TW201339247A - Glass fiber composite resin substrate - Google Patents

Abstract

A glass fiber composite resin substrate comprising a curable resin composition and glass fibers, wherein the curable resin composition contains (A) a cage-type silsesquioxane resin having at least one functional group selected from the group consisting of (meth)acryloyol groups, glycidyl groups, and vinyl groups, (B) an unsaturated compound other than the aforementioned cage-type silsesquioxane resin, having two or more unsaturated functional groups selected from the group consisting of functional groups represented by the following general formulas (1) and (2): -R1-CR2=CH2 (1) -CR2=CH2 (2) [In formula (1), R1 represents a functional group selected from the group consisting of alkylene groups, alkylidene groups, and -OCO- groups, and in formulas (1) and (2), R2 independently represent a hydrogen atom or an alkyl group.], and (C) a curing catalyst, the amount of the cage-type silsesquioxane resin (A) being 5 to 90 mass % with respect to the total amount of the curable resin composition.

Description

Glass fiber composite resin substrate

The present invention relates to a glass fiber composite resin substrate.

Glass has excellent characteristics such as transparency, heat resistance, low thermal expansion property, and chemical stability. In the past, optical glass, such as lenses, optical disks, and display substrates, has been widely used to contribute to industrial development. In recent years, with the lightening of various optical devices, it has been reviewed to reduce the thickness and weight of optical glass having a large specific gravity. However, glass has a drawback that it is easy to break due to weak impact, and if it is thinned, its mechanical strength is further lowered, so that there is a problem that the yield is lowered due to cracking during the manufacturing process.

For this reason, as a film substrate which is excellent in flexibility and heat resistance and which is intended to be easy to be ruptured, for example, JP-A-2004-50565 (Patent Document 1) discloses that a metal oxide polymer containing a machine base is used. The resin layer of the main component is laminated on the film sheet substrate on the surface of the glass substrate. However, since the sheet-like glass is used in the film sheet substrate, it is difficult to further reduce the weight and the mechanical strength is not sufficient.

In recent years, in view of the fact that it is easy to reduce the weight and thickness, and the workability is excellent, the transparent plastic is attracting attention as an optical member that can replace glass. The transparent plastic is exemplified by polymethyl methacrylate (PMMA), alicyclic polyolefin, epoxy resin, polyoxynoxy resin, etc., wherein PMMA or alicyclic polyolefin is called because of its excellent transparency. Plexiglass, used in optical lenses or liquid crystal display light guides, optical discs, etc. Use a lot. However, when forming an active element such as a TFT by forming a transparent electrode having a low resistance on a flexible substrate, for example, a temperature of at least 300 ° C to 350 ° C is required, and a resin such as PMMA is difficult to be used as a flexible one because heat resistance is lower than that of glass. Substrate. Further, since the material composed of the resin has a large coefficient of linear expansion, the linear expansion coefficient difference between the material of the element such as a transparent electrode or a TFT is large, and there is a problem that cracking or disconnection due to this occurs.

Therefore, as a method of improving the heat resistance and coefficient of linear expansion of a material, a method of combining a resin with a glass fiber has been developed. For example, JP-A-2004-231934 (Patent Document 2) and JP-A-2004-51960 (Patent Document 3) disclose that glass fibers such as glass cloth and Abbe's or refractive index are close to the glass. A composite resin obtained by compounding a curable resin such as an epoxy resin or an acrylate resin.

[Previous Technical Literature] [Patent Document]

Patent Document 1: JP-A-2004-50565

Patent Document 2: JP-A-2004-231934

Patent Document 3: JP-A-2004-51960

However, the present inventors have found that the composite resin described in Patent Documents 2 and 3 is slightly modified in heat resistance to heat of about 250 ° C. Good, but the glass transition temperature is less than 300 ° C. When the substrate made of the past composite resin is heated at a high temperature above the glass transition temperature, the elastic modulus of the substrate is lowered to cause expansion or deformation of the substrate, so it is still difficult. An inorganic layer such as a component material is laminated in a stable and uniform manner.

The present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide a glass fiber composite resin substrate having a high level of heat resistance and transparency and having a sufficiently small thermal expansion coefficient.

As a result of active research to achieve the above object, the present inventors have found that a glass fiber composite resin substrate composed of a curable resin composition and a glass fiber contains a (meth) acrylonitrile group and shrinkage. a specific cage type sesquiterpene oxide resin selected from the group consisting of a glyceryl group and a vinyl group, and a specific unsaturated compound having two or more unsaturated functional groups containing a carbon-carbon double bond and hardening A curable resin composition having a catalyst and a content of the cage sesquioxane resin in a specific range is used as the curable resin composition, and a high level of heat resistance and transparency can be obtained, and a thermal expansion coefficient is sufficiently small. The glass fiber composite resin substrate, thus completing the present invention.

In other words, the glass fiber composite resin substrate of the present invention is a glass fiber composite resin substrate made of a curable resin composition and a glass fiber, wherein the curable resin composition contains (A) having (meth) propylene. a cage-type sesquiterpene oxide resin selected from the group consisting of a mercapto group, a glycidyl group and a vinyl group, and (B) having two or more of the following formulas (1) to (2) An unsaturated compound other than the aforementioned cage sesquioxane having an unsaturated functional group selected from the group consisting of -R ¹ -CR ² =CH ₂ . . . (1)

-CR ² =CH ₂ . . . (2) In the formula (1), R ¹ represents any one selected from the group consisting of an alkylene group, an alkylene group and an -OCO- group, and in the formulae (1) to (2), each of R ² The content of the (A) cage sesquioxane resin is 5 to 90% by mass based on the entire curable resin composition, and the (C) curing catalyst is independently represented by the hydrogen atom or the alkyl group.

In the above-mentioned glass fiber composite resin substrate of the present invention, the (A) cage type sesquiterpene oxide resin is preferably a cage type sesquiterpene oxide resin represented by the following formula (3), [R ³ SiO _{3 /2} 〕 _n [R ⁴ SiO _3/2 ] _m . . . (3) In the formula (3), R ³ represents an organic group having a group selected from the group consisting of a (meth) acryl fluorenyl group, a glycidyl group, and a vinyl group, and R ⁴ represents a hydrogen atom and a carbon number. Any one selected from the group consisting of a hydrocarbon group of 1 to 20, an alkoxy group having 1 to 20 carbon atoms, and an alkyloxy group having 1 to 20 carbon atoms, and n and m are satisfied to satisfy the following formula (i) ~(iii) an integer representing the condition, n≧1. . . (i)

m≧0. . . (ii)

n+m=h. . . (iii)

[In the formula (iii), h represents an integer selected from the group consisting of 8, 10, 12 and 14], and when n and m are each 2 or more, R ³ and R ⁴ may be the same or different.

Further, in the glass fiber composite resin substrate of the present invention, in the above formula (3), the ratio of n to m (n:m) is from 10:0 to 4:6, and the above formula (3) The cage-type sesquiterpene oxide resin is preferably 50% by mass or more based on the entire (A) cage sesquioxane resin.

Further, in the glass fiber composite resin substrate of the present invention, the unsaturated functional group of the (B) unsaturated compound preferably has a group consisting of an acrylonitrile group, a methacryl group, an allyl group and a vinyl group. At least one group selected from the group, and the number of the aforementioned unsaturated functional groups of the (B) unsaturated compound is preferably from 2 to 10 per compound molecule.

Moreover, it is preferable that the glass fiber composite resin substrate of the present invention is obtained by impregnating the above-mentioned glass fiber with the curable resin composition, and curing the curable resin composition. Further, the mass ratio of the cured product of the curable resin composition to the aforementioned glass fiber (the quality of the cured product: glass fiber The quality of the dimension is preferably from 20:80 to 70:30, and the thickness is preferably from 0.03 to 0.5 mm.

According to the present invention, it is possible to provide a glass fiber composite resin substrate having a high level of heat resistance and transparency and having a sufficiently small thermal expansion coefficient.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments. The glass fiber composite resin substrate of the present invention is a glass fiber composite resin substrate composed of a curable resin composition and glass fibers, wherein the curable resin composition contains (A) a (meth) acrylonitrile group, a cage-type sesquiterpene oxide resin selected from the group consisting of a glycidyl group and a vinyl group, (B) having two or more groups represented by the above formula (1), and The compound (2) represents an unsaturated compound other than the above-mentioned cage sesquioxane resin selected from the group of unsaturated functional groups, and (C) a hardening catalyst and the aforementioned (A) cage half The content of the siloxane resin is 5 to 90% by mass based on the entire curable resin composition.

<(A) Cage sesquioxane resin>

In the present invention, the cage sesquioxane resin refers to a sesquioxane having a completely closed polyhedral structure or a partially decomposed azepine of a -Si-O-Si- bond in the above polyhedral structure, or An oligomer polymerized by using two or more cage type sesquiterpene oxide resins as a monomer. The cage type sesquiterpene oxide resin of the present invention has at least one selected from the group consisting of a (meth) acrylonitrile group, a glycidyl group, and a vinyl group (hereinafter collectively referred to as a curable functional group). The aforementioned hardenable functional group is preferably bonded directly or via a divalent organic group to a ruthenium atom disposed at the apex of the polyhedron of the cage sesquiterpene skeleton. The aforementioned divalent organic group is exemplified by an alkyl group and a phenyl group. Further, in the present invention, the (meth)acryl fluorenyl group means a methacryl fluorenyl group and an acryl fluorenyl group.

The cage type sesquioxane resin of the present invention is preferably a cage type based on the viewpoint of further increasing the crosslinking density of the curable resin composition and further improving the heat resistance of the glass fiber composite resin substrate. The apex of the polyhedral skeleton of the hemidecane skeleton is all bonded to the curable functional group, and the molecular weight distribution and molecular structure are controlled. However, one of the curable functional groups may be replaced with another group such as an alkyl group or a phenyl group. When one of the hardening functional groups is partially substituted with another group, the aforementioned curable functional group in the cage sesquioxane resin of the present invention and the aforementioned other moir are used from the viewpoint of avoiding a decrease in crosslinking density. The ratio ([the average number of moles of the curable functional group]: [the average number of moles of the other groups]) is preferably from 10:0 to 6:4. Further, in the present invention, the ratio of the number of the curable functional groups in the cage sesquioxane resin to the number of other groups can be ¹ H-NMR (instrument name: JNM-ECA400 (manufactured by JEOL Ltd.) ), Solvent: chloroform-d, temperature: 22.7 ° C, 400 MHz) The integrated ratio of the curable functional groups and the peaks of other groups was determined.

Further, in the case of forming a crosslinked structure having a rigid structure, the cage sesquioxane resin of the present invention is based on the viewpoint of further improving the heat resistance of the obtained glass fiber composite resin substrate and further reducing the thermal expansion coefficient. It is preferably a cage sesquiterpene oxide resin having a closed polyhedral structure represented by the following general formula (3).

[R ³ SiO _3/2 ] _n [R ⁴ SiO _3/2 ] _m . . . (3)

In the above formula (3), R ³ represents an organic group having any one selected from the group consisting of a (meth) acryl fluorenyl group, a glycidyl group, and a vinyl group. The organic group is exemplified by a (meth) acrylonitrile group; a glycidyl group; a vinyl group; a (meth) acryl fluorenyl group, a glycidyl group or a vinyl group bonded to a divalent hydrocarbon group such as an alkylene group or a phenyl group; . The alkylene group may be linear or branched, and the carbon number is preferably 1 to 1 because the bonding distance is short and the heat resistance of the glass fiber composite resin substrate is further improved. 3. The above-mentioned phenylene group is exemplified by, for example, an unsubstituted phenyl group, a 1,2-phenyl group having a lower alkyl group, and the like. In the above, the divalent hydrocarbon group is more preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of obtaining a raw material, and a glass fiber composite resin substrate having a higher crosslinking density. Good for stretching propyl.

Further, R ^{3 is} specifically a methacryloxypropyl group, a glycidoxy propyl group or an epoxycyclohexyl group, and among them, a methyl group is preferred because the raw material is easily obtained and the polymerization reactivity is high. Acryloxypropyl.

In the above formula (3), R ⁴ represents a group selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkyloxy group having 1 to 20 carbon atoms. One. The hydrocarbon group having 1 to 20 carbon atoms may be linear or branched, or may be cyclic, and is exemplified by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a carbon number of 3. ~20 cycloalkenyl, phenyl, styryl. The alkyl group having 1 to 20 carbon atoms may be linear or branched, and from the viewpoint of easily obtaining a skeleton of the cage sesquiterpene oxide, a chain alkane having 2 to 10 carbon atoms is preferred. base. The cycloalkyl group having 3 to 20 carbon atoms is exemplified by, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclohexyl group, etc., and among them, a cyclohexyl group is preferred from the viewpoint of easiness. . The cycloalkenyl group having 3 to 20 carbon atoms is exemplified by, for example, a cyclopentenyl group or a cyclohexenyl group. Among them, a cyclopentenyl group is preferred from the viewpoint of availability. Further, the alkoxy group having 1 to 20 carbon atoms is exemplified by, for example, a methoxy group, an ethoxy group, an isopropyl group or the like. Among them, a methoxy group is preferred from the viewpoint of improving reactivity. Further, the alkyl decyloxy group having 1 to 20 carbon atoms is exemplified by trimethyl decyloxy group, triethyl decyloxy group, triphenyl decyloxy group, dimethyl decyloxy group, and tert-butyl group. Methyl decyloxy and the like. In the above, from the viewpoint of easily obtaining a cage sesquiterpene skeleton, R ^{4 is} more preferably an alkyl group having 2 to 10 carbon atoms or a phenyl group.

Further, in the above formula (3), n and m represent integers satisfying the conditions expressed by the following formulas (i) to (iii), n ≧ 1. . . (i)

m≧0. . . (ii)

n+m=h. . . (iii)

[in the formula (iii), h represents an integer selected from the group consisting of 8, 10, 12 and 14]. By satisfying the condition expressed by the above formula (i), the cage type sesquiterpene oxide resin of the present invention has at least one hardening functional group, and is carried out by the (B) unsaturated compound of the present invention. By radical polymerization, a glass fiber composite resin substrate having a high level of heat resistance and transparency and having a sufficiently small thermal expansion coefficient can be obtained. Further, by satisfying the conditions expressed by the above formula (iii), n and m satisfy the condition that the cage type sesquiterpene oxide resin of the present invention is almost completely condensed into a cage structure, and is formed by radical polymerization. Since the structure of the crosslinked structure is structured, the glass fiber composite resin substrate can achieve high level of heat resistance and transparency and a sufficiently small coefficient of thermal expansion. Further, when n and m are each 2 or more, R ³ and R ⁴ may be the same or different from each other.

Further, in the cage type sesquioxane resin of the present invention, the ratio of n to m (n: m) is preferably from 10:0 to 4:6, more preferably from 10:0 to 5:5. When the number of m of n exceeds the above upper limit, the crosslinking density of the glass fiber composite resin substrate tends to decrease, the heat resistance decreases, and the thermal expansion coefficient tends to increase.

Further, in the present invention, the ratio of n to m (n: m), that is, the ratio of the number of hardening functional groups bonded to the apex of the polyhedron of the above-mentioned cage type hemi-oxyalkylene resin to the number of other groups may be It is obtained by the same method as described above.

Further, in the cage type sesquioxane resin of the present invention, in order to form a crosslinked structure having a rigid structure, the obtained glass fiber composite resin is further improved. The cage type sesquiterpene oxide resin represented by the above formula (3) is preferably the same as the cage type sesquiterpene oxide resin of the present invention from the viewpoint of the heat resistance of the substrate and the tendency to further reduce the coefficient of thermal expansion. 50% by mass or more, more preferably 70% by mass or more.

The method for obtaining the cage-type sesquiterpene oxide resin can be carried out, for example, by using the hydrazine compound (a) represented by the following formula (4) in the presence of water, an organic polar solvent and a basic catalyst, and optionally The hydrazine compound (b) represented by the following formula (5) is hydrolyzed to obtain: R ³ SiX ₃ . . . (4)

[Formula (4), R ³ in the general formula (3) in the same meaning as R ^3, X represents any one of the alkoxy group, an acetyl group, a halogen atom and a hydroxy group consisting of hydrolyzable group selected ], R ⁴ SiX ³ . . . (5)

[In the formula (5), R ⁴ in the general formula (3) in the same meaning as R ^4, X is synonymous with X in the general formula (4)] of.

In the above formulae (4) and (5), each of X is independently a hydrolyzable group selected from the group consisting of an alkoxy group, an ethenyloxy group, a halogen atom and a hydroxyl group. The hydrolyzable group is preferably an alkoxy group. The alkoxy group is exemplified by a methoxy group, an ethoxy group, a n- and an iso-propoxy group, a n-, an iso- and a tert-butoxy group, and the like, in terms of improving the reactivity, a methoxy group is used. good.

The above hydrazine compound (a) is exemplified by, for example, methacryloxymethyltriethoxydecane, methacryloxymethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane. , 3-methacryloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, allyltrimethoxydecane, allyltriethoxydecane, p-benzene Vinyl trimethoxy decane, p-styryl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-glycidoxy propyl trimethoxy decane, 3-glycidol Oxypropyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. Among these, the ruthenium compound (a) is preferably 3-methylpropenyloxypropyltrimethoxydecane or 3-propenyloxypropyltrimethoxydecane from the viewpoint of easy availability of the raw material. Further, the ruthenium compound (a) may be used alone or in combination of two or more.

The above hydrazine compound (b) is exemplified by, for example, phenyltrimethoxydecane, phenyltriethoxydecane, methyltrimethoxydecane, ethyltrimethoxydecane, n-propyltrimethoxydecane, n-propyltri Ethoxy decane, n-butyl trimethoxy decane, n-butyl triethoxy decane, tert-butyl trimethoxy decane, tert-butyl triethoxy decane, n-octyl trimethoxy decane, positive Octyl triethoxy decane, and the like. Further, the above-mentioned hydrazine compound (b) may be used alone or in combination of two or more.

The mixing ratio of the hydrazine compound (a) and the hydrazine compound (b) preferably satisfies the conditions expressed by the following formula (vi) with a mixed molar ratio (a: b). a:b=n:m. . . (vi)

[In the formula (vi), n and m are synonymous with n and m in the above formula (3)].

The water may be at least a sufficient mass to hydrolyze the hydrolyzable groups of the ruthenium compounds (a) and (b), and is preferably a hydrolyzable group calculated from the mass of the ruthenium compounds (a) and (b). The theoretical quantity of the number (mole) is 1.0 to 1.5 times the mass of the mole. Further, the water may be directly used as the water contained in the aqueous solution of the alkaline catalyst described later.

The organic polar solvent is exemplified by an alcohol such as methanol, ethanol or 2-propanol; acetone; tetrahydrofuran or the like, and one of these may be used alone or in combination of two or more. Among them, from the viewpoint of effectively forming a cage type sesquiterpene skeleton, it is preferred to use a lower alcohol having a carbon number of 1 to 6 which is soluble in a water tool, and it is preferable to use 2-propanol.

The alkaline catalyst is exemplified by an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide or barium hydroxide; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide or benzyl hydroxide; An ammonium hydroxide salt such as trimethylammonium or benzyltriethylammonium hydroxide. The alkaline catalyst of the present invention may be used alone or in combination of two or more. Among them, tetramethylammonium hydroxide is preferably used from the viewpoint of improving the activity of the catalyst. The amount of the basic catalyst is preferably from 0.1 to 10% by mass based on the total mass of the above ruthenium compounds (a) and (b). Further, since the alkaline catalyst is usually used in an aqueous solution, water contained in an aqueous solution of the basic catalyst may be used as the water.

In the above hydrolysis, the reaction time is preferably 2 hours or more, and the reaction temperature is preferably 0 to 50 ° C, more preferably 20 to 40 ° C. When the reaction time and the reaction temperature are not at the lower limit, the hydrolyzable group tends to remain in an unreacted state. Further, when the reaction temperature exceeds the above upper limit, a complicated condensation reaction is carried out because the reaction rate is too fast, and as a result, the polymerization of the hydrolyzed product is promoted, which is not preferable.

A reaction composition containing the cage type sesquiterpene oxide resin of the present invention can be obtained by this method. Further, in the reaction composition, in addition to the cage type sesquiterpene oxide resin of the present invention (completely condensed cage type sesquiterpene oxide resin (for example, the resin represented by the above formula (3)), a part of the cracking cage type half In addition to the decane resin, a plurality of ladder type sesquiterpene alkane resins and a random sesquioxane resin are also included as reaction by-products. In the reaction composition, the content of the cage sesquioxane resin of the present invention is directly compared with the above-mentioned reaction composition from the viewpoint of directly using the reaction composition as a raw material of the curable resin composition of the present invention. It is preferably 50% by mass or more. In addition, the content of the cage sesquioxane resin represented by the above formula (3) in the obtained cage sesquioxane resin is preferably 50% by mass based on the entire cage sesquioxane resin. The above is more preferably 70% by mass or more.

Further, in the present invention, the total content of the cage type sesquioxane resin of the present invention in the composition, and the content of the cage sesquioxane resin represented by the above formula (3) may be a liquid layer of the composition. Analytical mass analysis (LC-MS, HPLC: Agilent 1100 Series Systems (manufactured by Agilent Technology), MS: QSTAR ^R XL Hybrid LC/MS/MS System (manufactured by AB SCIEX), column: SunFire C18 column, mobile phase :H ₂ O-CH ₃ CN (30-70), speed: 1 ml/min, temperature: 40 ° C, detector: UV (254 nm)) The structure of the cage sesquioxane resin was obtained, and Gel permeation chromatography instrument (instrument name: HLC-8320GPC (manufactured by TOSOH), solvent: THF, column: super high speed SemiMicro SEC column SuperH series, temperature: 40 ° C, speed: 0.6 ml / min) (number average molecular weight) is obtained.

In the present invention, one of the cage sesquioxaxane resins may be used alone or in combination of two or more.

<(B) Unsaturated Compound>

The unsaturated compound of the present invention is a compound other than the above-mentioned cage sesquiterpene oxide resin having two or more unsaturated functional groups selected from the group consisting of the groups represented by the following general formulae (1) to (2). -R ¹ -CR ² =CH ₂ . . . (1)

-CR ² =CH ₂ . . . (2)

[In the formula (1), R ¹ represents any one selected from the group consisting of an alkylene group, an alkylene group and an -OCO- group, and in the formulae (1) to (2), R ² each independently represents a hydrogen atom or an alkane. base〕. Further, the group represented by the above formula (1) is excluded from the group contained in the group represented by the above formula (2).

In the above formula (1), R ¹ represents any one selected from the group consisting of an alkylene group, an alkylene group and an -OCO- group. The alkylene group and the alkylene group may be linear or branched, and the carbon number is preferably 1 in view of the fact that the bonding distance is short and the heat resistance of the glass fiber composite resin substrate is further improved. ~6. Further, in these terms, R ^{1 is} preferably an -OCO- group from the viewpoint of improving the reactivity tendency of radical polymerization.

In the formulae (1) and (2), R ² each independently represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched, and the carbon number is preferably from 1 to 3 from the viewpoint of further excellent reactivity of the radical polymerization. From the viewpoint of further excellent reactivity of radical polymerization, the R ^{2 is} preferably a hydrogen atom or a methyl group.

Specific examples of the unsaturated functional group are a acrylonitrile group, a methacryl group, an allyl group, and a vinyl group. The unsaturated compound of the present invention can be free-radically polymerized with the aforementioned (A) cage sesquiterpene oxide resin having the aforementioned curable functional group by having such an unsaturated functional group, and a high level of heat resistance can be obtained. The glass fiber composite resin substrate of the present invention is excellent in transparency and transparency and has a small thermal expansion coefficient.

The unsaturated compound of the present invention has two or more of the aforementioned unsaturated functional groups per molecule of the compound. When the number of the unsaturated functional groups is less than the lower limit, a sufficient cross-linking structure cannot be formed by radical polymerization with the above-mentioned cage type sesquiterpene oxide resin, so that the elastic mode of the glass fiber composite resin substrate at a high temperature is obtained. The number becomes low and the heat resistance is lowered. Further, from the viewpoint of further improving the elastic modulus and heat resistance, the number of the unsaturated functional groups is preferably from 2 to 10. Further, the unsaturated compound of the present invention may be a monomer or a polymer, and when the unsaturated compound is a polymer, the number of the unsaturated functional groups is an average value of each molecule of the compound. Further, the number (or average) of the unsaturated functional groups per molecule of the compound is determined by ¹ H-NMR (instrument name: JNM-ECA400 (manufactured by JEOL Ltd.), solvent: chloroform-d, temperature: 22.7 °C, 400MHz) Determination of the wave front area of the unsaturated functional group and gel permeation chromatography (GPC, (instrument name: HLC-8320GPC (manufactured by TOSOH), solvent: THF, column: ultra-high speed SemiMicro The molecular weight (or number average molecular weight) of the SEC column SuperH series, temperature: 40 ° C, speed: 0.6 ml / min) was determined.

The unsaturated compound of the present invention is not particularly limited as long as it has two or more of the above-mentioned unsaturated functional groups per molecule of the compound, but the molecular weight (weight average molecular weight in the case of a polymer) is preferably from 80 to 5,000. When the molecular weight is less than the lower limit, the unreacted unsaturated compound remains in the curing of the curable resin composition, and the unreacted unsaturated compound becomes a volatile component in the heat treatment such as heat treatment, and the weight change or size after hardening is caused. On the other hand, when the above-mentioned upper limit is exceeded, the solubility with the cage sesquioxane resin is lowered, and the viscosity of the obtained curable resin composition tends to be high, which tends to be difficult to handle.

The unsaturated compound is exemplified by, for example, dicyclopentyl diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, bisphenol fluorene diacrylate, Tetraethylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate. Among them, from the viewpoint of improving the solubility with the cage sesquioxane resin and improving the heat resistance of the obtained glass fiber composite resin substrate, it is preferably a hydrocarbon having 1 to 30 carbon atoms. The compound having two or more of the aforementioned unsaturated functional groups bonded to the compound is more preferably dicyclopentyl diacrylate, bisphenol fluorene diacrylate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate. Further, the unsaturated compounds of the present invention may be used alone or in combination of two or more.

<(C) Hardening Catalyst>

The curing catalyst of the present invention is a catalyst for promoting the hardening reaction (radical polymerization) of the above (A) cage sesquioxane resin and the above (B) unsaturated compound. The curing catalyst is exemplified by a radical polymerization initiator, and the radical polymerization initiator is exemplified by a photoradical polymerization initiator and a thermal radical polymerization initiator.

The photoradical polymerization initiator is exemplified by an acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, fluorenylphosphine oxide-based photopolymerization initiator, and specifically Is trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophene)-2-morpholinylpropan-1-one, benzoin methyl ether, benzyldimethylketal, benzophenone, thioxanthone, 2,4,6-three Methyl benzhydryl diphenyl phosphine oxide, methyl phenyl glycolate, camphorquinone, biphenyl hydrazine, hydrazine, Michael ketone, and the like. Further, the thermal radical polymerization initiator is, for example, a ketone peroxide system, a peroxyketal system, a hydrogen peroxide system, a dialkyl peroxide system, a dimercapto peroxide system, or a peroxy group. A dicarbonate-based or peroxyester-based thermal polymerization initiator. The curing catalyst of the present invention may be used alone or in combination of two or more. The photoradical polymerization initiator may be combined with the above. The above thermal radical polymerization initiator is used.

<Curable resin composition>

The curable resin composition of the present invention contains the above (A) cage sesquiterpene oxide resin and the above (B) unsaturated compound and the above (C) curing catalyst.

In the curable resin composition of the present invention, the content of the cage sesquioxane resin is required to be 5 to 90% by mass based on the total amount of the curable resin composition. When the content of the cage sesquioxane resin is less than the above lower limit, the glass transition temperature of the glass fiber composite resin substrate is lowered, and the thermal expansion coefficient is increased, so that heat resistance is insufficient. Further, when the ratio is more than the above upper limit, the crosslinking density of the cured product increases and the glass fiber composite resin substrate becomes brittle, so that handling becomes difficult.

In addition, from the viewpoint of further improving the heat resistance of the glass fiber composite resin substrate and further improving the strength, the content of the cage sesquioxane resin is preferably from 8 to 80% by mass. In addition, it is preferable that the cage type sesquiterpene oxide is 50% by mass or more (more preferably 70% by mass or more) based on the above-mentioned formula (3). In the curable resin composition of the present invention, the content of the cage sesquioxane resin represented by the above formula (3) is preferably from 2.5 to 90% by mass based on the total amount of the curable resin composition. Good for 5~80% by mass.

In the curable resin composition of the present invention, the content of the unsaturated compound is preferably from 5 to 90% by mass, more preferably from 10 to 70% by mass, based on the total amount of the curable resin composition. The content of the aforementioned unsaturated compound When the lower limit is not reached, the solubility of the curable resin composition is lowered, and the viscosity of the solution is increased. Therefore, the impregnation property to the glass fiber tends to be lowered, and when the upper limit is exceeded, the cured resin composition is cured. The glass transition temperature is lowered, and the heat resistance of the obtained glass fiber composite resin substrate tends to decrease.

In the curable resin composition of the present invention, the content of the curing catalyst is preferably from 0.1 to 5.0% by mass, more preferably from 0.1 to 3.0% by mass, based on the curable resin composition. When the content of the curing catalyst is less than the lower limit, the curing reaction tends to be insufficient, and the strength and rigidity of the obtained cured product tend to be lowered. When the content exceeds the upper limit, the cured product may be colored.

Further, the curable resin composition of the present invention may further contain the above-mentioned (A) cage sesquioxane resin and the hardenable compound other than the above (B) unsaturated compound (hereinafter referred to as a curable compound). The curable compound is not particularly limited as long as it can be cured by irradiation with heat or an active energy ray, but is preferably a compound having compatibility and reactivity with the cage sesquioxane resin.

Such a curable compound is exemplified by a reactive oligomer of a polymer having a repeating number of about 2 to 20 in a structural unit, and a low molecular weight and low viscosity reactive monomer. The aforementioned reactive oligomers are specifically exemplified by epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate. , polyene/thiol, polyoxy acrylate, polybutadiene, polystyrene ethyl methacrylate. Further, the aforementioned reactive monomer is specifically exemplified as benzene Ethylene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentene acrylate A monofunctional monomer such as benzyl ethyl ester, phenoxyethyl acrylate or trifluoroethyl methacrylate. The curable compound may be used alone or in combination of two or more.

When the curable resin composition of the present invention contains the curable compound, the content thereof is preferably 40% by mass or less based on the entire curable resin composition. When the content of the curable compound exceeds the above upper limit, it is difficult to form a sufficient crosslinked structure, and the heat resistance of the obtained glass fiber composite resin substrate tends to be lowered.

Moreover, the curable resin composition of the present invention may further contain various additives insofar as the effects of the present invention are not impaired. As for the aforementioned additives, for example, organic/inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, slip agents, antistatic agents, mold release agents, foaming agents, cores Agents, colorants, crosslinking agents, dispersing aids, and the like. When the additives are contained, the content thereof is preferably 30% by mass or less based on the total amount of the curable resin composition.

In addition, the curable resin composition of the present invention may further contain a solvent such as methyl ethyl ketone, toluene or ethyl acetate in order to adjust the viscosity, etc., but the solvent is removed in a volatile removal step, so that the production efficiency is low. In addition, the solvent remains in the interior of the obtained glass fiber composite resin substrate, and the properties of the substrate are lowered. Therefore, the content of the solvent is preferably 5% by mass or less based on the total amount of the curable resin composition, and more preferably no solvent.

<glass fiber>

The form of the glass fiber of the present invention is exemplified by a filament yarn, a glass cloth, a nonwoven fabric or the like. Among these, a glass cloth is preferable from the viewpoint of improving the effect of reducing the coefficient of thermal expansion. The raw material of the glass cloth is exemplified by E glass, C glass, A glass, S glass, D glass, NE glass, T glass, quartz glass, etc., in which the refractive index range is reduced. In the preferred range, E glass, S glass, T glass, and NE glass are preferable from the viewpoint of easy availability.

Moreover, in order to improve the wettability, affinity, and adhesion of the interface between the curable resin composition and the glass fiber, the glass fiber of the present invention may be a decane coupling agent or various surfactants. By surface treatment of inorganic acid; corona discharge treatment; ultraviolet irradiation treatment; plasma treatment.

Further, the difference between the refractive index of the glass fiber of the present invention and the refractive index of the cured product of the curable resin composition is preferably in the range of -0.02 to +0.02, more preferably in the range of -0.01 to +0.01. When the difference in refractive index is outside the above range, the interface scattering between the cured product of the curable resin composition and the glass fiber is increased, and the transparency of the glass fiber composite resin substrate is lowered, so that it is difficult to use it as a flexible display. Or the tendency of solar cells to replace substrates.

Further, when the form of the glass fiber of the present invention is glass cloth, non-woven fabric or the like, the thickness thereof can be appropriately selected depending on the purpose of using the glass fiber composite resin substrate, but the impregnation of the glass fiber by the curable resin composition is improved. From the viewpoint of sexual tendency, it is preferably from 30 to 100 μm.

<Glass fiber composite resin substrate>

The glass fiber composite resin substrate of the present invention is a composite of the curable resin composition and the glass fiber. The method for producing the glass fiber composite resin substrate is not particularly limited, and examples thereof include a method of curing the curable resin composition after impregnating the glass fiber with the curable resin composition.

In these methods, first, the (A) cage sesquiterpene oxide resin, the (B) unsaturated compound, the (C) hardening catalyst, and the like are mixed at room temperature (20 to 25 ° C). A curable resin composition of the present invention is obtained from another compound, a solvent or the like. Next, the curable resin composition is dropped onto the glass fibers, impregnated by a method such as immersion, and the solvent is removed as necessary. Then, the glass fiber impregnated with the curable resin composition is subjected to a heat treatment and/or an active energy ray irradiation treatment to cure the curable resin composition, thereby obtaining a glass fiber composite resin substrate of the present invention.

In the glass fiber composite resin substrate of the present invention, the mass ratio of the cured product of the curable resin composition per 1 m ² to the glass fiber (the mass of the cured product: the mass of the glass fiber) is preferably 20:80 to 70:30. More preferably 40:60~60:40. When the ratio of the glass fiber to the cured product is less than the lower limit, the heat resistance of the glass fiber composite resin substrate is lowered, and the thermal expansion coefficient tends to exceed 20 ppm/K, and when the upper limit is exceeded, the glass fiber is impregnated. It is insufficient, and there is a tendency that the transparency of the glass fiber composite resin substrate is lowered (the turbidity is increased) by leaving voids between the fibers. Therefore, in the impregnation, it is preferred to impregnate the ratio of the mass of the curable resin composition after curing to the mass of the glass fiber within the above range.

Further, the impregnation may be appropriately adjusted depending on the type of the glass fiber or the glass fiber composite resin substrate, but the thickness of the liquid crystal display or the organic EL display using the glass fiber composite resin substrate or the corresponding manufacturing process (roller) From the viewpoint of the roll), the thickness of the obtained glass fiber composite resin substrate is preferably from 0.03 to 0.5 mm, preferably from 0.05 to 0.2 mm.

Further, the heating temperature in the heat treatment may be appropriately adjusted depending on the curable resin composition, but is preferably 50 to 200 ° C, more preferably 80 to 180 ° C. When the heating temperature is less than the lower limit, the progress of the curing reaction may be insufficient, and a sufficient cross-linking structure may not be formed. When the temperature exceeds the upper limit, defects such as deterioration and volatilization before curing of the curable resin composition may occur. tendency. Further, the heating time of the heat treatment may not be generalized depending on the heating temperature or the curable resin composition, but is preferably from 30 to 60 minutes. In addition, the heat treatment is preferably carried out in an inert gas atmosphere such as nitrogen, from the viewpoint of suppressing the inhibition by oxygen in the radical polymerization reaction of the curable resin composition and forming a more sufficient crosslinked structure.

Further, the conditions of the active energy ray irradiation in the active energy ray irradiation treatment are preferably ultraviolet rays having a wavelength of from 10 to 400 nm, visible light having a wavelength of from 400 to 700 nm, and more preferably ultraviolet rays having a wavelength of from 200 to 400 nm. Further, the cumulative exposure amount is preferably from 2,000 to 10,000 mJ/cm ² . The sources of the aforementioned active energy rays are listed as low-pressure mercury lamps (output: 0.4~4W/cm), high-pressure mercury lamps (40~160W/cm), ultra-high pressure mercury lamps (173~435 W/cm), and metal halide lamps (80~160W). /cm), pulsed xenon lamp (80~120W/cm), electrodeless discharge lamp (80~120W/cm), etc.

In the glass fiber composite resin substrate of the present invention, in order to smooth the surface, a coating layer made of a resin may be further provided on one surface or both surfaces of the glass fiber composite resin substrate. The resin is preferably one having heat resistance, transparency, and chemical resistance, and the curable resin composition of the present invention is preferably used. Further, the glass fiber composite resin substrate of the present invention may further include a gas barrier layer for oxygen or water vapor as needed.

Example

Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. Further, in each of the preparation examples, the examples, and the comparative examples, the refractive index measurement, the total light transmittance measurement, and the heat resistance evaluation were carried out by the methods described below.

(refractive index measurement)

The curable resin composition obtained in each of the preparation examples was cast (cast) by a roll coater so as to have a thickness of 0.1 mm, and a high-pressure mercury lamp of 80 W/cm was used, and the cumulative exposure amount of 2000 mJ/cm ^{2 was used} . Hardening to obtain a flaky cured product. A refractive index (DR-M2, manufactured by Atago Co., Ltd.) was used for the obtained cured product, and the refractive index at 589 nm was measured.

(total light transmittance measurement)

For the glass fiber composite resin substrate obtained in each of the examples and the comparative examples, a total light transmittance (%) was measured using a turbidimeter (NDH2000, manufactured by Nippon Denshoku Co., Ltd.).

(heat resistance evaluation)

. Glass transition temperature measurement, dynamic viscoelasticity reduction rate determination

For the glass fiber composite resin substrate obtained in each of the examples and the comparative examples, a dynamic viscoelasticity measuring device (trade name: DVE-V4, manufactured by UBM Co., Ltd.) was used, and the temperature was raised at a rate of 5 ° C/min. The dynamic viscoelasticity measurement was carried out at a temperature of 30 to 300 ° C, and the peak temperature of Tan δ in the range of 30 to 300 ° C was used as the glass transition temperature (Tg (° C)). Moreover, the dynamic viscoelasticity reduction rate (ΔE'(%)) is obtained by the following equation: ΔE'(%)=(E' ₃₀ -E' ₃₀₀ )/E' ₃₀

[wherein E' ₃₀ represents the dynamic viscoelasticity at 30 ° C, and E' ₃₀₀ represents the dynamic viscoelasticity at 300 ° C]. Further, the higher the glass transition temperature and/or the smaller the dynamic viscoelasticity reduction rate, the higher the heat resistance of the glass fiber composite resin substrate.

. Thermal expansion coefficient (linear thermal expansion coefficient)

For the glass fiber composite resin substrate obtained in each of the examples and the comparative examples, a thermomechanical analyzer (TMA, trade name: TMA4000SA, manufactured by BRUKER) was used, and the temperature was increased by 5 ° C/min, and the compression load was 0.1. Under the condition of N, the average value of the elongation in the plane direction (X direction) of the glass fiber composite resin substrate (0.1 mm thick) in the range of 30 to 200 ° C was obtained, and the glass fiber composite resin was determined from the value. Thermal expansion coefficient (ppm/K) of the surface direction (X direction) of the substrate. Further, the smaller the coefficient of thermal expansion, the higher the heat resistance of the glass fiber composite resin substrate.

(Synthesis Example 1: Cage sesquioxane resin (I))

The cage sesquioxane resin (I) is produced according to the method described in JP-A-2004-143449. First, 40 ml of 2-propanol (IPA) as a solvent and 5% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution) as a basic catalyst were placed in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer. g. Further, 15 ml of IPA and 12.7 g of 3-methacryloxypropyltrimethoxydecane were placed in a dropping funnel to prepare an IPA solution of 3-methylpropenyloxypropyltrimethoxydecane. It was added dropwise to the above reaction vessel over 30 minutes while stirring at room temperature. After the completion of the dropwise addition, the mixture was stirred for 2 hours without heating. After stirring, IPA was removed under reduced pressure to obtain 7.5 g of a composition containing a cage-type sesquiterpene oxide resin (I). In the obtained composition, the cage type sesquioxane resin (I) of the present invention is relative to the aforementioned composition The amount of the cage-type sesquiterpene oxide resin represented by the formula (3) is 90% by mass based on the entire cage sesquioxane resin (I), and the liquid chromatograph is separated. As a result of the mass analysis, n in the formula (3) is 8, 10, and 12.

(Synthesis Example 2: cage type sesquioxanes resin (II))

15 ml of IPA, 7.2 g of 3-methacryloxypropyltrimethoxydecane and 5.7 g of phenyltrimethoxydecane were placed in a dropping funnel to prepare 3-methylpropenyloxypropyltrimethoxy. The IPA solution of decane and phenyltrimethoxydecane was used in the same manner as in Synthesis Example 1 except that the IPA solution of 3-methylpropenyloxypropyltrimethoxydecane was used instead, and the cage-containing sesquiterpene oxide was obtained. The composition of the resin (II) was 8.7 g. In the obtained composition, the cage sesquiterpene oxide resin (II) of the present invention is 96% by mass based on the entire composition, and the cage sesquioxane resin represented by the formula (3) is relative to the foregoing. The cage sesquioxane resin (II) was 92% by mass in total, and as a result of mass analysis after separation by a liquid chromatograph, n+m in the formula (3) was 8, 10, and 12. And, n:m is 4:4.

(Preparation Example 1: Curable resin composition (I))

The cage type sesquiterpene oxide resin (I) obtained in the synthesis example 1 was mixed: 60 parts by mass (calculated as a cage sesquioxane resin), trimethylolpropane triacrylate: 25 parts by mass, two rings Pentyl diacrylate: 15 parts by mass and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by mass to obtain a liquid curable resin composition (I). For the hardening The resin composition (I) was measured for refractive index, and the refractive index was 1.529, and it was confirmed that a transparent cured product was obtained. The composition of the obtained curable resin composition (I) is shown in Table 1.

(Preparation Example 2: Curable resin composition (II))

The cage type sesquiterpene oxide resin (I) obtained in Synthesis Example 1 was mixed: 30 parts by mass (calculated as a cage sesquioxane resin), dicyclopentyl diacrylate: 35 parts by mass, pentaerythritol tetraacrylic acid Ester: 35 parts by mass and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by mass to obtain a liquid curable resin composition (II). The refractive index of the curable resin composition (II) was measured, and the refractive index was 1.531, and it was confirmed that a transparent cured product was obtained. The composition of the obtained curable resin composition (II) is shown in Table 1.

(Preparation Example 3: Curable resin composition (III))

The cage type sesquiterpene oxide resin (I) obtained in Synthesis Example 1 was mixed: 10 parts by mass (calculated as a cage sesquioxane resin), trimethylolpropane triacrylate: 65 parts by mass, two rings Pentyl diacrylate: 35 parts by mass and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by mass to obtain a liquid curable resin composition (III). The refractive index of the curable resin composition (III) was measured, and the refractive index was 1.531, and it was confirmed that a transparent cured product was obtained. The composition of the obtained curable resin composition (III) is shown in Table 1.

(Preparation Example 4: Curable resin composition (IV))

The cage type sesquiterpene oxide resin (II) obtained in Synthesis Example 2: 15 parts by mass (calculated as a cage sesquioxane resin), trimethylolpropane triacrylate: 50 parts by mass, bisphenol Toluene diacrylate: 35 parts by mass and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by mass to obtain a liquid curable resin composition (IV). The refractive index of the curable resin composition (IV) was measured, and the refractive index was 1.558, and it was confirmed that a transparent cured product was obtained. The composition of the obtained curable resin composition (IV) is shown in Table 1.

(Preparation Example 5: Curable resin composition (V))

The cage type sesquiterpene oxide resin (II) obtained in Synthesis Example 2 was mixed: 35 parts by mass (calculated as a cage sesquioxane resin), pentaerythritol tetraacrylate: 25 parts by mass, bisphenol fluorene diacrylate 40 parts by mass and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by mass to obtain a liquid curable resin composition (V). The refractive index of the curable resin composition (V) was measured, and the refractive index was 1.560, and it was confirmed that a transparent cured product was obtained. The composition of the obtained curable resin composition (V) is shown in Table 1.

(Preparation Example 6: Curable resin composition (VI))

Mixed dicyclopentyl diacrylate: 35 parts by mass, pentaerythritol tetraacrylate: 65 parts by mass, and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by mass to obtain a liquid curable resin Composition (VI). The composition of the obtained curable resin composition (VI) is shown in Table 1.

(Preparation Example 7: Curable resin composition (VII))

Mixed pentaerythritol tetraacrylate: 25 parts by mass, bisphenol fluorene diacrylate: 40 parts by mass, and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by mass to obtain a liquid curable resin composition (VII). The composition of the obtained curable resin composition (VII) is shown in Table 1.

(Preparation Example 8: Curable resin composition (VIII))

The cage type sesquiterpene oxide resin (I) obtained in Synthesis Example 1 was mixed: 5 parts by mass, dicyclopentyl diacrylate: 40 parts by mass, pentaerythritol tetraacrylate: 55 parts by mass, and as a photopolymerization initiation 1-hydroxycyclohexyl phenyl ketone of the agent: 2.5 parts by mass to obtain a liquid curable resin composition (VIII). The composition of the obtained curable resin composition (VIII) is shown in Table 1.

(Example 1)

First, the curable resin composition (I) obtained in Preparation Example 1 was dropped on a T glass-based glass cloth (trade name: T Glass Yarn (manufactured by Nitto Bose Co., Ltd.), which was placed on a glass plate, and had a refractive index of 1.530. 96 μm), the upper surface was covered with a glass plate, and the glass plate was sandwiched from the upper and lower sides, and the curable resin composition was impregnated into the glass cloth while applying pressure. Then, the glass cloth impregnated material was placed in a glass plate, and a high-pressure mercury lamp of 80 W/cm was used to irradiate ultraviolet rays (wavelength: 365 nm) at a cumulative exposure amount of 2000 mJ/cm ² to harden the curable resin composition. . Subsequently, the mixture was heated at 250 ° C for 10 minutes in a nitrogen atmosphere to obtain a mass ratio of the cured product of the curable resin composition per 1 m ^{2 to} the glass fiber (the mass of the cured product: the mass of the glass fiber) of 46: A glass fiber composite resin substrate of 54. The results of the total light transmittance measurement and the heat resistance evaluation of the obtained glass fiber composite resin substrate are shown in Table 2.

(Example 2)

Prepared in Example 2 except that the obtained curable resin composition (II) in place of curable resin composition (I) except that I and Example 1, to obtain a thickness of 0.1mm, the cured composition per 1m ² of the curable resin A glass fiber composite resin substrate having a mass ratio of the material to the glass fiber (the mass of the cured product: the mass of the glass fiber) of 48:52. The results of the total light transmittance measurement and the heat resistance evaluation of the obtained glass fiber composite resin substrate are shown in Table 2.

(Example 3)

Preparation Example 3 except for using the obtained curable resin composition (III) in place of curable resin composition (I) except that I and Example 1, to obtain a thickness of 0.1mm, the cured composition per 1m ² of the curable resin A glass fiber composite resin substrate having a mass ratio of the object to the glass fiber (the mass of the cured product: the mass of the glass fiber) of 44:56. The results of the total light transmittance measurement and the heat resistance evaluation of the obtained glass fiber composite resin substrate are shown in Table 2.

(Example 4)

The curable resin composition (IV) obtained in Preparation Example 4 was used instead of the curable resin composition (I), and an E glass-based glass cloth (trade name: 2116/AS887AW (manufactured by Asahi Kasei E Materials Co., Ltd.), refractive index was used. 1.558 and a thickness of 96 μm, in addition to the T glass-based glass cloth, the mass ratio of the cured product of the curable resin composition per 1 m ² and the glass fiber was obtained in the same manner as in Example 1 (mass of the cured product: glass) The fiber mass is a 52:48 glass fiber composite resin substrate. The results of the total light transmittance measurement and the heat resistance evaluation of the obtained glass fiber composite resin substrate are shown in Table 2.

(Example 5)

The modulation obtained in Example 5 except that the curable resin composition (V) in place of curable resin composition (IV) except that the same I Example 4, to obtain a thickness of 0.1mm, the cured composition per 1m ² of the curable resin A glass fiber composite resin substrate having a mass ratio of the material to the glass fiber (the mass of the cured product: the mass of the glass fiber) of 48:52. The results of the total light transmittance measurement and the heat resistance evaluation of the obtained glass fiber composite resin substrate are shown in Table 2.

(Comparative Example 1)

Prepared in Example 6 except that the obtained curable resin composition (VI) in place of curable resin composition (I) except that I and Example 1, to obtain a thickness of 0.1mm, the cured composition per 1m ² of the curable resin A glass fiber composite resin substrate having a mass ratio of the material to the glass fiber (the mass of the cured product: the mass of the glass fiber) of 47:53. The results of the total light transmittance measurement and the heat resistance evaluation of the obtained glass fiber composite resin substrate are shown in Table 2.

(Comparative Example 2)

Preparation Example 7 except that the obtained curable resin composition (VII) in place of curable resin composition (I) except that in Example 4 with the same I, to obtain a thickness of 0.1mm, the cured composition per 1m ² of the curable resin A glass fiber composite resin substrate having a mass ratio of the material to the glass fiber (the mass of the cured product: the mass of the glass fiber) of 49:51. The results of the total light transmittance measurement and the heat resistance evaluation of the obtained glass fiber composite resin substrate are shown in Table 2.

(Comparative Example 3)

Preparation Example 8 except that the obtained curable resin composition (VIII) in place of curable resin composition (I) except that I and Example 1, to obtain a thickness of 0.1mm, the cured composition per 1m ² of the curable resin A glass fiber composite resin substrate having a mass ratio of the material to the glass fiber (the mass of the cured product: the mass of the glass fiber) of 47:53. The results of the total light transmittance measurement and the heat resistance evaluation of the obtained glass fiber composite resin substrate are shown in Table 2.

As is clear from the results shown in Table 2, the total light transmittance of the glass fiber composite resin substrate of the present invention is 90% or more, and the glass transition temperature is sufficiently large, and the dynamic viscoelasticity reduction rate is also maintained at 20% or less. High level of heat resistance and transparency. Further, the coefficient of thermal expansion was 15 ppm/K or less, and it was confirmed that the coefficient of thermal expansion was relatively small. On the other hand, in the conventional glass fiber composite resin substrate (Comparative Examples 1 and 2), although the total light transmittance was 90% or more, it was confirmed that the glass transition temperature was low, and the dynamic viscoelasticity reduction rate and the thermal expansion coefficient were also inferior.

[Industrial Applicability]

As described above, according to the present invention, it is possible to provide a glass fiber composite resin substrate having a high level of heat resistance and transparency and having a sufficiently small thermal expansion coefficient. The glass fiber composite resin substrate of the present invention has a high level of heat resistance even at a high temperature, and has high heat resistance. Therefore, it is used as a glass for use in applications such as flexible displays, touch panels, and solar cells. The substrate is very useful.

Claims (9)

A glass fiber composite resin substrate comprising a glass fiber composite resin substrate made of a curable resin composition and a glass fiber, wherein the curable resin composition contains (A) a (meth) acrylonitrile group, a cage-type sesquiterpene oxide resin selected from the group consisting of a glycidyl group and a vinyl group, and (B) having two or more bases represented by the following general formulae (1) to (2) An unsaturated compound other than the aforementioned cage sesquioxane resin selected from the group consisting of unsaturated functional groups, -R ¹ -CR ² =CH ₂ . . . (1) -CR ² =CH ₂ . . . (2) In the formula (1), R ¹ represents any one selected from the group consisting of an alkylene group, an alkylene group and an -OCO- group, and in the formulae (1) to (2), each of R ² The content of the (A) cage sesquioxane resin is 5 to 90% by mass based on the entire curable resin composition, and the (C) curing catalyst is independently represented by the hydrogen atom or the alkyl group. The glass fiber composite resin substrate according to claim 1, wherein the (A) cage type sesquiterpene oxide resin is a cage type sesquiterpene oxide resin represented by the following formula (3), [R ³ SiO _{3 / 2} ] _n [R ⁴ SiO _3/2 ] _m . . . (3) In the formula (3), R ³ represents an organic group having a group selected from the group consisting of a (meth) acryl fluorenyl group, a glycidyl group, and a vinyl group, and R ⁴ represents a hydrogen atom and a carbon number. Any one selected from the group consisting of a hydrocarbon group of 1 to 20, an alkoxy group having 1 to 20 carbon atoms, and an alkyloxy group having 1 to 20 carbon atoms, n and m are represented by the following formula (i) An integer of the condition shown in ~(iii): n≧1. . . (i) m≧0. . . (ii) n+m=h. . . (iii) [in the formula (iii), h represents an integer selected from the group consisting of 8, 10, 12 and 14], and when n and m are respectively 2 or more, R ³ and R ⁴ may be the same or different. . The glass fiber composite resin substrate according to claim 2, wherein a ratio (n: m) of n to m in the above formula (3) is from 10:0 to 4:6. The glass fiber composite resin substrate according to claim 2 or 3, wherein the cage type sesquiterpene oxide resin represented by the above formula (3) is 50 with respect to the entire (A) cage sesquioxane resin. More than % by mass. The glass fiber composite resin substrate according to any one of claims 1 to 4, wherein the (B) unsaturated compound has the aforementioned unsaturated functional group from an acrylonitrile group, a methacryl oxime group, an allyl group and an ethylene group. Base composition At least one basis selected by the group. The glass fiber composite resin substrate according to any one of claims 1 to 5, wherein the (B) unsaturated compound has a number of the unsaturated functional groups of from 2 to 10 per compound molecule. The glass fiber composite resin substrate according to any one of claims 1 to 6, wherein the curable resin composition is cured by impregnating the glass fiber with the curable resin composition. The glass fiber composite resin substrate according to claim 7, wherein the mass ratio of the cured product of the curable resin composition to the glass fiber (the mass of the cured product: the mass of the glass fiber) is 20:80 to 70:30. The glass fiber composite resin substrate according to any one of claims 1 to 8, which has a thickness of 0.03 to 0.5 mm.