CN104011118A - Glass fiber composite resin substrate - Google Patents

Glass fiber composite resin substrate Download PDF

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Publication number
CN104011118A
CN104011118A CN201280063174.1A CN201280063174A CN104011118A CN 104011118 A CN104011118 A CN 104011118A CN 201280063174 A CN201280063174 A CN 201280063174A CN 104011118 A CN104011118 A CN 104011118A
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glass fibre
group
cage
resin composition
curable resin
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汤浅正敏
村上悠子
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

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  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Silicon Polymers (AREA)
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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 fibre Composite resin substrate
[technical field]
The present invention relates to glass fibre Composite resin substrate.
[prior art]
Glass has the advantageous feature such as the transparency, thermotolerance, low heat expansion property, chemical stability, in the past, extensively utilizes the opticglass as lens, CD and display base plate etc., and contributes to industry development.In recent years, along with the lightweight of various optical devices, studied and made heavy opticglass slimming and lightweight.Yet glass has that impact is weak and crackly shortcoming makes its physical strength further reduce during slimming, while therefore thering is manufacturing process, break and cause the problem of decrease in yield.
Therefore, as flexibility and excellent heat resistance, and take and improve the film substrate easily breaking as object, for example JP 2004-50565 communique (patent documentation 1) has been recorded the metal oxide polymers of usining containing organic group laminated in the film flaky substrate of glass baseplate surface as the resin layer of principal constituent.Yet, in such film flaky substrate, owing to using plate glass, therefore have, be difficult to further lightweight, and physical strength inadequate problem still.
In addition, in recent years, from lightweight or slimming easily, the viewpoint of excellent in workability, as the optical component that can replace glass, transparent plastics is attracted attention.As such transparent plastics, can enumerate polymethylmethacrylate (PMMA), ester ring type polyolefine, epoxy resin, silicone resin etc., wherein PMMA or ester ring type polyolefine are called as synthetic glass owing to having especially the excellent transparency, in the purposes such as the light guiding plate of optical lens or liquid-crystal display, CD, are used in a large number.Yet, with respect to the temperature that at least needs 300 ℃～350 ℃ when low-resistance transparency electrode being formed to flexible base plate or forming the active members such as TFT, therefore the resins such as PMMA are because thermotolerance is difficult to adopt it as flexible base plate than glass is low.Moreover the material that comprises such resin is because linear expansivity is large, thus large with the difference of the linear expansivity of the element materials such as transparency electrode or TFT, can occur the be full of cracks that results from due to this or the problem of broken string.
Therefore, as improving the thermotolerance of material and the method for linear expansivity, developed the method for resin and glass fibre Composite of sening as an envoy to.For example, in JP 2004-231934 communique (patent documentation 2) and JP 2004-51960 communique (patent documentation 3), record respectively make the glass fibre such as woven fiber glass and Abbe (Abbe ' s) number or specific refractory power close to curable resin Composites such as the epoxy resin of described glass fibre or acrylate resins must Composite resin.
(prior art document)
(patent documentation)
Patent documentation 1: JP 2004-50565 communique
Patent documentation 2: JP 2004-231934 communique
Patent documentation 3: JP 2004-51960 communique
[summary of the invention]
(problem that invention will solve)
Yet, the inventor finds the Composite resin of being recorded as patent documentation 2 and 3, although improve slightly for the hot thermotolerance that reaches 250 ℃ of left and right, but second-order transition temperature is less than 300 ℃, when under the high temperature more than second-order transition temperature, heat packs contains the substrate of such Composite resin in the past, its modulus declines and the expansion or the distortion that produce substrate, therefore be still difficult to the stable and inorganic layer of laminated element material etc. equably.
The present invention completes in view of the problem that above-mentioned prior art has, and its object has high-caliber thermotolerance and the transparency for providing, and the abundant little glass fibre Composite resin substrate of thermal expansivity.
(in order to the means of dealing with problems)
The inventor is for reaching above-mentioned purpose active research, found that, in comprising the glass fibre Composite resin substrate of curable resin composition and glass fibre, as described curable resin composition, the curable resin composition that use contains following composition: there is freely (methyl) acryl of choosing, the specific cage-type silsesquioxane resin of at least any group in the group that glycidyl and vinyl form, specific unsaturated compound and the curing catalysts with the plural unsaturated functional group that contains carbon-to-carbon double bond, the content of wherein said cage-type silsesquioxane resin is in specified range, thus, can obtain and there is high-caliber thermotolerance and the transparency, thermal expansivity is little glass fibre Composite resin substrate fully, thereby complete the present invention.
Also, glass fibre Composite resin substrate of the present invention is the glass fibre Composite resin substrate that comprises curable resin composition and glass fibre,
Described curable resin composition contains
(A) there is the cage-type silsesquioxane resin of at least one group in the choosing group that freely (methyl) acryl, glycidyl and vinyl form,
(B) there is unsaturated compound unsaturated functional groups in the group that two above choosing groups that freely following general formula (1)～(2) represent form, beyond described cage-type silsesquioxane resin ,-R 1-CR 2=CH 2... (1)
-CR 2＝CH 2...(2)
[in formula (1), R 1represent to select free alkylene base, alkylidene group (or alkylidene) and-any one in group that OCO-base forms, in formula (1)～(2), R 2represent independently of one another hydrogen atom or alkyl.] and
(C) curing catalysts
And the content of described cage-type silsesquioxane resin (A) is all 5～90 quality % with respect to described curable resin composition.
As described glass fibre Composite resin substrate of the present invention, preferred described cage-type silsesquioxane resin (A) selects cage-type silsesquioxane resin for what represented by following general formula (3),
〔R 3SiO 3/2〕 n〔R 4SiO 3/2〕 m...(3)
In formula (3), R 3represent to have the organic group of the group in the choosing group that freely (methyl) acryl, glycidyl and vinyl form, R 4represent to be selected from any in the group that the alkyl siloxy of the alkyl of hydrogen atom, carbonatoms 1～20, the alkoxyl group of carbonatoms 1～20 and carbonatoms 1～20 forms, n and m represent to meet the integer of condition shown in following formula (i)～(iii):
n≧1...(i)
m≧0...(ii)
n+m＝h...(iii)
[in formula (iii), h represents the freely integer in 8,10,12 and 14 groups that form of choosing, and n and m are respectively 2 when above, R 3and R 4can distinguish identical also can be different.}。
In addition, as glass fibre Composite resin substrate of the present invention, in preferred described general formula (3), n is 10:0～4:6 with the ratio (n:m) of m, in addition more than the cage-type silsesquioxane resin-phase representing with described general formula (3), is all preferably 50 quality % for described cage-type silsesquioxane resin (A).
In addition; as glass fibre Composite resin substrate of the present invention; the described unsaturated functional group that described unsaturated compound (B) has is preferably at least one group in the group of selecting free acryl, methacryloyl, allyl group and vinyl composition; and the described unsaturated functional group number that described (B) unsaturated compound has is preferably 2～10 of each molecular compounds.
In addition, as glass fibre Composite resin substrate of the present invention, preferably make after described glass fiber impregnated described curable resin composition, described curable resin composition solidified form.In addition the cured article of described curable resin composition and the mass ratio of the described glass fibre (quality of cured article: the quality of glass fibre) be preferably 20:80～70:30, thickness is preferably 0.03～0.5mm.
Invention effect
According to the present invention, can provide there is high-caliber thermotolerance and the transparency, the abundant little glass fibre Composite resin substrate of thermal expansivity.
[embodiment]
Below, with preferred implementation, describe the present invention in detail.Glass fibre Composite resin substrate of the present invention is the glass fibre Composite resin substrate that comprises curable resin composition and glass fibre, wherein
Described curable resin composition contains
(A) there is the cage-type silsesquioxane resin of at least one group in the choosing group that freely (methyl) acryl, glycidyl and vinyl form,
(B) there is unsaturated compound unsaturated functional groups in the group that two above choosing groups that freely following general formula (1)～(2) represent form, beyond described cage-type silsesquioxane resin, and
(C) curing catalysts,
And the content of described cage-type silsesquioxane resin (A) is all 5～90 quality % with respect to described curable resin composition.
< (A) cage-type silsesquioxane resin >
In the present invention, so-called cage-type silsesquioxane resin has referred to the siloxanes of the fracture of the siloxanes of totally enclosed polyhedral structure or the part-Si-O-Si-key in described polyhedral structure, also can be the oligopolymer that plural cage-type silsesquioxane resin is formed as monomer polymerization.The cage-type silsesquioxane resin the present invention relates to has at least one group in the choosing group that freely (methyl) acryl, glycidyl and vinyl (being according to circumstances referred to as below solidified nature functional group) form.As described solidified nature functional group, preferably directly or be incorporated into the Siliciumatom on the polyhedron summit that is configured in cage-type silsesquioxane skeleton by divalent organic group.As described divalent organic group, can enumerate alkylidene group (or alkylene base), phenylene.Moreover in the present invention, so-called (methyl) acryl means methacryloyl and acryl.
As the cage-type silsesquioxane resin the present invention relates to, from thering is the cross-linking density of further raising curable resin composition, further improving the viewpoint of the stable on heating trend of glass fibre Composite resin substrate sets out, preferably on the polyhedron summit of cage-type silsesquioxane skeleton all in conjunction with described solidified nature functional group, and molecular weight distribution and molecular structure obtain to be controlled, but a part in described solidified nature functional group also can be substituted by other groups such as alkyl, phenyl.When the part in described solidified nature functional group is substituted by other groups, from the viewpoint of avoiding cross-linking density to decline, mol ratio ([average mol of solidified nature functional group]: [average mols of other groups]) as the described solidified nature functional group in the cage-type silsesquioxane resin the present invention relates to and described other groups, is preferably 10:0～6:4.Moreover in the present invention, the solidified nature functional group number in described cage-type silsesquioxane resin can be by using with the ratio of other group numbers 1the integration ratio of the solidified nature functional group that H-NMR (instrument name: JNM-ECA400 (Jeol Ltd.'s manufacture), solvent: chloroform-d, temperature: 22.7 ℃, 400MHz) measures and the crest of other groups is tried to achieve.
In addition, as the cage-type silsesquioxane resin the present invention relates to, in order to form the crosslinking structure with upright and outspoken structure, from thering is the thermotolerance of further raising gained glass fibre Composite resin substrate, the viewpoint that further reduces the trend of thermal expansivity is set out, and is preferably the cage-type silsesquioxane resin of the sealing polyhedral structure of following general formula (3) expression.
〔R 3SiO 3/2〕 n〔R 4SiO 3/2〕 m...(3)
In described formula (3), R 3represent to have the organic group of any group in the choosing group that freely (methyl) acryl, glycidyl and vinyl form.As such organic group, can enumerate (methyl) acryl; Glycidyl; Vinyl; The group that (methyl) acryl, glycidyl or vinyl are combined with bivalent hydrocarbon radicals such as alkylidene group (or alkylene base), phenylenes.As described alkylidene group (or alkylene base), can be straight chain shape and also can be branching shape, short from Binding distance, there is the viewpoint of the stable on heating trend of further raising gained glass fibre Composite resin substrate to set out, carbonatoms is preferably 1～3.As described phenylene, for example can enumerate unsubstituted phenylene, there is 1 of low alkyl group, 2-phenylene etc.Wherein, as described bivalent hydrocarbon radical, from raw material, obtain and be easy to viewpoint, more preferably the alkylidene group of carbonatoms 1～3 (or alkylene base), from obtaining the more viewpoint of the glass fibre Composite resin substrate of high crosslink density, is preferably propylidene.
In addition, as R 3, specifically can enumerate methacryloxypropyl, glycidoxypropyl, epoxy group(ing) cyclohexyl, wherein from raw material, obtain easily and the high viewpoint of polymerisation reactivity preferable methyl acryloxy propyl group.
In described formula (3), R 4represent to select any in the group that the alkyl siloxy of the alkyl of free hydrogen atom, carbonatoms 1～20, the alkoxyl group of carbonatoms 1～20 and carbonatoms 1～20 forms.As the alkyl of described carbonatoms 1～20, can be straight chain shape and also can be branching shape, also can be ring-type, can enumerate the alkyl of carbonatoms 1～20, the cycloalkyl of carbonatoms 3～20, the cycloalkenyl group of carbonatoms 3～20, phenyl, styryl.The alkyl of described carbonatoms 1～20 can be straight chain shape and also can be branching shape, from the viewpoint of the skeleton of easy acquisition cage-type silsesquioxane, is preferably the chain-like alkyl of carbonatoms 2～10.The cycloalkyl of described carbonatoms 3～20 can be enumerated such as cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, cyclohexyl etc., wherein from obtaining, is easy to viewpoint, preferably cyclohexyl.As the cycloalkenyl group of described carbonatoms 3～20, can enumerate such as cyclopentenyl, cyclohexenyl etc., wherein, from obtaining, be easy to viewpoint, cyclopentene base.In addition, the alkoxyl group of described carbonatoms 1～20 can be enumerated such as methoxyl group, oxyethyl group, sec.-propyl etc., wherein, from improving reactive viewpoint, preferred methoxyl group.In addition,, as the alkyl siloxy of described carbonatoms 1～20, can enumerate trimethylsiloxy, silicoheptane alcoxyl base, triphenyl siloxy-, dimethylsilane oxygen base, t-butyldimethylsilyloxy base etc.Wherein, from the viewpoint of easy acquisition cage-type silsesquioxane skeleton, as R 4the more preferably alkyl of carbonatoms 2～10, phenyl.
In addition, in described formula (3), n and m represent to meet the integer with the condition of following formula (i)～(iii) represent,
n≧1...(i)
m≧0...(ii)
n+m＝h...(iii)
(in formula (iii), h represents the integer being selected from 8,10,12 and 14 groups that form).By making n meet the condition representing with described formula (i), the cage-type silsesquioxane resin the present invention relates to is owing to having more than one solidified nature functional group, therefore by the unsaturated compound with the present invention relates to (B), carry out radical polymerization, can obtain there is high-caliber thermotolerance and the transparency, the abundant little glass fibre Composite resin substrate of thermal expansivity.In addition, by making n and m meet the condition representing with described formula (iii), make the cage-type silsesquioxane resin that the present invention relates to almost completely condensation become cagelike structure, glass fibre Composite resin substrate owing to utilizing, by radical polymerization, forms the crosslinking structure with upright and outspoken structure, therefore can be reached high-caliber thermotolerance and the transparency and abundant little thermal expansivity.Moreover n and m are respectively 2 R when above 3and R 4can be mutually the same also can be different.
In addition, in the cage-type silsesquioxane resin the present invention relates to, as n, be preferably 10:0～4:6, more preferably 10:0～5:5 with the ratio (n:m) of m.M surpasses described upper prescribing a time limit with respect to the number of n, and the cross-linking density that has glass fibre Composite resin substrate reduces, thermotolerance reduces and thermal expansivity becomes large trend.
Moreover, in the present invention, the ratio (n:m) of n and m, also, the solidified nature functional group number on polyhedron summit and the ratio of other group numbers that are incorporated into half times of described cage modle and are oxygen alkane resin can be tried to achieve by method as hereinbefore.
In addition, as the cage-type silsesquioxane resin the present invention relates to, in order to form the crosslinking structure with upright and outspoken structure, from thering is the thermotolerance of further raising gained glass fibre Composite resin substrate, the viewpoint that further reduces the trend of thermal expansivity is set out, more than the cage-type silsesquioxane resin-phase representing with described formula (3) is all preferably 50 quality % for the cage-type silsesquioxane resin the present invention relates to, more preferably more than 70 quality %.
As the method that obtains such cage-type silsesquioxane resin, can be for example by under existing at water, organic polar solvent and basic catalyst, the silicon compound (a) that following general formula (4) is represented, and the silicon compound (b) that following general formula (5) as required represents is hydrolyzed and obtains:
R 3SiX 3...(4)
(in formula (4), R 3with the R in above-mentioned general formula (3) 3synonym, X represents to select any hydrolization group in the group that free alkoxyl group, acetoxyl group, halogen atom and hydroxyl form),
R 4SiX 3...(5)
(in formula (5), R 4with the R in above-mentioned general formula (3) 4synonym, the X synonym in X and above-mentioned general formula (4)).
In described formula (4) and (5), X is independently of one another for selecting the hydrolization group in the group that free alkoxyl group, acetoxyl group, halogen atom and hydroxyl form.Described hydrolization group is preferably alkoxyl group.As described alkoxyl group, can enumerate methoxyl group, oxyethyl group, positive propoxy and isopropoxy, n-butoxy, isobutoxy and tert.-butoxy etc., from improving reactive viewpoint, preferred methoxyl group.
As described silicon compound (a), can enumerate for example methacryloxy Union carbide A-162, methacryloxy methyltrimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl trimethoxy silicane, allyltrimethoxysilanis, allyltriethoxysilane, p-styryl Trimethoxy silane, p-styryl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 2-(3, 4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane.Wherein, from raw material, obtain and be easy to viewpoint, as described silicon compound (a), be preferably 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl trimethoxy silicane.In addition, as described silicon compound (a), can be used alone a kind of, also two or more use capable of being combined.
As described silicon compound (b), can enumerate such as phenyltrimethoxysila,e, phenyl triethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, tert-butyl trimethoxy silane, tertiary butyl triethoxyl silane, n-octyl Trimethoxy silane, n-octyl triethoxyl silane etc.In addition, as described silicon compound (b), can be used alone a kind of, also two or more use capable of being combined.
As the ratio of mixture of described silicon compound (a) and described silicon compound (b), mix mol ratio (a:b) and preferably meet the condition that following formula (vi) represents,
a：b＝n：m...(vi)
(in formula (vi), n and m synonym in n and m and above-mentioned formula (3)).
As described water, so long as be more than or equal to the enough quality that make the hydrolysis of described silicon compound (a) and hydrolization group (b), be preferably be equivalent to the hydrolization group number of being calculated by described silicon compound (a) and quality (b) theoretical amount (mole) the quality of 1.0～1.5 times moles.Moreover, as described water, can directly use water contained in the aqueous solution of basic catalyst described later.
As described organic polar solvent, can enumerate the alcohols such as methyl alcohol, ethanol, 2-propyl alcohol; Acetone; Tetrahydrofuran (THF) etc., a kind of in them of can be used alone, also two or more use capable of being combined.Wherein, from the viewpoint of effective formation cage-type silsesquioxane skeleton, preferably use the lower alcohols having with the deliquescent carbonatoms 1～6 of water, more preferably use 2-propyl alcohol.
As described basic catalyst, can enumerate the alkali metal hydroxide of potassium hydroxide, sodium hydroxide, cesium hydroxide etc.; The ammonium hydroxide salt such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutylammonium, hydroxide benzyltrimethylammon.um, hydroxide benzyl triethyl ammonium ammonium.As the basic catalyst the present invention relates to, a kind of in them of can be used alone, also two or more use capable of being combined.Wherein, from improving the viewpoint of catalyst activity, preferably use tetramethyl ammonium hydroxide.As the amount of this basic catalyst, with respect to described silicon compound (a) and total quality optimization (b), be 0.1～10 quality %.Moreover described basic catalyst is used with the aqueous solution conventionally, therefore also can use water contained in the aqueous solution of this basic catalyst as described water.
In described hydrolysis, as the reaction times, be preferably more than 2 hours, as temperature of reaction, be preferably 0～50 ℃, more preferably 20～40 ℃.Described reaction times and temperature of reaction are less than described in limited time lower, have hydrolization group with the residual trend of unreacted state.In addition, temperature of reaction surpasses described in limited time upper, carries out complicated condensation reaction because speed of response is too fast, and result has promoted the polymer of hydrolysate to quantize so not preferred.
The response composite that contains cage-type silsesquioxane resin that utilizes such method to obtain to the present invention relates to.Moreover, in such response composite, for example, except the cage-type silsesquioxane resin the present invention relates to (the cage-type silsesquioxane resin of condensation cage-type silsesquioxane resin (resin that described formula (3) represents), part fracture completely), also contain multiple ladder type silsesquioxane resins, random silsesquioxane resins etc. as byproduct of reaction.In such response composite, content as the cage-type silsesquioxane resin the present invention relates to, viewpoint from direct use response composite as the raw material of the curable resin composition the present invention relates to, more than being all preferably 50 quality % with respect to described response composite.In addition, in gained cage-type silsesquioxane resin, the content of the cage-type silsesquioxane resin representing as described formula (3), more than being all preferably 50 quality % with respect to described cage-type silsesquioxane resin, more preferably more than 70 quality %.
Moreover, in the present invention, the total content of the cage-type silsesquioxane resin that the present invention in composition relates to, and the content of the cage-type silsesquioxane resin representing with described formula (3), can be by the gas chromatographic analysis (LC-MS of composition, HPLC:Agilent1100Series Systems (manufacture of Agilent Technology company), MS:QSTAR rxL Hybrid LC/MS/MS System (manufacture of AB SCIEX company), tubing string: SunFire C18 tubing string, mobile phase: H 2o-CH 3cN (30-70), speed: 1ml/min, temperature: 40 ℃, the structure of the cage-type silsesquioxane resin of detector: UV (254nm)) trying to achieve, and by with gel permeation chromatography (instrument name: HLC-8320GPC (DongソShe manufacture), solvent: THF, tubing string: セ ミ ミ Network ロ SEC post SuperH series, temperature: 40 ℃, speed: the molecular weight of 0.6ml/min) measuring (number molecular-weight average) is tried to achieve.
A kind of in the cage-type silsesquioxane resin that can be used alone such in the present invention, also two or more use capable of being combined.
< (B) unsaturated compound >
The compound unsaturated functional groups in the group that the unsaturated compound the present invention relates to forms for the groups that have two above choosings and freely represent with following general formula (1)～(2), beyond described cage-type silsesquioxane resin,
-R 1-CR 2＝CH 2...(1)
-CR 2＝CH 2...(2)
(in formula (1), R 1represent to select free alkylene base, alkylidene group (or alkylidene) and-any in group that OCO-base forms, in formula (1)～(2), R 2represent independently of one another hydrogen atom or alkyl).In addition, in the contained group of the group representing with described formula (2), get rid of the group representing with described formula (1).
In described formula (1), R 1expression by alkylene base, alkylidene group and-be selected from group that OCO-base forms any.As described alkylene base and alkylidene group (or alkylidene), can be straight chain shape and also can be branching shape, short based on Binding distance, the viewpoint with the thermotolerance trend that more improves gained glass fibre Composite resin substrate is set out, and carbonatoms is preferably 1～6.In addition, in them, from thering is the viewpoint of the trend that the reactivity of radical polymerization is high, as R 1, preferably-OCO-base.
In formula (1) and (2), R 2represent independently of one another hydrogen atom or alkyl.As described alkyl, can be straight chain shape and also can be branching shape, from the more excellent viewpoint of the reactivity of radical polymerization, preferred carbonatoms 1～3.From the more excellent viewpoint of the reactivity of radical polymerization, be preferably hydrogen atom or methyl.
As such unsaturated functional group, specifically can enumerate acryl, methacryloyl, allyl group and vinyl.Unsaturated compound of the present invention is by having such unsaturated functional group, and can carry out radical polymerization with the described cage-type silsesquioxane resin (A) with described solidified nature functional group, can obtain and there is fully little glass fibre Composite resin substrate of the present invention of high-caliber thermotolerance and the transparency and thermal expansivity.
As unsaturated compound of the present invention, each molecular compound has plural described unsaturated functional group.Described unsaturated functional group number is less than described in limited time lower, even also cannot form sufficient crosslinking structure owing to carrying out radical polymerization with described cage-type silsesquioxane resin, therefore modulus step-down, the thermotolerance of glass fibre Composite resin substrate when high temperature reduces.In addition, from the described modulus of further raising and stable on heating viewpoint, as the number of described unsaturated functional group, be preferably 2～10.Moreover, as unsaturated compound of the present invention, can be monomer and also can be polymkeric substance, when described unsaturated compound is polymkeric substance, the mean value that described unsaturated functional group number is each molecular compound.Moreover the unsaturated functional group number (or mean number) of each molecular compound is by utilizing 1h-NMR (instrument name: JNM-ECA400 (Jeol Ltd.'s manufacture), solvent: chloroform-d, temperature: 22.7 ℃, the crest area of the group of the unsaturated functional group of 400MHz) measuring and with gel permeation chromatography (GPC, (instrument name: HLC-8320GPC (manufacture of company of Dongソ society), solvent: THF, tubing string: ultra-high speed セ ミ ミ Network ロ SEC tubing string SuperH series, temperature: 40 ℃, speed: the molecular weight of 0.6ml/min) measuring (or number molecular-weight average) is tried to achieve.
As unsaturated compound of the present invention, so long as each molecular compound has plural described unsaturated functional group, be not particularly limited, but molecular weight (in the situation that of polymkeric substance, being weight average molecular weight) is preferably 80～5000.Molecular weight is less than described in limited time lower, in the situation of the unsaturated compound that solidifies middle remained unreacted of curable resin composition, having unreacted unsaturated compound in the heat treated such as thermal treatment becomes volatile component and causes changes in weight after solidifying or the possibility of dimensional change, on the other hand, surpass described in limited time upper, with the decreased solubility of cage-type silsesquioxane resin, have the viscosity of gained curable resin composition is uprised and unworkable trend.
As such unsaturated compound, can enumerate for example diacrylate two cyclopentyl esters, diacrylate tripropylene glycol ester, diacrylate 1,6-hexylene glycol ester, bisphenol A diglycidyl ether diacrylate, bisphenol fluorene diacrylate, tetraethylene glycol diacrylate, hydroxy new pentane acid neopentylglycol diacrylate, Viscoat 295, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate.Wherein, from high with the solvability of cage-type silsesquioxane resin, in addition, the viewpoint with the stable on heating trend of further raising gained glass fibre Composite resin substrate is set out, be preferably the compound forming in conjunction with plural described unsaturated functional group on the hydrocarbon compound of carbonatoms 1～30, more preferably two cyclopentyl diacrylates, bisphenol fluorene diacrylate, Viscoat 295, tetramethylol methane tetraacrylate.In addition, as the unsaturated compound the present invention relates to, can be used alone a kind of also capable of being combined two or more.
< (C) curing catalysts >
The curing catalysts the present invention relates to is for promoting the catalyzer of the curing reaction (Raolical polymerizable) of described (A) cage-type silsesquioxane resin and described (B) unsaturated compound.As such curing catalysts, can enumerate radical polymerization initiator, as described radical polymerization initiator, can enumerate optical free radical polymerization starter and hot radical polymerization starter.
As described optical free radical polymerization starter, can enumerate methyl phenyl ketone system, bitter almond oil camphor system, benzophenone series, thioxanthone system, the Photoepolymerizationinitiater initiater of acylphosphine oxide system, specifically can enumerate Trichloroacetophenon, diethoxy acetophenone, 1-phenyl-2-hydroxy-2-methyl third-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-thiotolene base)-2-morpholinyl third-1-ketone, benzoin methyl ether, benzyl dimethyl ketal, benzophenone, thioxanthone, 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, dihydroxy acetic acid aminomethyl phenyl ester, camphorquinone, dibenzoyl, anthraquinone, Michler's keton (Michler's ketone) etc.In addition, as described hot radical polymerization starter, can enumerate for example thermal polymerization of ketone peroxide system, peroxy ketal system, hydrogen peroxide system, dialkyl peroxide system, diacyl peroxide system, peroxide two carbonic ether systems, peroxy esters system.As the curing catalysts the present invention relates to, a kind of in them of can be used alone, also two or more use capable of being combined, also can be used in combination described optical free radical polymerization starter and described hot radical polymerization starter.
< curable resin composition >
The curable resin composition the present invention relates to contains described (A) cage-type silsesquioxane resin, described (B) unsaturated compound and described (C) curing catalysts.
In the curable resin composition the present invention relates to, the content of described cage-type silsesquioxane resin need to be all 5～90 quality % with respect to described curable resin composition.The content of described cage-type silsesquioxane resin is less than that described lower because the second-order transition temperature of glass fibre Composite resin substrate declines, and thermal expansivity becomes large in limited time, therefore that thermotolerance becomes is not enough.In addition, surpass described upper prescribing a time limit, the cross-linking density of cured article increases and glass fibre Composite resin substrate becomes fragile, therefore process, becomes difficulty.
In addition, from the thermotolerance of further raising glass fibre Composite resin substrate, and further put forward high-intensity viewpoint and set out, the content of described cage-type silsesquioxane resin is preferably 8～80 quality %.In addition, from viewpoint as hereinbefore, 50 quality % above (more preferably more than 70 quality %) in described cage-type silsesquioxane resin are preferably the cage-type silsesquioxane resin representing with described formula (3), as the curable resin composition the present invention relates to, the content of the cage-type silsesquioxane resin representing with described formula (3) is all preferably 2.5～90 quality % with respect to described curable resin composition, more preferably 5～80 quality %.
In addition, in curable resin composition of the present invention, as the content of described unsaturated compound, with respect to described curable resin composition, be all preferably 5～90 quality %, more preferably 10～70 quality %.The content of described unsaturated compound is less than described in limited time lower, solvability reduction due to curable resin composition, or soltion viscosity increases, therefore the trend that has the dipping of pair glass fibre to reduce, on the other hand, surpass described upper prescribing a time limit, the second-order transition temperature that has the cured article of curable resin composition reduces, the trend that the thermotolerance of the glass fibre Composite resin substrate of gained reduces.
In addition,, in curable resin composition of the present invention, as the content of described curing catalysts, with respect to described curable resin composition, be all preferably 0.1～5.0 quality %, more preferably 0.1～3.0 quality %.The content of described curing catalysts is less than described in limited time lower, has curing reaction and becomes not enough, and the trend that the intensity of gained cured article, rigidity reduce, on the other hand, over having cured article on described in limited time, painted possibility occurs.
In addition, as the curable resin composition the present invention relates to, can and then contain described (A) cage-type silsesquioxane resin and described (B) unsaturated compound curable compound (being according to circumstances called below solidified nature compound) in addition.As such solidified nature compound, the curing compound so long as can utilize heating or the irradiation of active energy ray, there is no particular restriction, but be preferably consistency and the reactive compound having with described cage-type silsesquioxane resin.
As such solidified nature compound, can enumerate for example repeated structural unit number is reactive oligomers, lower molecular weight and the low viscous reactive monomer of the polymkeric substance of 2～20 left and right.As described reactive oligomers, specifically can enumerate epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinylacrylic acid ester, polyenoid/mercaptan, organic silicon acrylic ester, polyhutadiene, polystyrene β-dimethyl-aminoethylmethacrylate.In addition, described reactive monomer specifically can be enumerated the monofunctional monomers such as the just own ester of vinylbenzene, vinyl-acetic ester, NVP, butyl acrylate, 2-EHA, vinylformic acid, cyclohexyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems, isobornyl acrylate, vinylformic acid two cyclopentenes oxygen base ethyl esters, vinylformic acid phenoxy group ethyl ester, trifluoroethyl methacrylate.Solidified nature compound as such, can be used alone a kind of, also two or more use capable of being combined.
When the curable resin composition the present invention relates to contains described solidified nature compound, as its content, with respect to described curable resin composition, be all preferably below 40 quality %.The content of described solidified nature compound surpasses described in limited time upper, is difficult to form sufficient crosslinking structure, the trend that the thermotolerance of the rewarding glass fibre Composite resin substrate of meeting reduces.
In addition, as the curable resin composition the present invention relates to, in the scope that does not hinder effect of the present invention, can and then contain various additives.As described additive, can enumerate such as organic/inorganic weighting agent, softening agent, fire retardant, thermo-stabilizer, antioxidant, photostabilizer, UV light absorber, lubricant, static inhibitor, releasing agent, whipping agent, nucleator, tinting material, linking agent, dispersing auxiliary etc.While containing such additive, as its content, with respect to described curable resin composition, be all preferably below 30 quality %.
In addition, as the curable resin composition the present invention relates to, in order to adjust its viscosity etc., also can and then contain methyl ethyl ketone, toluene, ethyl acetate equal solvent, but because the volatilization of solvent is removed, step needs the time therefore production efficiency is low, and, have dissolvent residual makes the characteristic reduction of substrate possibility in the inside of gained glass fibre Composite resin substrate, pretend the content for described solvent, with respect to described curable resin composition, be all preferably below 5 quality %, more preferably not containing solvent.
< glass fibre >
As the form of glass fibre of the present invention, can enumerate thread yarn, woven fiber glass, non-woven etc.In them, the high viewpoint of effect reducing from thermal expansivity, preferred glass cloth.Raw material as described woven fiber glass, according to the composition of glass, can enumerate E glass, C glass, A glass, S glass, D glass, NE glass, T glass, silica glass etc., in them, from making, the scope of specific refractory power drops in preferable range, other handy viewpoint, preferably E glass, S glass, T glass, NE glass.
In addition, as the glass fibre the present invention relates to, wettability, affinity, the adaptation at the interface of improving described curable resin composition and described glass fibre of take is object, also can use the washing that utilizes silane coupling agent, various tensio-active agent, utilizes mineral acid; Corona discharge Treatment; Uviolizing is processed; Cement Composite Treated by Plasma etc. impose surface-treated glass fibre.
In addition, as the specific refractory power of the glass fibre the present invention relates to, with the specific refractivity of the cured article of described curable resin composition preferably in-0.02～+ 0.02 scope, more preferably in-0.01～+ 0.01 scope.Described specific refractivity is outside described scope time, due to the cured article of curable resin composition and the interface scattering of glass fibre increase, the transparency of glass fibre Composite resin substrate is reduced, therefore there is the trend being difficult to as the alternative substrate use of flexible display or used for solar batteries glass.
In addition, when the form of the glass fibre the present invention relates to is woven fiber glass, non-woven etc., its thickness can suitably be selected according to using the object of glass fibre Composite resin substrate, but from having, improve the viewpoint of curable resin composition to the dipping trend of glass fibre, be preferably 30～100 μ m.
< glass fibre Composite resin substrate >
Glass fibre Composite resin substrate of the present invention is the substrate that described curable resin composition and described glass fibre Composite are formed.As the manufacture method of such glass fibre Composite resin substrate, there is no particular restriction, but for example can enumerate, described curable resin composition be impregnated in after described glass fibre, makes the curing method of described curable resin composition.
In such method, first at lower described (A) cage-type silsesquioxane resin, described (B) unsaturated compound, described (C) curing catalysts and other compounds as required or the solvent etc. of mixing of room temperature (20～25 ℃), obtain the curable resin composition the present invention relates to.Then, described curable resin composition is dripped in described glass fibre, utilize impregnating method to flood, as required except desolventizing.Then, to flooding the glass fibre of described curable resin composition, impose heat treated and/or active energy ray radiation treatment, described curable resin composition is solidified, obtain glass fibre Composite resin substrate of the present invention.
As glass fibre Composite resin substrate of the present invention, preferred every 1m 2the cured article of described curable resin composition and the mass ratio of the described glass fibre (quality of cured article: the quality of glass fibre) be 20:80～70:30, more preferably 40:60～60:40.Glass fibre is less than described in limited time lower with respect to the ratio of described cured article, the thermotolerance that has glass fibre Composite resin substrate reduces, and thermal expansivity surpasses the trend of 20ppm/K, on the other hand, surpass described in limited time upper, the dipping of glass fibre is become to insufficient, have residual clearance between fiber and make the transparency of glass fibre Composite resin substrate reduce the trend of (mist degree increase).Therefore, in described dipping, preferably so that the mode that the quality of described curable resin composition after solidifying and the mass ratio of described glass fibre become in described scope flood.
In addition, in described dipping, can suitably adjust according to using the kind of glass fibre or the object of glass fibre Composite resin substrate, but from the liquid-crystal display of application glass fibre Composite resin substrate or the viewpoint corresponding to thickness or manufacturing process's (volume to volume) of OLED display, preferably, so that the thickness of gained glass fibre Composite resin substrate becomes 0.03～0.5mm, the mode that preferably becomes 0.05～0.2mm is flooded.
In addition, as the Heating temperature in described heat treated, can suitably adjust according to described curable resin composition, but be preferably 50～200 ℃, more preferably 80～180 ℃.Heating temperature is less than that described lower what have a curing reaction carries out insufficiently, cannot form the trend of full cross-linked structure in limited time, on the other hand, surpass described in limited time upper, the trend of the defect of i.e. rotten, volatilization before can being created in curable resin composition and solidifying.In addition, as the heat-up time of described heat treated, different according to described Heating temperature or described curable resin composition, therefore cannot lump together, but be preferably 30～60 minutes.In addition, as described heat treated, from the Raolical polymerizable that suppresses curable resin composition because of the obstruction due to oxygen, can form the viewpoint of the trend of more full cross-linked structure, preferably under the non-active gas atmosphere such as nitrogen, carry out.
In addition, the condition of irradiating as the active energy ray in described active energy ray radiation treatment, preferably the ultraviolet ray of illumination wavelength 10～400nm is, the visible ray of wavelength 400～700nm, the more preferably near-ultraviolet ray of illumination wavelength 200～400nm.In addition, cumulative exposure amount is preferably 2000～10000mJ/cm 2.0.4～4W/cm), high voltage mercury lamp (40～160W/cm), ultrahigh pressure mercury lamp (173～435W/cm), metal halide lamp (80～160W/cm), pulsed xenon lamp (80～120W/cm), electrodeless discharge lamp (80～120W/cm) etc. as the generation source of described active energy ray, can enumerate low pressure mercury lamp (output:.
As glass fibre Composite resin substrate of the present invention, for making surface smoothing, also the coat that comprises resin can and then be set on a surface of described glass fibre Composite resin substrate or two surfaces.As described resin, preferably there is thermotolerance, the transparency, chemical-resistant, particularly preferably use the described curable resin composition the present invention relates to.In addition, as glass fibre Composite resin substrate of the present invention, also the gas-barrier layer to oxygen or water vapour can as required and then be set.
Embodiment
Below, based on embodiment and comparative example, the present invention is more specifically described, but the present invention is not limited to following embodiment.Moreover in each modulation example, embodiment and comparative example, detecting refractive index, full light transmittance are measured, Evaluation of Heat Tolerance system is undertaken by method shown below respectively.
(detecting refractive index)
Use roller spreader, with become the mode of thickness 0.1mm cast (curtain coating) respectively modulate the curable resin composition obtaining in example, and use the high voltage mercury lamp of 80W/cm, with 2000mJ/cm 2cumulative exposure amount it is solidified, obtain the cured article of sheet.For gained cured article, use index meter (DR-M2, アタ go society system), be determined at respectively the specific refractory power of 589nm.
(full light transmittance is measured)
For the glass fibre Composite resin substrate obtaining in each embodiment and comparative example, use haze meter (NDH2000, Japanese electric look system), measure full light transmittance (%).
(Evaluation of Heat Tolerance)
. second-order transition temperature is measured, dynamic viscoelastic reduced rate is measured
For the glass fibre Composite resin substrate obtaining in each embodiment and comparative example, use Measurement of Dynamic Viscoelasticity device (trade(brand)name: DVE-V4, manufacturing company's name: UBM company system), condition with 5 ℃/min of heat-up rate, in the scope of 30～300 ℃ of temperature, carry out Measurement of Dynamic Viscoelasticity, and using the peak temperature of the Tan δ in the scope of 30～300 ℃ of temperature as second-order transition temperature (Tg (℃)).In addition, dynamic viscoelastic reduced rate (△ E ' is (%)) is to be tried to achieve by following formula:
△E’(％)＝(E’ 30-E’ 300)/E’ 30
(in formula, E ' 30be shown in the dynamic viscoelastic of 30 ℃, E ' 300be shown in the dynamic viscoelastic of 300 ℃).Moreover second-order transition temperature is higher and/or dynamic viscoelastic reduced rate is less, represent that the thermotolerance of glass fibre Composite resin substrate is higher.
. thermal expansivity (coefficient of linear thermal expansion) is measured
For the glass fibre Composite resin substrate obtaining in each embodiment and comparative example, use thermo-mechanical analysis device (TMA, trade(brand)name: TMA4000SA, manufacturing company's name: BRUKER company system), with 5 ℃/min of heat-up rate, the condition of compressive load 0.1N, try to achieve the mean value of elongation of the face direction (directions X) of the glass fibre Composite resin substrate (0.1mm is thick) in the scope of 30～200 ℃ of temperature, by this value, tried to achieve the thermal expansivity (ppm/K) of the face direction (directions X) of glass fibre Composite resin substrate.Moreover thermal expansivity is less, represent that the thermotolerance of glass fibre Composite resin substrate is higher.
(synthesis example 1: cage-type silsesquioxane resin (I))
Cage-type silsesquioxane resin (I) is according to the method manufacture of recording in JP 2004-143449 communique.First, in the reaction vessel that possesses agitator, dropping funnel and thermometer, pack 2-propyl alcohol (IPA) 40ml as solvent into, as the 5% tetramethyl ammonium hydroxide aqueous solution (the TMAH aqueous solution) 3.1g of basic catalyst.In addition, IPA15ml and 3-methacryloxypropyl trimethoxy silane 12.7g are packed in dropping funnel and the IPA solution of modulation 3-methacryloxypropyl trimethoxy silane, and limit is at room temperature stirred limit and was dripped in described reaction vessel in 30 minutes.After dropping finishes, do not heat and stir again 2 hours.After stirring, under reduced pressure remove IPA, obtain the composition 7.5g containing cage-type silsesquioxane resin (I).In resulting composition, the cage-type silsesquioxane resin (I) the present invention relates to is all 97 quality % with respect to described composition, wherein, the cage-type silsesquioxane resin-phase that the formula (3) of take represents is all 90 quality % for described cage-type silsesquioxane resin (I), the result of the mass analysis after gas chromatograph separation, the n in formula (3) is 8,10,12.
(synthesis example 2: cage-type silsesquioxane resin (II))
IPA15ml, 3-methacryloxypropyl trimethoxy silane 7.2g and phenyltrimethoxysila,e 5.7g are packed in dropping funnel, the IPA solution of modulation 3-methacryloxypropyl trimethoxy silane and phenyltrimethoxysila,e, use it to replace the IPA solution of 3-methacryloxypropyl trimethoxy silane, in addition, same with synthesis example 1, obtain the composition 8.7g containing cage-type silsesquioxane resin (II).In resulting composition, the cage-type silsesquioxane resin (II) the present invention relates to is all 96 quality % with respect to described composition, wherein, the cage-type silsesquioxane resin-phase that the formula (3) of take represents is all 92 quality % for described cage-type silsesquioxane resin (II), the result of the mass analysis after gas chromatograph separation, the n+m in formula (3) is 8,10,12.And n:m is 4:4.
(modulation example 1: curable resin composition (I))
Using the cage-type silsesquioxane resin (I) obtaining in synthesis example 1: 60 mass parts (being converted into cage-type silsesquioxane resin), Viscoat 295: 25 mass parts, two cyclopentyl diacrylates: 15 mass parts and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 mass parts are mixed, and obtain aqueous curable resin composition (I).For this curable resin composition (I), carry out detecting refractive index, specific refractory power is 1.529, confirms to obtain transparent cured article.The composition of gained curable resin composition (I) is shown in table 1.
(modulation example 2: curable resin composition (II))
Using the cage-type silsesquioxane resin (I) obtaining in synthesis example 1: 30 mass parts (being converted into cage-type silsesquioxane resin), two cyclopentyl diacrylates: 35 mass parts, tetramethylol methane tetraacrylate: 35 mass parts and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 mass parts are mixed, and obtain aqueous curable resin composition (II).For this curable resin composition (II), carry out detecting refractive index, specific refractory power is 1.531, confirms to obtain transparent cured article.The composition of gained curable resin composition (II) is shown in table 1.
(modulation example 3: curable resin composition (III))
Using the cage-type silsesquioxane resin (I) obtaining in synthesis example 1: 10 mass parts (being converted into cage-type silsesquioxane resin), Viscoat 295: 65 mass parts, two cyclopentyl diacrylates: 35 mass parts and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 mass parts are mixed, and obtain aqueous curable resin composition (III).For this curable resin composition (III), carry out detecting refractive index, specific refractory power is 1.531, confirms to obtain transparent cured article.The composition of gained curable resin composition (III) is shown in table 1.
(modulation example 4: curable resin composition (IV))
Using the cage-type silsesquioxane resin (II) obtaining in synthesis example 2: 15 mass parts (being converted into cage-type silsesquioxane resin), Viscoat 295: 50 mass parts, bisphenol fluorene diacrylate: 35 mass parts and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 mass parts are mixed, and obtain aqueous curable resin composition (IV).For this curable resin composition (IV), carry out detecting refractive index, specific refractory power is 1.558, confirms to obtain transparent cured article.The composition of gained curable resin composition (IV) is shown in table 1.
(modulation example 5: curable resin composition (V))
Using the cage-type silsesquioxane resin (II) obtaining in synthesis example 2: 35 mass parts (being converted into cage-type silsesquioxane resin), tetramethylol methane tetraacrylate: 25 mass parts, bisphenol fluorene diacrylate: 40 mass parts and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 mass parts are mixed, and obtain aqueous curable resin composition (V).For this curable resin composition (V), carry out detecting refractive index, specific refractory power is 1.560, confirms to obtain transparent cured article.The composition of gained curable resin composition (V) is shown in table 1.
(modulation example 6: curable resin composition (VI))
Using two cyclopentyl diacrylates: 35 mass parts, tetramethylol methane tetraacrylate: 65 mass parts and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 mass parts are mixed, and obtain aqueous curable resin composition (VI).The composition of gained curable resin composition (VI) is shown in table 1.
(modulation example 7: curable resin composition (VII))
Using tetramethylol methane tetraacrylate: 25 mass parts, bisphenol fluorene diacrylate: 40 mass parts and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 mass parts are mixed, and obtain aqueous curable resin composition (VII).The composition of gained curable resin composition (VII) is shown in table 1.
(modulation example 8: curable resin composition (VIII))
Using the cage-type silsesquioxane resin (I) obtaining in synthesis example 1: 5 mass parts, two cyclopentyl diacrylates: 40 mass parts, tetramethylol methane tetraacrylate: 55 mass parts and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 mass parts are mixed, and obtain aqueous curable resin composition (VIII).Gained curable resin composition (VIII) composition is shown in table 1.
(table 1)
(embodiment 1)
First, it is woven fiber glass (trade(brand)name: T ガ ラ ス ヤ ー Application (day east twist flax fibers and weave society's system) that the curable resin composition (I) obtaining in modulation example 1 is dripped in being arranged on T glass on sheet glass, specific refractory power 1.530, thickness 96 μ m), above covering with sheet glass, from top and bottom, with sheet glass, clamp, while exerting pressure, make woven fiber glass dipping curable resin composition.Then,, so that this woven fiber glass macerate is held on the state in sheet glass, use the high voltage mercury lamp of 80W/cm, with 2000mJ/cm 2cumulative exposure amount irradiation ultraviolet radiation (wavelength: 365nm), curable resin composition is solidified.Then, under nitrogen atmosphere, 250 ℃ of heating 10 minutes, obtain thickness 0.1mm, every 1m 2the cured article of curable resin composition and the mass ratio of the glass fibre (quality of cured article: the quality of glass fibre) be the glass fibre Composite resin substrate of 46:54.For gained glass fibre Composite resin substrate, carry out the table 2 that the results are shown in of full light transmittance mensuration and Evaluation of Heat Tolerance.
(embodiment 2)
The curable resin composition (II) obtaining in using modulation example 2 replaces, curable resin composition (I), similarly to Example 1, obtaining thickness 0.1mm, every 1m 2the cured article of curable resin composition and the mass ratio of the glass fibre (quality of cured article: the quality of glass fibre) be the glass fibre Composite resin substrate of 48:52.For gained glass fibre Composite resin substrate, carry out the table 2 that the results are shown in of full light transmittance mensuration and Evaluation of Heat Tolerance.
(embodiment 3)
The curable resin composition (III) obtaining in using modulation example 3 replaces, curable resin composition (I), similarly to Example 1, obtaining thickness 0.1mm, every 1m 2the cured article of curable resin composition and the mass ratio of the glass fibre (quality of cured article: the quality of glass fibre) be the glass fibre Composite resin substrate of 44:56.For gained glass fibre Composite resin substrate, carry out the table 2 that the results are shown in of full light transmittance mensuration and Evaluation of Heat Tolerance.
(embodiment 4)
Use the curable resin composition (IV) obtaining in modulation example 4 to replace curable resin composition (I), using E glass is that woven fiber glass (trade(brand)name: 2116/AS887AW (manufacture of イ ーマ テリアル society of Asahi Chemical Industry), specific refractory power 1.558, thickness 96 μ m) replacement T glass is woven fiber glass, in addition, similarly to Example 1, obtain thickness 0.1mm, every 1m 2the cured article of curable resin composition and the mass ratio of the glass fibre (quality of cured article: the quality of glass fibre) be the glass fibre Composite resin substrate of 52:48.For gained glass fibre Composite resin substrate, carry out the table 2 that the results are shown in of full light transmittance mensuration and Evaluation of Heat Tolerance.
(embodiment 5)
The curable resin composition (V) obtaining in using modulation example 5 replaces, curable resin composition (IV), similarly to Example 4, obtaining thickness 0.1mm, every 1m 2the cured article of curable resin composition and the mass ratio of the glass fibre (quality of cured article: the quality of glass fibre) be the glass fibre Composite resin substrate of 48:52.For gained glass fibre Composite resin substrate, carry out the table 2 that the results are shown in of full light transmittance mensuration and Evaluation of Heat Tolerance.
(comparative example 1)
The curable resin composition (VI) obtaining in using modulation example 6 replaces, curable resin composition (I), similarly to Example 1, obtaining thickness 0.1mm, every 1m 2the cured article of curable resin composition and the mass ratio of the glass fibre (quality of cured article: the quality of glass fibre) be the glass fibre Composite resin substrate of 47:53.For gained glass fibre Composite resin substrate, carry out the table 2 that the results are shown in of full light transmittance mensuration and Evaluation of Heat Tolerance.
(comparative example 2)
The curable resin composition (VII) obtaining in using modulation example 7 replaces curable resin composition (I), similarly to Example 4 remaining, obtains thickness 0.1mm, every 1m 2the cured article of curable resin composition and the mass ratio of the glass fibre (quality of cured article: the quality of glass fibre) be the glass fibre Composite resin substrate of 49:51.For gained glass fibre Composite resin substrate, carry out the table 2 that the results are shown in of full light transmittance mensuration and Evaluation of Heat Tolerance.
(comparative example 3)
The curable resin composition (VIII) obtaining in using modulation example 8 replaces, curable resin composition (I), similarly to Example 1, obtaining thickness 0.1mm, every 1m 2the cured article of curable resin composition and the mass ratio of the glass fibre (quality of cured article: the quality of glass fibre) be the glass fibre Composite resin substrate of 47:53.For gained glass fibre Composite resin substrate, carry out the table 2 that the results are shown in of full light transmittance mensuration and Evaluation of Heat Tolerance.
(table 2)
* 1:>300, represents that second-order transition temperature is more than 300 ℃.
Result is as shown in Table 2 known, the full light transmittance of glass fibre Composite resin substrate of the present invention is more than 90%, and second-order transition temperature is enough large, dynamic viscoelastic reduced rate also maintains below 20%, confirms to have high-caliber thermotolerance and the transparency.In addition, thermal expansivity is below 15ppm/K, also confirms that thermal expansivity is very little.With respect to this, in glass fibre Composite resin substrate in the past (comparative example 1,2), though full light transmittance is more than 90%, confirm that second-order transition temperature is low, dynamic viscoelastic reduced rate and thermal expansivity are also poor.
(utilizability in industry)
As described above, according to the present invention, can provide and there is high-caliber thermotolerance and the transparency, and the abundant little glass fibre Composite resin substrate of thermal expansivity.Glass fibre Composite resin substrate of the present invention so especially when high temperature modulus also do not reduce and there is high-caliber thermotolerance, therefore it is very useful that the glass, using such as the purposes of flexible display, contact panel, solar cell etc. substitutes substrate.

Claims (9)

1. glass fibre Composite resin substrate, it is the glass fibre Composite resin substrate that comprises curable resin composition and glass fibre, described curable resin composition contains
(A) there is the cage-type silsesquioxane resin of at least one group in the choosing group that freely (methyl) acryl, glycidyl and vinyl form,
(B) there is unsaturated compound unsaturated functional groups in the group that two above choosing groups that freely following general formula (1)～(2) represent form, beyond described cage-type silsesquioxane resin,
-R 1-CR 2＝CH 2...(1)
-CR 2＝CH 2...(2)
In formula (1), R 1represent to select free alkylene base, alkylidene group and-any one in group that OCO-base forms, in formula (1)～(2), R 2represent independently of one another hydrogen atom or alkyl, and
(C) curing catalysts
And the content of described cage-type silsesquioxane resin (A) is all 5～90 quality % with respect to described curable resin composition.
2. glass fibre Composite resin substrate as claimed in claim 1, wherein said cage-type silsesquioxane resin (A) is the cage-type silsesquioxane resin that following general formula (3) represents,
〔R 3SiO 3/2〕 n〔R 4SiO 3/2〕 m...(3)
In formula (3), R 3represent to have the organic group of the group in the choosing group that freely (methyl) acryl, glycidyl and vinyl form, R 4represent to be selected from any in the group that the alkyl siloxy of the alkyl of hydrogen atom, carbonatoms 1～20, the alkoxyl group of carbonatoms 1～20 and carbonatoms 1～20 forms, n and m represent to meet the integer of condition shown in following formula (i)～(iii):
n≧1...(i)
m≧0...(ii)
n+m＝h...(iii)
In formula (iii), h represents to select the integer in free 8,10,12 and 14 groups that form,
N and m are respectively 2 when above, R 3and R 4can distinguish identical also can be different.
3. glass fibre Composite resin substrate as claimed in claim 2, in wherein said general formula (3), n is 10:0～4:6 with the ratio (n:m) of m.
4. glass fibre Composite resin substrate as claimed in claim 2 or claim 3, wherein said take cage-type silsesquioxane resin-phase that general formula (3) represents for described cage-type silsesquioxane resin (A) all more than 50 quality %.
5. the glass fibre Composite resin substrate as described in any one in claim 1～4, the described unsaturated functional group that wherein said unsaturated compound (B) has is at least one group selecting in the group that free acryl, methacryloyl, allyl group and vinyl form.
6. the glass fibre Composite resin substrate as described in any one in claim 1～5, the number of the described unsaturated functional group that wherein said unsaturated compound (B) has is 2～10 of each molecular compounds.
7. the glass fibre Composite resin substrate as described in any one in claim 1～6, it makes after described glass fiber impregnated described curable resin composition, described curable resin composition is solidified forms.
8. glass fibre Composite resin substrate as claimed in claim 7, is the quality of cured article at the cured article of wherein said curable resin composition and the mass ratio of described glass fibre: the quality of glass fibre is 20:80～70:30.
9. as the glass fibre Composite resin substrate of any one in claim 1～8, its thickness is 0.03～0.5mm.
CN201280063174.1A 2011-12-22 2012-12-18 Glass fiber composite resin substrate Pending CN104011118A (en)

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