups produced by hydrolysis, and alcohol is produced | generated further between a hydroxyl group and an alkoxy group. By this condensation reaction, the hydrolysis condensate (a1) is vitrified.

In the condensation reaction, a conventionally known condensation catalyst can be used. The formic acid has a high catalytic activity and acts not only as a catalyst for the hydrolysis reaction but also as a catalyst for the condensation reaction. Therefore, it is preferable that the said condensation catalyst is formic acid. Reaction temperature and reaction time in the said condensation reaction can be arbitrarily set according to the reactivity of component (a11), respectively. The said reaction temperature is about 40-150 degreeC normally, Preferably it is 60-100 degreeC. The reaction time is about 30 minutes to 12 hours.

It is preferable to advance the said condensation reaction so that [total mole number of an unreacted hydroxyl group and an unreacted alkoxy group] / [total mole number of the alkoxy groups contained in component (a11)] (henceforth molar ratio B) is 0.3 or less. Do. As for the said molar ratio B, it is more preferable that it is 0.2 or less. When the molar ratio B satisfies the above preferred upper limit, the unreacted hydroxyl group and the alkoxy group are condensation-reacted during storage of the transparent resin (a), making it difficult to gel. Moreover, condensation reaction becomes difficult to advance in hardened | cured material, and it becomes difficult to produce a crack in hardened | cured material.

At the time of the said condensation reaction, the minimum with preferable concentration of a component (a11) is 2 weight%, a more preferable minimum is 15 weight%, a preferable upper limit is 80 weight%, and a more preferable upper limit is 60 weight%. It is preferable to use a solvent having a higher boiling point than water and alcohol produced by the condensation reaction. In this case, the solvent can be easily removed from the reaction system. When the said concentration is in the said range, it will become difficult to gelatinize during reaction, the molecular weight of a hydrolysis-condensation product (a1) will not become large too much, and the storage stability of a hydrolysis-condensation product (a1) will become still higher.

In the condensation reaction, it is preferable to use a solvent having a higher boiling point than water and alcohol produced by the condensation reaction. Only 1 type may be used for the said solvent, and 2 or more types may be used together. Moreover, the said crosslinkable compound can also be used as a solvent.

After the condensation reaction, it is preferable to remove the catalyst. By removing a catalyst, the storage stability of a hydrolysis-condensation product (a1) can be improved. The removal method of the said catalyst can select a well-known method suitably according to the kind of catalyst. As a removal method of the said catalyst, the method of heating above the boiling point of a catalyst, the method of pressure reduction, etc. are mentioned. When the catalyst is formic acid, formic acid can be easily removed by these methods.

It is preferable that a transparent resin hardened | cured material (A) is hardened | cured material of transparent resin containing the compound which has a fluorene skeleton. It is preferable that transparent resin (a) contains the compound which has a fluorene skeleton. Content of the compound which has a fluorene skeleton in 100 weight% of transparent resin (a) becomes like this. Preferably it is 1 weight% or more, More preferably, it is 5 weight% or more, More preferably, it is 10 weight% or more. The upper limit of the content of the compound having a fluorene skeleton is not particularly limited. Content of the compound which has a fluorene skeleton in 100 weight% of transparent resin (a) is about 70 weight% or less, Preferably it is 50 weight% or less.

It is preferable that the transparent resin hardened | cured material (A) is hardened | cured material of the transparent resin containing the compound which has a structural unit represented by following formula (11), The structural unit represented by following formula (11), a (meth) acryloyl group, and an allyl group Or it is more preferable that it is hardened | cured material of transparent resin containing the compound which has an epoxy group, It is still more preferable that it is hardened | cured material of transparent resin containing the compound which has a fluorene skeleton represented by following formula (2), following formula (3) or formula (4). . It is preferable that the compound which has the said fluorene skeleton is a compound which has a structural unit represented by following formula (11), and is a compound which has a structural unit represented by following formula (11), and a (meth) acryloyl group, an allyl group, or an epoxy group. It is more preferable, and it is more preferable that it is a compound which has a fluorene skeleton represented by following formula (2), (3) or (4). The compound which has a fluorene skeleton represented by following formula (2) has a (meth) acryloyl group. The compound which has a fluorene skeleton represented by following formula (3) has an allyl group. The compound which has a fluorene skeleton represented by following formula (4) has an epoxy group.

The transparent resin cured product (A) is preferably a cured product of a transparent resin containing a compound having a structural unit represented by the following general formula (12), and a structural unit represented by the following general formula (12) and a (meth) acryloyl group or an allyl group It is more preferable that it is hardened | cured material of transparent resin containing the compound which has, and it is still more preferable that it is hardened | cured material of transparent resin containing the compound which has a fluorene skeleton represented by following formula (2) or following formula (3). It is preferable that the compound which has the said fluorene skeleton is a compound which has a structural unit represented by following formula (12), It is more preferable that it is a compound which has a structural unit represented by following formula (12), and a (meth) acryloyl group or an allyl group. It is more preferable that it is a compound which has a fluorene skeleton represented by following formula (2) or (3).

<Formula 11>

In said Formula (11), R13 and R14 represent the organic group containing a hydrogen atom, a methyl group, or an epoxy group, respectively. In said Formula (11), it is preferable that R13 and R14 respectively represent a hydrogen atom or a methyl group. In addition, the binding site of the group couple | bonded with two benzene rings in the said Formula (11) is not specifically limited.

<Formula 12>

In said Formula (12), R15-R18 represents a hydrogen atom or a methyl group, respectively, and p1 and p2 represent the integer of 0-2, respectively.

<Formula 2>

In said Formula (2), R <3> -R <8> represents a hydrogen atom or a methyl group, respectively, and m1 and m2 represent 1 or 2, respectively.

<Formula 3>

In said Formula (3), R9-R12 represent a hydrogen atom or a methyl group, respectively, n1 and n2 represent the integer of 0-2, respectively.

&Lt; Formula 4 >

In said Formula (4), R21 and R22 represent a hydrogen atom or a methyl group, respectively, q1 and q2 represent the integer of 0-2, respectively, X1 and X2 represent the organic group containing a hydrogen atom or an epoxy group, respectively.

In said Formula (4), it is preferable that X <1> is a group represented by a hydrogen atom or the following formula (4a), and X2 is a group represented by a hydrogen atom or the following formula (4b).

<Formula 4a>

In said Formula (4a), R23 represents a hydrogen atom or a methyl group, q3 represents the integer of 0-2.

<Formula 4b>

In said Formula (4b), R24 represents a hydrogen atom or a methyl group, q4 represents the integer of 0-2.

The present inventors have found that the use of a compound having a fluorene skeleton greatly contributes to enhancing the image sharpness in the transparent composite sheet. In addition, the present inventors have also found that the compound having the fluorene skeleton represented by the above formulas (2), (3) or (4) greatly contributes to greatly increasing the image sharpness. In addition, the present inventors have also found that the compound having the fluorene skeleton represented by the above formula (2) or (3) greatly contributes to significantly increasing the image sharpness.

The transparent resin (a) is a compound having an epoxy group in addition to a hydrolysis condensate (a1), a compound having the fluorene skeleton, or a mixture of the hydrolysis condensate (a1) and a compound having the fluorene skeleton, and the like (hereinafter, And an epoxy compound (a2)) and a compound having an isocyanate group (hereinafter also referred to as isocyanate compound (a3)) are preferably further included. In this case, the transparent resin (a) can be efficiently crosslinked and cured by heating.

The epoxy compound (a2) is not particularly limited. As an epoxy compound (a2), a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, Hydrogenated bisphenol F type epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, triphenol phenol methane type An epoxy resin, an alkyl modified triphenol methane type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene skeleton containing epoxy resin, a naphthalene skeleton containing epoxy resin, an arylalkylene type epoxy resin, etc. are mentioned. Only 1 type may be used for an epoxy compound (a2), and 2 or more types may be used together.

It is preferable that the compound (epoxy compound (a2)) which has the said epoxy group has a fluorene skeleton. By use of the epoxy compound which has a fluorene skeleton, the said image sharpness in a transparent composite sheet can be improved further.

The epoxy compound (a2) is hydrogenated bisphenol A type epoxy resin (trade name "Epicoat 828" made by Japan epoxy resin company, etc.), bisphenol F type epoxy resin (trade name "Epicoat 807" made by Japan epoxy resin company), hydrogenation It is preferable that it is bisphenol-A epoxy resin (brand name "Santoto ST-3000" by Toto Kasei Co., Ltd.), or an alicyclic epoxy resin (brand name "Celoxide 2021" by Daicel Chemical Industries, Ltd.). By use of these preferable epoxy compounds (a2), transparency and heat resistance of the hardened | cured material of a transparent composite material can be improved further.

It is preferable that the molecular weight of the said epoxy compound (a2) is higher. By use of a high molecular weight epoxy compound (a2), the flexibility of the hardened | cured material of a transparent composite material becomes high. Examples of the high molecular weight epoxy compound (a2) include epoxy resins having an epoxy equivalent of 2000 g / equivalent or more (trade names "Epicoat 1010" and "Epicoat 4007P" manufactured by Japan Epoxy Resin Co., Ltd.) and epoxy modified silicone resins (Shin-Etsu Chemical Co., Ltd.). The brand name "X-22-163A" etc. made from Kagaku Kogyo Co., Ltd., polyethyleneglycol diglycidyl ether, etc. are mentioned. Especially, polyethyleneglycol diglycidyl ether is preferable.

Isocyanate compound (a3) is not specifically limited. As an isocyanate compound (a3), aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, etc. are mentioned, for example. Specifically as an isocyanate compound (a3), 1, 5- naphthylene diisocyanate, 4,4'- diphenylmethane diisocyanate, 4,4'- diphenyl dimethyl methane diisocyanate, 4,4'- dibenzyl isocyanate , Dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate , Isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, hydrogenation Xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexyl methane-4,4'-diisocyanae There may be mentioned 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, and m- tetramethyl xylylene diisocyanate, and dimer acid dimer of a carboxyl group of the isocyanate group call member diisocyanate. Only 1 type may be used for an isocyanate compound (a3), and 2 or more types may be used together.

From the viewpoint of increasing the transparency and heat resistance of the cured product of the transparent composite material, the isocyanate compound (a3) is preferably isophorone diisocyanate.

The higher the molecular weight of the isocyanate compound (a3) is preferable. By use of a high molecular weight isocyanate compound (a3), the flexibility of the hardened | cured material of a transparent composite material becomes high. Examples of the high molecular weight isocyanate compound (a3) include diisocyanate modified products of polyols, and polymer MDI (trade name "Cosmonate M" manufactured by Mitsui Takeda Chemical Co., Ltd.). Examples of the polyols include polycarbonate diols, polyester diols, and the like.

In order to accelerate hardening reaction of the transparent resin (a) by heating, you may use together an epoxy compound (a2) and a catalyst. As a catalyst used together with an epoxy compound (a2), tertiary amine, imidazole, organic phosphine, tetraphenyl boron salt, etc. are mentioned, for example.

Examples of the tertiary amines include 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like. have. As said imidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazole, etc. are mentioned. Examples of the organic phosphine include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine. As said tetraphenyl boron salt, tetraphenyl phosphonium tetraphenyl borate, 2-ethyl-4-methyl imidazole tetraphenyl borate, N-methylmorpholine tetraphenyl borate, etc. are mentioned.

It is preferable to use the said isocyanate compound (a3) and a catalyst together. As a catalyst used together with an isocyanate compound (a3), an organic tin compound, tertiary amine, etc. are mentioned.

Dibutyltin dilaurate, tin octylate, etc. are mentioned as said organic tin compound. Examples of the tertiary amines include 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like. Can be.

It is preferable that content of the catalyst used together with the said epoxy compound (a2) and an isocyanate compound (a3) with respect to 100 weight part of transparent resin (a) exists in the range of 0.01-5 weight part.

In 100 weight% of transparent resin (a), the compounding ratio of a hydrolysis-condensation product (a1) and at least 1 sort (s) in an epoxy compound (a2) and an isocyanate compound (a3) can be suitably determined according to a use.

[Moles of thiol group contained in hydrolysis-condensation product (a1)] / [moles of total sum of epoxy group contained in epoxy compound (a2) and isocyanate group contained in isocyanate compound (a3)] (hereinafter also referred to as molar ratio C) ) Is preferably in the range of 0.9 to 1.1. When the said molar ratio C is 0.9 or more, an epoxy group and an isocyanate group will hardly remain after hardening, and the weather resistance of the hardened | cured material of a transparent composite material will become high. When the molar ratio is 1.1 or less, the thiol group is less likely to remain, and odor due to decomposition of the thiol group is less likely to occur.

In addition to the hydrolysis-condensation product (a1), the transparent resin (a) preferably further contains a compound having a carbon-carbon double bond (hereinafter also referred to as an unsaturated compound (a4)). By use of the said unsaturated compound (a4), a transparent composite material can be hardened by heating and irradiation of an actinic light.

The unsaturated compound (a4) is not particularly limited. As said carbon-carbon double bond of an unsaturated compound (a4), a vinyl group, a (meth) acryloyl group, an allyl group, etc. are mentioned. The carbon-carbon double bond reacts with the thiol group of the hydrolysis condensate (a1) (en-thiol reaction). The reaction mechanism of this reaction differs depending on the presence or absence of a polymerization initiator. For this reason, a hydrolysis-condensation product (a1) and an unsaturated compound (a4) are adjusted suitably for the optimal compounding quantity.

When the said polymerization initiator is not used, one thiol group add-reacts with respect to one carbon-carbon double bond. When the polymerization initiator is used, in addition to one thiol group addition reaction to one carbon-carbon double bond, a chain radical reaction proceeds. As a result, when the said polymerization initiator is not used, it reacts with the thiol group contained in a hydrolysis condensate (a1), and the carbon-carbon double bond contained in an unsaturated compound (a4) in 1: 1 (molar ratio). When the said polymerization initiator is used, it does not react as 1: 1 (molar ratio) with the thiol group contained in a hydrolysis-condensation product (a1), and the carbon-carbon double bond contained in an unsaturated compound (a4).

In view of the above, when the polymerization initiator is not used, the compounding ratio of the hydrolysis condensate (a1) and the unsaturated compound (a4) is [moles of thiol groups contained in the hydrolysis condensation product (a1)] / [unsaturated compound The number of moles of carbon-carbon double bonds contained in (a4)] (hereinafter also referred to as molar ratio D1) is preferably in the range of 0.9 to 1.1. As for the said molar ratio D1, it is more preferable that it is 1.0. When the said molar ratio D1 is 0.9 or more, carbon-carbon double bond will hardly remain after hardening, and the weather resistance of the hardened | cured material of a transparent composite material will become high. When the molar ratio is 1.1 or less, the thiol group is less likely to remain, and odor due to decomposition of the thiol group is less likely to occur.

When the polymerization initiator is used, the compounding ratio of the hydrolysis condensate (a1) and the unsaturated compound (a4) is contained in [moles of thiol groups contained in the hydrolysis condensate (a1)] / [unsaturated compound (a4) Mole number of carbon-carbon double bond] (hereinafter also referred to as molar ratio D2) is preferably in the range of 0.01 to 1.1. When the said molar ratio D2 is 0.01 or more, the water vapor barrier property of the hardened | cured material of a transparent composite material can be improved further. In addition, carbon-carbon double bonds hardly remain after curing, and the weather resistance of the cured product of the transparent composite material is increased. When the molar ratio D2 is 1.1 or less, the thiol group is less likely to remain, and odor due to decomposition of the thiol group is less likely to occur.

Moreover, in order to suppress reaction of the functional groups which have a carbon-carbon double bond, rather than the reaction of the functional group which has a carbon-carbon double bond, and a thiol group, it is preferable that an unsaturated compound (a4) has an allyl group.

Examples of the compound having one allyl group include cinnamic acid, monoallyl cyanurate, monoallyl isocyanurate, pentaerythritol monoallyl ether, trimethylolpropane monoallyl ether, glycerin monoallyl ether, bisphenol A monoallyl ether, and bisphenol F Monoallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, and tripropylene glycol monoallyl ether.

Examples of the compound having two allyl groups include diallyl phthalate, diallyl isophthalate, diallyl cyanurate, diallyl isocyanurate, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, glycerin diallyl ether, and bisphenol A Diallyl ether, bisphenol F diallyl ether, ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, propylene glycol diallyl ether, dipropylene glycol diallyl ether, and tripropylene glycol diallyl ether Etc. can be mentioned.

Examples of the compound containing three or more allyl groups include triallyl isocyanurate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropanetriallyl ether, and the like. It is particularly preferable that the compound having an allyl group is triallyl isocyanurate, diallyl phthalate or pentaerythritol triallyl ether.

It is preferable that the molecular weight of an unsaturated compound (a4) is high. The use of a high molecular weight unsaturated compound (a4) increases the flexibility of the cured transparent resin (A). As a high molecular weight unsaturated compound (a4), the copolymer which consists of methyl allylsiloxane and dimethylsiloxane, the copolymer which consists of epichlorohydrin and allyl glycidyl ether (trade name "Epiclomer" by the Daiso company, and Nihon Xeon company The brand name "Gechron" etc. of manufacture, the allyl-group terminal polyisobutylene polymer (brand name "Epion" by Kaneka Corporation), etc. are mentioned.

[Moles of carbon-carbon double bond contained in unsaturated compound (a4)] / [Moles of unsaturated compound (a4)] (hereinafter also referred to as molar ratio E) is preferably 2 or more. The molar ratio E represents the average number of carbon-carbon double bonds contained in one molecule. When the said molar ratio E is 2 or more, sclerosis | hardenability of a transparent resin (a) becomes high and the crosslinking density of the transparent resin hardened | cured material (A) becomes high. For this reason, there exists a tendency for the heat resistance and hardness of a transparent resin hardened | cured material (A) to become high.

When using a hydrolysis-condensation product (a1), you may not use a polymerization initiator. However, the transparent composite material may contain a polymerization initiator even when it contains a hydrolysis condensate (a1). As said polymerization initiator, a photocationic polymerization initiator, an optical radical polymerization initiator, etc. are mentioned.

Examples of the photocationic polymerization initiator include sulfonium salts, iodonium salts, metallocene compounds, benzointosylate, and the like, which are compounds which generate acids by irradiation with ultraviolet rays. As a commercial item of the said photocationic polymerization initiator, brand names "Suracure UVI-6970", "Suracure UVI-6974" and "Suracure UVI-6990" by the Union Carbide company, and the brand name "Il "Cure 264", the brand name "CIT-1682" by Nippon Soda Co., etc. are mentioned.

As said radical photopolymerization initiator, the brand names "Darcure 1173", "Irgacure 651", "Irgacure 184", "Irgacure 907", and the benzophenone by Ciba Japan Corporation are mentioned.

The minimum with preferable content of the said polymerization initiator is 1 weight part, a preferable upper limit is 15 weight part, a more preferable upper limit is 10 weight part, and a further preferable upper limit is 5 weight part with respect to 100 weight part of transparent resin (a).

In order to further improve the storage stability of the transparent resin (a), an en-thiol reaction inhibitor can be used. Examples of the en-thiol reaction inhibitors include phosphorus compounds, radical polymerization inhibitors, tertiary amines, imidazoles, and the like.

Triphenyl phosphine, triphenyl phosphite, etc. are mentioned as said phosphorus compound. Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, and 2,2. '-Methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylaminealuminum salt, and di Phenyl nitrosoamine etc. are mentioned. Examples of the tertiary amines include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, diazabicycloundecene and the like. As said imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylhexyl imidazole, 2-undecyl imidazole, and 1-cyanoethyl-2-methylimidazole Etc. can be mentioned.

Among the above phosphorus compounds, triphenyl phosphite is preferred. Since triphenyl phosphite has a high inhibitory effect of the en-thiol reaction and is liquid at room temperature, handling is easy. It is preferable that content of the said phosphorus compound exists in the range of 0.1-10 weight part with respect to 100 weight part of transparent resin (a). En-thiol reaction can fully be suppressed as content of the said phosphorus compound is 0.1 weight part or more. When content of the said phosphorus compound is 10 weight part or less, the amount of residual of the said phosphorus compound after hardening will become small, and the fall of the physical property of the transparent resin hardened | cured material (A) derived from the said phosphorus compound can be suppressed.

Among the radical polymerization inhibitors, N-nitrosophenylhydroxylamine aluminum salt is preferable. Even if a small amount of said N-nitrosophenyl hydroxylamine aluminum salt can suppress an n-thiol reaction, the transparency of hardened | cured resin (A) can be improved. It is preferable that content of the said radical polymerization inhibitor exists in the range of 0.0001-0.1 weight part with respect to 100 weight part of transparent resin (a). En-thiol reaction can fully be suppressed as content of the said radical polymerization inhibitor is 0.001 weight part or more. If content of the said radical polymerization inhibitor is 0.1 weight part or less, there exists a tendency for sclerosis | hardenability to become high.

Among the tertiary amines, benzyldimethylamine is preferable. Since said benzyldimethylamine has a high inhibitory effect of an en-thiol reaction and is liquid at room temperature, handling is easy. It is preferable that content of the said tertiary amine exists in the range of 0.001-5 weight part with respect to 100 weight part of transparent resin (a). En-thiol reaction can fully be suppressed as content of the said tertiary amine is 0.001 weight part or more. When content of the said tertiary amine is 5 weight part or less, condensation reaction of the unreacted hydroxyl group and alkoxy group in a hydrolysis-condensation product (a1) will become difficult to occur, and gelatinization will become difficult to occur.

The compounding ratio of the hydrolysis-condensation product (a1) and the unsaturated compound (a4) can be appropriately changed depending on the use. In addition, when using a hydrolysis-condensation product (a1) and an unsaturated compound (a4) together, a solvent can be mix | blended as needed.

It is preferable that the Abbe number of a transparent resin hardened | cured material (A) exists in the range of 35-50. When the Abbe number of a transparent resin (a) exists in the said range, the light transmittance of a transparent composite sheet can be made higher.

A transparent resin hardened | cured material (A) is obtained also by hardening the material which does not add the glass cloth (b), for example at the time of preparation of the said transparent composite material. In addition, a transparent resin hardened | cured material (A) is obtained also by hardening the mixture which mixed transparent resin (a) and at least one of a photoinitiator, a hardening | curing agent, etc. for hardening the said transparent resin (a), for example. .

(Glass cloth (b))

It is preferable that the filament diameter of glass cloth (b) is 3-10 micrometers. If the filament diameter is 3 µm or more, the tensile strength is further increased. When filament diameter is 10 micrometers or less, bending strength becomes still higher.

It is preferable that the thickness of a single yarn is 10-20 in tex count. If it is 10 or more times, the thickness of the glass cloth (b) becomes thick, and the effect of reducing strength or thermal expansion can be sufficiently obtained. If it is 20 or less, opening processing is easy.

The number of twists of the single yarn is preferably 2 / inch or less. If the number of twists is 2 / inch or less, the carding process of the carding machine 2 or more is easy.

The density (weave density) of the warp and weft of the glass cloth (b) is preferably 40 to 70 pieces / inch, respectively. If it is 40 pieces / inch or more, the eye (basket hole) of the glass cloth (b) becomes small enough, and the unevenness | corrugation of the surface of a transparent composite sheet can be reduced. When it is 70 pieces / inch or less, the carding process becomes easy without the eye of the glass cloth (b) becoming too clogged.

From the viewpoint of further reducing the deformation of the transparent image of the transparent composite sheet, it is preferable that the glass cloth (b) is a glass cloth that has been opened with a carding treatment so that the degree of opening of the following formula (X) is in the range of 2 to 4.

<Equation X>

Opening degree = diameter of the fiber width / glass fiber single yarn of the fiber bundle in the glass cloth (b) after the opening degree processing

In view of the above, in particular, from the viewpoint of further reducing the see-through deformation of the transparent composite sheet, the glass cloth (b) included in the transparent composite sheet according to the present invention has a filament diameter of 3 to 10 µm and a tex count of 10. It is formed by the glass fiber single yarn of 20 to 20, or less twisting number 2 / inch, the glass cloth (b) is a woven fabric having a density of 40 to 70 / inch of warp and weft yarn, the fineness of the formula (X) It is preferable that it is the glass cloth which open-processed so that may exist in the range of 2-4.

Since the thickness of the glass cloth (b) changes according to the kind of yarn used, the weave density, and the degree of fineness, it is difficult to define a precise range. When thickness of glass cloth (b) is illustrated, it is about 40-80 micrometers in the thick part which inclines and weft cross.

As a material of glass cloth (b), soda glass, borosilicate glass, an alkali free glass, etc. are used. Especially, an alkali free glass is preferable. By using an alkali free glass, when a transparent composite sheet is used as a display element substrate or a solar cell substrate, the alkali component derived from the glass cloth (b) will not adversely affect a semiconductor element.

It is preferable that the fiber of glass cloth (b) is E glass or T glass. The said E glass is widely used as a core material for glass fiber reinforced circuit boards. The E glass is equipped with various standard products in terms of fiber diameter, fiber bundle diameter, weight per unit area as the glass cloth, weave density and thickness, and the like. In addition, in view of performance, cost and ease of availability, E glass is preferably used.

As for the fiber of glass cloth (b), it is more preferable that it is T glass. T glass fibers are superior to E glass fibers in terms of high strength and low thermal expansion.

The lower limit of the tensile modulus of the glass cloth (b) is preferably 5 GPa, more preferably 10 GPa, more preferably 500 GPa, and more preferably 200 GPa. If the tensile modulus is too low, the strength of the transparent composite sheet tends to be low.

The minimum with preferable content of a glass cloth (b) is 50 weight part, more preferable 100 weight part, a preferable upper limit is 300 weight part, and a more preferable upper limit with respect to 100 weight part of transparent resin (a) is 200 weight part. When there is too little content of the glass cloth (b), there exists a tendency for the reducing effect of thermal expansion by a glass cloth (b) to become inadequate. When there is too much content of a glass cloth (b), it will become difficult to impregnate the glass cloth (b) with a transparent resin (a), and a space | gap will arise in the surface or inside of a transparent composite sheet, and transparency will fall easily.

(Other ingredients)

The transparent composite material may contain a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a brightener, a colorant, a conductive agent, a mold releasing agent, a surface treatment agent, a viscosity modifier and the like according to necessity in various applications. have.

(Transparent composite sheet)

The transparent composite sheet which concerns on this invention contains the transparent resin hardened | cured material (A) which the transparent resin (a) hardened | cured, and the glass cloth (b) embedded in the said transparent resin hardened | cured material (A).

Although it does not specifically limit as a manufacturing method of the transparent composite sheet which concerns on this invention, For example, the following methods are mentioned.

The transparent resin (a) having fluidity at normal temperature or under heating is applied onto the substrate. Next, the glass cloth (b) is superposed on the transparent resin (a) on a board | substrate, and the transparent resin (a) is impregnated (absorbed) by the glass cloth (b), and a transparent composite material is obtained. Thereafter, it is dried as necessary, pressed or laminated with another base material, the thickness of the transparent composite material is adjusted, homogenized, and a sheet is formed. Next, at least one of heating and irradiation of actinic light crosslinks and hardens a sheet-like transparent composite material, and forms a transparent composite sheet. Thereafter, the substrate is peeled off from the transparent composite sheet to obtain a transparent composite sheet.

The glass cloth (b) may be immersed in the transparent resin (a), and the transparent resin (a) may be impregnated into the glass cloth (b) while irradiating ultrasonic waves.

Although the thickness of the transparent composite sheet which concerns on this invention is not specifically limited, It is preferable to exist in the range of 50-200 micrometers from the specification of a glass cloth (b) and the ratio of a transparent resin (a) and a glass cloth (b).

When the thickness of a transparent composite sheet needs to exceed 200 micrometers, it is hard to laminate | stack and cure a plurality of sheet-like transparent composite materials, or to repeat the sheeting and hardening of a transparent composite material, and to obtain a transparent composite sheet. desirable. It is also possible to laminate a transparent composite sheet via a suitable adhesive layer.

It is preferable that the light transmittance of the transparent composite sheet which concerns on this invention is 80% or more, It is more preferable that it is 85% or more, It is more preferable that it is 90% or more, It is especially preferable that it is 92% or more. When the light transmittance is higher, for example, when an image display device is obtained by using a transparent composite sheet for a display element substrate such as a liquid crystal display element or an organic EL display element or the like, the display quality becomes higher and the image becomes clearer.

The said light transmittance can be calculated | required by measuring the total light transmittance of wavelength 550nm using a commercially available spectrophotometer.

From the viewpoint of improving the water vapor barrier property of the transparent composite sheet, the water vapor transmission rate of the transparent composite sheet according to the present invention is preferably 1 × 10 ⁻¹ g / m ² · day or less. From the viewpoint of improving the dimensional stability of the transparent composite sheet, the average linear expansion coefficient at 30 to 250 ° C. of the transparent composite sheet according to the present invention is preferably 20 ppm / ° C. or less.

It is preferable that the haze value of the transparent composite sheet which concerns on this invention is 10% or less, It is more preferable that it is 3% or less, It is more preferable that it is 2% or less.

The said haze value is measured based on JISK7136. As the measuring device, a commercially available haze maker is used. As a measuring apparatus, Tokyo Denshoku Co., Ltd. "full automatic haze meter TC-HIIIDPK" etc. are mentioned, for example.

In the transparent composite sheet according to the present invention, a surface smoothing layer, a hard coating layer or a gas barrier layer may be laminated.

When forming the said surface smoothing layer or a hard coating layer, a known surface smoothing agent or a hard coating agent is apply | coated on a transparent composite sheet, for example, and it is dried in order to remove a solvent as needed. Next, the surface leveling agent or the hard coating agent is cured by at least one of heating and irradiation of actinic light.

The method of applying the surface leveling agent or the hard coating agent on the transparent composite sheet is not particularly limited. For example, a conventionally known method such as a roll coating method, spin coating method, wire bar coating method, dip coating method, extrusion method, curtain coating method or spray coating method can be adopted.

By laminating the gas barrier layer on the transparent composite sheet according to the present invention, the barrier property of water vapor and oxygen can be enhanced. The gas barrier layer is not particularly limited. As the material of the gas barrier layer, for example, a silicon compound, magnesium oxide, aluminum oxide, and zinc oxide of a metal, such as SiO ₂ and SiN of aluminum or the like. From the viewpoint of improving the adhesion between the water vapor barrier properties, transparency and the transparent hybrid sheet and a silicon compound such as SiO ₂ and SiN is preferred.

The method of forming a gas barrier layer is not specifically limited, Wet dry methods, such as a vapor deposition method and sputtering method, and wet methods, such as a sol-gel method, are mentioned. Especially, sputtering method is preferable. The gas barrier layer formed by the sputtering method is dense, has excellent gas barrier properties, and has good adhesion to a transparent composite sheet.

Hereinafter, an Example and a comparative example are given and this invention is concretely demonstrated. This invention is not limited only to a following example.

(Example 1)

50 parts by weight of tricyclodecanedimethanoldimethacrylate (NK ester DCP, manufactured by Shin-Nakamura Chemical Industries, Ltd.) and 9,9-bis [4- (acryloyloxyethoxy) phenyl] as a transparent resin (a). 48 parts by weight of fluorene (NK ester A-BPEF, manufactured by Shin-Nakamura Chemical Industries, Ltd.), 1-hydroxycyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Shiba Japan) as a photopolymerization initiator 0.5 A weight part was added and mixed, and the transparent resin liquid 1 was obtained.

A glass cloth having a thickness of 42 μm, which was opened by weaving an E glass fiber single yarn having a filament diameter of 5 μm, a texture number of 11, and a twist number of 1 / inch at a density of 53 warps / weft of 53 / inch, b) was prepared. Glass cloth (b) is immersed in obtained transparent resin liquid 1 so that transparent resin (a) and glass cloth (b) may be content shown in following Table 1, and transparent resin liquid 1 is glass cloth (b) irradiating an ultrasonic wave. Impregnation).

Thereafter, the glass cloth (b) impregnated with the transparent resin solution 1 was pulled up, placed on a stainless steel plate, and dried at 80 ° C. for 10 minutes in an oven. In addition, after degassing | defoaming in the pressure-reduction chamber to the pressure of 10 Pa, it decomposed | segmented by the glass plate and pressurized for 3 minutes by the pressure of 0.01 MPa from the top, and thickness was uniformed. 2000 mJ / cm <^2> (365 nm) UV light was irradiated, bridge | crosslinked, and hardened with the high pressure mercury lamp from the glass plate side, and the transparent composite sheet was obtained.

(Example 2)

30 parts by weight of 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.) and a bisaryl fluorene system as transparent resin (a) Epoxy resin (Oncoat EX-1010, manufactured by Nagase Sangyo Co., Ltd., represented by the formula (4), wherein in formula (4), q1 and q2 each represent 0, and X1 and X2 correspond to compounds each representing a hydrogen atom) 20 To parts by weight, 42 parts by weight of a 7: 3 (weight ratio) mixture (lycaside MH-700, manufactured by Shin-Nipbon Chemical Co., Ltd.) of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride as a curing agent, and a curing accelerator (hischorin PX- 4 ET, manufactured by Nippon Chemical Industries, Ltd.) 1 A weight part was added and mixed, and the transparent resin liquid 2 was obtained.

A glass cloth with a thickness of 70 μm, which was opened by weaving an E glass fiber single yarn having a filament diameter of 6 μm, a texture number of 17 and a twist number of 1 / inch at a density of 60 warps and weft yarn of 60 per inch, b) was prepared. Glass cloth (b) is immersed in obtained transparent resin liquid 2 so that transparent resin (a) and glass cloth (b) may become content shown in following Table 1, and transparent resin liquid 2 is glass cloth (b) irradiating an ultrasonic wave. Impregnation).

Thereafter, the glass cloth (b) impregnated with the transparent resin liquid 2 was pulled up, placed on a stainless steel plate, and degassed while depressurizing to a pressure of 10 Pa in a decompression chamber, and then sandwiched by a glass plate to a pressure of 0.01 MPa from the top. It pressed for 3 minutes and made the transparent composite material into a sheet form. Next, the sheet-like transparent composite material was heated in an oven at 100 ° C. for 60 minutes, further heated at 180 ° C. for 180 minutes, crosslinked, and cured to obtain a transparent composite sheet.

(Example 3)

Photopolymerization initiator to 50 parts by weight of polysilsesquioxane (HBSQ101 corresponding to the hydrolysis-condensation product (a1), manufactured by Arakawa Chemical Industries, Ltd.) and 30 parts by weight of triallyl isocyanurate as the transparent resin (a) 0.2 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (Irgacure 907, manufactured by Shiba Japan Co., Ltd.) as a polymer was added, mixed, and a transparent resin Liquid 3 was obtained.

A glass cloth having a thickness of 42 μm, which was opened by weaving an E glass fiber single yarn having a filament diameter of 5 μm, a texture number of 11, and a twist number of 1 / inch at a density of 53 warps / weft of 53 / inch, b) was prepared. Glass cloth (b) is immersed in obtained transparent resin liquid 3 so that transparent resin (a) and glass cloth (b) may become content shown in following Table 1, and transparent resin liquid 3 is glass cloth (b) irradiating an ultrasonic wave. Impregnation).

Thereafter, the glass cloth (b) impregnated with the transparent resin liquid 3 is pulled up, placed on a stainless steel plate, and degassed while depressurizing to a pressure of 10 Pa in a decompression chamber. It pressed for 3 minutes and made the transparent composite material into a sheet form. Next, 2000 mJ / cm <^2> (365 nm) UV light was irradiated with the high pressure mercury lamp from the glass plate side, the sheet-like transparent composite material was bridge | crosslinked, it was hardened | cured, and the transparent composite sheet was obtained.

(Example 4)

To 70 parts by weight of a polysilsesquioxane solution (comparase SQ102-1 corresponding to the hydrolysis condensate (a1), manufactured by Arakawa Chemical Industries, Ltd.) as a transparent resin (a) and 50 parts by weight of isophorone diisocyanate, 0.2 weight part of dibutyltin dilaurates as a reaction catalyst were added and mixed, and the transparent resin liquid 4 was obtained.

A glass cloth with a thickness of 70 μm, which was opened by weaving an E glass fiber single yarn having a filament diameter of 6 μm, a texture number of 17 and a twist number of 1 / inch at a density of 60 warps and weft yarn of 60 per inch, b) was prepared. Glass cloth (b) is immersed in obtained transparent resin liquid 4 so that transparent resin (a) and glass cloth (b) may become content shown in following Table 1, and transparent resin liquid 4 is glass cloth (b) irradiating an ultrasonic wave. Impregnation).

Thereafter, the glass cloth (b) impregnated with the transparent resin liquid 4 was pulled up, placed on a stainless steel plate, and dried at 80 ° C. for 10 minutes in an oven. Next, it sandwiched with another stainless steel plate and pressurized for 3 minutes by the pressure of 0.01 Mpa from the top, and made the transparent composite material into the sheet form. Next, the sheet-like transparent composite material was heated in an oven at 120 ° C. for 20 minutes, crosslinked, and cured to obtain a transparent composite sheet.

(Example 5)

30 parts by weight of polysilsesquioxane (HBSQ101 corresponding to the hydrolysis condensation product (a1), Arakawa Chemical Industries, Ltd.) as the transparent resin (a), tricyclodecane dimethanol dimethacrylate (NK ester DCP, 2-methyl-1- [as a photoinitiator, to 25 parts by weight of Shin-Nakamura Chemical Industries, Ltd.) and 23 parts by weight of 9,9-bis [4- (allyloxyethoxy) phenyl] fluorene (prototype). 0.2 parts by weight of 4- (methylthio) phenyl] -2-moripolynopropane-1-one (Irgacure 907, manufactured by Shiba Japan Co., Ltd.) was added and mixed to obtain a transparent resin solution 5.

A glass cloth having a thickness of 42 μm, which was opened by weaving an E glass fiber single yarn having a filament diameter of 5 μm, a texture number of 11, and a twist number of 1 / inch at a density of 53 warps / weft of 53 / inch, b) was prepared. Glass cloth (b) is immersed in obtained transparent resin liquid 5 so that transparent resin (a) and glass cloth (b) may become content shown in following Table 1, and transparent resin liquid 5 is glass cloth (b) irradiating an ultrasonic wave. Impregnation).

Thereafter, the glass cloth (b) impregnated with the transparent resin solution 5 was pulled up, placed on a stainless steel plate, and degassed while depressurizing to a pressure of 10 Pa in a decompression chamber. It pressed for 3 minutes and made the transparent composite material into a sheet form. Next, 2000 mJ / cm <^2> (365 nm) UV light was irradiated with the high pressure mercury lamp from the glass plate side, the sheet-like transparent composite material was bridge | crosslinked, it was hardened | cured, and the transparent composite sheet was obtained.

(Comparative Example 1)

The thickness of the glass cloth (b) after weaving an E glass fiber single yarn having a filament diameter of 5 μm, a number of twists of 11, and a number of twists of 4.4 / inch at a density of 53 warps / weft of 53 / inch and then weaving it to have an openness of 2. A transparent composite sheet was produced in the same manner as in Example 3 except that the glass cloth (b) was changed to 60 µm, and the transparent resin (a) and the glass cloth (b) were used so as to have the contents shown in Table 1 below. It was.

(Comparative Example 2)

After weaving the glass cloth (b) with an E glass fiber single yarn having a filament diameter of 7 μm, a tex count of 22.5 and a twist number of 1.0 / inch, with a density of warp of 60 per inch and a density of weft of 58 per inch, It was the same as Example 3 except having changed into the glass cloth (b) of thickness 95micrometer processed to open to 5, and using transparent resin (a) and glass cloth (b) to content shown in following Table 1. To prepare a transparent composite sheet.

(Comparative Example 3)

1-hydroxycyclohexyl as a photoinitiator to 100 parts by weight of ethoxylated bisphenol A diacrylate (EO: 3 mol) (NK ester ABE-300, manufactured by Shin-Nakamura Chemical Industries, Ltd.) as the transparent resin (a). 0.5 weight part of -phenyl- ketone (Irgacure 184, the Shiva Japan company make) was added, it mixed, and the transparent resin liquid 6 was obtained.

Using the transparent resin liquid 6 obtained instead of the transparent resin solution 1, it carried out similarly to Example 1, and obtained the transparent composite sheet.

(Reference Example 1)

The transparent resin solution 3 used in Example 3 was developed on a stainless plate, sandwiched with a glass plate, and then irradiated with 2000 mJ / cm ² (365 nm) of UV light with a high pressure mercury lamp and cured into a sheet to form a transparent composite sheet. Was produced.

(evaluation)

(1) the thickness of the transparent composite sheet

The thickness of the transparent composite sheet was measured using the thickness gauge manufactured by Ozaki Seisakusho.

(2) refractive index and Abbe's number

The refractive index nD (wavelength 589.3 nm) and Abbe number were measured with the digital Abbe refractometer (made by Elma).

(3) phase clarity

Based on JIS K7374, the filamentous property of the obtained transparent composite sheet was measured using the filamentimeter ICM-1T (made by Suga Shikeki Co., Ltd.). Image sharpness (%) in optical comb width 0.125 mm was calculated | required.

(4) light transmittance

The light transmittance at 550 nm of the obtained transparent composite sheet was measured using the spectrophotometer UV-310PC (made by Shimadzu Corporation).

(5) haze value

Based on JIS K7136, haze of the obtained transparent composite sheet was measured using the fully automatic haze meter TC-HIIIDPK (made by Tokyo Denshoku Co., Ltd.).

(6) tensile strength

In accordance with JIS K7164, the tensile strength of the obtained transparent composite sheet was measured using the Tensilon universal material tester RTC-1310A (made by Orientec). The width of the test piece was 25 mm.

(7) linear expansion coefficient

After using the TMA / EXSTAR6000 type thermal stress deformation measuring apparatus (manufactured by Seiko Denshi Co., Ltd.), the resultant transparent composite sheet was heated at a rate of 10 ° C./min from 30 ° C. to 250 ° C., and then 0 ° C. at a rate of 10 ° C./min. Cooled to. Then, it heated up again at the speed of 10 degree-C / min, and calculated | required the average linear expansion coefficient in 30 degreeC-250 degreeC at the time of this temperature rising.

The results are shown in Table 1 below.

In following Table 1, content of the transparent resin (a) and glass cloth (b) used when obtaining a transparent composite sheet was shown. Moreover, the thickness of the obtained transparent composite sheet was shown. Furthermore, the transparent resin solutions 1-6 used in the Example and the comparative example were hardened, and the refractive index and Abbe number of the hardened | cured material (transparent resin hardened | cured material (A)) of the transparent resin (a) used by the Example and the comparative example are measured. The measurement results are shown in Table 1 below. In addition, the refractive index and Abbe's number of glass cloth (b) are shown in following Table 1.

In the transparent composite sheets of Examples 1 to 5, compared with the transparent composite sheets of Comparative Examples 1 to 3, the deformation of the perspective image was small, and the deformation of the perspective image was hardly seen.

Claims (11)

It contains a transparent resin hardened | cured material and the glass cloth embedded in the said transparent resin hardened | cured material,
A transparent composite sheet having an image sharpness defined in JIS K7374 at least 50% at an optical comb width of 0.125 mm. The glass cloth according to claim 1, wherein the glass cloth is formed by a glass fiber single yarn having a filament diameter of 3 to 10 µm, a Tex number of 10 to 20, and a twist number of 2 / inch or less,
The glass cloth is a transparent composite sheet is a glass cloth that is subjected to a carding treatment of the woven fabric having a density of warp and weft of 40 to 70 / inch so that the opening degree of the formula (X) is in the range of 2 to 4.
<Equation X>
Opening degree = diameter of the yarn width / glass fiber single yarn of the fiber bundle in the glass cloth after opening processing The transparent composite sheet according to claim 1 or 2, wherein a refractive index difference between the transparent resin cured product and the glass cloth is 0.01 or less. The transparent composite sheet in any one of Claims 1-3 whose Abbe number of the said transparent resin hardened | cured material exists in the range of 35-50. The transparent composite sheet according to any one of claims 1 to 4, wherein the cured transparent resin is a cured product of a transparent resin containing a hydrolysis condensate of a thiol group-containing silane compound represented by the following formula (1).
&Lt; Formula 1 >
R1Si (OR2) ₃
(In Formula 1, R1 represents a C1-8 organic group having a thiol group and no aromatic ring, or an organic group having a thiol group and having an aromatic ring, and R2 represents a hydrogen atom or C1-8 having no aromatic ring. An organic group having an organic group or an aromatic ring) The transparent composite sheet according to claim 5, wherein the transparent resin further comprises a compound having a carbon-carbon double bond. The transparent composite sheet according to any one of claims 1 to 6, wherein the transparent resin cured product is a cured product of a transparent resin containing a compound having a fluorene skeleton. The transparent composite sheet according to claim 7, wherein the compound having a fluorene skeleton is a compound having a fluorene skeleton represented by the following formula (2) or (3).
(2)

(In Formula 2, R3 to R8 each represent a hydrogen atom or a methyl group, and m1 and m2 each represent 1 or 2).
(3)

(In Formula 3, R9 to R12 each represent a hydrogen atom or a methyl group, and n1 and n2 each represent an integer of 0 to 2). The transparent composite sheet according to any one of claims 5 to 8, wherein the transparent resin further comprises at least one of a compound having an epoxy group and a compound having an isocyanate group. The transparent composite sheet according to claim 9, wherein the compound having an epoxy group has a fluorene skeleton. The transparent composite sheet according to any one of claims 1 to 10, wherein the fibers of the glass cloth are E glass fibers or T glass fibers.