KR101127313B1 - Process for producing transparent composite sheet - Google Patents

Abstract

The present invention provides a transparent composite sheet having a low thermal expansion coefficient by compounding a glass cloth and hardly causing irregularities on the surface of the glass cloth. The transparent composite sheet 1 according to the present invention has opposing first and second surfaces 1a and 1b. The transparent composite sheet 1 which concerns on this invention contains the transparent resin hardened | cured material and the glass cloth embedded in the said transparent resin hardened | cured material. In the transparent composite sheet 1 according to the present invention, the amplitude of the surface irregularities coinciding with the period of inclination or weft of the glass cloth on the sheet surface is 0.5 to 5 μm on the first surface 1a, and the second surface ( 0.4 μm or less in 1b).

Description

Production method of transparent composite sheet {PROCESS FOR PRODUCING TRANSPARENT COMPOSITE SHEET}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a transparent composite sheet used for applications in which transparency, such as a substrate for display elements, is required, and more particularly, a glass cloth embedded in a cured transparent resin and the cured transparent resin. A transparent composite sheet containing a cloth), a method for producing the transparent composite sheet, and a laminated sheet and a liquid crystal display device using the transparent composite sheet.

Glass substrates are widely used for substrates for display elements such as liquid crystal display elements or organic EL display elements, substrates for solar cells, and the like. There is a problem that the glass substrate is fragile, has low bendability, and can not be made lightweight. For this reason, in recent years, using a plastic substrate instead of a glass substrate is examined.

However, the thermal expansion coefficient of the conventional plastic substrate may be about 10 to 20 times larger than the thermal expansion coefficient of glass. In display elements and solar cells, the semiconductor layer or the conductive layer is often made of an inorganic material. Therefore, when a display element or a solar cell is manufactured using a plastic substrate having a large thermal expansion coefficient, the difference in thermal expansion coefficient between the plastic substrate and the inorganic material layer in a heating and cooling step for forming a semiconductor layer, a conductive layer, or the like. As a result, cracks may occur in the inorganic material layer. Moreover, when a display element is manufactured using the plastic substrate with a large thermal expansion coefficient, the dimension of a plastic substrate will change large by the temperature variation in a manufacturing process. For this reason, mask alignment in a photolithography process may become difficult.

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

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 substrate. For this reason, there exists a problem that distortion arises on the permeation | transmission seen through a plastic substrate.

Moreover, when the unevenness | corrugation which reflected the fiber shape of a glass cloth arises on the surface of a plastic substrate, when this plastic substrate is used as a board | substrate for liquid crystal display elements, the thickness of a liquid crystal sealing layer will become nonuniform. As a result, nonuniformity arises in a display image, so-called cell gap nonuniformity arises.

An object of the present invention is a transparent composite sheet and a method for producing the transparent composite sheet, which can not only lower the coefficient of thermal expansion by compounding the glass cloth but also make it difficult to form irregularities on the surface reflecting the fiber shape of the glass cloth, and It is providing the laminated sheet and liquid crystal display element which used the said transparent composite sheet.

The transparent composite sheet according to the present invention has opposing first and second surfaces. The transparent composite sheet which concerns on this invention contains the transparent resin hardened | cured material and the glass cloth embedded in the said transparent resin hardened | cured material, and the amplitude of the surface asperity which matched the inclination of the glass cloth of the sheet surface or the period of the weft of the said sheet | seat is said 0.5 to 5 μm in the first face and 0.4 μm or less in the second face.

The laminated sheet provided in any specific aspect of the present invention includes a transparent composite sheet of the present invention, a polarizing plate laminated on the first surface of the transparent composite sheet, the polarizing plate so as to bond the polarizing plate to the transparent composite sheet, The adhesive layer arrange | positioned between the said 1st surface of the said transparent composite sheet is provided.

The liquid crystal display element which concerns on this invention is equipped with the 1st board | substrate, the 2nd board | substrate which opposes the said 1st board | substrate through the gap, and the liquid crystal layer arrange | positioned between the said 1st and 2nd board | substrate. At least one of the said 1st and 2nd board | substrate of the said transparent composite sheet is made to bond the said transparent composite sheet, the polarizing plate laminated | stacked on the said 1st surface of the said transparent composite sheet, and the said polarizing plate to the said transparent composite sheet. It is a laminated sheet provided with the adhesive layer provided between 1 side and the said polarizing plate.

The manufacturing method of the transparent composite sheet which concerns on this invention is the process of preparing the glass cloth in which the curable transparent resin which has transparency after impregnation, and at least 1 sort (s) of material chosen from the group which consists of a metal, glass, and a ceramic is flat. A glass cloth impregnated with the curable transparent resin is sandwiched between a rigid body having a surface and a flexible body having a flat surface and more flexible than the rigid body, and the curable transparent resin is formed by at least one of heating and irradiation with light. It is equipped with the process of hardening. As the flexible body, a resin film is preferably used. In the process of hardening the said curable transparent resin, it is preferable to irradiate a light ray to the said curable transparent resin, and to heat the said curable transparent resin.

In the transparent composite sheet of the present invention, since the glass cloth is embedded in the cured transparent resin, the coefficient of thermal expansion can be lowered. Moreover, in the transparent composite sheet of this invention, since the amplitude of the unevenness | corrugation of the surface which reflected the fiber shape of glass cloth is 0.5-5 micrometers in a 1st surface, and is 0.4 micrometer or less in a 2nd surface, it is 1st in a 2nd surface. Flatness with respect to the surface is increased. In the conventional transparent composite sheet in which the glass cloth is embedded, the unevenness of the surface is larger than 0.5 µm while reflecting the fiber shape of the glass cloth, while in the transparent composite sheet of the present invention, the flatness of the second surface is effectively increased. Therefore, when a transparent composite sheet is used as a liquid crystal element substrate of a liquid crystal display element so that a 2nd surface may be located, for example on the liquid crystal layer side of a liquid crystal display element, the variation of a cell gap can be made small.

In addition, as in the laminated sheet of the present invention, by bonding the polarizing plate through the pressure-sensitive adhesive layer to the first surface side where the amplitude of the surface irregularities reflecting the fiber shape of the glass cloth is relatively large at 0.5 to 5 µm, Unevenness can be buried. Therefore, the distortion of the transmission image visually recognized through the board | substrate which is a laminated sheet using a transparent composite sheet can be reduced.

Therefore, the display quality of a liquid crystal display element is improved by using the laminated sheet which has the transparent composite sheet which concerns on this invention in at least one of the 1st and 2nd substrate of the liquid crystal display element which has the 1st and 2nd substrate which seals a liquid crystal. It becomes possible to raise.

BRIEF DESCRIPTION OF THE DRAWINGS The partially cutaway sectional drawing which shows typically the transparent composite sheet which concerns on one Embodiment of this invention.
Fig. 2 is a partially cutaway sectional view schematically showing a laminated sheet using the transparent composite sheet shown in Fig. 1.
3 is a partially cutaway cross-sectional view schematically showing an example of use of the transparent composite sheet shown in FIG. 1.
4 is a partially cut-away sectional view showing a liquid crystal display device using the transparent composite sheet shown in FIG. 1.

Hereinafter, the present invention will be described in detail.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to reduce the distortion of the transparent image in the display element using the transparent composite sheet in which glass cloth is embedded in the transparent resin hardened | cured material. As a result, when the glass cloth is impregnated with a transparent resin and cured, the rigid body is cured in a state where one surface is brought into contact with a rigid body such as a metal or glass and the other surface is sandwiched so as to be in contact with a flexible body such as a resin film. It has been found that the unevenness of the surface can be effectively reduced on one surface in contact with the. The surface where this unevenness | corrugation is relatively small is made into a 2nd surface, and the surface on the opposite side to a 2nd surface is made into a 1st surface.

As mentioned above, in the transparent composite sheet in which the transparent glass was impregnated with the conventional glass cloth, the unevenness | corrugation which the fiber shape of a glass cloth reflects arises in the surface. On the contrary, when the transparent resin of the glass cloth impregnated with the transparent resin in the state of being in contact with the flat surface of the rigid body as described above, the flat surface of the rigid body in the second surface is a rigid body, so the stress due to the curing shrinkage Hard to get. Therefore, the second surface in contact with the flat surface of the rigid body becomes flatter than the surface of the conventional transparent composite sheet.

On the other hand, since the first surface is in contact with the flat surface of the member which is softer than the rigid body, the first surface is affected by the stress at the time of curing shrinkage, and has a larger unevenness than the second surface. However, when using a transparent composite sheet, for example as a board | substrate of a display element, when the flatness of a 2nd surface becomes high, light transmittance can be ensured by embedding a part of an adhesive layer with respect to the unevenness | corrugation in a 1st surface side.

That is, the characteristic of this invention is a transparent composite sheet which has an opposing 1st, 2nd surface, Comprising: The said transparent composite sheet contains the transparent resin hardened | cured material and the glass cloth embedded in the said transparent resin hardened | cured material, Although the amplitude of the surface asperity reflecting the fiber shape is relatively large in the range of 0.5 to 5 탆 on the first side, it is very small at 0.4 탆 or less on the second side. For this reason, when using, by laminating an adhesive etc. on the unevenness | corrugation of a 1st surface, when using a transparent composite sheet as a board | substrate through which the light of a display element permeate | transmits, the distortion of a perspective image can be reliably reduced.

Hereinafter, the detail of each component used for obtaining the transparent composite sheet which concerns on this invention, and the manufacturing method of a transparent composite sheet are demonstrated.

(Transparent Resin Cured Product (A))

The transparent resin cured material used for the transparent composite sheet (A) which concerns on this invention will not be specifically limited if it is a resin cured material which has transparency. As transparent resin (a) which provides the hardened | cured material which has such transparency, it is a polyester resin, a polyethylene resin, a poly (meth) acrylic resin, a polystyrene resin, a polycarbonate resin, a polyamide resin, a polyacetal resin, a polyphenylene sulfide resin. , (Meth) acrylic resin, epoxy resin, phenol resin, vinyl ester resin, polyimide resin, melamine resin, urea resin and the like. Only 1 type may be used for the said transparent resin (a), and may be used together 2 or more types.

In the present specification, the (meth) acryl refers to acryl and methacryl generically, and may be acryl or methacryl. Similarly, the (meth) acrylate may be an acrylate or methacrylate. (Meth) acryloyl represents acryloyl and methacryloyl.

Transparent resin (a) is curable transparent resin. It is preferable that transparent resin (a) is liquid curable resin at room temperature (25 degreeC) before hardening. If it is a liquid at room temperature (25 degreeC), it can be easily impregnated into a glass cloth at room temperature.

As said transparent resin (a), it is preferable that it is at least 1 sort (s) chosen from the group which consists of a (meth) acrylic resin, an epoxy resin, and an allyl resin from the point which is easy to obtain a liquid curable resin at room temperature (25 degreeC) before the said hardening. In particular, since both heat resistance and transparency can be improved, a transparent resin having a silsesquioxane skeleton is preferable.

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 at least one of heating and irradiation of active light. The hardened | cured material of the said (meth) acrylic resin has high transparency with respect to visible light. The (meth) acrylic resin preferably has two or more (meth) acryloyl groups because it obtains a crosslinked structure that enhances heat resistance such that a TFT element or a color filter can be formed.

As for the said (meth) acrylic resin, it is more preferable that it is (meth) acrylate which has a (meth) acrylate which has an alicyclic structure, or a triazine ring structure. It is preferable that the (meth) acrylate which has the said alicyclic structure is norbornane dimethylol di (meth) acrylate or dicyclopentadiene dimethanol di (meth) acrylate. The (meth) acrylate having the triazine ring structure is preferably isocyanuric acid tris (2-acryloyloxyethyl) or ε-caprolactone modified isocyanuric acid tris (2-acryloyloxyethyl) . By use of these preferable (meth) acrylate resins, transparency and heat resistance of a transparent composite sheet can be improved further.

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

When transparent resin (a) is a (meth) acrylic resin, the method of irradiating actinic light is preferable. From the viewpoint of improving the production efficiency of the transparent composite sheet while reliably completing the curing reaction, it is preferable to irradiate the active resin with the transparent resin (a) and to heat the transparent resin (a). That is, it is preferable to irradiate an active light beam to the heated transparent resin (a) in the state in which the transparent resin (a) was heated. Moreover, after hardening only by actinic light, hardening reaction can be completed more reliably also by further heating.

In the case of transparent resins, polymerization activation is easy, rapid reaction with high energy is possible, it is also widely used as an irradiation source, and the shielding is easy, so the active light is preferably ultraviolet light. As a light source for irradiating this ultraviolet-ray, a metal halide lamp, a high pressure mercury lamp, etc. are mentioned, for example.

In order to crosslink and harden transparent resin (a) by irradiation of actinic light, it is preferable to use the transparent resin composition containing the said transparent resin (a) and a photoinitiator. Hereinafter, the composition containing other components, such as a transparent resin (a) and a photoinitiator, is made into a transparent resin composition. When transparent resin (a) is the said (meth) acrylic resin, as a photoinitiator, the photoinitiator which generate | occur | produces a radical is used preferably.

Although the said photoinitiator is not specifically limited, For example, benzophenone, N, N'- tetraethyl-4,4'- diamino benzophenone, 4-methoxy-4'- dimethylamino benzophenone, 2, 2- Diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydrate Oxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2,6-dimethylbenzoyl Diphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraqui , 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothia Sol, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine, and the like. 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 with respect to 100 weight part of transparent resin (a), 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. As there is much content of the said photoinitiator, hardening of a transparent resin (a) advances reliably and quickly. In particular, when the content of the photopolymerization initiator is more than the above preferred lower limit, the transparent resin can be sufficiently cured. If content of the said photoinitiator is more than the said preferable upper limit, hardening reaction will advance rapidly and it will become easy to produce problems, such as a crack at the time of hardening and coloring of hardened | cured transparent resin further.

After crosslinking and hardening a transparent resin (a) by at least one of heating and irradiation of an actinic light, heat processing can also be performed at high temperature further. The crosslinking reaction can be further advanced by heat treatment to improve the chemical resistance and the like of the transparent composite sheet, and to stabilize the properties such as the coefficient of linear expansion. It is preferable that the said heat processing conditions are the temperature of 150-250 degreeC, and the conditions of 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. An epoxy resin 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 a cresol novolak type, a triglycidyl isocyanurate type, or Nitrogen-containing cyclic epoxy resins such as hydantoin type, alicyclic epoxy resins, aliphatic epoxy resins, naphthalene type epoxy resins, glycidyl ether type epoxy resins, biphenyl type epoxy resins, and dicyclopentadiene types 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. Moreover, since both heat resistance and transparency can be improved, the epoxy resin which has a silsesquioxane skeleton can also be used. 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 resin composition may contain a hardening | curing agent. When transparent resin (a) is an epoxy resin especially, it is preferable that the said transparent resin composition contains a hardening | curing agent. Although it does not specifically limit as said hardening | curing agent, An organic acid compound, an amine compound, an acid anhydride compound, etc. are mentioned. Only 1 type may be used for hardening | curing agents, and 2 or more types may be used together. It is preferable that the said transparent resin composition contains at least 1 sort (s) of a photoinitiator and a hardening | curing agent.

Tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc. are mentioned as said organic acid compound. Examples of the amine compound include ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, metaphenylenediamine, diaminediphenylmethane, diaminodiphenylsulfonic acid, and the like. 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. Dihydrazide etc. are mentioned as said hydrazide compound. Examples of the imidazole compound include methylimidazole, 2-ethyl-4-methylimidazole, ethyldiimidazole, isopropylimidazole, 2,4-dimethylimidazole, phenylimidazole, and undecyl. Midazole, 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, undecyl Imidazoline, heptadecylimidazoline, 2-phenyl-4-methylimidazoline, and the like.

An acid anhydride compound can also be used as said hardening | curing agent. By use of the said acid anhydride compound, discoloration of a transparent composite sheet can be prevented further. Examples of the acid anhydride compound include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, nadic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methyltetra Hydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, dodecenyl succinic anhydride, dichlorosuccinic anhydride, benzophenonetetracarboxylic anhydride and 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 lower limit of the equivalent of the acid anhydride of the acid anhydride compound is preferably 0.5 equivalent, more preferably 0.7 equivalent, more preferably 1.5 equivalent, and more preferably 1.2 equivalent with respect to 1 equivalent of the epoxy group of the epoxy resin. When the equivalent of the said hardening | curing agent is more than the said preferable minimum, coloring of a transparent composite sheet can be fully suppressed. When the equivalent of the said hardening | curing agent is less than the said preferable upper limit, moisture resistance of a transparent composite sheet will become favorable.

The said transparent resin composition may contain a hardening accelerator. The said hardening accelerator is not specifically limited. As said hardening accelerator, a tertiary amine, an imidazole compound, a quaternary ammonium salt, a quaternary phosphonium salt, an organometallic salt, a phosphorus compound, a 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 compound, 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 is more than the said preferable minimum, a transparent resin composition can be fully hardened. When content of the said hardening accelerator is less than the said preferable upper limit, coloring of a transparent composite sheet can be suppressed further.

As transparent resin (a), curable resin which is a thiol group containing compound which has a silsesquioxane skeleton can also be used.

The thiol group-containing compound having the silsesquioxane skeleton is a hydrolysis condensate (hereinafter also referred to as a hydrolysis condensate (a1)) of a thiol group-containing silane compound represented by the following formula (1). By using curable resin which is a thiol group containing compound which has a silsesquioxane skeleton, transparency and heat resistance of a transparent resin hardened | cured material (A) can be improved further.

In the formula (1), R1 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 R2 has 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. As said R2, a hydrogen atom, a C1-C8 aliphatic hydrocarbon group, a C1-C8 alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc. are mentioned specifically ,. The "hydrocarbon group" in the case of having a thiol group is a group which contains 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 a thiol group containing silane compound represented by the said Formula (1), 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl tripropoxysilane, 3-mercaptopropyl tri part Methoxysilane, 1,4-dimercapto-2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxy Silyl) butane, 1,4-dimercapto-2- (tributoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltrier Methoxysilane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2-mercaptomethyl-3-mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2 -Dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-dimercaptoethyltributoxysilane, etc. are mentioned. Especially, 3-mercaptopropyl trimethoxysilane is preferable because it is easy to obtain while having high reactivity of the hydrolysis reaction. 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 one using the 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.

In addition to the hydrolysis-condensate (a1), the transparent resin (a) is at least one of a compound having an epoxy group (hereinafter also referred to as an epoxy compound (a2)) and a compound having an isocyanate group (hereinafter also referred to as an isocyanate compound (a3)). It is preferable to further contain 1 type. In this case, the transparent resin (a) can be efficiently crosslinked and cured by heating.

Although it does not specifically limit as an epoxy compound (a2), For example, 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, tri A phenol phenol methane type 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 aryl alkylene 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.

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

It is preferable that the molecular weight of the said epoxy compound (a2) is higher. The use of a high molecular weight epoxy compound (a2) increases the flexibility of the cured transparent resin (A). Examples of the high molecular weight epoxy compound (a2) include epoxy resins having epoxy equivalents of 2000 g / equivalent or more (trade names "Epicoat 1010" and "Epicoat 4007P" manufactured by Mitsubishi Chemical Corporation) and epoxy modified silicone resins (Shin-Etsu Chemical Co., Ltd.). Trade name "X-22-163A" manufactured by Kagaku Kogyo Co., Ltd.), polyethyleneglycol diglycidyl ether, etc. are mentioned. Especially, polyethyleneglycol diglycidyl ether is preferable.

Although an isocyanate compound (a3) is not specifically limited, For example, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, etc. are mentioned. 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-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, hydrogenation Xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexyl methane-4,4'- diisocyanate, 1, 3-bis (isocyanate methyl) cyclohexane, methylcyclohexane diisocyanate, and m-tetramethyl xylylene diisocyanate, and dimer diisocyanate which converted the carboxyl group of dimer acid into an isocyanate group, etc. are mentioned. Only 1 type may be used for an isocyanate compound (a3), and 2 or more types may be used together.

It is preferable that an isocyanate compound (a3) is isophorone diisocyanate from a viewpoint of improving transparency and heat resistance of a transparent resin hardened | cured material (A).

It is preferable that the molecular weight of an isocyanate compound (a3) is higher. The use of a high molecular weight isocyanate compound (a3) increases the flexibility of the cured transparent resin (A). 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.). As said polyol, polycarbonate diol, polyester diol, etc. are mentioned.

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), a tertiary amine, an imidazole compound, an 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. Can be. As said imidazole compound, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazole, etc. are mentioned. Examples of the organic phosphine include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, and the like. As said tetraphenyl boron salt, tetraphenyl phosphonium tetraphenyl borate, 2-ethyl-4-methylimidazole 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, octylic acid tin, 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 mentioned.

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) of 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 a transparent resin hardened | cured material (A) 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 resin composition 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 depends 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 to an optimal compounding quantity.

When the polymerization initiator is not used, one thiol group is added and reacted with one carbon-carbon double bond. In the case where the polymerization initiator is used, in addition to reaction of one thiol group with respect to one carbon-carbon double bond, a chain radical reaction proceeds. As a result, when the said polymerization initiator is not used, the thiol group contained in a hydrolysis-condensation product (a1), and the carbon-carbon double bond contained in an unsaturated compound (a4) react in 1: 1 (molar ratio). When the said polymerization initiator is used, the thiol group contained in a hydrolysis-condensation product (a1) and the carbon-carbon double bond contained in an unsaturated compound (a4) do not react at 1: 1 (molar ratio).

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), that is, [mole number of thiol groups contained in the hydrolysis condensate (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 a transparent resin hardened | cured material (A) 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 a polymerization initiator is used, the compounding ratio of the hydrolysis condensate (a1) and the unsaturated compound (a4), that is, the number of moles of thiol group contained in the hydrolysis condensate (a1) / unsaturated compound (a4) Mole number of carbon-carbon double bonds to be referred to hereinafter (hereinafter also referred to as molar ratio D2) is preferably in the range of 0.01 to 1.1. When the molar ratio D2 is 0.01 or more, the water vapor barrier property of the transparent resin cured product (A) can be further improved. Moreover, carbon-carbon double bond remains after hardening, and it becomes difficult, and the weather resistance of a transparent resin hardened | cured material (A) becomes high. 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, tripropylene glycol monoallyl ether, etc. are mentioned. .

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 and the like.

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). Examples of the high molecular weight unsaturated compound (a4) include copolymers of methylallylsiloxane and dimethylsiloxane, copolymers of epichlorohydrin and allyl glycidyl ether (trade name "Epiclomer" manufactured by Diso Corporation, and Nihon Xeon And the allyl group-terminated polyisobutylene polymer (trade name "Epion" manufactured by Kaneka Corporation).

[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), a polymerization initiator may not be used. However, even when the said transparent resin composition contains a hydrolysis-condensation product (a1), it may contain a polymerization initiator. As said polymerization initiator, a photocationic polymerization initiator, an optical radical polymerization initiator, etc. are mentioned. Only 1 type may be used for the said polymerization initiator, and 2 or more types may be used together.

As said photocationic polymerization initiator, the sulfonium salt which is a compound which generate | occur | produces an acid by irradiation of an ultraviolet-ray, an iodonium salt, a metallocene compound, benzointosylate, etc. are mentioned. As a commercial item of the said photocationic polymerization initiator, the brand names "Suracure UVI-6970", "Suracure UVI-6974" and "Suracure UVI-6990" by the Union Carbide company, and the brand name "Iru" by the Ciba Japan company The cure 264 ", and the brand name" CIT-1682 "by the Nippon Soda company are mentioned.

The said radical photopolymerization initiator is not specifically limited. As said radical photopolymerization initiator, a benzophenone, N, N'- tetraethyl-4,4'- diamino benzophenone, 4-methoxy-4'- dimethylamino benzophenone, and 2, 2- diethoxy are mentioned, for example. Acetophenone, benzoin, benzoin methyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutyl phenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclo Hexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2,6-dimethylbenzoyldiphenyl Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2- Ethyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoan Laquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercapto Benzoxazole, 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine, and the like. Especially, 1-hydroxycyclohexyl phenyl ketone is preferable at the point which can suppress coloring of cured resin. In addition, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- has the effect of suppressing the en-thiol reaction and can enhance the storage stability of the transparent resin (a). 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morph Preferred alpha-aminoalkyl phenone type radical photopolymerization initiators, such as a polylin-4-yl-phenyl) -butan-1-one, are preferable.

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

In order to further improve the storage stability of the transparent resin (a), an en-thiol reaction inhibitor can be used. As said en-thiol reaction inhibitor, a phosphorus compound, a radical polymerization inhibitor, a tertiary amine, an imidazole compound, etc. are mentioned.

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, 2, 2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine aluminum salt, and Diphenyl 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 compound, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylhexyl imidazole, 2-undecyl imidazole, and 1-cyanoethyl-2-methyl are Midazoles and the like.

Among the above phosphorus compounds, triphenyl phosphite is preferred. The triphenyl phosphite has a high inhibitory effect of the en-thiol reaction and is easy to handle since it is a liquid at room temperature. 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.

N-nitrosophenyl hydroxyl amine aluminum salt is preferable among the said radical polymerization inhibitors. The said N-nitrosophenyl hydroxylamine aluminum salt can suppress en-thiol reaction even in a small quantity, and can improve transparency of hardened | cured resin (A). 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. The benzyldimethylamine has a high inhibitory effect on the en-thiol reaction and is easy to handle since it is a liquid at room temperature. It is preferable that content of the said tertiary amine is 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 a hydrolysis-condensation product (a1) and an unsaturated compound (a4) can be suitably changed according to a 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 hardened | cured material (A) exists in the said range, the light transmittance of a transparent composite sheet can be made still higher.

A transparent resin hardened | cured material (A) is obtained, for example also by hardening | curing the material which does not add the glass cloth (b) at the time of preparation of the said transparent composite sheet. 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 the filament diameter is 10 μm or less, the bending strength is further increased.

It is preferable that the thickness of the single yarn is 10 to 20 in the number of times of Tex. If it is ten 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.

It is preferable that the twist count of single yarn is 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 transparent composite sheet surface 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.

Since the distortion of the transparent image of the transparent composite sheet can be further reduced, the glass cloth (b) is preferably a glass cloth that has been opened by the opening treatment so that the opening degree of the following formula (X) is within the range of 2 to 4.

Opening degree = diameter of fiber bundle / fiberglass single yarn of fiber bundle in glass cloth (b) after opening processing. Formula (X)

Since the distortion of the transparent composite sheet can be further reduced, the glass cloth (b) included in the transparent composite sheet according to the present invention has a filament diameter of 3 to 10 µm, a number of tex counts of 10 to 20, and a twist number of 2 /. The glass cloth (b) is made of glass fiber single yarn of inch or less, and the cloth cloth (b) has a density of 40 to 70 pieces / inch of warp and weft yarn so that the fineness of the formula (X) is within the range of 2 to 4. It is preferable that it is the glass cloth which opened the opening.

Since the thickness of the glass cloth (b) changes with the kind of yarn used, the weave density, and the degree of fineness, it is difficult to define the exact range. Illustrating the thickness of glass cloth (b), 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 using a transparent composite sheet as a display element substrate or a solar cell substrate, the alkali component derived from a 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. With respect to fiber diameter, fiber bundle diameter, weight per unit area as the glass cloth, weave density and thickness, and the like, the E glass is equipped with various standard products. In addition, E glass is preferably used in view of performance improvement, cost reduction, and ease of availability.

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 said transparent resin composition, the said hardened | cured resin (A), and the said transparent composite sheet are respectively a plasticizer, a weathering agent, antioxidant, a heat stabilizer, a lubricating agent, an antistatic agent, a whitening agent, a coloring agent, and an electroconductive agent according to necessity in various uses. Agent, a release agent, a surface treating agent, a viscosity modifier, and the like.

(Transparent composite sheet)

In FIG. 1, the transparent composite sheet which concerns on one Embodiment of this invention is typically shown with partial notch cross section.

As shown in FIG. 1, the transparent composite sheet 1 has the 1st surface 1a and the 2nd surface 1b. In this embodiment, the 1st surface 1a has an unevenness, and the 2nd surface 1b is a flat surface. The amplitude of the surface irregularities is 0.5 to 5 탆 on the first face 1a and 0.4 탆 or less on the second face 1b.

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

As a manufacturing method of the transparent composite sheet which concerns on this invention, when a glass cloth is impregnated and hardened | cured, one side is made to contact a rigid body, such as a metal or glass, and the other side (other side) is made of the same as a resin film. The manufacturing method which hardens a transparent resin (a) in the state sandwiched so that it may contact a flexible body is mentioned. As a result, surface irregularities due to hardening shrinkage are less likely to occur in the surface in contact with the rigid body, and surface irregularities are concentrated in the surface in contact with the flexible body. Therefore, in the obtained transparent composite sheet, one side becomes flat and only one side has an unevenness | corrugation.

The rigid body has a flat surface. It is preferable that the said rigid body has at least 1 sort (s) of material chosen from the group which consists of a metal, glass, and a ceramic. The flexible body has a flat surface. The flexible body is a flexible body more flexible than the rigid body.

Although it does not specifically limit as a specific manufacturing method, For example, the following methods are mentioned.

A transparent resin (a) having fluidity is applied on the glass cloth (b) at room temperature or under heating, and the transparent resin (a) is impregnated (absorbed) into the glass cloth (b) to obtain a composite material. The composite material is a transparent composite material. The composite material is a glass cloth impregnated with a curable transparent resin. Next, the composite material is dried as necessary. Thereafter, the composite material is sandwiched between the metal roll and the resin film. Thereby, one side of a composite material is made to contact a metal roll, and the other side is made to contact a resin film. The thickness is made uniform while adjusting the thickness of the transparent composite material in this state, and at least one of heating and irradiation of actinic light is performed in this state. Thereby, the transparent composite material is crosslinked and cured to form a transparent composite sheet. Then, a transparent composite sheet is obtained by peeling a transparent composite sheet from a metal roll and a resin film.

In addition, when impregnating the transparent resin (a) in the glass cloth (b), the glass cloth (b) is immersed in the transparent resin (a), and the transparent resin (a) is glass cloth ( b) can also be impregnated.

In addition, the transparent composite material may be sandwiched between the metal belt and the resin film using a metal belt instead of a metal roll. In addition, a flexible body more flexible than the rigid body may be used instead of the resin film.

Moreover, in order to complete hardening reaction reliably, after hardening a transparent resin (a) only by actinic light, it can also heat further.

Moreover, actinic light can also be irradiated to the composite material which contacted the said rigid body, in the state heated the rigid bodies, such as a metal roll. That is, heating and irradiation of actinic light may be performed simultaneously, and hardening by heating and hardening by irradiation of an actinic light may be advanced simultaneously.

Moreover, without using a resin film, one side of a transparent composite material can be made to contact a metal roll, and a transparent composite material can also be hardened in the state which makes nothing contact with another side. In this case, however, the amount of resin on the glass cloth on the surface where nothing is in contact with it is likely to fluctuate. Therefore, warpage is likely to occur in the resulting transparent composite sheet.

The thickness of the transparent composite sheet according to the present invention is not particularly limited, but considering the specifications of the glass cloth (b) and the ratio of the transparent resin (a) and the glass cloth (b), the thickness is preferably in the range of 25 to 200 μm. Do.

When it is necessary to make thickness of a transparent composite sheet thicker than 200 micrometers, it is preferable to laminate | stack and cure a plurality of sheet-like transparent composite materials, or to harden, or to repeat sheeting and hardening of a transparent composite material, and to obtain a transparent composite sheet. Do. In addition, a plurality of transparent composite sheets may be laminated through a suitable adhesive layer.

(Size of surface irregularities)

The transparent composite sheet according to the present invention has opposing first and second surfaces, and an amplitude of surface irregularities coinciding with a period of inclination or weft of the glass cloth on the surface of the sheet is 0.5 to 5 μm in the first surface. And 0.4 μm or less in the second aspect. As is clear from the above-described method for producing a transparent composite sheet, unevenness occurs on the surface in the surface where the transparent composite material is in contact with the flexible body such as a resin film, and uneven surface in the surface in contact with the rigid body such as metal, glass or ceramic. It is hard to occur in. Thus, the surface in contact with the flexible body becomes the first surface, the surface in contact with the rigid body becomes the second surface, and the specific amplitude range is realized respectively. From the viewpoint of further minimizing the cell gap variation or further reducing the distortion of the transmission phase, the amplitude of the surface irregularities is preferably 0.3 µm or less, and more preferably 0.2 µm or less in the second aspect.

In addition, the amplitude of the surface irregularities can be measured using a general stylus type surface measuring device.

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 high, and the image becomes clear.

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

In order to improve the water vapor barrier property of a transparent composite sheet, it is preferable that the water vapor transmittance of the transparent composite sheet which concerns on this invention is 1 * 10 <^-1> g / m <^2> days or less in 40 degreeC and 90% of a relative humidity. In order to improve 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 meter is used. As a measuring apparatus, "All-automatic haze meter TC-HIIIDPK" by the Tokyo Denshoku Co., etc. is 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 surface smoothing layer or the hard coating layer, a known surface smoothing agent or a hard coating agent is applied, for example, on a transparent composite sheet and dried to remove the solvent as necessary. Next, the surface smoothing 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, conventionally known methods such as roll coating, spin coating, wire bar coating, dip coating, extrusion, curtain coating or spray coating can be employed.

By laminating the gas barrier layer on the transparent composite sheet according to the present invention, the barrier property of water vapor or 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.

(Application of Laminated Sheet and Transparent Composite Sheet)

In FIG. 2, an example of the laminated sheet using the transparent composite sheet shown in FIG. 1 was shown typically by partial notch sectional drawing.

As shown in FIG. 2, the laminated sheet 11 has a transparent composite sheet 1, a polarizing plate 12, and an adhesive layer 13. The polarizing plate 12 is laminated | stacked on the 1st surface 1a of the transparent composite sheet 1. The adhesive layer 13 is provided between the polarizing plate 12 and the 1st surface 1a of the transparent composite sheet 1. The pressure-sensitive adhesive layer 13 is provided to be bonded to the polarizing plate 12 and the first surface 1a of the transparent composite sheet 1.

In the transparent composite sheet which concerns on this invention, the unevenness | corrugation which is larger in a surface than the 2nd surface side in the 1st surface side is present. However, as mentioned above, when using a transparent composite sheet as a board | substrate of display elements, such as a liquid crystal display element, the influence of the unevenness | corrugation of the surface of a 1st surface by laminating | stacking an adhesive layer on a 1st surface, etc. You can alleviate or eliminate it.

Therefore, this invention can be used suitably for the laminated sheet used for optical uses, such as a liquid crystal display element. As such a laminated sheet, the transparent composite sheet of this invention, the polarizing plate laminated | stacked on the 1st surface of a transparent composite sheet, and the polarizing plate and the 1st surface of a transparent composite sheet so that the said polarizing plate may be bonded to the 1st surface of a transparent composite sheet The laminated sheet provided with the adhesive layer provided in between is mentioned. In this laminated sheet, a polarizing plate is laminated indirectly on the 1st surface of a transparent composite sheet. In this case, since the influence of the unevenness | corrugation of the 1st surface of a transparent composite sheet is alleviated or eliminated by an adhesive layer, using a transparent adhesive layer can make it hard to produce the distortion of the permeation | transmission of the light which permeate | transmitted the laminated sheet.

Moreover, the laminated sheet which concerns on this invention may have a structure which has two transparent composite sheets of this invention, and is laminated and integrated by bonding the 2nd surface of two transparent composite sheets together. That is, like the laminated sheet 21 shown in FIG. 3, two transparent composite sheets 1 can also be bonded together and the 2nd surface 1b can be used. In this case, a polarizing plate is bonded to the 1st surface located in each outer side of two transparent composite sheets through the adhesive layer as above, respectively. In the laminated sheet thus obtained, the influence of the unevenness on the surface of the first surface is alleviated or eliminated by the pressure-sensitive adhesive layer, and in the part where the transparent composite sheets are joined, the second surfaces having less unevenness of the surface face each other. Therefore, distortion of the transmission image is unlikely to occur. In addition, when bonding the 2nd surface of a transparent composite sheet, you may use an appropriate adhesive.

Further, the transparent composite sheet is used as a laminated sheet in which one transparent composite sheet is laminated on one surface of a member from a first surface side, and the other transparent composite sheet is laminated on the other surface of the member from a first surface side. It may be. In this laminated sheet, the outer surface becomes the second surface of the transparent composite sheet.

Moreover, in this invention, the said transparent composite sheet and laminated sheet are used suitably as a light transmissive substrate of display elements, such as a liquid crystal display element, for example. As such a liquid crystal display element, the suitable liquid crystal display element provided with a 1st board | substrate, the 2nd board | substrate opposing the said 1st board | substrate through the gap, and the liquid crystal layer arrange | positioned between 1st and 2nd board | substrate are mentioned. have. According to this invention, in this liquid crystal display element, at least one of a 1st and 2nd board | substrate is a transparent composite sheet which the transparent composite sheet of this invention, the polarizing plate laminated | stacked on the 1st surface of the said transparent composite sheet, and a polarizing plate It is a laminated sheet provided with the adhesive layer provided between the 1st surface of a transparent composite sheet and a polarizing plate so that it may be bonded to the 1st surface of the transparent composite sheet. Therefore, in the said laminated sheet, since the distortion of a transmission image hardly arises, the display quality of the characteristic of a liquid crystal display element can be improved.

In FIG. 4, an example of the liquid crystal display element using the transparent composite sheet shown in FIG. 1 was shown typically in cross section.

The liquid crystal display element 31 shown in FIG. 4 is provided with the laminated sheet 11 which is a 1st board | substrate, the laminated sheet 11 which is a 2nd board | substrate, and the liquid crystal layer 32. As shown in FIG. The laminated sheet 11 which is a 1st board | substrate and the laminated sheet 11 which is a 2nd board | substrate oppose across gaps. The liquid crystal layer 32 is arrange | positioned between the laminated sheet 11 which is a 1st board | substrate, and the laminated sheet 11 which is a 2nd board | substrate. In addition, the liquid crystal layer 32 includes the second surface 1b of the transparent composite sheet 1 in the laminated sheet 11 that is the first substrate and the transparent composite sheet 1 of the laminated sheet 11 that is the second substrate. It is in contact with the 2nd surface 1b of ().

In this case, the laminated sheet which has a structure which laminated | stacked two transparent composite sheets can also be used. That is, the laminated sheet which bonded the 2nd surface of two transparent composite sheets, and laminated | stacked the polarizing plate through the adhesive layer on the outer side of the 1st surface of each transparent composite sheet can also be used. In other words, the laminated sheet includes a second transparent composite sheet laminated so that the second surfaces are bonded to the second surface of the transparent composite sheet, a second polarizing plate laminated on the first surface of the second transparent composite sheet, You may further include the 2nd adhesive layer provided between the 1st surface of a 2nd transparent composite sheet and a 2nd polarizing plate.

Hereinafter, an Example and a comparative example are given and this invention is demonstrated concretely. 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 Co., Ltd.) and bis [4- (acryloyloxyethoxy) phenyl] fluorene (og) 0.5 parts by weight of 1-hydroxycyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Japan) as a photopolymerization initiator was added to 48 parts by weight of Sol EA-0200, manufactured by Osaka Gas Chemical Co., Ltd. 1 was obtained.

In the obtained transparent resin liquid 1, glass cloth (b) which is E glass of thickness 42 micrometers and the weight of 48 g / m <^2> per unit area was immersed continuously, and the transparent resin liquid 1 was immersed in the glass cloth (b). In this way, a transparent composite material was obtained.

Subsequently, while the transparent resin liquid 1 superposed the polyester film (The Toyobo company make, article number Cosmo shine A4100) of 100 micrometers in thickness on one surface of the transparent composite material impregnated in the glass cloth (b), the surface was flat. The polyester film was laminated on the transparent composite material on the metal roll, and the thickness of the transparent composite material was uniformed. Next, 2000 mJ / cm <^2> (365 nm) UV light was irradiated with the high pressure mercury lamp from the polyester film side, conveying the transparent composite material which the polyester film laminated on the metal roll, and bridge | crosslinking the transparent resin in a transparent composite material And hardened. Thereafter, the polyester film was peeled off to obtain a transparent composite sheet.

(Example 2)

30 parts by weight of 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.), which is a transparent resin (a), and a bisaryl fluorene system 7: 3 (weight ratio) mixture of methylhexahydro phthalic anhydride and hexahydro phthalic anhydride which is a hardening | curing agent in 20 weight part of epoxy resins (Oncoat EX-1010, Nagase Sangyo Co., Ltd.) (Ricaside MH-700, Shin-Nihon Rika) 42 parts by weight) and 1 part by weight of a curing accelerator (Hiskorin PX-4ET, manufactured by Nippon Chemical Industries, Ltd.) were added and mixed to obtain a transparent resin solution 2.

The glass cloth (b) which is E glass of thickness 68micrometer and the weight 81g / m <^2> per unit area was immersed in the obtained transparent resin liquid 2, and the transparent resin liquid 2 was impregnated into the glass cloth (b), irradiating an ultrasonic wave. Thus, the transparent composite material in which the transparent resin liquid 2 was impregnated into the glass cloth (b) was obtained.

Thereafter, the transparent composite material was pulled up, placed on a flat stainless steel plate, and degassed while depressurizing to a pressure of 10 Pa in the decompression chamber. A 75 μm-thick polyimide film (Toray DuPont Co., product No. Kapton 300H) was superimposed on the surface of the transparent composite material on the stainless steel plate taken out of the pressure reduction chamber, and passed through a laminator to uniform the thickness of the transparent composite material. Next, after heating for 60 minutes at 100 degreeC in oven, it heated further at 200 degreeC for 180 minutes, bridge | crosslinking and hardening the transparent resin in a transparent composite material. Thereafter, the polyimide film was peeled off to obtain a transparent composite sheet.

(Example 3)

50 parts by weight of a thiol group-containing compound having a silsesquioxane skeleton which is a transparent resin (a) (HBSQ101, manufactured by Arakawa Chemical Industries, Ltd., corresponding to the hydrolysis-condensation product (a1)) and isocyanurate triallyl 30 0.2 weight part of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholino propane- 1-one (irgacure 907, Ciba Japan company) which is a photoinitiator is added to a weight part, and it mixes The transparent resin liquid 3 was obtained.

In the obtained transparent resin liquid 3, glass cloth (b) which is E glass of thickness 42 micrometers and the weight of 48 g / m <^2> per unit area was immersed continuously, and the transparent resin liquid 3 was immersed in the glass cloth (b). Thus, the transparent composite material in which the transparent resin liquid 3 was impregnated into the glass cloth (b) was obtained.

Subsequently, a polyester film was laminated on the transparent composite material on a metal roll having a flat surface while superposing a polyester film (Toyobo Co., Ltd. product number Cosmoshine A4100) having a flat surface of 100 μm on one side of the transparent composite material. And thickness was equalized. Next, 2000 mJ / cm <^2> (365 nm) UV light was irradiated from the polyester film side, conveying the transparent composite material laminated | stacked the polyester film on the metal roll, and the sheet-like transparent composite material was crosslinked and hardened | cured. . Thereafter, the polyester film was peeled off to obtain a transparent composite sheet.

(Example 4)

A transparent composite sheet was obtained in the same manner as in Example 3 except that the glass cloth (b) was changed to a glass cloth having a thickness of 92 μm and a weight of 104 g / m ² per unit area.

(Example 5)

To 70 parts by weight of a polysilsesquioxane solution (comparable to SQ102-1, manufactured by Arakawa Chemical Industries, Ltd., corresponding to the hydrolysis-condensation product (a1)) of transparent resin (a) and 50 parts by weight of isophorone diisocyanate And 0.2 weight part of dibutyltin dilaurate which is a reaction catalyst were added, and it mixed, and obtained the transparent resin liquid 4.

In the obtained transparent resin liquid 4, the glass cloth (b) which is E glass of thickness 68 micrometers and the weight 81 g / m <^2> per unit area was immersed, and the transparent resin liquid 4 was impregnated into the glass cloth (b), irradiating an ultrasonic wave. In this way, a transparent composite material was obtained.

Thereafter, the transparent composite material was pulled up, placed on a flat stainless steel plate, and dried at 80 ° C. for 10 minutes in an oven. Next, the surface of the transparent composite material on the stainless steel plate is superimposed on the surface of a 100 μm polyester film (Toyobo Co., Ltd. product number Cosmoshine A4100) while passing through a laminator to uniform the thickness of the transparent composite material, and in the oven 20 minutes at 120 degreeC, it bridge | crosslinked and hardened the transparent composite material which the polyester film laminated. Thereafter, the polyester film was peeled off to obtain a transparent composite sheet.

(Comparative Example 1)

The glass cloth (b) which is E glass of thickness 42 micrometers and the weight of 48 g / m <^2> per unit area was continuously immersed in the transparent resin liquid 1 produced in Example 1, and the transparent resin liquid 1 was immersed in the glass cloth (b). Impregnated. In this way, a transparent composite material was obtained.

Subsequently, it laminated on the metal roll, superimposing a polyester film on both surfaces of a transparent composite material, and made the thickness of a transparent composite material uniform. Next, 2000 mJ / cm <^2> (365 nm) UV light was irradiated with the high pressure mercury lamp from the polyester film side, conveying on a metal roll, and the transparent composite material laminated | stacked the polyester film was hardened. Then, the polyester film was peeled off and the transparent composite sheet was obtained.

(Comparative Example 2)

The transparent resin solution 2 prepared in Example 2 was immersed in the glass cloth (b), which is an E glass having a thickness of 68 μm and a weight of 81 g / m ² per unit area, and the transparent resin solution 2 was coated with a glass cloth (b). Impregnation). In this way, a transparent composite material was obtained.

Thereafter, the transparent composite material is pulled up and placed on a 75 μm-thick polyimide film (Toray DuPont Co., Ltd. product Kapton 300H) in which the periphery is affixed on a stainless steel plate and fixed, Defoaming. The polyimide film taken out from the pressure reduction chamber was allowed to pass through a laminator while superimposing a 75 μm thick polyimide film (Toray Dupont Co., product No. Kapton 300H) on the exposed surface of the transparent composite material on the stainless steel plate to which the polyimide film was attached. The thickness of the material was uniformed. Next, after heating for 60 minutes at 100 degreeC in oven, it heated further at 180 degreeC for 180 minutes, bridge | crosslinking and hardening the laminated composite material which the polyester film laminated. Thereafter, the polyimide film was peeled off to obtain a transparent composite sheet.

(Example 6)

27 parts by weight of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (A-BPEF, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a transparent resin (a) and ethoxylated isocyanur 63 parts by weight of acid triacrylate (A-9300, manufactured by Shinnakamura Chemical Industries, Ltd.), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one which is a polymerization initiator (Irgacure 907, manufactured by Ciba Japan Co., Ltd.) 0.2 parts by weight was added and mixed to obtain a transparent resin solution 6.

In the obtained transparent resin liquid 6, glass cloth (b) which is E glass of thickness 42 micrometers and the weight of 48 g / m <^2> per unit area was immersed continuously, and the transparent resin liquid 6 was impregnated into the glass cloth (b). In this way, a transparent composite material was obtained.

Subsequently, the surface temperature of the transparent resin liquid 6 was superimposed on one surface of the transparent composite material impregnated in the glass cloth (b) while superposing a polyester film having a flat surface having a thickness of 100 μm (manufactured by Toyobo Co., Ltd. product No. Cosmo shine A4100). The polyester film was laminated on the transparent composite material on a metal roll having a surface heated to 130 ° C., and the thickness of the transparent composite material was uniformed. Next, 2000 mJ / cm <^2> (365 nm) UV light was irradiated with the high pressure mercury lamp from the polyester film side, conveying the transparent composite material in which the polyester film was laminated on the heated said metal roll, and transparent in a transparent composite material The resin was crosslinked and cured. After peeling from a metal roll, the polyester film was peeled further and the transparent composite sheet was obtained.

(Example 7)

48 parts by weight of ethoxylated isocyanuric acid triacrylate (A-9300, manufactured by Shin-Nakamura Chemical Industries, Ltd.), which is a transparent resin (a), ε-caprolactone modified ethoxylated isocyanuric acid triacrylate (A-9300 -1CL, 48 parts by weight of Shin-Nakamura Chemical Industries, Ltd., and 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (A-BPEF, manufactured by Shin-Nakamura Chemical Industries, Ltd.) 0.4 part by weight of 1-hydroxycyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Japan) as a polymerization initiator was added to 4 parts by weight of the resulting mixture, and a transparent resin solution 7 was obtained.

In the obtained transparent resin liquid 7, glass cloth (b) which is T glass with a thickness of 70 micrometers and a weight of 80 g / m <^2> per unit area was continuously immersed, and the transparent resin liquid 7 was immersed in the glass cloth (b). In this way, a transparent composite material was obtained.

Subsequently, the surface temperature of the transparent resin liquid 7 was superimposed on one surface of the transparent composite material impregnated in the glass cloth (b) while superimposing a polyester film (Toyobo Co., Ltd. product number Cosmoshine A4100) having a flat surface of 100 µm in thickness. The polyester film was laminated on the transparent composite material on a metal roll having a surface heated to 100 ° C., and the thickness of the transparent composite material was uniformed. Next, 2000 mJ / cm <^2> (365 nm) UV light was irradiated with the high pressure mercury lamp from the polyester film side, conveying the transparent composite material in which the polyester film was laminated on the heated said metal roll, and transparent in a transparent composite material The resin was crosslinked and cured. After peeling from a metal roll, the polyester film was peeled further and the transparent composite sheet was obtained.

(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

The refractive index nD (wavelength 589.3 nm) was measured by the digital Abbe refractometer (made by Elmer). The transparent resin solutions 1-7 used in the Example and the comparative example were hardened, and the refractive index of the hardened | cured material (transparent resin hardened | cured material (A)) of the transparent resin (a) used by the Example and the comparative example was evaluated. The manufacturer's nominal value was adopted for the refractive index of the glass cloth (b).

(3) Surface irregularities (amplitude)

The shape of the transparent composite sheet surface was measured by the stylus type surface shape measuring apparatus P-16 + (made by KLA-Tencor). On the surface of the transparent composite sheet, a line passing through the intersection point of the warp and the weft and the point (basket hole) in which there is no fiber surrounded by the warp and the weft in a direction forming approximately 45 ° with the warp and the weft of the glass cloth in the sheet. The surface shape of the phase was measured, and the amplitude of the surface irregularities appearing periodically at the intersection of the warp and the weft and the point where the fiber surrounded by the warp and the weft did not exist (a basket hole) were determined.

(4) phase clarity

In accordance with JIS K7374, the filamentous property of the obtained transparent composite sheet was measured using the filamentation measuring instrument ICM-1T (made by Suga Shikeki Co., Ltd.). Image sharpness (%) in optical comb trace width 0.125 mm was calculated | required.

(5) 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).

(6) 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.).

(7) 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.

(8) coefficient of linear expansion

After using the TMA / EXSTAR6000 type thermal stress distortion measuring device (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.

(9) glass transition temperature (Tg)

Using the DVA-200 type viscoelasticity measuring device (manufactured by Haiti Keisoku Seiko Co., Ltd.), the resultant transparent composite sheet was heated at a rate of 20 ° C./min from room temperature to 300 ° C., then cooled to 30 ° C., and then 20 ° C. / The temperature was raised at the rate of minutes and the viscoelastic properties were measured. The peak temperature of tan-delta at the time of the second temperature increase was made into glass transition temperature.

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.

1: transparent composite sheet
1a: first side
1b: second side
11: laminated sheet
12: polarizer
13: adhesive layer
21: laminated sheet
31: liquid crystal display element
32: liquid crystal layer

Claims (5)

Preparing a glass cloth impregnated with a curable transparent resin having transparency after curing;
A glass cloth in which the curable transparent resin is impregnated between a rigid body having at least one material selected from the group consisting of metal, glass and ceramic and having a flat surface and a flexible body having a flat surface and more flexible than the rigid body The manufacturing method of the transparent composite sheet provided with the process of sandwiching and hardening the said curable transparent resin by at least one of heating and irradiation of a light ray. The manufacturing method of the transparent composite sheet of Claim 1 which uses a resin film as said flexible body. delete delete delete

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