TW201211011A - Curable composition and transparent composite sheet - Google Patents

Abstract

Provided is a curable composition which provides a cured product that has excellent transparency and high heat resistance and is capable of withstanding an inorganic material layer-forming process at 200 DEG C or more. This curable composition contains at least one (meth)acrylate compound selected from among (meth)acrylate compounds having a triazine skeleton and represented by formula (1) and (meth)acrylate compounds having a triazine skeleton and represented by formula (2). A cured product obtained by curing this curable composition has a refractive index at 589 nm of 1.525-1.535 (inclusive) and a glass transition temperature of 200 DEG C or more; or alternatively, the cured product obtained by curing this curable composition has a refractive index at 589 nm of 1.557-1.571 (inclusive) and a glass transition temperature of 200 DEG C or more.

Description

201211011 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a curable composition capable of producing a cured product excellent in transparency and heat resistance. Further, the present invention relates to a transparent composite sheet which is used in applications requiring transparency such as a substrate for display elements, and has a cured product obtained by curing the curable composition and a glass embedded in the cured product. fiber. [Prior Art] A glass substrate is widely used for a display element substrate such as a liquid crystal display element or an organic EL (Electro Luminescence) display element, and a solar cell substrate. However, the glass substrate has a problem that it is easily broken, the bendability is low, and the weight cannot be reduced. Therefore, in recent years, the use of a plastic substrate in place of a glass substrate has been studied. For example, Patent Document 1 discloses a plastic substrate obtained by impregnating a glass cloth with a resin composition and drying it to obtain a prepreg, and then pressing the prepreg while pressing the prepreg. Heat hardened. [Prior Art] [Patent Document 1] [Patent Document 1] JP-A-2004-1 5 1291 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] In a display element and a solar cell, an inorganic material is often used. The inorganic material layer is formed as a semiconductor layer or a conductive layer. In the process of forming the inorganic material layer, the substrate is heated to about 200 to 300 °C. Since the glass substrate is highly resistant to heat, it can withstand a high temperature of about 200 to 3 〇〇 °c. With this

Reduced to a large extent. Particularly in the use of a plastic substrate, the deformation caused by heating and the decrease in the modulus of elasticity are a major problem in the process of forming an inorganic material layer. The deformation and the modulus of elasticity caused by the heating of the plastic substrate are clearly expressed by the glass transition temperature of the resin material (curable compound) used in the plastic substrate. Therefore, for the heat resistance of the plastic substrate, the glass transition temperature of the resin material constituting the plastic substrate is important. On the other hand, in order to solve the problem of heat resistance of a plastic substrate, a technique for forming an inorganic material layer at a relatively low temperature (e.g., about 180 ° C) has been studied. However, in the low-temperature process, it is difficult to sufficiently ensure the characteristics of the semiconductor or the conductor as the inorganic material layer and the reliability of the operation of the element. Therefore, in order to form an inorganic material layer, a temperature of about 200 ° C is required. Further, in the conventional plastic substrate, not only heat resistance is low, but also transparency and toughness are low. An object of the present invention is to provide a curable composition and a transparent composite sheet using the curable composition, which is capable of producing a cured product which is excellent in transparency and has high heat resistance and can be manufactured to withstand 158155.doc 201211011 A cured product of a process of forming an inorganic material layer above 200 °C. A limited object of the present invention is to provide a curable composition and a transparent composite sheet using the curable composition, which is capable of producing a cured product having excellent transparency and high heat resistance, and can be produced. A hardened material capable of withstanding a process of forming an inorganic material layer above 220 °C. A further object of the present invention is to provide a curable composition and a transparent composite sheet using the curable composition, which is capable of producing a cured product excellent in toughness. [Technical means for solving the problem] According to a broad aspect of the present invention, a curable composition comprising a (meth) acrylate compound having a three-till skeleton represented by the following formula (1) and At least one of the (meth) acrylate compounds having a three-till skeleton represented by the formula (2), and the cured product after hardening has a refractive index of 1.525 or more and 1.535 or less at 589 nm, and the cured product The glass transition temperature is 200 ° C or higher; or, the cured product after hardening has a refractive index of 1.575 or more and 1.571 or less at 589 nm, and the glass transition temperature of the cured product is 200 ° C or higher. [1] R1 H2C II C-C 0

R2 I 0 a CH-CH

Formula (1) 158155.doc 201211011 In the above formula (1), 1 or 2 is also indicated. R1 to R6 represent a hydrogen atom or a methyl group, respectively, and n1 to n3 are divided into two groups.

In the above formula (2), R1 to R6 each represent a hydrogen atom or a methyl group, and the total of the coffee grains 113 is S, and represents 0.5 to 3. The curable composition of the formula (7) is preferably a curable composition which is used by embedding a glass fiber in a cured product after curing. In a specific aspect of the curable composition of the present invention, the (meth) acrylate compound having the three-till skeleton represented by the above formula (1) and the three-call represented by the above formula (2) are contained. Skeletal (meth) acrylate vinegar compound. In another specific aspect of the curable composition of the present invention, further comprising a refractive index modifier, in another specific aspect of the curable composition of the present invention, the (fluorenyl) acrylic acid having a dicyclopentyl skeleton is contained. An ester compound, a (fluorenyl) acrylate compound having a first skeleton, a (fluorenyl) acrylate compound having a dioxane skeleton, or a bismaleimide compound is used as the above-mentioned refractive index modifier. In another specific aspect of the curable composition of the present invention, a (meth)acrylic acid g-containing compound having a dicyclopentyl skeleton, a (meth) acrylate compound having an anthracene skeleton, or a dioxane skeleton is contained. The (meth) acrylate 158155.doc 201211011 compound is used as the above refractive index modifier. In still another specific aspect of the curable composition of the present invention, the (meth) acrylate compound having a dicyclopentyl skeleton is a dicyclopentyl skeleton represented by the following formula (3) ( Mercapto) acrylate compound. [11], 11?12 H2C=C-g-〇一CH厂开-C=CH2 Formula (3) In the above formula (3), R11 and R12 each represent a hydrogen atom or a fluorenyl group. In still another specific aspect of the curable composition of the present invention, the refractive index adjusting agent is a (fluorenyl) acrylate compound having a dicyclopentyl skeleton represented by the above formula (3). In still another specific aspect of the curable composition, the (meth) acrylate compound having an anthracene skeleton is a (fluorenyl) acrylate compound having an anthracene skeleton represented by the following formula (11), and is as follows The (meth)acrylic acid vinegar compound having an anthracene skeleton represented by the formula (12) or the (fluorenyl)acrylic acid vinegar compound having an anthracene skeleton represented by the following formula (13). [Chemical 4]

Formula (11) 158155.doc • 8 - 201211011 In the above formula (11), R11 to R14 each represent a hydrogen source & thick or methyl group, and ml and m2 respectively represent 1 or 2. [Chemical 5]

Formula (12) In the above formula (12), 'R11 and R12 each represent a hydrogen atom or a methyl group.

N I Η Ο X Ο R12 Formula (13) In the above formula (13), R11 and R12 each represent a hydrogen atom or a fluorenyl group. In still another specific aspect of the curable composition of the present invention, the refractive index adjusting agent is a (fluorenyl) acrylate compound having an anthracene skeleton represented by the above formula (1), and is represented by the above formula (12) The (fluorenyl) acrylate compound having an anthracene skeleton or the (fluorenyl) acrylate compound having a tibia drug represented by the above formula (13). In another specific aspect of the curable composition of the present invention, the (meth) acrylate compound having a disulfide skeleton is a (meth) acrylate compound represented by the following formula (21). 158155.doc 201211011 [Chemistry 7]

C—Ο—CH2

Formula (21) In the above formula (21), R11 and R12 each independently represent a hydrogen atom or a methyl group. In still another specific aspect of the curable composition of the present invention, the refractive index adjusting agent is a (meth)acrylic acid S compound having a dinonankane skeleton represented by the above formula (21). In another specific aspect of the curable composition of the present invention, the bismaleimine compound is a bismaleimide compound represented by the following formula (31). [化8]

In the above formula (31), R21 to R24 each independently represent a hydrogen atom or a fluorenyl group, and R25 and R26 each independently represent a hydrogen atom, a fluorenyl group or an ethyl group. In another specific aspect of the curable composition of the present invention, the refractive index adjusting agent is a bismaleimine compound represented by the above formula (31). In other specific aspects of the curable composition of the present invention, the cured product after hardening has a refractive index of not less than 1.525 and not more than 1.535 at 889 nm, and the glass transition temperature of the cured product is 200. (: above. 158155.doc -10- 201211011 In another specific aspect of the curable composition of the present invention, the cured product after hardening has a refractive index of 1.575 or more and 1.571 or less at 589 nm, and the cured product The glass transition temperature is 20 (TC or more. The transparent composite sheet of the present invention has a cured product obtained by curing the curable composition according to the present invention, and a glass fiber embedded in the cured product. In a specific aspect of the transparent composite panel, the glass fiber is T glass or E glass. The glass fiber is preferably τ glass, and more preferably bismuth glass. Other specifics of the transparent composite board of the present invention In the aspect, the transmittance at a wavelength of 550 nm is 85% or more. In another specific aspect of the transparent composite panel of the present invention, the average linear expansion coefficient at ~2〇〇〇c is 20 ppm/ Further, in another specific aspect of the transparent composite sheet of the present invention, the thickness is 25 to 200 μm 〇 [Effect of the invention] The curable composition of the present invention contains three represented by the formula (丨). Well skeleton (methyl) propyl At least one of the acid ester compound and the (meth) acrylate compound having a triple whistle: skeleton represented by the formula (2), and the cured product after hardening has a refractive index of 1.525 or more and 1.535 or less at 589 nm. Or the cured product after hardening has a refractive index of 1 557 or more and 1.571 or less at 589 nm. Therefore, it is possible to produce a cured product excellent in transparency. Further, the glass transition of the cured product after hardening of the curable composition of the present invention Since the temperature is 200 ° C or higher, the heat of the cured product of the curable composition can be improved by the heat of the 158155.doc 11·201211011. Moreover, the transparency of the glass fiber can be embedded in the hardened composition of the curable composition. The heat-resistant property of the composite sheet is improved. Therefore, the curable composition of the present invention can withstand a process of forming an inorganic material layer or the like of TC or more. [Embodiment] Hereinafter, the present invention will be described in detail. The curable composition contains a (meth) acrylate compound of a three-till skeleton represented by the following formula (1) and a (meth) acrylate having a three-till skeleton represented by the following formula At least one species of the compound [Chemical 9]

R2 0—CH—CH.

R3 CH2—CH—OH—C—C=CH〇R5 CH2—CH—〇—(—c-.c_CHa , 〇R4 f . (1) In the above formula (1), R1 to R6 each represent a hydrogen atom or Methyl, do not mean 1 or 2 [10] n\ "4,4rLcH2, human, -CH-ΟΊ R5

2) 158 158155.doc -12· 201211011 In the above formula (2), R1 to R6 each represent a hydrogen atom or a fluorenyl group, and n1 and 〇. Ten means “0.5 to 3 on average”. The sum of nl, n2 and n3 is preferably 〇5 to 2 on average. In addition, the average of the total of nl, n2, and ιι3 in the above formula (2) is a (meth) acrylate compound having a three-till skeleton represented by the formula (2) contained in the curable composition. The value of the whole. That is, for example, as a compound represented by the above formula (2), a compound containing nl = l, n2 = 0, and n3 = 〇 (nl + n2 + n3 = 1) in the same amount and nl = 1, n2 In the case of compounds of ==1 and n3=〇(nl+n2+n3=2), the total of nl, n2 and n3 is 1.5 on average. Further, the refractive index of the cured product after curing of the curable composition of the present invention at 589 nm is 丨 525 or more, I·535 or less, or 1.575 or more and 1. 5 71 or less. The glass transition temperature of the cured product after curing of the curable composition of the present invention is 200 eC or more in the case where the refractive index is 1.525 or more and 1.535 or less. The glass transition temperature of the hardened cured product of the curable composition of the present invention is also 200 when the refractive index is 1.575 or more and 1571 or less. (In the above, in the curable composition of the present invention, it is preferred that the cured product after curing has a refractive index of 1.525 or more and 1.535 or less at 589 nm, and the glass transition temperature of the cured product is 200 ° C or higher. It is also preferred that the cured product after hardening has a refractive index of 1.575 or more and 1.571 or less at 589 nm, and the glass transition temperature of the cured product is 20 (TC or more. By having the above-described constitution, the curable composition is The transparency of the cured product is good. For example, the cured product may have a haze value of 1% or less, or 158155.doc -13·201211011 of 5% or less. Therefore, by using the curability of the present invention. In the composition, a transparent transparent composite plate can be obtained. Further, by adopting the above configuration, the heat resistance of the cured product of the curable composition can be improved. Here, the heat resistance is expressed when the heat resistance is low. The plastic material is decomposed by heating, which in turn means that the plastic material is largely deformed by heating, or the elastic modulus of the plastic material is largely reduced by heating. In display elements and solar cells, The inorganic material layer is formed as a semiconductor layer or a conductive layer using an inorganic material. In the process of forming the inorganic material layer, the substrate is heated to about 180 to 300 ° C. The heat resistance of the cured product of the curable composition of the present invention is higher. It is high enough to withstand the formation of an inorganic material layer of 2 Å or more. The cured product of the curable composition of the present invention is difficult to decompose and is difficult to be deformed to a large extent even when exposed to a high temperature of 200 ° C or higher. Moreover, it is difficult to reduce the elastic modulus to a large extent. When the glass transition temperature of the cured product after hardening of the curable composition of the present invention is 220 ° C or more, it can withstand 220. The process of the material layer. Even if the cured product is exposed to a high temperature of 22 〇 or more, it is difficult to decompose, it is difficult to deform to a large extent, and the elastic modulus is difficult to be largely reduced. Further, 'by adopting the above composition' The hardenability of the curable composition can be improved. The curable composition of the present invention is preferably a curable composition used for embedding glass fibers. The composition is preferably used to obtain a transparent composite sheet having a cured product obtained by hardening the curable composition and a glass fiber embedded in the cured product. The curable composition of the present invention is 158155.doc - 14 to 201211011 The material is preferably a hardenable composition for embedding T glass or E glass as glass fiber. The curable composition of the present invention is preferably hardened by embedding T glass as glass fiber. The curable composition which is used as the E glass of the glass fiber is also preferably used. The transparent composite sheet of the present invention has a cured product obtained by curing the curable composition, and is embedded in the hardened material. The glass fiber in the article can be obtained by curing the curable composition by heating and irradiating at least one of the active rays. The transparent composite sheet can be obtained, for example, by impregnating a glass fiber with a curable composition and then curing the curable composition. Hereinafter, the details of each component contained in the curable composition of the present invention and the transparent composite sheet of the present invention will be described. [Curable compound] The curable composition of the present invention contains a (meth) acrylate compound having a three-till skeleton represented by the above formula (1) (hereinafter sometimes abbreviated as (meth) acrylate compound (1) And at least one of a (meth) acrylate compound (hereinafter sometimes abbreviated as (meth) acrylate compound (2)) having a three-till skeleton represented by the above formula (2). The (meth) acrylate compound and the (meth) acrylate compound (2) are curable compounds and are polymerizable compounds. "(Meth)acrylate" means acrylate and methacrylate. The cured products of the (meth) acrylate compound (1) and the (fluorenyl) acrylate compound (2) have refractive indices of 丨52 〇 or more and i 545 or less, respectively. At least one of the (meth) propyl acetoacetate compound (1) and the (meth) acrylic acid vinegar compound (2) is appropriately selected and used, and (meth) acrylate is compounded as needed 158155.doc -15- 201211011 The at least one of the hydrazine and the (meth) acrylate compound (2) is mixed with a suitable refractive index adjusting agent to adjust the refractive index of the cured product of the curable composition to 1,525 or more and i.53 or less; Or adjusted to 1. (5) or more and 1.571 or less. The refractive index of the cured product can be adjusted to 丨525 by using the (meth) acrylate compound (1) and the (meth) acrylate compound (2) in combination. The above may be 1.535 or less. The refractive index of the cured product may be adjusted to 1 525 by using at least one of a (meth) acrylate compound and a (meth) acrylate compound (2) in combination with a refractive index adjusting agent. The above is not more than 1.535. Further, the refractive index of the cured product can be obtained by using at least one of the (fluorenyl) acrylate compound (1) and the (fluorenyl) acrylate compound (2) in combination with the refractive index adjusting agent. Adjusted to 1.557 or more, 1 Further, the glass transition temperature of the cured product of the (meth) acrylate compound (丨) is about 250 to 280 ° C. The glass transition temperature of the cured product of the (meth) acrylate compound is 200 to 250 ° Therefore, by using the (meth) acrylate compound (1) or the (meth) acrylate compound (2), the heat resistance of the cured product of the curable composition can be improved and the cured product can be made The glass transition temperature is 200 ° C or higher. Further, by using the (fluorenyl) acrylate compound (1), the glass transition temperature of the cured product can be 22 Å or more. Further, by using (methyl group) A curable composition capable of producing a cured product capable of withstanding a high temperature process of forming a display element and a layer of an inorganic material in a solar cell, by using a propyl acrylate compound (丨) or a (meth) acrylate vine compound (2) 0 The curable composition of the present invention may further contain a refractive index adjusting agent when the refractive index of the cured product of the curable composition is 1 557 or more and 1.571 158155.doc 16-201211011 or less. Preferably, the curable composition of the present invention contains a refractive index adjusting agent. When the refractive index of the cured product of the curable composition is 1525 or more and 1.535 or less, the (meth) acrylate compound (1) is present. The refractive index of the cured product is relatively high. Therefore, by suitably selecting a component having a low refractive index and a component of the (meth) acrylate compound (1), the cured product of the curable composition can be easily used. The refractive index of the cured product of the (mercapto)acrylic acid vinegar compound (?) is relatively low. Therefore, by appropriately selecting a component for increasing the refractive index, (Meth) acrylate compound (2) - When used together, the refractive index of the cured product of the curable composition can be easily made 1 525 or more and 1.535 or less. When the refractive index of the cured product of the curable composition is 1 55 Å or more and 1.571 or less, the above (meth) acrylate compound (hardened yttrium and the above (fluorenyl) acrylate compound (2) The refractive index of the curable composition is used in combination with the (meth) acrylate compound (1) by appropriately selecting a component for increasing the refractive index, and the refractive index of the cured product of the curable composition is 1.557 or more and 1.571 or less. The refractive index adjusting agent is preferably a refractive index improving agent. Examples of the refractive index adjusting agent include a (meth) acrylate compound having a dicyclopentyl skeleton and a (methyl) group having an anthracene skeleton. An acrylate compound, a (meth) acrylate compound having a dioxin skeleton, and a bismaleimide compound. However, a refractive index modifier other than the above may preferably be used as the curable combination of the present invention. Containing a (meth) acrylate compound having a bicyclopentyl bone 158155.doc -17- 201211011, a (meth) acrylate compound having an anthracene skeleton, having a (meth) acrylate compound or a bismaleimide compound of a decane skeleton. Preferably, the curable composition of the present invention is a (meth) acrylate compound having a dicyclopentyl skeleton and having an anthracene skeleton. (meth) acrylate compound, (meth) acrylate compound having a dioxane skeleton or bismaleimide compound. The above refractive index modifier may be (meth)acrylic acid having a dicyclopentyl skeleton The ester compound or the (meth) acrylate compound having the first skeleton may be a (meth) acrylate compound having a cyclopentyl skeleton or a (meth) acrylate compound having a dioxane skeleton, and may have a first skeleton (fluorenyl) acrylate compound or (fluorenyl) acrylate compound having a dioxane skeleton, which may be a (fluorenyl) acrylate compound or a bismaleimide compound having an anthracene skeleton, or may be a double horse The imide compound may be a combination of refractive index modifiers other than the above. More preferably, the curable composition of the present invention contains a dicyclopentyl skeleton. a (fluorenyl) acrylate compound, a (meth) acrylate compound having an anthracene skeleton, or a (meth) acrylate compound having a dioxane skeleton. The preferred refractive index adjusting agent is used for the above curable composition When the refractive index of the cured product is 1.525 or more and 丨.535 or less, it is preferably used. The refractive index adjusting agent is a (meth)acrylic acid oxime compound having a dicyclopentyl skeleton and having an anthracene skeleton. a (meth) acrylate compound or a (meth) acrylate compound having a monomolecular skeleton. By using the preferred refractive index modifier, the refractive index of the cured product of the curable composition can be controlled to be preferred. In the range, the transparency of the cured product can be further improved. 158155.doc 201211011 It is preferred that the curable composition of the present invention contains a (fluorenyl) acrylate compound or a bismaleimide compound having an anthracene skeleton. A preferred refractive index adjusting agent can be preferably used when the refractive index of the cured product of the curable composition is 1.557 or more and 1.571 or less. The curable composition of the present invention preferably contains a (meth) acrylate compound having an anthracene skeleton, preferably a bimaleimide compound, by using the preferred refractive index modifier. The refractive index of the cured product of the curable composition is controlled within a preferred range, and the transparency of the cured product can be further improved. The above (meth)acrylic acid having a dicyclopentyl skeleton can be obtained by controlling the refractive index of the cured product of the curable composition to a further more preferable range and further improving the transparency of the cured product. Particularly preferred as the ester compound is a (meth) acrylate compound having a dicyclopentyl skeleton represented by the following formula. Further, the refractive index adjusting agent preferably has a dicyclopentyl group from the viewpoint of controlling the refractive index of the cured product of the curable composition to a further better range and further improving the transparency of the cured product. The (meth)acrylic acid 8-form compound is particularly preferably a (meth) acrylate compound having a dicyclopentyl skeleton represented by the following formula (?). [11] [11] In the formula (3), in: (10): called and Sichuan respectively represent a gas atom or a methyl group. , a bonding site of two groups on the pentadienyl skeleton and is specifically defined by 158155.doc 201211011. The (meth) acrylate compound having the first skeleton is preferably from the viewpoint of controlling the refractive index of the cured product of the curable composition to a further preferable range and further improving the transparency of the cured product. The (meth) acrylate compound having an anthracene skeleton represented by the following formula (π) is a (meth) acrylate compound having an anthracene skeleton represented by the following formula (12), or is represented by the following formula (13) A (meth) acrylate compound having an anthracene skeleton. Further, from the viewpoint of controlling the refractive index of the cured product of the curable composition to a further preferable range and further improving the transparency of the cured product, the refractive index adjusting agent preferably has an anthracene skeleton ( The (meth) acrylate compound is more preferably a (meth)acrylic acid vinegar compound having a haw frame represented by the following formula (n) and having an anthracene skeleton represented by the following formula (12) ( A (meth) acrylate compound or a (meth) acrylate compound having an anthracene skeleton represented by the following formula (13). [化 12]

R11 I HZC=C-C

In the above formula (11), m2 represents 1 or 2, respectively. RU~R14 represent a hydrogen atom or a methyl group, respectively, ml and 158155.doc •20- 201211011 [Chem. 13]

··· (12) In the above formula (12), R11 and R12 each represent a hydrogen atom or a methyl group.

Formula (13) In the above formula (13), R11 and R12 each independently represent a hydrogen atom or a fluorenyl group. The above (meth) acrylate compound having a dioxane skeleton is particularly preferable in terms of controlling the refractive index of the cured product of the curable composition to a further preferable range and further improving the transparency of the cured product. It is a (fluorenyl) acrylate compound having a diazane skeleton represented by the following formula (21). Further, the refractive index adjusting agent preferably has a dioxane skeleton from the viewpoint of controlling the refractive index of the cured product of the curable composition to a further preferable range and further improving the transparency of the cured product. The (meth) acrylate compound is particularly preferably an (f-based) acrylate compound having a dithicyclic skeleton represented by the following formula (21). 158155.doc •21- 201211011 [11] 11H3 /0—ch2 ch2 - CH3 H2C=CC-0-CH2—C-HC^ X (21) o ch3 〇-ch2 ^ch2-〇- Cc=ch2 O R12 In the above formula (21), R11 and R12 each represent a hydrogen atom or a methyl group. The above-described bismaleimide compound is not particularly limited. Examples of the above-mentioned bismaleimide compound include N,N'-(1,3-phenylene) bismaleimide, and N,NL[1,3-(2-methylphenylene). )]Bismaleimide, anthracene, Ν^[1,3-(4-methylphenylene)] bismaleimide, N,N'-(1,4-extended base) double Maleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl- 5,5·-diethyl-4,4'-diphenylmethane bismaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimine) Phenyl) anthracene, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl)one, bis(4-maleimidocyclohexyl)anthracene Alkane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidofluorenyl)cyclohexane, 1,4-double (Malay)醯iminofluorenyl) benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, double [4-(3-Maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy) Phenyl]methane, 1,1_bis[4-(3-maleimidophenoxy)phenyl]ethane, M-bis[4-(4-maleimidophenoxy) Phenyl]ethane, 1,2_bis[4_(3_maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimide) Phenoxy group) phenyl] Ethylene, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2·bis [4·(4- 158155. Doc • 22· 201211011 Maleic iminophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2 - bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl] -1 , 1,1,3,3,3·hexafluoropropane, 2,2_bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3, 3-hexafluoropropane, 4,4·bis(3-maleimidophenoxy)biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, double [ 4-(3-maleimidophenyloxy)phenyl]one, bis[4-(4-maleimidophenoxy)phenyl, 2,2'-bis (4) - Maleic iminophenyl) disulfide, bis(4-maleimido) Thioether, bis[4-(3-maleimidophenoxy)phenyl] sulfide, bis[4-(4-maleimidophenoxy)phenyl] sulfide, double [4-(3-maleimidophenoxy)phenyl] sulfoxide, double μ-(4-maleimidophenoxy)phenyl]anthracene, bis[4-(3 -Maleic iminophenoxy)phenyl b, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleide) Phenyloxy)phenyl]ether, bis[4-(4-maleimidophenyloxy)phenyl]ether, 1,4-bis[4-(4-maleimide benzene) Oxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-Bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimide) Phenyloxy)_α,α-dimercaptobenzyl]benzene, 1,4-bis[4-(4·maleimidophenoxy)_3,5-diindenyl-α,α_ Methyl] benzene, 1,3_bis-[4-maleimidophenoxy)-3,5-dimethyl-α,α-dimercaptobenzyl]benzene, anthracene, 4_bis[4_(3_Maleidanilideoxy)-3,5-dimethyl-αα_二Mercaptobenzyl]benzene, 13 bismaleimidophenoxy)-3,5·dimethyl-α,α-dimercaptobenzyl]benzene, 4—mercapto_1}3_benzene Base bismaleimide and polyphenylmethane maleate. The above-mentioned double 158155.doc •23· 201211011 The maleimide compound may be used only by m, or two or more kinds may be used in combination to control the refractive index of the cured product of the curable composition within a range of a good step, and From the viewpoint of further improving the transparency of the cured product, the bismaleimide compound is particularly preferably a bismaleimide compound represented by the following formula (1). x, the refractive index adjusting agent is preferably a double horse from the viewpoint of controlling the refractive index of the hard 2 of the curable composition to a further preferable range and further improving the transparency of the cured product. The imine compound is particularly preferably an imine compound which is represented by the formula (1)). [Chemistry 16]

In the above formula (31), R21 to R24 each represent a hydrogen atom or a methyl group, and R25 and R26 each represent a hydrogen atom, a methyl group or an ethyl group. The above (meth) propylene having an anthracene skeleton The acid vinegar compound and the above-described bismaleimide compound are uniformly miscible with the (meth) acrylate compound (1). Therefore, the cured product of the curable composition also has high transparency to visible light. The cured product of the (meth) acrylate compound having an anthracene skeleton and the cured product of the bismaleimine compound have a relatively high glass transition temperature. The cured product of the (meth) acrylate compound having a tibia frame and the cured product of the bismaleimide compound have a glass transition temperature of 250 to 300 ° C. Therefore, by using 158155.doc •24-201211011 (meth) acrylate compound or bismaleimide compound with (meth) acrylate compound (1) or (meth) acrylate The ester compound (2) is used in combination to 'further increase the glass transition temperature of the cured product of the curable composition' and further improve the heat resistance of the cured product. The transparent composite sheet of the present invention is obtained by embedding a glass fiber in a curable composition and curing the curable composition. In the transparent composite sheet of the present invention, 'the transparency is further higher by making the cured product of the curable composition close to the refractive index of the glass fiber. In general, in order to obtain transparency which can be sufficiently applied to a display element substrate or the like, it is preferable that the difference in refractive index between the cured product of the hardening compound which becomes the matrix and the glass fiber which is embedded in the cured product is 〇〇〇5 below. It is difficult to make the refractive index of the cured product of the hardening compound which becomes the matrix completely coincide with the refractive index of the glass fiber throughout the entire visible light region. In the present invention, the scattering of light is minimized by appropriately designing the refractive index of the cured product of the curable compound which is a matrix with respect to the glass fiber. The above glass fiber is preferably T glass or E glass. In the present invention, as the glass fiber, it is preferred to use T glass, and it is also preferred to use εκ glass. In the present invention, as the glass fiber, τ glass is preferably used. The refractive index of bismuth glass at 589 nm is about 1.525. When the refractive index of the cured product of the curable composition at 589 nm is 1.525 or more and 1.535 or less, light scattering, that is, haze value, of the cured composite sheet having the cured composition and the glass fiber can be minimized. Chemical. 158155.doc •25- 201211011 Therefore, the refractive index of the cured product of the curable composition of the present invention at 589 nm is 1.525 or more and 1.535 or less, and the glass transition temperature of the cured product is 200 eC or more. In the case of the curable composition of the present invention, a curable composition for embedding T glass as a glass fiber is preferred. The cured product of the curable composition of the present invention preferably has a refractive index at 589 nm of 1.527 or more, preferably 丨.533 or less. When the refractive index of the cured product is not less than the above lower limit and not more than the above upper limit, the transparency of the transparent composite sheet can be improved, and the haze value of the transparent composite sheet can be further reduced. Further, in the present invention, as the glass fiber, E glass is preferably used. The E glass of E glass has a refractive index of about 1.560 at 589 nm. By causing the cured product of the curable composition to have a refractive index of 1.575 or more and 5.771 or less at 589 nm, light scattering of the cured composite material having the curable composition and the glass fiber can be achieved, that is, The haze value is extremely small. Therefore, in the case where the cured product of the curable composition of the present invention has a refractive index at 589 nm of ι·557 or more, Lsn or less, and the glass transition temperature of the cured product is 200 T: or more, the present invention The curable composition is preferably a curable composition which is used as an E glass which is a glass fiber. The cured product of the curable composition of the present invention preferably has a refractive index at 5 89 nm of 1.560 or more, preferably L568 or less. When the refractive index of the cured product is not less than the above lower limit and not more than the above upper limit, the transparency of the transparent composite sheet can be improved, and the haze value of the transparent composite sheet can be further reduced. In the curable composition of the present invention, at least one of (meth)propyl 158155.doc -26-201211011 enoate compound (1) and (meth) acrylate compound (2) is used as appropriate, or The type and amount of the refractive index modifier used together with at least one of the (meth) propyl acrylate compound (1) and the (meth) acrylate compound (2) can be appropriately adjusted, whereby the sclerosing combination can be combined The refractive index of the cured product at 589 nm is adjusted to 1.525 or more and 1.535 or less, or adjusted to 1557 or more and 1.571 or less. The curable composition of the present invention may contain a (meth) acrylate compound ((meth) acrylate compound (1)) having a three-well structure represented by the above formula (1), and the above formula (2) A (mercapto) acrylate compound ((meth) acrylate compound (2)) having a three-well skeleton. In this case, the curable composition of the present invention may also contain no refractive index modifier. In this case, however, the curable composition of the present invention may also contain a refractive index modifier. In order to control the refractive index of the cured product within an optimum range, the ratio of the (meth) acetaminophen compound (1) to the (mercapto) acetoacetic acid compound (7) and the refractive index adjuster can be arbitrarily set. Further, the total of at least one component (hereinafter, abbreviated as component (X)) and a refractive index modifier in at least one of (meth)acrylic acid-based compound (1) and (meth)acrylic acid vinegar compound (2) (10) The content of the component (X) is preferably in the form of a total amount of the component (X) (in the case of using the (indenyl) acrylic acid vinegar compound (1) and the hydrazine condensate compound (7) in combination). The content of the refractive index adjusting agent is (four) amount %. The amount of the curable compound in the present curable composition is 1% by weight. The weight % is the component (X). It may also be the total of the curable compound, () in order to control the refractive index of the cured product within the optimum range of 158155.doc •27·201211011, and more preferably the total of the composition (χ) and the refractive index modifier 1〇〇 The content of the component (X) in the weight o/〇 is 30 to 70% by weight, and the content of the refractive index adjusting agent is 30 to 70% by weight. . Further, in order to control the refractive index of the cured product within an optimum range, it is more preferable that the content of the component (X) is 40 to 60% by weight, and the content of the refractive index adjusting agent is 1% by weight of the curable compound. 40 to 60% by weight, in the case where the refractive index of the cured product of the curable composition is 丨557 or more and 1.571 or less, in order to control the refractive index of the cured product within an optimum range, it is preferably a component. In the total of 100% by weight of (X) and the refractive index adjusting agent, the content of the component (X) is 5 Å to 9 Å by weight, and the content of the refractive index adjusting agent is 10 5% to 5% by weight. Further, in order to control the refractive index of the cured product within an optimum range, it is preferred that the content of the component (X) is from 50 to 90% by weight based on the weight of the curable compound. /. The content of the refractive index adjusting agent is 10 to 50% by weight. In the case where the "content of the refractive index adjusting agent" is used, when a (fluorenyl) acrylate compound having an anthracene skeleton and a bismaleimide compound are used as a refractive index adjusting agent, "the base having an anthracene skeleton" The total content of the acrylate compound and the bismaleimide compound"; when the (meth) acrylate compound having the first skeleton or the bismaleimide compound is used as the refractive index modifier, The content of the (meth)propionate compound or the bismaleimide compound of the anthracene skeleton". In order to withstand 20 〇. (The process of forming the inorganic material layer or the like in the above, the glass transition temperature of the cured product of the curable composition of the present invention is 2 〇〇β (: above the process of forming the inorganic material layer t, sometimes the substrate is heated to 158155 .doc -28- 201211011 200 ° C or more, and sometimes heated to nearly 22 ° C. Therefore, the glass transition temperature of the cured product of the curable composition of the present invention is preferably 22 〇. It is more than 200 ° C, more preferably 205 ° C or more, particularly preferably 23 5 ° C or more, and most preferably 250. (: Above. In the curable composition of the present invention, in order to make a curable compound It is preferable to contain a polymerization initiator by curing by polymerization. As a method of curing the curable composition of the present invention, a method of curing by heating and hardening by active rays are mentioned. The method may be used in combination with hardening by heating and hardening by active rays. From the viewpoint of shortening the reaction time and ending the hardening reaction, it is preferred that the curable composition is cured by active light rays. And by The active light ray is preferably ultraviolet ray. The light source for illuminating the ultraviolet ray is, for example, a metal dentate lamp, a high pressure mercury lamp, or the like. When the curable composition is cured by heating, the curable composition is cured. An oven, a heater, etc. are used. In order to suppress deterioration of the color and the curable compound due to oxidation, it is preferred to cure the curable composition by heating, in a nitrogen atmosphere or in a vacuum state, at 150 to 30. (heating at TC for 1 to 24 hours. In order to cure the curable composition by heating, it is preferred that the curable composition contains a thermal polymerization initiator. The above thermal polymerization initiator is preferably a radical polymerization. The radical polymerization initiator may, for example, be a peroxide-based radical polymerization initiator, an azo-based radical polymerization initiator, a redox-based radical polymerization initiator, or the like. A thermal polymerization initiator other than the above. The above thermal polymerization initiator may be used alone or in combination of two types of 158155.doc -29-201211011. Examples of the initiator include azobisisobutyronitrile, azobiscyclohexylcarbonitrile, and azobisquinone valeronitrile. Examples of the peroxide-based radical polymerization initiator include di-branched radicals. a polymerization initiator, a peroxyester-based radical polymerization initiator, a dialkyl-based radical polymerization initiator, a peroxycarbonate-based radical polymerization initiator, a ketone peroxide-based radical polymerization initiator, and the like Examples of the diterpene-based radical polymerization initiator include oxidized laurel and benzoyl peroxide. Examples of the peroxyester-based radical polymerization initiator include tert-butylperoxybenzene. Formate, tert-butyl peroxyacetate, tert-butyl peroxypivalic acid vinegar, and tert-butylperoxy-2-ethylhexanoic acid vinegar; 'as the above-mentioned dialkyl radical polymerization Examples of the initiator include dicumyl peroxide and ditributyl peroxide. The peroxycarbonate-based radical polymerization initiator may, for example, be peroxydicarbonate diisopropyl vinegar or the like. Examples of the above-mentioned peroxy (tetra) radical polymerization initiators include butylene peroxide and the like. The above redox radical polymerization initiator contains, for example, a peroxide hydrazine reducing agent or a metal-containing compound. Specific examples of the redox-based radical polymerization initiator may be a mixture of oxidized benzamidine and an organic amine, and the above-mentioned peroxyester-based free field polymerization initiator and sulfur. A mixture of a reducing agent such as an alcohol, and a mixture of peroxidized butanone and an organic cobalt salt. From the viewpoint of further improving the attractiveness of the cured product, a peroxide-based radical polymerization initiator is preferred. The amount of heat-initiating starter used is limited by the helmet. It is preferred that the content of the thermal polymerization initiator is ο·〇5 to 5 parts by weight with respect to 100 parts by weight of the curable composition in the curable composition. 158155.doc -30-201211011 Since the curable composition of the present invention contains at least one of the (meth) acrylate compound (1) and the (meth) acrylate compound (2), it is efficiently carried out by irradiation with active rays. Polymerization and hardening. Therefore, in order to harden the curable composition by irradiating the active light, it is preferred that the above-mentioned hardening = - the composition contains a photopolymerization initiator. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and the like. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more. The photoradical polymerization initiator is not particularly limited, and examples thereof include diphenyl fluorenone, anthracene, Ν·-tetraethyl-4,4,-diaminodibenzophenone, and analmethoxy group- 4·-Dimethylaminobiphenyl-, 2,2-diethoxyacetophenone, benzoin, benzoin ether, benzoin propyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, α -hydroxyisobutylphenylhydrazine, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-methylthio)phenyl phenylpropan-1-one, 2-benzyl Benzyl-2-didecylaminomorpholinophenyl)-butanone-1,2,6-dimethylazinocarbyldiphenylphosphine oxide, 2,4,6-trimercaptobenzoquinone Diphenylphosphine oxide, tert-butylphosphonium, chloropurine, 2,3-dioxane, 3-ox-2-mercaptopurine, 2-ethylpyrene, anthracene-5-naphthoquinone , 9,10-phenanthrene, 1,2-benzopyrene, J,4-dimethylindole, 2-phenyl: 蒽醌, 2-(o-chlorophenyl)-4,5-di Imidazolyl 2mer, 2_mercaptobenzothiazole, 2-mercaptobenzoxazole, and 4_(p-methoxyphenyl)_2,6-di-(trichloromethyl)-allosin, etc. . The photoradical polymerization initiator may be used alone or in combination of two or more. The photocationic polymerization initiator is not particularly limited. For example, 158155.doc -31 · 201211011 can be used as a salt, a sulfonium salt, a metallocene compound, and a benzoin tosylate. The photocationic polymerization initiator may be used singly or in combination of two or more. As a commercial item of the said photocationic polymerization initiator, it can mention

Cyracure UVI-6970, Cyracure UVI-6974 and Cyracure UVI_6990 (all manufactured by Union Carbide Corporation), Irgacure 264 (manufactured by Ciba Co., Ltd.), and CIT-1682 (manufactured by Nippon Soda Co., Ltd.). Preferably, the photopolymerization initiator is present in an amount of from 1 to 1 part by weight based on the amount of the curable compound in the curable composition. When the content of the photopolymerization initiator is at least the above lower limit, the curable composition can be sufficiently cured. When the content of the polymerization initiator is not more than the above upper limit, it is difficult to cause a problem that polymerization is difficult to be rapidly performed, birefringence is increased, coloring, cracking during curing, and the like. In the case where the photopolymerization initiator is a photoradical polymerization initiator, the content of the photoradical polymerization initiator is preferably at least 1 part by weight based on the weight of the curable compound in the curable composition. It is 1 part by weight or more, more preferably 0.1 part by weight or more, more preferably 2 parts by weight or less, still more preferably 1 part by weight or less. In the case where the photopolymerization initiator is a photocationic polymerization initiator, the content of the photocationic polymerization initiator is preferably 1 part by weight based on 100 parts by weight of the curable compound in the curable composition. The above is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. The above curable composition may also contain (f) base different from the above (meth) acrylate compound (1), (meth) acrylate compound (2), and having a dicyclopentyl skeleton 158155.doc • 32-201211011 An acrylic vinegar compound, a (meth) acrylate compound having a first skeleton, a (meth) acrylate compound having a dioxane skeleton, and another curable compound of a bismaleimide compound. The other curable compound may be a thermosetting compound or a photocurable compound. The other curable compound is not particularly limited, and examples thereof include a polyfunctional thiol compound and an epoxy compound. The domain hardening composition preferably contains a polyfunctional thiol compound or an epoxy compound, and more preferably contains a polyfunctional thiol compound. By further including the polyfunctional thiol compound or the epoxy compound, the curing rate can be adjusted or improved, and the softness, toughness, chemical resistance, and the like of the cured product can be adjusted. The above epoxide is preferably a polyfunctional epoxy compound. Examples of the polyfunctional thiol compound include i,2-ethanedithiol, 1,2-propanedithiol, hydrazine, 3-propylenedithiol, 13 dimethyldithiol, hydrazine, and tetrabutylene. Mercaptan, 2'3-butanedithiol, ι5_pentanedithiol, hexanedithiol, 1,9-nonanedithiol, 1> 8-octanedithiol, u〇·癸dithiol, w• Butanediol dithiopropionate, butanediol bis-mercaptoacetate, ethylene glycol bis-thioglycolate, ethylene glycol dithiopropionate, 1> 2-benzenedithiol , hydrazine, 3-phenyldithiol, 1,4-dithiol, toluene-3,4-dithiol, 3,6-digas·12 dithiol, 1,5-naphthalene dithiol, Benzene dimercaptan thiol, ι> 3- phantom dimethyl thiol, 1,4- benzene dimethyl thiol, 4, 4, thio bis thiophenol phenolic acid 2 2 -di-n-butylamino group _4 , 6_dimercapto-average three-ploughing, 2,5-dimercapto-^, thiadiazole, anthracene, 8·dimercapto-3,6-dioxaoctane, anthracene, 5_diyl _3_thiapentane, 1,4·bis(3·succinyloxy) butyl, trimethyl methacrylate trisyl acetate, trishydroxypropyl propane trithiopropionate, Trimethylolpropane tris (3. thiol 158155.doc -33- 201211011 butyric acid) Cool, pentaerythritol tetrakisacetate vinegar, pentaerythritol tetrathiopropionate, pentaerythritol tetrakis(3-mercaptobutyrate), tris-propionic acid tris(2-hydroxyethyl)isocyanurate, 1,3, 5-tris(3-mercaptobutoxyethyl)-1,3,5-trinol-2,4,6-trione, 1,4-didecylmercaptobenzene, 2,4,6-three Mercapto-average three-ploughing, 2-(N,N-dibutylamino)-4,6-diindenyl-average three-till and thiol-containing sesquiterpene oxide compounds. The commercially available product of the thiol group-containing sesquiterpene oxide compound of the polyfunctional thiol compound may, for example, be "Compoceran HBSQ Series" manufactured by Arakawa Chemical Industries. In general, the hardenability of the hardening composition and the softness and toughness of the cured product are improved by using a polyfunctional thiol compound. On the other hand, if the amount of the polyfunctional thiol compound used is too large, the glass transition temperature of the cured product is liable to lower. Therefore 'the weight of the curable compound 1 〇〇. The content of the polyfunctional thiol compound is preferably 2% by weight or more, preferably 40% by weight or more. Hereinafter, it is more preferably 2% by weight or less. From the viewpoint of suppressing a decrease in the glass transition temperature of the cured product and further improving the hardenability of the hardened composition and the softness and toughness of the cured product, the poly-t-energy thiol compound is preferably more preferred than the third sulfhydryl group. Acid trihydroxyethyl)isocyanurate, 1,3,5-tris(3-disyloxyethyl)-1'3,5-trisole-2,4,6-trione, or A sesquioxane compound containing a thiol group. Further, the above-mentioned thiol group-containing sesquiramose-oxygen compound is preferably "c〇mpoceran fiBSQ Series" manufactured by Arakawa Chemical Industry Co., Ltd.. The above epoxy compound may be a previously known epoxy resin. Examples of the resin include bisphenol A type epoxy resin, double type _ 曰 曰 曰 phenol S type epoxy resin, and phenol novolak type epoxy tree 158155.doc -34- 201211011 Road varnish type epoxy resin Triglycidyl isocyanuric acid vinegar, epoxy resin, alicyclic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, naphthalene epoxy resin, glycidyl (tetra) epoxy resin, hydrazine, This type of epoxy resin, bicyclic decadiene type cyclic oxime resin, ester type epoxy tree moon 曰 and shouting epoxy resin. Gasification or modification of such epoxy resins can also be used. From the viewpoint of preventing discoloration of the curable composition, preferred are (iv) fluorene type epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate type epoxy resin or dicyclopentadiene type. Epoxy resin. These epoxy compounds may be used alone or in combination of two or more. The curable composition of the present invention may also contain a curing agent. The hardening composition of the present invention may also contain an epoxy compound and a curing agent. Examples of the curing agent' include an organic acid 'amine compound, a guanamine compound, a ruthenium compound taste compound, a stilbene compound, a compound, a gland compound, a polysulfide, and an acid anhydride. The above-mentioned hardening agent may be used alone or in combination of two or more. Examples of the organic acid include tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. Examples of the amine compound include ethylenediamine, propylenediamine, diethylenetriamine, diethylenetetramine, m-phenylenediamine, diaminodiphenylaloxane, and diaminodiphenylsulfonic acid. . As the above hardener, these amine adducts can also be used. Examples of the above guanamine compound include dicyanodiamine and polyamine. The above hydrazine compound may, for example, be a hydrazine or the like. Examples of the imidazole compound include methylimidazole, 2-ethyl-4-f-imidazole, ethyldiimidazole, isopropyl imidazole, 2,4-dimethylimidazole, phenylimidazole, and undecyl 158155.doc. -35- 201211011 Imidazole, heptadecylimidazole and 2-phenylidene-4-methylimidazole. Examples of the imidazoline compound include methyl imidazoline, 2-ethyl-4-methylimidazoline, ethyl imidazoline, isopropyl imidazoline, 2,4-dimethylimidazoline, and phenylimidazoline. , undecyl imidazoline, heptadecyl imidazoline and 2-phenyl-4-methylimidazoline. The above-mentioned hardener is preferably an acid anhydride from the viewpoint of preventing discoloration of the curable composition. Examples of the acid anhydride include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, ceric anhydride, glutaric anhydride, tetrahydrophthalic anhydride, and methyltetrahydrogen. O-phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexafluorophthalic anhydride, methylic acid anhydride, twelve Carbonyl succinic anhydride, digas succinic anhydride, benzophenone tetracarboxylic dianhydride, and chlorin anhydride anhydride, etc. The ratio of the above epoxy compound to the above-mentioned curing agent is not particularly limited. The acid anhydride equivalent is preferably 0.5 equivalent or more, more preferably 7 equivalents or more, more preferably 1.5 equivalents or less, still more preferably 1.2 equivalents or less, based on the epoxy group equivalent of the epoxy compound. When the equivalent of the above acid anhydride is at least the above lower limit, the transparency of the cured product is further improved. When the above acid anhydride equivalent is at most the above upper limit, the moisture resistance of the cured product is improved. The curable composition of the present invention may also contain a hardening accelerator. The hardening accelerator is not particularly limited, and examples thereof include a tertiary amine, an imidazole, a quaternary ammonium salt, a quaternary phosphonium salt, an organic metal salt, a phosphorus compound, and a urea compound. Among them, particularly preferred are tertiary amines, imidazoles or quaternary scale salts. These hardening accelerators may be used alone or in combination of two or more. 158155.doc -36 - 201211011 The content of the hardening accelerator is preferably 0.05 parts by weight or more, more preferably 〇 2 parts by weight or more, based on 100 parts by weight of the epoxy compound. It is 7.0 parts by weight or less, more preferably 3 parts by weight or less. When the content of the hardening accelerator is at least the above lower limit, the curable composition can be sufficiently cured. When the content of the hardening accelerator is not more than the above upper limit, the transparency of the cured product is further improved. The curable composition of this month may also contain a solvent as needed depending on the purpose of adjusting the viscosity and the like. As the solvent, a solvent which does not react with a component in the curable composition is preferred. Since the hardening reaction of the curable composition is carried out by drying by heating in an oven or a hot plate and decompression in a decompression chamber, a volatile solvent is preferred. The curable composition of the present invention may optionally contain a weathering agent, an antioxidant, a thermal stabilizer, an antistatic agent, a whitening agent, a coloring agent, a conductive agent, a releasing agent, a surface treating agent, and a viscosity adjusting agent. (Transparent composite sheet) The transparent composite sheet of the present invention has a cured product obtained by curing the curable composition, and a glass fiber embedded in the cured product. After the curable composition of the present invention is formed into a plate shape, the curable composition is crosslinked and cured by irradiation with heat or active light, whereby a transparent composite plate can be obtained. Examples of the glass fiber include a strand of glass fiber, a woven fabric of glass fiber, and a nonwoven fabric of glass fiber. The above glass fiber is preferably a woven fabric of glass fibers. The woven fabric of the above-mentioned glass fiber can be obtained, for example, by the following method: 158155.doc •37·201211011 Obtained: a cross section of about 100 to 800 is circular or elliptical, and the longest path of the section is 3 to 10 μm. Yarns obtained by twisting long and left long fibers (filaments) are used as warp yarns and weft yarns to woven the yarns in a staggered manner. Examples of the spinning method include plain weave, twill weave, satin weave, and the like. The thickest portion of the thickness of the above glass fibers is usually from 1 〇 to 5 〇〇 pm. The thickest portion of the thickness of the glass fiber is preferably 15 to 350 μm. The above glass fibers are preferably bismuth or bismuth glass. The above glass fiber is preferably a bismuth glass. By using the curable composition of the present invention in combination with bismuth glass, the haze value of the transparent composite sheet can be made considerably reduced. Further, the bismuth glass is used as a core material for a glass fiber reinforced circuit board. Regarding the fiber diameter, the fiber bundle diameter, the basis weight of the glass cloth, the textile density, and the thickness, the above-mentioned glass-lined various specifications are all available. In particular, since the coefficient of thermal expansion of the bismuth glass is small, bismuth glass can be preferably used from the viewpoint of thermal dimensional stability of the resulting transparent composite sheet. The glass fiber is also preferably a bismuth glass. By using the curable composition of the present invention in combination with bismuth glass, the haze value of the transparent composite sheet can be considerably reduced. Further, the bismuth glass is widely used as a core material for a glass fiber reinforced circuit board. Regarding the fiber diameter, the fiber bundle diameter, the basis weight of the glass cloth, the textile density, and the thickness, the above-mentioned glass-lined various specifications are available. Further, in view of performance, cost, and ease of obtaining, bismuth glass can be preferably used. The tensile modulus of the glass fiber is preferably 5 GPa or more, more preferably 10 GPa or more, more preferably 5 Å GPa or less, still more preferably 200 158 I55.doc -38 to 201211011 GPa or less. When the tensile elastic modulus is at least the above lower limit, the strength of the transparent composite sheet becomes high. The thickness of the transparent composite sheet of the present invention is not particularly limited. The thickness of the transparent composite sheet of the present invention is preferably 20 to 1 Å. When the thickness of the transparent composite sheet is 20 μm or more, the substrate for a display device can maintain sufficient strength and rigidity. When the thickness of the transparent composite sheet is 1 μm or less, the volume shrinkage at the time of hardening the hardening composition is small, and it is difficult to cause a phase difference due to the residual of the stress, and it is difficult to cause a decrease in contrast of the display. Further, if the thickness of the transparent composite sheet is 1000 μm or less, the transparent composite sheet becomes difficult to warp, and the thickness of the transparent composite sheet becomes uniform. In order to be preferably used for display elements and solar cells, the thickness of the transparent composite sheet of the present invention is more preferably 25 or more, and still more preferably 2 〇〇 μπι or less. The thickness of the transparent composite sheet is not less than the above lower limit and not more than the above upper limit, so that heat resistance can be sufficiently improved. The above "thickness" means the average thickness. For glass cloths such as glass cloth and glass non-woven fabric, only one sheet can be used, and a plurality of sheets can be used in combination. When the thickness of the transparent composite sheet exceeds 1000 μπχ, when the transparent composite sheet of the present invention is obtained, it can be divided. It is a plurality of plates and the plate is laminated and then hardened. Further, it is also possible to repeat the slab formation and hardening to obtain a laminate of the sheets. The transparency of the transparent composite sheet of the present invention at 550 nm is preferably 80% or more, more preferably 85°/. In the above, it is preferable that the light transmittance is 90% or more, and the image display device 158155.doc is obtained by using a transparent composite plate as a substrate for a liquid crystal display device or an organic EL display device substrate, for example. 39. In the case of 201211011, 'obtain a clear image with high quality. The transmittance can be determined by measuring the total transmittance at a wavelength of 550 nm using a commercially available spectrophotometer. The haze value of the transparent composite sheet of the present invention is preferably 10% or less, more preferably

It is 5°/. Below, particularly preferred is 4% or less. The haze value described above was measured based on JIS K71 36. As a measuring device, a commercially available haze meter was used. As the measuring device, for example, a "automatic mist meter TC-HIIIDPK" manufactured by Tokyo Denshoku Co., Ltd., or the like can be exemplified. The transparent composite sheet of the present invention is 50 to 200 from the viewpoint of improving the dimensional stability of the transparent composite sheet. (The average linear expansion coefficient below is preferably 2 〇 ppm / ° C or less. On the transparent composite plate of the present invention, a surface smoothing layer, a hard coat layer or a gas barrier layer can be laminated to form the surface smoothing When layering or hard coating, for example, coating a known surface smoothing agent or hard coating agent on a transparent composite board, and drying as needed to remove the solvent. Then, by heating or irradiating the active light to make the surface smoothing agent or The hard coating agent is hardened. The method of applying the surface smoothing agent or the hard coating agent on the transparent composite plate is not particularly limited, and for example, a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, or the like can be employed. A conventionally known method such as an extrusion coating method, a curtain coating method, and a nozzle coating method. The gas barrier layer is preferably used as a gas barrier layer, and is particularly limited to, for example, a metal such as a metal. 2 and sm and other oxime compounds 'alumina oxide, and oxidized singular materials. Among them, jj # ': property, adhesion to the substrate layer and transparency 158155.doc 201211011 is excellent, so it is preferred to use Anthracene compounds such as si〇2 and SiN. The method of the gas barrier layer is not particularly limited, and examples thereof include a dry method such as a vapor deposition method and a sputtering method, and a wet method such as a sol-gel method, etc. Among them, dense and gas barrier properties are formed, and the base is excellent. The transparent composite plate of the present invention can be preferably used for a plastic substrate for a liquid crystal display element, a plastic substrate for an organic EL display element, and a sun, from the viewpoint of a gas barrier layer having a good adhesion to a material. The present invention will be specifically described below by way of examples and comparative examples. The present invention is not limited to the following examples. (Example 1) In the case of isomeric cyanuric acid (2-propene)醯oxyethyl) ester (A-93 00, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 parts by weight, and ε-hexine, modified triiso(octylate) The ester (corresponding to a (meth) acrylate compound having a tri-skeleton represented by the formula (2), 50 parts by weight of "A-9300-1CL" manufactured by Shin-Nakamura Chemical Co., Ltd.) is added as a photopolymerization. Starting agent 2-methyl·1-[4-(methylthio)phenyl]-2-morpholinpropanone (Ciba J) 0.2 parts by weight of "Irgacure 9〇7" manufactured by Apan Co., Ltd., and heated to i 〇 (stirring, mixing and dissolving while rc) to prepare a curable composition. As a glass fiber, iPC#2013 as a T glass fiber is prepared. A glass cloth (manufactured by Nitto Denko Co., Ltd.) was immersed in a curable composition heated to 7 ° C to impregnate the glass cloth with a hardening composition, and then pulled up the curable composition. The glass cloth impregnated with the curable composition is placed on the release-treated glass plate, and the glass plate is impregnated with 158155.doc • 41 - 201211011 glass cloth having a hardening composition as a thickness of 100 μm. (Poly ethylene Terephthalate, polyethylene terephthalate) film ("COSMOSHINE A4100" manufactured by Toyobo Co., Ltd.) was covered, and the thickness was made uniform by a laminator adjusted to a temperature of 50 °C. Then, the curable composition was cured by irradiating ultraviolet rays of 2000 mJ/cm2 (365 nm) from the glass plate side with a high-pressure mercury lamp, and the cured plate was peeled off from the pet film and the glass plate to obtain a transparent composite plate. The resulting transparent composite sheet had a thickness of 80 μm. (Example 2) Tricyclodecane dimethanol diacrylic acid was added to 50 parts by weight of tris(2-propenyloxyethyl) isophthalate ("-9-300" manufactured by Shin-Nakamura Chemical Co., Ltd.) S ("a_dcp" manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 parts by weight, and 2-mercapto 444-(methylthio)phenyl]_2-morpholinpropan-1-one as a photopolymerization initiator ( "Irgacure 9〇7" manufactured by Ciba Japan Co., Ltd.) 〇 2 weight of the wound surface was heated to 100 C to be mixed, mixed and dissolved to prepare a curable composition. Using the obtained curable composition, a transparent composite sheet was obtained in the same operation and conditions as in Example i. The obtained transparent composite plate has a thickness of 8 () μιη 〇 (Example 3) modified with vinegar-modified isopropyl tris(2-propanyloxyethyl) vinegar (equivalent to the formula ( 2) In the "Α_痛·心" (9) parts by weight of the new Nakamura Chemical Co., Ltd. which has a three-skeleton (meth)acrylic acid vinegar compound, tricyclodecanedioxane diacrylate vinegar is added. Nakamura Chemical Co., Ltd. 158I55.doc • 42-201211011 "A-DCP" made 50 parts by weight, and 2_mercapto 444-(sulfonylthio) styryl]-2-indan-1-one (Ciba) 0.2 parts by weight of "907" manufactured by Japan, and the mixture was heated to 10 (rc) while stirring, mixing and dissolving to prepare a curable composition. The obtained curable composition was used in the same manner as in Example 及 and A transparent composite plate was obtained under the conditions. The obtained transparent composite plate had a thickness of 8 μm η 实施 (Example 4) modified ε-hexine modified isocyanuric acid tris(2-propyleneoxyethyl) vinegar ( "A_93" manufactured by Shin-Nakamura Chemical Co., Ltd., which is a (meth) acrylate compound having a three-till skeleton represented by formula (2) 〇_1CL") 1 part by weight of 1-hydroxy-cyclohexyl-phenyl ketone ("Irgacure 184" manufactured by Ciba Japan Co., Ltd.) 4. 4 parts by weight, and heated to 1 〇〇〇c - Surface preparation, mixing, and dissolution 'Preparation of a curable composition. Using the obtained curable composition, a transparent composite sheet was obtained under the same operation and conditions as in Example 。. The thickness of the obtained transparent composite sheet was μηι. (Comparative Example 1) Addition as a photopolymerization initiator = 100 parts by weight of triiso(2-propenyloxyethyl) ester ("-9-300" manufactured by Shin-Nakamura Chemical Co., Ltd.) · Methyl·methylthio)phenyl]_2_morpholinpropane ketone ("Irgacure 9〇7" by Ciba Co., Ltd.) 〇 2 parts by weight, - the surface is heated to i 〇〇 ° c - surface for stirring, Mixing and dissolving to prepare a curable composition. Using the obtained curable composition, a transparent composite sheet was obtained under the same operation as in Example i and 158155.doc • 43-201211011. The thickness of the obtained transparent composite sheet was (9) Ιιη 〇 (Example 5), in iso-cyanuric acid tris (2· propylene oxide) Ethyl (4) ("Α·93〇〇" manufactured by Shin-Nakamura Chemical Co., Ltd.) was added as a photopolymerization initiator = 2-methyl(methylthio)phenyl]_2morpholinepropane as a starting component. 2 parts by weight of "Irgacure 9〇7" manufactured by ah Co., Ltd., while heating to i〇〇°c, the mixture is stirred, mixed and dissolved to prepare a curable composition. The resulting curable composition is used in combination with In the same operation and conditions as in Example i, a transparent composite plate before heating was obtained, and further, heat treatment was performed in an oven of 22 (TC) for 1 hour to obtain a transparent composite plate. The thickness of the transparent composite sheet after the heat treatment was 80 μm. (Comparative Example 2) 2-methyl 1 was added as a photopolymerization initiator to 1 part by weight of dicyclodecane dimethanol diacrylate ("A-DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.). 0.2 parts by weight of (methylthio)-based ketone ketone ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.) was stirred, mixed, and dissolved to prepare a curable composition. Using the obtained curable composition, the thickness of the transparent composite sheet obtained by obtaining the transparent composite sheet under the same operation and conditions as in Example 1 except that the temperature of the bonding machine was set to room temperature was 80 μm. (Example 6) 48.5 parts by weight of ε·caprolactone modified by diiso(2-propanyloxyethyl)g ("A-9300" manufactured by Shinkomura Chemical Co., Ltd.) Iso-cyanuric acid 158155.doc •44· 201211011 Tris(2-propenyloxyethyl) ester (corresponding to the new Nakamura of the (meth) acrylate compound having the three-till skeleton represented by formula (2) 48.5 parts by weight of "8-9300-10; 1^" manufactured by Chemical Company, and 9,9,_bis[4-(2-acryloxyethoxy)phenyl] as a refractive index modifier (corresponding to 3 parts by weight of "A-BPEF" manufactured by Shin-Nakamura Chemical Co., Ltd. of the (meth) acrylate compound having an anthracene skeleton represented by the formula (11)), 2- as a photopolymerization initiator 0.2 parts by weight of fluorenyl-1-[4-(indolylthio)phenyl]-2-morpholinanone ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.), and the mixture was heated to 100 ° C while stirring. The mixture is dissolved and dissolved to prepare a curable composition. Using the obtained curable composition, a transparent composite sheet was obtained in the same operation and conditions as in Example 。. The thickness of the obtained transparent composite plate was 8 μm μm (Example 7) to tris(2-propenyloxyethyl) isocyanurate ("Α-9300" manufactured by Shin-Nakamura Chemical Co., Ltd.) 48 weight. And ε_caprolactone modified tris(2·acryloxyethyl) isocyanate (corresponding to a (fluorenyl) acrylate compound having a three-till skeleton represented by formula (2) 48 parts by weight of "Α_ 9300-1 CL" manufactured by Shin-Nakamura Sakagyo Co., Ltd., and a synthetic bisphenol fluorene diepoxide acrylate as a refractive index modifier (corresponding to the first skeleton represented by the formula (12) "Irgacure9" manufactured by 2-methyl-M4_(methylthio)phenyl]_2-morpholinepropane ketone Japan Co., Ltd. as a photopolymerization initiator was added to 4 parts by weight of the (meth) acrylate compound. 〇7") 2 parts by weight, while stirring, mixing and dissolving while heating to 10 ° C, a curable composition was prepared. Using the obtained curable composition, a transparent composite sheet was obtained in the same manner as in Example i and under the conditions of 158155.doc -45·201211011. The result is obtained (4). complex. The thickness of the plate is 80 (Example 8), 47 parts by weight of the "A-9300" (manufactured by Shin-Nakamura Chemical Co., Ltd.), and ε_ Vinegar-modified isocyanuric acid tris(2-propenyloxyethyl (4) (corresponding to the new Nakamura Chemical Co., Ltd., which has a three-sprayed (meth) acrylic acid compound represented by formula (7) · 93〇〇_1CL") 47 parts by weight, and as a synthesis of a refractive index modifier, a double-dip quinone diamino phthalic acid acrylic acid 3 (corresponding to the formula having the first skeleton represented by the formula (13) 2-methyl small [4. (indolylthio)phenyl] 2 phenanthrene-propanthine (Irgacure manufactured by Ciba Japan Co., Ltd.) as a photopolymerization initiator is added to 6 parts by weight of the methyl acrylate compound. 9〇7") 〇 2 parts by weight of 'one side is heated to 100 ° C. - The side is made, the person &&&&&&&&&&& The transparent composite sheet obtained by the transparent composite sheet 1 having the same operation and conditions as in Example i has a thickness of 80 μηι 〇 (Example 9) on the hetero-cyanide Dioxanediol diacrylate (corresponding to formula (21)) is added to 8 parts by weight of tris(2-propenyloxyethyl) ester ("-9300" manufactured by Shin-Nakamura Chemical Co., Ltd.) "A_D〇G" manufactured by Shin-Nakamura Chemical Co., Ltd. of a (meth) acrylate compound having a dioxane skeleton, 2 parts by weight, and 2 fluorenyl group as a photopolymerization initiator [4 (methyl sulphide) Phenyl]-2-morpholinopropan-1-one ("Bus (3) generation 158155.doc • 46 - 201211011, which is stirred and mixed with 907") manufactured by Ciba Japan Co., Ltd. 0.2 part by weight, and heated to the surface Dissolved to prepare a curable composition. The same operation and thickness was 80. Using the obtained curable composition 'A transparent composite plate was obtained under the conditions of Example 1. The obtained transparent composite plate μηι 〇 (Examples 1 to 9) And evaluation of Comparative Examples 1 and 2) a) Refractive Index Preparation Two glass plates subjected to mold release treatment were prepared. The two glass plates are separated by a gap of μμη, and the obtained curable composition is sandwiched between the glass plates, and uv (uitraw〇iet, ultraviolet) light of 2000 mJ/cm 2 (365 nm) is irradiated with a high pressure mercury lamp. The curable composition is crosslinked and hardened. Thereafter, the cured product was peeled off from the glass plate, and heat-treated in a box of 2 ° C for 1 hour to prepare a test piece (cured product). The refractive index nD (sodium D line (589 nm) ' 25 ° C) of the test piece was measured using an Abbe refractometer ("NAR_1T" manufactured by Atago Corporation). Regarding the refractive index of the glass fiber, the nominal value of the manufacturer (曰东纺) is used. b) Linear expansion coefficient The obtained transparent composite plate was heated from 30 °C to 300 at a speed using a thermal stress strain measuring device ("TMA/EXSTAR6000 model" manufactured by Seiko Instruments Inc.). (: After cooling to 30 ° C ° at a rate of 20 ° C / min, the temperature of the transparent composite plate was further increased from 30 ° C to 3 ° ° C at a rate of 10 ° C / 丨 min. 50. (: average linear expansion coefficient at ~200 ° C. c) glass transition temperature 158155.doc •47· 201211011 Using a dynamic viscoelasticity measuring device ("DVA-200" manufactured by it Meter and contro丨), The obtained transparent composite plate was heated from 30 ° C to 300 ° C at a rate of 10 ° C / min, and the tensile mode was measured. The peak temperature of tan § was taken as the glass transition temperature. The glass transition temperature was equivalent to hardening. The glass transition temperature of the cured product obtained by hardening the composition d. The transmittance is measured by a spectrophotometer ("1; 乂 _ 3 1 0PC" manufactured by Shimadzu Corporation), and the obtained transparent composite plate is measured at 550 nm. Transmittance. When the transmittance is 85% or more, the transparency is excellent. e) Haze value The haze value of the obtained transparent composite plate was measured using a haze meter ("automatic fog meter TC_HIIIDPK" manufactured by Tokyo Denshoku Co., Ltd.). When the haze value is 5% or less, the transparency is excellent. f) Softness The resulting transparent composite sheet was wound around a round rod of different radii to observe cracks and peeling of the interface between the cured layer and the glass fiber. Observation by visual observation "The minimum diameter of the round bar which did not cause cracks and peeling of the interface between the cured layer and the glass fiber was taken as a value of flexibility. The minimum diameter of the rounded bar which is free from cracks and the interface between the cured layer and the glass fiber is preferably 2 mm or more, more preferably 4 mm or more. The evaluation results are shown in Table 1 below. 158155.doc •48- 201211011 Example 9 〇1 1.528 Tf (Ν—· 〇205 *r\ »n 00 Example 8 Ό 〇s 1 1.529 〇〇(N 5: 〇»ri 00 Example 寸 inch η 〇 1.5 1.530 〇 235 00 — 00 Example 6 48.5 48.5 m (Ν 〇Μ ΓΛ 〇 245 1 51 · 00 Comparative Example 2 〇«•a (Ν 〇 1.530 〇% o wS 00 Example 5 〇d 1 L532 〇\ ΓΊ cs uS 00 Comparative Example 1 〇<N Ο § 1 1.536 〇〇wj ΓΊ 5: 15.2 00 Example 4 〇ο 1.525 〇\ 〇00 Example 3 CM 茗 茗 1.528 On S η 5: o wi 00 Example 2 <s ο g 1 1.532 s cs Os 00 - 00 Example 1 04 Ο 〇ο ο m Pair · 00 1 1 1 [Parts by weight] 1 1 [ppm/°C] P i I Shame 1) 0 Td 〇\ι| ιι| ^ 'Ί Silver 铋 2 , 丨 1 1 at Η = 逋ώ already tricyclodecane dimethanol diacrylate 9,9 ·- bis [4-(2-acryloxy ethoxy ethoxylate) Base) phenyl]» bisphenol second epoxy enoate bisphenol second amino carboxylic acid acrylate di-alkane diacetate O acrylate Os υ i Si s Thickness of 1 hardened composition of hardened composition (nD) Refractive index of glass woven (nD) Average linear expansion coefficient Glass transition temperature Light transmittance (550 nm) Haze value softness (III rod (M) acrylate compound (1) (meth) acrylate compound (2) Compound having a dicyclopentyl skeleton, compound having a first skeleton, compound having a dioxane skeleton, photopolymerization initiator hardening composition Characteristics of the composition of the transparent composite plate·49· 158155.doc 201211011 (Example ίο) Tris(2-propenyloxyethyl) isopropyl cyanide ("A-9300" manufactured by Shin-Nakamura Chemical Co., Ltd.) 70 parts by weight of t, adding 9,9,-bis[4·(2-propanyloxyethoxy)-based] oxime (corresponding to (methyl) having the first skeleton represented by the formula (Π) 30 parts by weight of "A BPEF" manufactured by Shin-Nakamura Chemical Co., Ltd. of the acrylate compound, 2-methyl(methylthio)phenyl]-2-morpholinepropane-i-ketone as a photopolymerization initiator 0.2 parts by weight ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.), and stirred while heating to 1 〇〇〇c Mixed and dissolved to prepare a curable composition. As a glass fiber, a glass cloth (manufactured by Dairo Spinning Co., Ltd.) equivalent to ipc#2013 of E glass fiber was prepared. The glass cloth was immersed in a curable composition heated to 1 Torr (5c), and the curable composition was impregnated into the glass cloth while irradiating the ultrasonic wave. Thereafter, the glass cloth impregnated with the curable composition was pulled out. And placed on a glass plate which has been subjected to release treatment, and the glass cloth impregnated with the curable composition on the glass plate is covered with a thickness of 1 〇〇pmiPET film ("COSMOSHINE A4100" manufactured by Toyobo Co., Ltd.), and passed through The bonding machine was adjusted to a temperature of 70 eC to make the thickness uniform. Then, from the PET film side, a high-pressure mercury lamp was used to irradiate 2 μm/cm 2 (365 nm) of ultraviolet rays to harden the curable composition. The hardened plate was peeled off from the pET film and the glass plate, and heat-treated in an oven for 1 hour to obtain a transparent composite plate. The thickness of the obtained transparent composite plate was 80 μηι. (Example 11) Addition of 3,3'-dioxin to 65 parts by weight of tris(2-propenyloxyethyl) isocyanurate ("A-9300" manufactured by Shin-Nakamura Chemical Co., Ltd. 158155.doc • 50· 201211011) 5-,5,-diethyl-4,4'-diphenyl Alkanic bismaleimide ("MBI-5100" manufactured by Daiwa Kasei Co., Ltd.) 35 parts by weight, and 2-mercapto-anthracene [4-(indolylthio)phenyl]μ2_morpholinepropane-1-oxime ( "Igacure 907" manufactured by Ciba Japan Co., Ltd.) 5.5 Weight damage 'When warmed to 12 〇 ° C - the surface is spoiled, mixed and dissolved to prepare a curable composition. The resulting sclerosing composition is used to Example 1 A transparent composite board was obtained under the same operation and conditions. The obtained transparent composite sheet had a thickness of 75 μηι 〇 (Example 12) on isocyanuric acid tris(2-propenyloxypropyl) ester 6 3,3'-dimercapto-5,5'-diethyl-4,4,-diphenylnonane bismaleimide ("ΜΒΙ_51〇〇" manufactured by Daiwa Kasei Co., Ltd. ") 4 parts by weight, and 2-mercaptomethylthio)phenyl]_2-morpholinepropane ("Igacure 907" manufactured by Ciba Japan Co., Ltd.) as a photopolymerization initiator, 5 parts by weight, plus The curable composition was prepared by stirring, mixing and dissolving at a temperature of 120 ° C. The same hardening composition was used, and the same operation as in Example J was carried out. The transparent composite plate was obtained under the conditions. The thickness of the obtained transparent composite plate was 75 μm (Example 13) in bis(2-propanyloxyethyl) vinegar (manufactured by Shin-Nakamura Chemical Co., Ltd.) 62-9300") 62 parts by weight, added 9,9,-bis[4-(2-acryloxyethoxy)phenyl]anthracene ("Nakamura Co., Ltd." "Α_ I58155.doc -51 · 201211011 BPEF") 28 parts by weight, and 2 methyl_ι·[4_(methylthio)carbyl]-2-oxaprofen-1-one (manufactured by Ciba Japan Co., Ltd.) as a photopolymerization initiator 0.2 parts by weight of Irgacure 907"), while heating to 1 〇〇〇c, the mixture was stirred and dissolved to obtain a solution. Then, the obtained solution was cooled to 7 〇 ' Add 1,3,5-tris(3-sulfobutoxyethyl)triphthyl 2,4,6-trione (Karenz, manufactured by Showa Denko) 10 parts by weight of MT NR1") was mixed and mixed to prepare a curable composition. Using the obtained curable composition, a transparent composite sheet was obtained under the same operation and conditions as in Example 1 except that the temperature at the time of impregnation was changed to 70 C. The resulting transparent composite sheet had a thickness of 75 μm. (Example 14) 9,9,-double [4] was added to 60 parts by weight of tris(2-propenyloxyethyl) isocyanurate ("-9-300" manufactured by Shin-Nakamura Chemical Co., Ltd.). -(2-Acryloxyethoxy)phenyl]indole ("Α_BPEF" manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by weight, and 2_methyl_丨_[4_ ( as a photopolymerization initiator) Methylthio)benzamine-2-(?)-0.2_嗣 ("Irgacure 907" manufactured by Ciba J ap an) 0.2 parts by weight, and heated to 100 on one side. The mixture was stirred while stirring to obtain a solution. Then, the obtained solution was cooled to 7 〇〇c, and 15 parts by weight of a sesquioxanane compound ("Compoceran HBSQ101" manufactured by Arakawa Chemical Industries, Ltd.) having a plurality of thiol groups was added thereto, and the mixture was mixed and prepared. A curable composition. Using the obtained curable composition, the transparent composite sheet was obtained under the same operation and conditions as in Example 1 except that the temperature at the time of impregnation was changed to 7 °C. The resulting transparent composite sheet had a thickness of 80 μm. I58I55.doc -52· 201211011 (Comparative Example 3) In 6 parts by weight of tris(2-propanoloxyethyl) vinegar ("A-9300" manufactured by Shin-Nakamura Chemical Co., Ltd.), Adding 99·bis[4(2·acrylic ethoxyethoxy)phenyl] ("A_" by Shin-Nakamura Chemical Co., Ltd.) 40 parts by weight, and 2 methyl group as a photopolymerization initiator) BenQ] 2-Merlin propyl ketone (made by ciba japan)

Irgacure 907") was added in an amount of 2 parts by weight, and the mixture was heated to 1 Torr <> c while stirring, mixing and dissolving to prepare a curable composition. Using the obtained curable composition, a transparent composite sheet was obtained in the same operation and conditions as in the examples. The resulting transparent composite sheet has a thickness such as μηη. (Comparative Example 4) 』 Adding 99, bis[4 (2 propylene) to 80 parts by weight of "a-9300j" manufactured by Shin-Nakamura Chemical Co., Ltd. 20 parts by weight of decyloxyethoxy)phenyl] burial ("a_EF" manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2 methyl(methylthio)phenyl]-2- as a photopolymerization initiator 0.2 parts by weight of porphyrinone ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.) was stirred, mixed, and dissolved while heating to prepare a curable composition. Using the obtained curable composition, a transparent composite sheet was obtained under the same operation and conditions as in Example 1. The thickness of the obtained transparent composite plate was 8 〇μπι 〇 (Comparative Example 5) in the production of tris(2-propenyloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd. 158155.doc -53·201211011) In the A5300"), 25 parts by weight of bis[4(2 propylene methoxy ethoxy) phenyl] fluorene ("A_ BPEF" manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to S5 parts by weight, and photopolymerization was carried out. 0.2 parts by weight of the initiator 2·曱基卜[4·(indolyl)phenyl]-2-morpholinepropane_丨-ketone (Ciba (Irgacure 907 manufactured by 卩(10))) was heated to one side. 1 〇〇 <>c Stir and dissolve to obtain a solution. Then, the obtained solution was cooled to 7 ° C, and 1,3,5-tris(3·succinyloxyethyl)135 tri-n-tanning 2-4 4 6-one ketone (Karenz MT manufactured by Showa Denko Co., Ltd.) was added. NR1") 20 parts by weight, stirred and mixed to prepare a curable composition. Using the obtained curable composition, a transparent composite plate was obtained under the same operation and conditions as in Example except that the temperature at the time of impregnation was changed to 70 C. The thickness of the obtained transparent composite plate was 75 (Example 15) in 50 parts by weight of tris(2-propenyloxyethyl) isocyanurate ("Α-9300" manufactured by Shin-Nakamura Chemical Co., Ltd.). 25 parts by weight of 9,9--bis[4-(2-propenyloxyethoxy)phenyl] ("Α_BPEF" manufactured by Shin-Nakamura Chemical Co., Ltd.), and as a photopolymerization initiator 2 methyl small [4_(methylthio)phenyl r ]-2-morpholinepropan-1-one ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.) 0.2 parts by weight, heated to 1 一面〇c Stir and dissolve to obtain a solution. Then, the obtained solution was cooled to 7 ° C, and a sesquioxanes compound having a plurality of thiol groups ("Compoceran HBSQ101" manufactured by Arakawa Chemical Industries Co., Ltd.) was added in an amount of 25 parts by weight ', and stirred and mixed to prepare. A curable composition. Using the obtained curable composition, except that the temperature at the time of impregnation was set to 158155.doc • 54-201211011 7〇°C, a transparent composite plate was obtained under the same operation and conditions as in Example 1. The resulting transparent composite panel had a thickness of 80 μm. (Comparative Example 6) Addition to 70 parts by weight of 2,2·-bis[4-(acryloxypolyethoxy)phenyl]propane ("ABE-300" manufactured by Shin-Nakamura Chemical Co., Ltd.) 9,9,-bis [4-. (2-acryloxyethoxy)phenyl]indole ("A-BPEF" manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts by weight, and as a photopolymerization initiator 2_曱基4·[4-(Methylthio)-based]-2-Merline-propan-1-yin ((Irgacure 907) manufactured by 2^卩 1111 Company) 0.2 parts by weight The curable composition was prepared by stirring, mixing, and dissolving to 100 〇c. The obtained curable composition was used to obtain a transparent composite sheet under the same operation and conditions as in Example 1. The obtained transparent composite sheet was obtained. The thickness was 8 〇μηι. (Evaluation of Examples 10 to 15 and Comparative Examples 3 to 6) Examples 10 to 15 and Comparative Examples 3 to 6 were the same as Examples 1 to 9 and Comparative Examples 1 and 2. Evaluation of project implementation evaluation. The evaluation results are shown in Table 2 below. 158155.doc •55· 201211011

[<N<I——I Comparative Example 6 O CM 〇»n 00 «η »η *Λ 〇§ <N rn ίΝ Example 15 sn η 〇is 〇(N % ΓΊ rn (N Comparative Example 5 in ΓΊ <s ο jn *nv〇*〇 inch w-> 00 % CS cn <N Comparative Example 1 4 ss rJ ο g «〇w-> § <N § ΓΛ - For Comparative Example 1 3 3 ο r4 ο 运»n w-> cs o wS Embodiment 1 14 § »r> ΓΊ rJ ο S »r>v〇»〇w-> fN ?N wn rn <N Example 1 13 S 00 η 〇η ο JQ VO in o <N (S 00 ΓΟ CS Example | 12 〇ΙΛ iC s ΓΛ 沄 (N § rn Example 丨η.——_ S V-> m <rj 1C s »n 2 § (N g v-> rn inch embodiment 10 o CM § § •Λ \D w-> Ό CN % m inch [parts by weight] ε a 1 1 1 [ppmTC] 1 r-^ P τ | 羞温〇e逋铋敢ιι| « Mystery u| C 9,9·-双[4-(2-Acryloxyethoxy) Stupid]苒〇«I 7\f «ίΓ Ιΐ "5 1,3,5-tris(3-sulfylbutoxyethyl)-1,3,5-three tillage-2,4,6-trione σ C/D CQ X 1 U uo CL So u 2,2'-bis[4·(propyleneoxypolyethoxy)phenyl]propane § Ε 3 Refractive index of the hardened composition of the thickness-hardening composition (nD) Refractive index of the glass woven dimension (nD Average linear expansion coefficient Glass transition temperature 1 Light transmittance (550 nm) Haze value flexibility (round rod diameter) (Meth) acrylate compound (1) 1_ Compound with double oxime skeleton Functional thiol compound Other compound Photopolymerization initiator tl哒 Transparent composite sheet characteristics 158155.doc -56- 201211011 Further 'Use the equivalent of the (meth) acrylate compound having the three-flavor skeleton represented by the formula (1) Tris(2-propenyloxyethyl) polycyanate, and 9,9,_ as a refractive index modifier corresponding to a (meth) acrylate compound having a Lacquer skeleton represented by the formula (u) Bis[4_(2-propenyloxyethoxy)phenyl] is prepared as a curable composition in which the blending ratios are changed. a total of 1% by weight of tris(2-propenyloxyethyl)-isocyanate and 99, bis[4-(2-propenyloxyethoxy)phenyl]indole Relationship between the blending ratio (% by weight) of tris(2-propenyloxyethyl)cyanate and the refractive index nD of the cured product and the haze value of the transparent composite sheet (transparent sheet) produced using the curable composition Conduct an evaluation. The results are shown in Fig. 1. Further, Fig. 1 includes the evaluation results in Example 1, 比较, Comparative Example 3, and Comparative Example 4. From the viewpoint of making the refractive index and the haze value of the cured product good, according to the results shown in Fig. 1, it is known that triiso(2-propenyloxyethyl)ester and 9,9 are used. - in the case of bis[4-(2-propenyloxyethoxy)phenyl], in the total of 100% by weight of the total, triisocyanocyanate (2·acryloxyethyl) The content of vinegar is 63% by weight or more and 78% by weight. /〇The following is more reasonable. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the blending ratio of tris(2-propenyloxyethyl) isocyanate and the refractive index nD of the cured product of the curable composition and the haze value of the transparent composite sheet. The map of the relationship. 158155.doc •57-

Claims (1)

201211011 VII. Patent application scope: 1. A curable composition containing a (mercapto) acrylate compound having a three-till skeleton represented by the following formula (1) and represented by the following formula (2) At least one of the (indenyl) acetoacetate compound having a tri-skeleton, and the cured product after hardening has a refractive index of 5.525 or more and 1.535 or less at 589 nm, and the glass transition temperature of the cured product It is 2 〇〇. (: Above; or, the cured product after hardening has a refractive index of 1.575 or more at 589 nm, 1.571 or less, and the glass transition temperature of the cured product is 200 ° C or more, [Chemical 1] In the above formula (1), R1 to R6 each represent a hydrogen atom or a methyl group, and nb n3 represents 1 or 2, respectively. 158155.doc 201211011 In the above formula (2), R1 to R6 each represent a hydrogen atom or a combination of methyl groups 'nl, n2 and n3, on average, representing 0.5 to 3. 2. A curable composition which is obtained by embedding glass fibers in a hardened body after hardening, and having a bismuth (methyl) acrylate having a three-hook skeleton represented by the following formula (1) The at least one of the cerium compound and the (mercapto) acrylic acid vinegar compound having a tridentate skeleton represented by the following formula (7), the cured product after hardening has a refractive index of 1 525 or more and 1.535 or less at 589 nm. And the glass transition temperature of the cured product is 2 〇〇 <> or more; or, the cured product after hardening has a refractive index of 丨 557 or more and 1.571 or less at 589 nm, and the glass transition temperature of the cured product is 2〇〇It is above, [Chemical 3] R1 〇 H2C=rc-C II In the above formula (1), R1 to R6 each represent a hydrogen atom or a methyl group, and n1 to n3 respectively represent 1 or 2, 158155.doc 201211011 [Chemical 4] R1 Ο / 0\ R2ι ιι L Λ η \ ι H2C=CCl〇—C5H10—CJO-CH—CH ,CH2—CH-0 十 C—C5H10—〇}BC=CH2 ?3 Ο R4 Formula (2) CHa—CH—〇|C-c5H10-〇Vc-C=CH2 R5 \0 l〇R6 In 2), R1 to R6 each represent a hydrogen atom or a methyl group, and "the total of the core and the n3 is an average of 0.5 to 3". 3. The hardenable composition of claim 1 or 2, which contains the above formula (1) A (meth) acrylate compound having a three-till skeleton and a (fluorenyl) acrylate compound having a three-till skeleton represented by the above formula (2). 4_ Requesting item 1 or 2 The curable composition further contains a refractive index adjusting agent. 5. The curable composition according to claim 4, which comprises a (meth) acrylate compound having a dicyclopentyl skeleton and a fluorenyl group having a first skeleton An acrylate compound, a (fluorenyl) acrylate compound having a dioxane skeleton or a bismaleimide compound as the above-mentioned refractive index modifier. 6. The curable composition according to claim 4, which has a bicyclic ring a (meth) acrylate compound having a pentyl skeleton, a (meth) acrylate compound having an anthracene skeleton, Or a (fluorenyl) acrylate compound having a dioxane skeleton as the above-mentioned refractive index adjusting agent. The hardening composition according to claim 5 or 6, wherein the above (fluorenyl) acrylate having a dicyclopentyl skeleton The compound is a (fluorenyl) acrylate compound having a dicyclopentyl skeleton represented by the following formula (3), 158155.doc 201211011 [Chemical 5] h2c-c~^-〇-ch_ Ο B12 O Formula (3) In the above formula (3), R11 and R12 each represent a hydrogen atom or a methyl group. 8. The curable composition according to claim 7, wherein the refractive index modifier is a (meth)acrylic acid vinegar compound having a dicyclopentyl skeleton as shown in Table 7F of the formula (3). 9. The curable composition according to claim 5 or 6, wherein the (meth) acrylate compound having an anthracene skeleton is a (meth) acrylate compound having an anthracene skeleton represented by the following formula (11) a (meth) acrylate compound having an anthracene skeleton represented by the following formula (12) or a (meth) acrylate compound having an anthracene skeleton represented by the following formula (13), [Chem. 6] In the above formula (11), R11 to R14 each represent a hydrogen atom or a methyl group, and mi and m2 respectively represent 1 or 2, 158155.doc 201211011 In the above formula (12), R11 and R12 each represent a hydrogen atom or a methyl group. Formula (13) In the above formula (13), R11 and R12 each independently represent a hydrogen atom or a fluorenyl group. 10. The curable composition of claim 9, wherein the refractive index adjusting agent is a compound having a skeletal structure represented by the above formula (11), which is represented by the above formula (12) A (fluorenyl) acryl vinegar compound having an anthracene skeleton or a (fluorenyl) acrylate compound having an anthracene skeleton represented by the above formula (13). 11. The curable composition according to claim 5 or 6, wherein the (mercapto) acrylate compound having the second calcined skeleton is a compound of the formula (21) represented by the following formula (21). , 158155.doc 201211011 [Chemical 9] 〒H3 /0—CH2 -C-HC; C: I \ / ch3 o—ch2 R11 H2C=C — C—Ο一ΟΗ〇~ ιι ο xh2—ch3 όη2-ο— C—c=ch2 0 R12 .. (21) In the above formula (21), R11 and R12 each independently represent a hydrogen atom or a fluorenyl group. The curable composition according to claim 11, wherein the refractive index modifier is a (meth)acrylic acid vinegar compound having a two-P alkane skeleton represented by the above formula (21). The sclerosing composition according to claim 5 or 6, wherein the bismaleimide compound is a bismaleimine compound represented by the following formula (31), [Chem. 10] In the above formula (31), R21 to R24 each represent a hydrogen atom or a methyl group, and R25 and R26 each independently represent a hydrogen atom, a fluorenyl group or an ethyl group. The curable composition according to claim 13, wherein the refractive index modifier is a bismaleimide compound represented by the above formula (31). The hardenable composition according to claim 1 or 2, wherein the cured product after hardening has a refractive index of 1.525 or more and MU or less at 589 nm, and the glass transition temperature of the cured product is 200. (1) The hardening composition according to claim 1 or 2, wherein the hardened 158155.doc -6 - 201211011 has a refractive index of 557 or more and 1 571 or less at 589 nm, and The glass transition temperature of the cured product is 2 〇〇 ° C or more. 17. A transparent composite sheet comprising: a cured product obtained by curing the curable composition according to any one of claims 1 to 16, and buried The glass fiber of the above-mentioned hardened material. The transparent composite board of claim 17, wherein the glass fiber is τ glass or E glass. The transparent composite board of claim 18, wherein the glass fiber is 20. The transparent composite sheet of claim 18, wherein the glass fiber is e-glass. 21. The transparent composite sheet of claim 17 or 18, which has a transmittance of 85% or more at a wavelength of 550 nm. 22. The transparent composite panel of claim 17 or 18 which has an average linear expansion coefficient of from 5 MPa to 200 ° C of less than 20 ppm/° C. 23. The transparent composite sheet of claim 17 or 18 The thickness is 25~200 μηι. 158155.doc