JP6557041B2 - Laminate comprising light or thermosetting resin composition - Google Patents

Description

  The present invention relates to a laminate having a hard coat layer formed on a film, and relates to the production of a film having low cure shrinkage.

  In recent years, in a wide range of fields such as optical lenses, home appliance display boards, automobile parts, electrical equipment covers, building materials, etc., by applying a film with a thin hard coat layer on the plastic surface, the product's scratch and chemical resistance A method for improving the above is being studied. However, there has been a problem that the film is deformed (warped) due to curing shrinkage when forming the hard coat layer, resulting in poor appearance and poor adhesion during bonding and molding.

  In Patent Document 1, curing shrinkage is reduced by mixing a large amount of bifunctional (meth) acrylate in polyfunctional (meth) acrylate. However, this technique has a problem in that the scratch density and chemical resistance are also lowered because the crosslinking density is lowered together with the curing shrinkage.

  In Patent Document 2, by forming hard coat layers on both sides of a base film, the uneven distribution of stress applied to the base film is dispersed to reduce warpage. However, this method cannot cope with a stress higher than the rigidity (durability) of the base film, that is, the hard coat layer cannot be provided thick.

JP2014-134673A JP2015-007732A

  An object of the present invention is to provide a resin laminate that is excellent in scratch resistance and chemical resistance and is less warped due to low curing shrinkage.

  As a result of intensive studies to solve the above-described conventional drawbacks, the present inventors have applied the present invention to a hard coat layer made of a siloxane-based resin containing a poxy structure-containing group on a resin sheet. It came to complete.

The present invention is shown below.
[1] A laminate obtained by applying a heat or photocurable resin composition on an organic resin substrate having a thickness of 1 μm to 1 mm and curing the composition.
The laminated body characterized by satisfying the following conditions (1) and (2).
Condition (1)
The curable resin composition is
The following general formula (I):
_{^{R 1 - (SiR 2 a (}} OR 3) 3-a) (I)
(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms whose terminal is substituted with an epoxy structure-containing group, and R ² is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or 6 carbon atoms. A monovalent hydrocarbon group selected from an aryl group having ˜25 and an aralkyl group having 7 to 12 carbons, and R ³ is each independently a hydrogen atom or an alkyl group having 1 to 10 carbons. A silane compound (I) having a hydrolyzable silyl group represented by:
The following general formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(Wherein, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and is selected from substituted aryl group, .R ² are each independently a group having no epoxy structure-containing group And a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and R ³ is independently A hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2), and a silane compound (II) having a hydrolyzable silyl group,
Consists of a condensate (A) obtained by hydrolysis / condensation with a molar ratio of the silane compound (II) to the silane compound (I) of 9 or less, and a curing agent (B) for curing the epoxy group.
Condition (2)
The condensate (A) uses a neutral salt (C) as a hydrolysis / condensation catalyst,
The neutral salt is a combination of any one selected from the group consisting of Group I element ions and Group II element ions as cations and any one selected from the group consisting of chloride ions, bromide ions, and iodide ions as anions. It is a salt.
[2] Regarding the condensate (A), the condensate (A) is directly bonded to the silicon atom of the condensate (A) with respect to the mole number X of the OR ³ group directly bonded to the silicon atom of the silane compounds (I) and (II) as raw materials. The laminate according to [1], wherein the ratio Y / X of the number of moles Y of the OR ³ groups bonded is 0.5 or less.
[3] The laminate according to [1] or [2], wherein the curing agent (B) that cures the epoxy group is a cationic polymerization initiator.
[4] The laminate according to [3], wherein the cationic polymerization initiator is at least one selected from the group consisting of a fluorophosphoric acid type, a fluoroantimonic acid type, and a fluorophenylboronic acid type. body.

  According to the present invention, high scratch resistance is obtained by applying and curing a siloxane resin-based hard coat layer having an epoxy structure-containing group on an organic resin substrate (resin film or resin sheet) having a thickness of 1 μm to 1 mm. A resin sheet having chemical resistance and less warpage due to low curing shrinkage can be obtained.

The curable composition comprising a siloxane-based resin containing an epoxy structure-containing group according to the present invention is a neutral salt or a silane compound having a hydrolyzable silyl group represented by the following general formulas (I) and (II). It contains a condensate (A) obtained by hydrolysis and condensation using a basic compound as a catalyst, and a curing agent (B) for curing the epoxy group.
Formula (I):
_{^{R 1 - (SiR 2 a (}} OR 3) 3-a) (I)
(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms whose terminal is substituted with an epoxy structure-containing group, and R ² is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or 6 carbon atoms. A monovalent hydrocarbon group selected from an aryl group having ˜25 and an aralkyl group having 7 to 12 carbons, and R ³ is each independently a hydrogen atom or an alkyl group having 1 to 10 carbons. It is an integer of ~ 2.)
General formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(Wherein, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and is selected from substituted aryl group, .R ² are each independently a group having no epoxy structure-containing group And a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and R3 is independently hydrogen. An atom or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2)
Further, the silane compound (II) is hydrolyzed and condensed with a basic compound or neutral salt as a catalyst at a molar ratio of the silane compound (II) to the silane compound (I) of 9 or less, and a weight average molecular weight of 30,000. or less, to the moles X of oR ³ groups bonded directly to silicon atoms silane compound (I) and the silane compound (II) has, moles of oR ³ groups bonded directly to silicon atoms condensate (a) has The ratio Y / X of the number Y is 0.2 or less.

<(A) Condensate>
The silane compound (I) having a hydrolyzable silyl group has the following general formula (I):
_{^{R 1 - (SiR 2 a (}} OR 3) 3-a) (I)
(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms whose terminal is substituted with an epoxy structure-containing group, and R ² is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or 6 carbon atoms. A monovalent hydrocarbon group selected from an aryl group having ˜25 and an aralkyl group having 7 to 12 carbons, and R ³ is each independently a hydrogen atom or an alkyl group having 1 to 10 carbons. It is an integer of ~ 2.

The silane compound (II) having a hydrolyzable silyl group has the following general formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(Wherein, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and is selected from substituted aryl group, .R ² are each independently a group having no epoxy structure-containing group And a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and R ³ is independently A hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2)
It is represented by

Specific examples of the alkyl group in which the terminal in R ¹ of the general formula (I) is substituted with an epoxy structure-containing group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, Examples thereof include an isoamyl group, a hexyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a heptyl group, an isoheptyl group, an n-octyl group, an isooctyl group, and a 2-ethylhexyl group.

The epoxy structure-containing group in R ¹ of the general formula (I) only needs to contain an epoxy group, and examples thereof include an epoxy group, a glycidyl ether group, and an epoxycyclohexyl group.

R ^{2 in the} general formula (I) is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. Examples of such hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, phenyl, tolyl, xylyl, naphthyl, Examples include a benzyl group and a phenethyl group.

R ^{3 in the} general formulas (I) and (II) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group. From the viewpoint of easily hydrolyzing and condensing a silane compound having a hydrolyzable silyl group, the alkyl group of R ³ preferably has 1 to 3 carbon atoms, most preferably 1.

R ^{4 in the} general formula (II) is a group having no epoxy group, which is selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and a substituted aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an amyl group, an isoamyl group, a hexyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, and a heptyl group. , Isoheptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, and the like. Examples of the substituent of the alkyl group include a thiol group, an amino group, an isocyanate group, a (meth) acryloyl group, a phenyl group, and a chloro group. Examples of the alkenyl group include vinyl group, allyl group, 1-methylethenyl group, 2-methylethenyl group, 2-propenyl group, 1-methyl-3-propenyl group, 3-butenyl group, 4-pentenyl group, and 5-hexenyl. Group, cyclohexenyl group, bicyclohexenyl group, 6-heptenyl group, 7-octenyl group, decenyl group, pentadecenyl group, eicocenyl group, tricocenyl group and the like. Examples of the substituted aryl group include a styryl group.

Among these, from the point that the storage stability is good, the curing rate is high, and the occurrence of cracks in the obtained coating film can be suppressed, R ⁴ is an unsubstituted alkyl group, and has 3 to 10 carbon atoms. It is preferable that it is a C3 or more and 6 or less alkyl group.
In the case of a substituted alkyl group, the alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and the substituent includes a phenyl group, a cyclohexyl group, and (meth) acryloyl. Groups are preferred.
When it is an alkenyl group, a vinyl group or an allyl group is preferred. As the substituted aryl group, a styryl group is preferable.
If the unsubstituted alkyl group has 2 or less carbon atoms, or if the substituted alkyl group is not bulkier than the phenyl group, cyclohexyl group, or (meth) acryloyl group, the cross-linked structure becomes dense during crosslinking, and the gel It may become. Moreover, when the carbon number of the alkyl group is 11 or more, or when the substituent is a substituted alkyl group and is bulkier than the phenyl group, cyclohexyl group, or (meth) acryloyl group, the hydrophobicity increases and the hydrolysis rate increases. It may be extremely reduced or the curing rate may be reduced.

  A in general formula (I) and general formula (II) is an integer of 0 to 2, and is appropriately selected according to the physical properties required for the curable composition.

Specific examples of the silane compound (I) include, for example, 1-glycidyloxymethyltrimethoxysilane, 1-glycidyloxymethylmethyldimethoxysilane, 1-glycidyloxymethyltriethoxysilane, 1-glycidyloxymethylmethyldiethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxy Propylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 4-glycidyloxybutyltrimethoxy Orchid, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 6-glycidyloxyhexyltrimethoxysilane, 6-glycidyloxyhexylmethyldimethoxysilane, 6- Glycidyloxyhexyltriethoxysilane, 6-glycidyloxyhexylmethyldiethoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 8-glycidyloxyoctylmethyldimethoxysilane, 8-glycidyloxyoctyltriethoxysilane, 8-glycidyloxyoctylmethyl Diethoxysilane,
1- (3,4-epoxycyclohexyl) methyltrimethoxysilane, 1- (3,4-epoxycyclohexyl) methylmethyldimethoxysilane, 1- (3,4-epoxycyclohexyl) methyltriethoxysilane, 1- (3 4-epoxycyclohexyl) methylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propylmethyldimethoxy Silane, 3 (3,4-epoxycyclohexyl) propyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propylmethyldiethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4 -Epoxycyclohexyl) butylmethyldimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butylmethyldiethoxysilane, 6- (3,4-epoxycyclohexyl) Hexyltrimethoxysilane, 6- (3,4-epoxycyclohexyl) hexylmethyldimethoxysilane, 6- (3,4-epoxycyclohexyl) hexyltriethoxysilane, 6- (3,4-epoxycyclohexyl) hexylmethyldiethoxysila 8- (3,4-epoxycyclohexyl) octyltrimethoxysilane, 8- (3,4-epoxycyclohexyl) octylmethyldimethoxysilane, 8- (3,4-epoxycyclohexyl) octyltriethoxysilane, 8- (3 , 4-epoxycyclohexyl) octylmethyldiethoxysilane,
Epoxytrimethoxysilane, epoxymethyldimethoxysilane, epoxytriethoxysilane, epoxymethyldiethoxysilane, 1-epoxymethyltrimethoxysilane, 1-epoxymethylmethyldimethoxysilane, 1-epoxymethyltriethoxysilane, 1-epoxymethylmethyl Diethoxysilane, 2-epoxyethyltrimethoxysilane, 2-epoxyethylmethyldimethoxysilane, 2-epoxyethyltriethoxysilane, 2-epoxyethylmethyldiethoxysilane, 3-epoxypropyltrimethoxysilane, 3-epoxypropylmethyl Dimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxypropylmethyldiethoxysilane, 4-epoxybutyltrimethoxysilane, 4-epoxybutylmethan Rudimethoxysilane, 4-epoxybutyltriethoxysilane, 4-epoxybutylmethyldiethoxysilane, 6-epoxyhexyltrimethoxysilane, 6-epoxyhexylmethyldimethoxysilane, 6-epoxyhexyltriethoxysilane, 6-epoxyhexylmethyl Examples include diethoxysilane, 8-epoxyoctyltrimethoxysilane, 8-epoxyoctylmethyldimethoxysilane, 8-epoxyoctyltriethoxysilane, and 8-epoxyoctylmethyldiethoxysilane.

As described above, from the viewpoint of easily hydrolyzing and condensing a silane compound having a hydrolyzable silyl group, the alkyl group of R ³ in the general formula (I) preferably has 1 to 3 carbon atoms, most preferably 1 It is. Further, from the viewpoint of the reactivity (mobility) of the epoxy group at the time of curing, the number of carbon atoms of the alkylene group that bonds the epoxy group and the silicon atom is important, and the number of carbon atoms is preferably 1 to 6, more preferably 2 or 3.

In combination with the above viewpoint, the silane compound (I) includes 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 3- (3,4 -Epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propylmethyldimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane 3-glycidyloxypropylmethyldimethoxysilane is preferred. Among these, compounds in which R ¹ is a 2- (3,4-epoxycyclohexyl) ethyl group and a 3-glycidyloxypropyl group are preferable.

Among the silane compounds (II), those in which R ⁴ in the general formula (II) is an unsubstituted alkyl group include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Methoxysilane, ethylmethyldimethoxysilane, ethyltriethoxysilane, ethylmethyldiethoxysilane, propyltrimethoxysilane, propylmethyldimethoxysilane, propyltriethoxysilane, propylmethyldiethoxysilane, butyltrimethoxysilane, butylmethyldimethoxysilane, Butyltriethoxysilane, butylmethyldiethoxysilane, hexyltrimethoxysilane, hexylmethyldimethoxysilane, hexyltriethoxysilane, hexylmethyldiethoxysilane, oxy Examples include tiltrimethoxysilane, octylmethyldimethoxysilane, octyltriethoxysilane, and octylmethyldiethoxysilane.

Further, R ⁴ in the general formula (II) is as those substituted alkyl group are given below. Here, the substituent is not particularly limited, but a thiol group, an isocyanate group, a (meth) acryloyl group, a phenyl group, a cyclohexyl group, and a chloro group are preferable from the viewpoint of availability.
However, among these substituents, the thiol (mercapto) group may react with the epoxy group during the hydrolysis / condensation reaction of the hydrolyzable silyl group. It is preferable to select an epoxysilane compound having an epoxycyclohexyl group that is not susceptible to nuclear attack.
On the other hand, since a silane compound having an amino group or an acid anhydride group as a substituent has a high possibility of reacting with an epoxy group during hydrolysis / condensation reaction of a hydrolyzable silyl group over a mercapto group, It is not preferable to use it in this application.

Examples of the compound in which R ⁴ is a thiol group-substituted alkyl group include 1-mercaptomethyltrimethoxysilane, 1-mercaptomethylmethyldimethoxysilane, 1-mercaptomethyltriethoxysilane, 1-mercaptomethylmethyldiethoxysilane, and 2-mercapto. Ethyltrimethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Triethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 4-mercaptobuty Lutriethoxysilane, 4-mercaptobutylmethyldiethoxysilane, 6-mercaptohexyltrimethoxysilane, 6-mercaptohexylmethyldimethoxysilane, 6-mercaptohexyltriethoxysilane, 6-mercaptohexylmethyldiethoxysilane, 8-mercaptooctyl Examples include trimethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctyltriethoxysilane, and 8-mercaptooctylmethyldiethoxysilane.

Examples of the compound in which R ⁴ is an isocyanate group-substituted alkyl group include 1-isocyanate methyltrimethoxysilane, 1-isocyanatemethylmethyldimethoxysilane, 1-isocyanatemethyltriethoxysilane, 1-isocyanatemethylmethyldiethoxysilane, and 2-isocyanate. Ethyltrimethoxysilane, 2-isocyanatoethylmethyldimethoxysilane, 2-isocyanateethyltriethoxysilane, 2-isocyanateethylmethyldiethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropyl Triethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 4-isocyanatobutyltrimethoxysilane, 4- Isocyanatobutylmethyldimethoxysilane, 4-isocyanatobutyltriethoxysilane, 4-isocyanatobutylmethyldiethoxysilane, 6-isocyanatohexyltrimethoxysilane, 6-isocyanatohexylmethyldimethoxysilane, 6-isocyanatohexyltriethoxysilane, 6-isocyanate Examples include hexylmethyldiethoxysilane, 8-isocyanate octyltrimethoxysilane, 8-isocyanatooctylmethyldimethoxysilane, 8-isocyanate octyltriethoxysilane, and 8-isocyanate octylmethyldiethoxysilane.

Examples of the compound in which R ⁴ is a (meth) acryloyl group-substituted alkyl group include 1- (meth) acryloyloxymethyltrimethoxysilane, 1- (meth) acryloyloxymethylmethyldimethoxysilane, and 1- (meth) acryloyloxymethyltri Ethoxysilane, 1- (meth) acryloyloxymethylmethyldiethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 2- (meth) acryloyloxyethylmethyldimethoxysilane, 2- (meth) acryloyloxyethyltriethoxy Silane, 2- (meth) acryloyloxyethylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acrylic Royloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 4- (meth) acryloyloxybutylmethyldimethoxysilane, 4- (meth) acryloyl Oxybutyltriethoxysilane, 4- (meth) acryloyloxybutylmethyldiethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 6- (meth) acryloyloxyhexylmethyldimethoxysilane, 6- (meth) acryloyloxy Hexyltriethoxysilane, 6- (meth) acryloyloxyhexylmethyldiethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 8- (meth) acryloyloxyoct Methyl dimethoxysilane, 8- (meth) acryloyloxy octyltriethoxysilane, 8- (meth) acryloyloxyoctyl diethoxysilane and the like.

Examples of the compound in which R ⁴ is a phenyl group-substituted alkyl group include benzyltrimethoxysilane, benzyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-phenylpropyltrimethoxysilane, 3-phenylpropylene. Rutriethoxysilane, 4-phenylbutyltrimethoxysilane, 4-phenylbutyltriethoxysilane, 5-phenylpentyltrimethoxysilane, 5-phenylpentyltriethoxysilane, 6-phenylhexyltrimethoxysilane, 6-phenylhexyltriethoxy And silane.

Examples of the compound in which R ⁴ is a cyclohexyl group-substituted alkyl group include cyclohexylmethyltrimethoxysilane, cyclohexylmethyltriethoxysilane, 2-cyclohexylethyltrimethoxysilane, 2-cyclohexylethyltriethoxysilane, 3-cyclohexylpropyltrimethoxysilane, 3-cyclohexylpropyltriethoxysilane, 4-cyclohexylbutyltrimethoxysilane, 4-cyclohexylbutyltriethoxysilane, 5-cyclohexylpentyltrimethoxysilane, 5-cyclohexylpentyltriethoxysilane, 6-cyclohexylhexyltrimethoxysilane, 6- Examples include cyclohexylhexyltriethoxysilane.

Examples of the compound in which R ⁴ is a chloro group-substituted alkyl group include chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, and 3-chloropropyltrimethoxy. Silane, 3-chloropropyltriethoxysilane, 4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 5-chloropentyltrimethoxysilane, 5-chloropentyltriethoxysilane, 6-chlorohexyltrimethoxysilane, Examples thereof include 6-chlorohexyltriethoxysilane.

Examples of the compound in which R ⁴ is an alkenyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyltriethoxysilane, allylmethyldi Ethoxysilane, 1-oxetanyloxymethyltrimethoxysilane, 1-oxetanyloxymethylmethyldimethoxysilane, 1-oxetanyloxymethyltriethoxysilane, 1-oxetanyloxymethylmethyldiethoxysilane, 2-oxetanyloxyethyltrimethoxysilane, 2 -Oxetanyloxyethylmethyldimethoxysilane, 2-oxetanyloxyethyltriethoxysilane, 2-oxetanyloxyethylmethyldiethoxysilane, 3 -Oxetanyloxypropyltrimethoxysilane, 3-oxetanyloxypropylmethyldimethoxysilane, 3-oxetanyloxypropyltriethoxysilane, 3-oxetanyloxypropylmethyldiethoxysilane, 4-oxetanyloxybutyltrimethoxysilane, 4-oxetanyloxybutyl Methyldimethoxysilane, 4-oxetanyloxybutyltriethoxysilane, 4-oxetanyloxybutylmethyldiethoxysilane, 6-oxetanyloxyhexyltrimethoxysilane, 6-oxetanyloxyhexylmethyldimethoxysilane, 6-oxetanyloxyhexyltriethoxysilane, 6-oxetanyloxyhexylmethyldiethoxysilane, 8-oxetanyloxyoctyltrimethoxysilane, 8 Oxetanylmethyl oxy-octyl methyl dimethoxy silane, 8-oxetanyl oxy octyltriethoxysilane, 8-oxetanylmethyl oxy-octyl methyl diethoxy silane, and the like.

Examples of the compound in which R ⁴ is a substituted aryl group include p-styryltrimethoxysilane and p-styryltriethoxysilane.

  In the condensate (A) of the present invention, each of the silane compounds (I) and (II) may be contained alone or in combination of two or more.

In the curable composition of the present invention, when the scratch resistance and chemical resistance are required as the physical properties of the cured product, it is important that crosslinking of the epoxy group in the condensate (A) proceeds sufficiently, and the silane compound Hydrolysis / condensation under the condition that the molar ratio of silane compound (II) to (I) [= number of moles of silane compound (II) / number of moles of silane compound (I)] is 0 or more and 9 or less is a condensate ( It is preferred to obtain A).
Even if the molar ratio of the functional group other than the epoxy structure-containing group exceeds 9, a cured product having high scratch resistance and chemical resistance can be obtained, but there may be a problem in other performance such as curing shrinkage. . For example, when the molar ratio of the (meth) acryloyl group exceeds 9, a cured product having high scratch resistance and chemical resistance can be obtained, but since the curing shrinkage is larger than the crosslinking of the epoxy group, The warp of the resin sheet becomes large, and cracks may occur in the hard coat layer when an environmental load due to heat or humidity is applied.
On the other hand, since curing with an epoxy structure-containing group involves a ring-opening reaction, there is little shrinkage, and a cured product can be obtained with little curing shrinkage.

  Further, for example, when methyltrimethoxysilane is used as the silane compound (II), the bulk is low relative to the organic group of the silane compound (I), and in addition to not inhibiting the curing of the epoxy group, in one molecule High scratch resistance and high chemical resistance can be expressed in combination with a high siloxane ratio (a ratio of the sum of Si and O in the molecule) and a high siloxane crosslinking density in the resulting condensate (A). Considering the above viewpoint, the molar ratio is more preferably 0 or more and 7 or less, further preferably 0 or more and 6 or less, and particularly preferably 0 or more and 5 or less.

The condensation degree of the condensate (A) of the present invention is preferably a 2-200 mer in which a silane compound is hydrolyzed and condensed to form a siloxane bond, and a 4-100 mer is more preferable.
When the condensation degree of the condensate (A) is smaller than the tetramer, there is a concern that the condensate (A) volatilizes at a high temperature or under a high reduced pressure. However, when the condensate (A) contains the silane compound (II), the average number of epoxy groups per molecule is preferably 2 or more.
Moreover, when the condensation degree of a condensate (A) is larger than a 200-mer, there exists a possibility that compatibility with an organic solvent, hardened | cured material, etc. may fall remarkably.

The weight average molecular weight of the condensate (A) of the present invention is preferably 500 or more, more preferably 1,000 or more, and further preferably 2,000 or more. Further, the weight average molecular weight is preferably 30,000 or less, more preferably 28,000 or less, and further preferably 25,000 or less.
If the weight average molecular weight of the condensate (A) is less than 500 (or less than 1,000), it may be volatile, and part or all of it may volatilize before curing at high temperature or under high reduced pressure. is there. If the weight average molecular weight exceeds 30,000, the compatibility with organic solvents, cured products and the like is lowered, and there is a risk of clouding when forming a coating film.
The weight average molecular weight is a weight average molecular weight measured by GPC.

  Here, the weight average molecular weight of the siloxane resin can be controlled by appropriately selecting the amount of water used in the reaction and the type and amount of the catalyst. For example, the weight average molecular weight can be increased by increasing the amount of water initially charged.

The silicon atom of the condensate (A) with respect to the number of moles X of the OR ³ group directly bonded to the silicon atom of the silane compound (I) and the silane compound (II) as the raw material of the condensate (A) of the present invention The ratio Y / X of the number of moles Y of the OR ³ groups directly bonded is preferably 0.5 or less, more preferably 0.3 or less, particularly preferably 0.2 or less, and substantially 0. Is most preferred.
If Y / X exceeds 0.5, the coating film may shrink over time after curing to cause cracks, or the storage stability of the epoxy group may be impaired. In particular, when Y / X is 0.2 or less, reaction with time after curing hardly occurs.
Y / X can be determined by measuring with ¹ H-NMR and ²⁹ Si-NMR.
Here, Y / X can be made 0.5 or less by appropriately selecting the amount of water to be used and the type and amount of the catalyst. For example, as the amount of water increases, hydrolysis is promoted and Y / X becomes a lower value.

  From the viewpoint of increasing the crosslink density due to the epoxy groups in the cured product and improving the hardness and scratch resistance of the cured product, the residual ratio of the epoxy structure-containing groups in the condensate (A), that is, the silane that is the raw material The ratio of the number of moles of the epoxy structure-containing group in the condensate (A) to the number of moles of the epoxy structure-containing group of the compound (I) is preferably higher.

Specifically, the residual ratio of the epoxy structure-containing group of the present invention is preferably 20% or more, more preferably 40% or more, and further preferably 60% or more.
The residual ratio of the epoxy structure-containing group can be determined by ¹ HNMR measurement.

Moreover, even when the residual ratio of the epoxy structural group in the condensate (A), and even when the number of epoxy structural groups in one molecule is small, when R ¹ , R ² , R ⁴ are not bulky groups, Since the crosslinking density resulting from the epoxy group in the cured product can be increased, R ¹ , R ² and R ⁴ are preferably groups that are not bulky.

<Hydrolysis / condensation catalyst>
In synthesizing the condensate (A) of the present invention, the hydrolysis / condensation reaction is preferably carried out using a neutral salt or a basic compound as a catalyst.
By carrying out the hydrolysis / condensation reaction using a neutral salt or a basic compound as a catalyst, it becomes difficult to deactivate the epoxy group before and after the hydrolysis / condensation reaction and during storage.
On the other hand, when the hydrolysis / condensation reaction is carried out using an acidic compound as a catalyst, the hydrolysis of the epoxy group tends to occur at the same time, and the residual rate of the epoxy structural group decreases. In addition, the resulting condensate (A) is acidic, and if the storage container is made of metal, it tends to cause rust, and if it is a resin, it tends to cause degradation due to hydrolysis, so it needs to go through a removal step and a neutralization step. . On the other hand, the condensate (A) obtained using a neutral salt or a basic compound as a catalyst can be suitably used because it has a low corrosive action on materials used as a general-purpose storage container.

  Furthermore, when the epoxy group is cured by cationic polymerization, it is not preferable that the residual catalyst acts as a cation trapper. From this viewpoint, it may be preferable to use a neutral salt as a catalyst rather than a basic compound.

<(C) Neutral salt>
The neutral salt used in the present invention is a normal salt composed of a strong acid and a strong base. For example, as a cation, a group 1 element ion, a group 2 element ion, a tetraalkylammonium ion, or a guanidinium ion. And a salt composed of a combination of any one selected from the group consisting of Group 17 element ions excluding fluoride ions, sulfate ions, nitrate ions and perchlorate ions as anions.

As a specific compound of the neutral salt in the present invention, for example,
Lithium chloride, sodium chloride, potassium chloride, rabidium chloride, cesium chloride, francium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, radium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, Tetrabutylammonium chloride, tetrapentylammonium chloride, tetrahexylammonium chloride, guanidinium chloride;
Lithium bromide, sodium bromide, potassium bromide, rabidium bromide, cesium bromide, francium bromide, beryllium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, radium bromide, bromide Tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, guanidinium bromide;
Lithium iodide, sodium iodide, potassium iodide, rabidium iodide, cesium iodide, francium iodide, beryllium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, radium iodide, iodide Tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrapentylammonium iodide, tetrahexylammonium iodide, guanidinium iodide;
Lithium sulfate, sodium sulfate, potassium sulfate, rabidium sulfate, cesium sulfate, francium sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, radium sulfate, tetramethylammonium sulfate, tetraethylammonium sulfate, tetrapropylammonium sulfate, Tetrabutylammonium sulfate, tetrapentylammonium sulfate, tetrahexylammonium sulfate, guanidinium sulfate;
Lithium nitrate, sodium nitrate, potassium nitrate, rabidium nitrate, cesium nitrate, francium nitrate, beryllium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, radium nitrate, tetramethylammonium nitrate, tetraethylammonium nitrate, tetrapropylammonium nitrate, nitric acid Tetrabutylammonium nitrate, tetrapentylammonium nitrate, tetrahexylammonium nitrate, guanidinium nitrate;
Lithium perchlorate, sodium perchlorate, potassium perchlorate, rabidium perchlorate, cesium perchlorate, francium perchlorate, beryllium perchlorate, magnesium perchlorate, calcium perchlorate, strontium perchlorate, Barium perchlorate, radium perchlorate, tetramethylammonium perchlorate, tetraethylammonium perchlorate, tetrapropylammonium perchlorate, tetrabutylammonium perchlorate, tetrapentylammonium perchlorate, tetrahexylammonium perchlorate Guanidinium perchlorate, and the like. These neutral salts can be used alone or in combination of two or more.

  Among these neutral salts, from the viewpoint of use as a catalyst, group 17 element ions having high nucleophilicity are more preferable as anions, and cations are not bulky so as not to inhibit nucleophilic action. More preferred are group 1 element ions and group 2 element ions.

  Furthermore, considering availability and safety during handling, neutral salts include lithium chloride, sodium chloride, potassium chloride, rabidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, lithium bromide, bromide. Sodium, potassium bromide, rabidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, lithium iodide, sodium iodide, potassium iodide, rabidium iodide, cesium iodide, magnesium iodide, Calcium iodide and strontium iodide are particularly preferred.

In the present invention, the greater the amount of neutral salt used, the more the hydrolysis / condensation reaction of the silane compound will be promoted. .
The amount of the neutral salt used in the present invention is preferably 0.000001 mol or more and 0.1 mol or less, more preferably 0.000001 mol or more and 0.01 mol or less with respect to 1 mol of the hydrolyzable silyl group of the silane compound. Preferably, 0.000005 mol to 0.05 mol is particularly preferable, and 0.000005 mol to 0.01 mol is most preferable.

<Basic compound>
The basic compound used in the present invention is not particularly limited as long as it is basic. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, carbonate Inorganic bases such as potassium hydrogen and ammonia;
Organic bases such as triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used.
Among these, an inorganic base is preferable in consideration of ease of removal from the condensate (A).

  In the present invention, the larger the amount of the basic compound used, the more the hydrolysis / condensation reaction of the silane compound is promoted. However, when the transparency of the condensate and the purification process are taken into account, the smaller the amount added, the better. .

  The amount of the basic compound used in the present invention is preferably 0.000001 mol or more and 0.1 mol or less, more preferably 0.000001 mol or more and 0.01 mol or less with respect to 1 mol of the hydrolyzable silyl group of the silane compound. Preferably, 0.000005 mol to 0.05 mol is particularly preferable, and 0.000005 mol to 0.01 mol is most preferable.

  When considered as a hydrolysis / condensation reaction catalyst for a silane compound containing an epoxy structural group, the residual ratio of the epoxy structural group after the hydrolysis / condensation reaction is high, and the corrosivity of the condensate (A) to the storage container is lower. In addition, a neutral salt is preferred from the viewpoint that the adverse effects on the human body are often low in the handling process.

In the production of the condensate (A) of the present invention, the amount of water necessary for the hydrolysis / condensation reaction is preferably 0.2 to 20 equivalents relative to the OR ³ group directly bonded to the silicon atom, 0.4 to 3 equivalents are more preferable, and 0.45 to 2 equivalents are more preferable.
If the amount of water is less than 0.2 equivalents, the shrinkage of curing may be increased during hard coat curing due to the remaining OR ³ groups without hydrolysis. If the amount of water exceeds 20 equivalents, the hydrolysis / condensation reaction rate is too high to produce a high molecular weight condensate, which may reduce the physical properties and transparency of the coating film.

In the production of the condensate (A) of the present invention, it is preferable to carry out the reflux of a diluting solvent and alcohol generated by hydrolysis in consideration of production safety.
The dilution solvent used in the production of the condensate (A) of the present invention refers to an alcohol or ether compound, and is preferably water-soluble.
The reason for this is that the silane compounds (I) and (II) used in the present invention often have low compatibility with the neutral salt (A) or water used for hydrolysis, so that the reaction can proceed smoothly. This is because the reaction solution is preferably compatible.
On the other hand, ketone and ester solvents are not suitable because they have a carbonyl group and easily inhibit the reaction.

The boiling point of the dilution solvent used in the production of the condensate (A) of the present invention is preferably 40 ° C or higher and 200 ° C or lower, more preferably 50 ° C or higher and 200 ° C or lower, even more preferably 60 ° C or higher and 250 ° C or lower, 60 ° C. or higher and 230 ° C. or lower is particularly preferable.
If the boiling point of the diluting solvent is less than 40 ° C., it tends to be in a reflux state at a low temperature and hinders the reaction. If it exceeds 200 ° C., it is too high to be difficult to remove after the reaction. It may be necessary to incorporate this complicated process.

Specific examples of the dilution solvent used in the production of the condensate (A) of the present invention include, for example, methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 2-methyl-2-propanol, 1-methoxy- Examples include 2-propanol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, and propylene glycol dimethyl ether.
These dilution solvents may be used alone or in combination of two or more.

The amount of the dilution solvent used in the production of the condensate (A) of the present invention is preferably such that the total amount of the silane compounds (I) and (II) is 90% by mass or less as the total amount of water and the dilution solvent, and 30% by mass. % To 80% by mass is more preferable, and 40% to 80% by mass is particularly preferable.
When there is too much usage-amount of a dilution solvent, there exists a concern that the density | concentration of the silane compound in a reaction system will fall, and reaction rate may fall. On the other hand, it is important to select an appropriate amount because it is possible to improve the compatibility between water and the silane compound, and to suppress the increase in viscosity in the system accompanying the progress of the reaction and to suppress the decrease in the reaction rate. It is.
On the other hand, when one or both of the silane compounds (I) and (II) have high hydrophilicity, the progress of the condensation reaction after hydrolysis may be slow. This is because silanol groups generated by hydrolysis are dispersed and stabilized for reasons such as hydration, and contact / condensation reactions between silanol groups are less likely to occur. In such a case, the reaction may be promoted by adding a hydrophobic solvent.

The reaction temperature in the production of the condensate (A) of the present invention is preferably in the range of 40 to 200 ° C, more preferably in the range of 50 to 250 ° C, and still more preferably in the range of 60 to 230 ° C.
When the reaction temperature is lower than 40 ° C., the catalytic activity of the neutral salt tends to decrease and the reaction time tends to increase significantly. When the reaction temperature is higher than 200 ° C., the organic substituent undergoes side reaction. There is concern that it will wake you up.

<(B) Curing agent for curing epoxy group>
There is no restriction | limiting in particular as a hardening | curing agent (B) which hardens an epoxy group with respect to the epoxy group containing siloxane type condensate (A) of this invention, Generally what is known as an epoxy resin hardening | curing agent can be used. .
Examples of preferable curing agents include acid anhydride curing agents, cationic polymerization initiators, organic phosphorus compounds, amine curing agents, and tertiary amines.

When the curing agent (B) is a curing agent that promotes the polymerization of epoxy groups in the condensate (A) (hereinafter sometimes referred to as “polymerization type curing agent”), 0.5 to 10 parts by weight Is preferable, and 0.5 to 5 parts by weight is more preferable.
When the amount of the curing agent (polymerization type curing agent) that promotes the polymerization of the epoxy group is less than 0.5 parts by weight, the polymerization of the epoxy group may not proceed sufficiently, and when the amount exceeds 10 parts by weight In some cases, the polymerization degree of the epoxy group does not sufficiently proceed due to an increase in the polymerization starting point. Moreover, it may remain in the coating film as a plasticizer without acting as a polymerization starting point.

In the case where the curing agent (B) has active hydrogen and is a curing agent that undergoes an addition reaction with the epoxy group in the condensate (A) (hereinafter sometimes referred to as “addition-type curing agent”). 10 to 150 parts by weight, preferably 30 to 150 parts by weight.
If the amount of the curing agent (addition type curing agent) that undergoes addition reaction with the epoxy group is less than 10 parts by weight, curing may not proceed sufficiently, and if it exceeds 150 parts by weight, the curing agent is excessive. However, although the crosslinking of the epoxy group proceeds sufficiently, the remaining curing agent (B) may become a plasticizer, and the crosslinking density may not be sufficiently high.

  The details of the acid anhydride curing agent, cationic polymerization initiator, organophosphorus compound, and other usable curing agents are described below.

(B-1) Acid anhydride curing agent The curing agent that cures the epoxy group in the present invention is preferably an acid anhydride curing agent from the viewpoint of heat resistance. The acid anhydride curing agent is classified into a polymerization type / addition type composite curing agent.

Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazeline acid anhydride. , Polysebacic anhydride, poly (ethyl octadecanedioic anhydride), poly (phenylhexadecanedioic anhydride), tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthal Acid anhydride, methyl hymic acid anhydride, tetrahydrophthalic acid anhydride, trialkyltetrahydrophthalic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bis trimellitate dianhydride, head Acid anhydride Nadic acid anhydride, methyl nadic acid anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxyl -1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and the like.
These acid anhydride curing agents may be used alone, or two or more kinds may be used in any combination and blending amount.

  When using an acid anhydride curing agent, it is preferable to use an equivalent ratio of the functional group in the curing agent to the epoxy group in the condensate (A) in the range of 0.5 to 10. It is preferable for the equivalent ratio to be in the range of 0.5 to 110 because unreacted epoxy groups and functional groups of the curing agent hardly remain.

(B-2) Cationic polymerization initiator As the curing agent for curing the epoxy group in the present invention, a cationic polymerization initiator is preferred from the viewpoint of physical properties such as wear resistance and chemical resistance of the resulting cured product. The cationic polymerization initiator is classified as a polymerization type curing agent.

  Examples of the cationic polymerization initiator include a thermal cationic polymerization initiator that generates a cationic species and / or a Lewis acid by heat, a photocationic polymerization initiator that generates a cationic species and / or a Lewis acid by light, and the like. In addition, there is no clear division between a thermal cationic polymerization initiator and a photocationic polymerization initiator, and some of them act as curing agents for both heat and light.

Examples of the thermal cationic polymerization initiator include onium salt-based cationic polymerization initiators such as sulfonium salts, ammonium salts, pyridinium salts, phosphonium salts, iodonium salts;
Examples include a combination of an aluminum complex and a silanol compound, and an aluminum complex composite cationic polymerization initiator such as a combination of an aluminum complex and bisphenol S.
Examples of the photocationic polymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, and the like.

  The cationic polymerization initiator can be obtained as a commercial product. For example, FC-520 [more than 3M company], UVR-6990, UVR-6974 [more than Union Carbide company], UVE-1014, UVE-1016 [more than General Electric company], KI-85 [ Degussa, Inc.], SP-15, SP-170 [above, Asahi Denka Co., Ltd.], SI-60L, SI-80L, SI-100L [above, Sanshin Kagaku Kogyo Co., Ltd.], CPI -100P, CPI-101A, CPI-200K, CPI-200S [above, manufactured by San Apro Co., Ltd.], WPI-124, WPI-113, WPI-116, WPI-169, WPI-170, WPI-124 [above, Wako Pure Chemical Industries, Ltd.], Rhodesil 2074 [above, Rhodia, Inc.], IRGACURE PAG250, PAG290 [above, B SF Co., Ltd.], and the like.

Among these cationic polymerization initiators, onium salts are preferable from the viewpoint of handleability. Furthermore, among onium salts, diazonium salts, iodonium salts, sulfonium salts, and phosphonium salts are particularly preferable.
These cationic polymerization initiators may be used alone, or two or more kinds may be used in any combination and blending amount.

The addition amount of the cationic polymerization initiator needs to be adjusted according to the generation amount and generation rate of the acid to be generated. Preferably, 0.5-5 weight part is more preferable, and 0.1-5 weight part is further more preferable.
When the addition amount of the cationic polymerization initiator is in the range of 0.01 to 15 parts by mass, the abrasion resistance and chemical resistance of the cured epoxy resin are improved, which is preferable.

Furthermore, when cured by cationic ring-opening polymerization using a super strong acid such as fluorophosphate, fluoroantimonate or fluoroborate, the polymerization of the epoxy group proceeds rapidly due to its high acid strength. A cured product having high wear resistance and chemical resistance can be obtained.
Further, a cured product obtained by using a cationic polymerization initiator as a curing agent (B) for curing an epoxy group has a characteristic of expanding at the time of curing.

(B-3) Organophosphorus compound The curing agent for curing the epoxy group in the present invention is preferably an organophosphorus compound from the viewpoint of promoting the effect reaction. The organophosphorus compound is classified as a polymerization type curing agent.

Examples of organic phosphorus compounds include organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; methyltributylphosphonium dimethylphosphate, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyl Examples thereof include phosphonium salts such as triphenylborate and tetrabutylphosphonium / tetrabutylborate.
These organophosphorus compounds may be used alone, or two or more of them may be used in any combination and blending amount.

  The amount of the organic phosphorus compound added needs to be adjusted according to the amount of acid generated and the rate of generation, but is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the condensate (A) (solid content). 0.5 to 5 parts by weight is more preferable.

(B-4) Amine-based curing agent As the curing agent for curing the epoxy group in the present invention, an amine-based curing agent (excluding tertiary amine) is preferable from the viewpoint of availability and cost. The amine curing agent is classified as an addition type curing agent.

  Examples of amine-based curing agents (excluding tertiary amines) include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like.

Examples of the aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, Examples thereof include bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and tetra (hydroxyethyl) ethylenediamine.
Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like.

  Examples of alicyclic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3 -Aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like.

Examples of aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2 , 4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4′-diaminodiphenyl Sulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ) Ethylamine, diaminodi Examples thereof include ethyldimethyldiphenylmethane and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene.
These amine-based curing agents may be used alone, or two or more of them may be used in any combination and blending amount.

  The amine curing agent is preferably 10 to 150 parts by weight, and more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the condensate (A) (solid content).

(B-5) Tertiary amine As the curing agent for curing the epoxy group in the present invention, a tertiary amine is preferable from the viewpoint of availability and cost. The tertiary amine is classified as a polymerization type curing agent.
Examples of the tertiary amine include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like. Can be mentioned.
These tertiary amines may be used alone, or two or more thereof may be used in any combination and mixing ratio.

  The tertiary amine is preferably 0.5 to 10 parts by weight and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the condensate (A) (solid content).

(B-6) Other curing agent As the curing agent for curing the epoxy group in the present invention, an acid anhydride curing agent, a cationic polymerization initiator and an organic phosphorus compound, an amine curing agent (excluding tertiary amine) ), Other than tertiary amines, for example, amide-based curing agents, phenol-based curing agents, imidazoles, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanates. Examples thereof include a system curing agent and a blocked isocyanate curing agent. These other curing agents may be used alone or in combination of two or more.

  Further, when the condensate (A) of the present invention is cured by heat or light, a (meth) acrylate compound (C), an epoxy compound (D), and metal oxide fine particles (E) are mixed as necessary. It can be cured.

<(C) (Meth) acrylate compound>
The (meth) acrylate compound (CD) in the present invention can be used for the purpose of increasing the crosslinking density immediately after curing by light or heat by the reaction heat at the time of curing and improving the adhesion to the organic substrate.

  As the component (C), there is no particular problem as long as it is a compound having a (meth) acryloyl group used in normal radical curing.

  Specific examples of the (meth) acrylate compound (C) include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. , Di (meth) acrylates such as tripropylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triisocyanuric acid tri (meth) ) Tri (meth) acrylates such as acrylate; Tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate and tetramethylolmethanetetra (meth) acrylate; Toruhekisa (meth) 4 or more functional (meth) acrylates such as acrylate.

Furthermore, as commercial products, NK Oligo UA-122P, NK Oligo U-4HA, NK Oligo U-6LPA (above, Shin-Nakamura Chemical Co., Ltd.), AT-600, UA-306H, UA-510H (above, Kyoeisha Chemical) (Manufactured by Co., Ltd.), polyfunctional urethane acrylates such as EBECRYL220, EBECRYL8210, and EBECRYL8311 (above, manufactured by Daicel Cytec Co., Ltd.); NK oligo EA-1020, NK oligo EA-6310, NK oligo EA-7120 (above, Shin-Nakamura Chemical Co., Ltd.), epoxy ester 70PA and epoxy ester 3002A (above, manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL600 and EBECRYL 6040 (above, manufactured by Daicel-Cytec Co., Ltd.) be able to.
The (meth) acrylate compound (C) may be used alone or in combination.

The mixing ratio of the (meth) acrylate compound (CD) to the condensate (A) in the curable composition of the present invention is preferably 1 to 9900 parts by weight with respect to 100 parts by weight of the condensate (A). 1900 weight part is more preferable, 1-900 weight part is further more preferable, and 10-200 weight part is more preferable.
When the mixing ratio of the component (C) to the condensate (A) is less than 1 part by weight, crosslinking by radical polymerization tends not to proceed sufficiently, and when it exceeds 9900 parts by weight, crosslinking by an epoxy group cannot proceed sufficiently. Tend.

<(D) Epoxy compound not containing silane>
In the present invention, the epoxy compound that does not contain silane as the component (D) can be co-crosslinked with the condensate (A) at the time of curing, and is used for the purpose of reducing the viscosity of the condensate (A) and reducing costs. I can do it.

  The epoxy compound (D) containing no silane is not particularly limited as long as it is a compound having an epoxy group, and known compounds can be used, and include aromatic epoxides, alicyclic epoxides and aliphatic epoxides.

  Examples of the aromatic epoxide include glycidyl ethers of monovalent or polyvalent phenols (phenol, bisphenol A, phenol novolac and compounds obtained by adducting these alkylene oxides) having at least one aromatic ring. As the alicyclic epoxide, a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, etc.) Is mentioned.

  Aliphatic epoxides include aliphatic polyhydric alcohols or polyglycidyl ethers of this alkylene oxide adduct (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), aliphatic polybasic acids. Examples thereof include polyglycidyl esters (such as diglycidyl tetrahydrophthalate) and epoxidized products of long chain unsaturated compounds (such as epoxidized soybean oil and epoxidized polybutadiene).

The mixing ratio of the silane-containing epoxy compound (D) to the condensate (A) in the curable composition of the present invention is preferably 0 to 100 parts by weight with respect to 100 parts by weight of the condensate (A). -70 weight part is more preferable, and 1-50 weight part is further more preferable.
When the mixing ratio of the epoxy compound (D) containing no silane with respect to the condensate (A) exceeds 100 parts by weight, the crosslinking by the epoxy group tends not to proceed sufficiently. This is because most of the epoxy compounds are bifunctional, and there are many compounds having a planar structure such as a bisphenol structure, and in the case of a polyfunctional epoxy compound, a condensate (A ) Due to a decrease in compatibility.

By the way, when a laminated body is used as a transparent member, the condensate (A) and the (meth) acrylate compound (C) or the epoxy compound (D) containing no silane must be compatible.
When not compatible before curing, a cloudy cured product is obtained, and it is difficult to use as a transparent member. In addition, when the cured product is cloudy, the cured product of the condensate (A) and the components (C) and (D) are not bonded to each other, and an interpenetrating network (IPN) can be formed so much. The physical properties such as hardness, scratch resistance, and chemical resistance tend to be slightly deteriorated.
If they are compatible with each other and a transparent cured product is obtained, they can form dispersion / IPN at the nanoscale and exhibit high hardness, high scratch resistance, and high chemical resistance even if they are not bonded to each other. is there.
On the other hand, when they are not bonded to each other and the cured product is not three-dimensionally crosslinked or high molecular weight, even if it is transparent immediately after curing, the IPN is unraveled due to the application of heat and humidity, etc. In some cases, phase separation proceeds and white turbidity may occur.

  From this viewpoint, the (meth) acrylate compound (C) and the epoxy compound (D) not containing silane are preferably low-molecular. More specifically, the molecular weight of the (meth) acrylate compound (C) and the epoxy compound (D) in the present invention is preferably 30000 or less, more preferably 25000 or less, and 20000 or less. Further preferred.

The number of functional groups of the (meth) acrylate compound (C) and the epoxy compound (D) containing no silane in the present invention is preferably 2 or more and less than 200, and more preferably 2 or more and less than 100.
When the number of functional groups is less than 2, the cured product may not be three-dimensionally cross-linked / high molecular weight, and may become cloudy due to heat and humidity even if it is transparent immediately after curing. Moreover, when the number of functional groups exceeds 200, the molecular weight of the (meth) acrylate compound (C) or the epoxy compound (D) containing no silane becomes too large, and there is a concern that they will not be compatible before curing.

<(E) Metal oxide fine particles>
In the condensate (A) of the present invention, metal oxide fine particles (E) can be used as necessary. By blending the metal oxide particles (E), the scratch resistance of the coating film may be further improved.

Examples of the metal oxide fine particles (E) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), tin oxide (SnO ₂ ), zirconia (ZrO ₂ ), zinc oxide (ZnO), and titania (TiO ₂ ). And ITO (tin / indium oxide), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ), and composite fine particles thereof.
Among these, silica, alumina, zirconia, and antimony oxide are preferable from the viewpoint of high hardness. In particular, silica fine particles and alumina fine particles are preferable from the viewpoint of availability, cost, surface hardness and the like, and silica fine particles are particularly preferable.
These metal oxide fine particles may be used alone or in combination of two or more.

The metal oxide fine particles (E) in the present invention are preferably powdery or solvent-dispersed sol.
When the metal oxide fine particles are a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoints of compatibility with other components and dispersibility. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and δ-butyrolactone. And esters such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, and amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. it can. Of these, alcohols, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate are preferable.

The average particle size (average primary particle size) of the metal oxide fine particles (E) in the present invention is preferably 100 nm or less, more preferably 40 nm or less, still more preferably 20 nm or less.
If the average particle diameter of the metal oxide fine particles exceeds 100 nm, the transparency of the resulting coating film tends to be impaired.

  Commercially available silica fine particle dispersions include colloidal silica, methanol silica sol, IPA-ST, MGK-ST, NBA-ST, XBA-ST, DMAC-ST, MIBK-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. (above, manufactured by Nissan Chemical Industries, Ltd.), OSCAL series, GLGCOM series (above, JGC Catalysts & Chemicals) And the like).

  Examples of the powder silica include Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, etc. (above, manufactured by Nippon Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122, etc. Asahi Glass Co., Ltd.), G220A, G220 and the like (above, Nippon Silica Industry Co., Ltd.), SYLYSIA470 (Fuji Silysia Co., Ltd.), SG Flakes (Nihon Sheet Glass Co., Ltd.) and the like.

  Examples of the alumina fine particle dispersion include NANOBYK-3601, NANOBYK-3602, NANOBYK-3610, etc. (above, manufactured by Big Chemie Japan Co., Ltd.), and alumina isopropanol dispersion includes AS-150I (Sumitomo Osaka Cement Co., Ltd.). Product), as a toluene dispersion of alumina, AS-150T (manufactured by Sumitomo Osaka Cement Co., Ltd.), and as a toluene dispersion of zirconia, HXU-110JC (manufactured by Sumitomo Osaka Cement Co., Ltd.), alumina, titania, tin oxide, Examples of powders and solvent dispersions of indium oxide, zinc oxide, etc. include trade names such as Nanotech (manufactured by C-I Kasei Co., Ltd.).

  Among these, GLGCOM V-8802 and GLGCOM V-8804 (manufactured by JGC Catalysts & Chemicals Co., Ltd.) have high dispersibility of fine particles in the coating liquid, and the transparency, hardness, and abrasion resistance of the resulting coating film are high. This is preferable because it improves further.

0-100 weight part is preferable with respect to 100 weight part of condensates (A), and, as for the usage-amount of metal oxide particle (E), More preferably, it is 0-50 weight part.
When the usage-amount of a metal oxide particle (E) exceeds 100 weight part, when the coating film cannot be formed or the transparency of a coating film may fall.

In the present invention, since the metal oxide fine particles (E) do not adversely affect the strength of the coating film, they can be present together with the condensate (A). However, some metal hydroxides, such as silanol groups on the surface of silica particles, have high acidity and may cause cationic polymerization of oxirane rings such as epoxy groups and vinyl ethers. [Condensate (A) and (meth) acrylate compound (C), silane-free epoxy compound (D), metal oxide fine particles (E) sum divided by the total weight of the curable composition] Needs to be adjusted to 0.1 to 0.6.
When the density | concentration used as the matrix in a curable composition is lower than 0.1, there exists a tendency for the viscosity of a coating liquid to become low too much and to adjust film thickness. When the density | concentration used as the matrix in a curable composition is higher than 0.6, there exists a concern which gelatinizes during storage.

  By the way, when it is desired to increase the concentration, chemical modification that seals silanol groups, such as alkoxylation of the surface of the metal hydroxide fine particles (E), is effective. In addition, the above-mentioned ELECOM V-8802, ELECOM V-8804, etc. are products having improved dispersion in organic components by sealing silanol groups, and are effective.

<(F) Radical polymerization initiator>
In the present invention, when the (meth) acrylate compound (C) is used, or when the silane compound (II) used in the synthesis of the condensate (A) has a (meth) acryloyl group, radical polymerization starts as a curing agent. It is necessary to use the agent (F).

As the radical polymerization initiator (F), any compound that is generally known as a compound that generates radicals by applying light or heat energy can be used.
There are carbon radicals, oxygen radicals, thiyl radicals, etc. that can be used as radical species to be generated, but compounds that generate thiyl radicals are poor in storage stability, and it is difficult to prohibit polymerization using a general polymerization inhibitor. . From these viewpoints, the radical source is preferably one that generates a carbon radical or an oxygen radical, and as the radical generator, for example, a photo radical generator, a thermal radical generator, or the like can be used. Specific examples are given below.

(F-1) Photoradical generator The photoradical generator (H-1) in the present invention is a compound that generates radicals when exposed to active energy rays, and acts as a polymerization initiator for the component (C). To do.

Specific examples of the photo radical generator (f-1) include, for example, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketer. 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Carbonyl compounds, sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Kill. IRGACURE series such as IRGACURE 184 and IRGACURE 819, DAROCUR series such as DAROCUR1173 and DAROCUR TPO (above, manufactured by BASF), KAYACURE series such as KAYACURE DETX-S, KAYACURE CTX, manufactured by TA Chemical Co., Ltd., TA -110 and other TAZ series (manufactured by Midori Chemical Co., Ltd.) are commercially available.
These photo radical generators (f-1) may be used alone or in combination of two or more in consideration of the curing rate and the like.

The addition amount of the photo radical generator (f-1) needs to be adjusted according to the amount of generated radicals and the target molecular weight, but is 0.05 to 100 parts by weight with respect to 100 parts by weight of the (meth) acrylate compound (C). The amount is preferably 50 parts by weight, more preferably 0.1 to 30 parts by weight.
When the added amount of the photo radical initiator (f-1) is less than 0.05 parts by weight, the generated radical is insufficient, the (meth) acrylate compound (C) may not be sufficiently cured, and tack may occur. If it exceeds the parts by weight, problems such as coloration and deterioration of weather resistance tend to occur.

(F-2) Thermal radical generator The thermal radical generator (f-2) in the present invention is a compound that generates radicals upon heating, and acts as a polymerization initiator for the (CD) component.

Specific examples of the thermal radical generator (g-2) include typical polymerization initiators. Examples of the thermal polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, and lauroyl. Diacyl peroxides such as peroxides and acetyl peroxides; Peroxys such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate Examples thereof include esters; percarbonates such as diisopropyl peroxydicarbonate and di-sec-butylperoxydicarbonate; azo compounds such as azobisisobutyronitrile.
These thermal radical generators (f-2) may be used alone or in combination of two or more in consideration of the curing rate.

The amount of the thermal radical generator (f-2) added needs to be adjusted according to the amount of radicals to be generated and the target molecular weight, but is 0.05 to 100 parts by weight of the (meth) acrylate compound (C). 50 parts by weight is preferable, and 0.1 to 30 parts by weight is more preferable.
When the addition amount of the thermal radical initiator (f-2) is less than 0.05 parts by weight, the generated radicals are insufficient, and the (meth) acrylate compound (C) may not be sufficiently cured and may cause tackiness. If it exceeds the parts by weight, problems such as coloration and deterioration of weather resistance tend to occur.

  Further, the photo radical generator (f-1) and the heat radical generator (f-2) may be mixed and used. When the photo radical generator (f-1) is used, a known polymerization accelerator such as a tertiary amine can be used in combination.

<(G) Photosensitizer>
In the curable composition of the present invention, when the cationic polymerization initiator (b-2) and the radical polymerization initiator (F) exhibit performance by irradiating active energy rays, their photosensitivity is improved. For the purpose, a photosensitizer (G) can be used as necessary.

  As the photosensitizer (G), one that can absorb light in a wavelength region that cannot be absorbed by the photoinitiator to be used is more efficient.

Although it does not specifically limit as a photosensitizer (G), For example, an anthracene derivative, a benzophenone derivative, a thioxanthone derivative, an anthraquinone derivative, a benzoin derivative etc. are mentioned.
Among these, those having a low oxidation potential and high excitation energy in a singlet or triplet state involved in electron transfer are ideal. From the viewpoint of photoinduced electron donating properties, anthracene derivatives, thioxanthone derivatives, and benzophenones Derivatives are preferred.

More specifically, for example, 9,10-dialkoxyanthracene, 2-alkylthioxanthone, 2,4-dialkylthioxanthone, 2-alkylanthraquinone, 2,4-dialkylanthraquinone, p, p′-aminobenzophenone, 2-hydroxy- 4-alkoxybenzophenone, benzoin ether and the like can be mentioned.
More specifically, anthrone, anthracene, 9,10-diphenylanthracene, 9-ethoxyanthracene, pyrene, perylene, coronene, phenanthrene, benzophenone, benzyl, benzoin, methyl 2-benzoylbenzoate, butyl 2-benzoylbenzoate , Benzoin ethyl ether, benzoin-i-butyl ether, 9-fluorenone, acetophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylaminobenzophenone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4- Diethylthioxanthone, phenothiazine, acridine orange, benzoflavin, cetoflavin-T, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-ni Roaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramid, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), 9,10 -Dibutoxyanthracene, 9,10-dipropoxyanthracene, etc. are mentioned.
These photosensitizers may be used alone or in combination of two or more.

The addition amount in the case of using the photosensitizer (G) may be appropriately adjusted according to the intended curing rate, but is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the photoinitiator, 0.5 parts by weight or more is more preferable, 10 parts by weight or less is preferable, and 5 parts by weight or less is more preferable.
If the addition amount of the photosensitizer (G) is less than 0.1 parts by weight, the effect of the intended photosensitizer tends to be difficult to obtain. There is a tendency to lead to up.

<(H) UV absorber>
In the condensate (A) of the present invention, an ultraviolet absorber (H) can be used as necessary.

  Examples of the ultraviolet absorber (H) contained in the condensate (A) include benzotriazole-based, benzophenone-based, salicylic acid phenyl ester-based, and triazine-based ultraviolet absorbers in order to maintain the transparency of the acrylic resin layer. Can be mentioned.

  Examples of the benzotriazole ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H. -Benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylenebutyl) -6- (2H- Benzotriazol-2-yl) phenol] and the like.

  Examples of benzophenone-based ultraviolet absorbers include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4′-chlorobenzophenone, and 2,2-dihydroxy-4-methoxy. Examples thereof include benzophenone and 2,2-dihydroxy-4,4′-dimethoxybenzophenone.

  Examples of the salicylic acid phenyl ester ultraviolet absorber include pt-butylphenyl salicylic acid ester.

  Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy- 4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy- 4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- ( 2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5- Riazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl)- Examples include 1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-4-butoxyethoxy) -1,3,5-triazine.

The content of the UV absorber (H) in the condensate (A) depends on the UV absorbing ability of the UV absorber used and the thickness of the coating film obtained by curing the condensate (A). Preferably it is 0.01-3 weight%.
When the content of the UV absorber (H) is less than 0.01% by weight, the UV resistance is insufficient, and when it exceeds 3% by weight, the condensate (A) is colored peculiar to the UV absorber. It tends to become cloudy beyond the saturated dissolution amount in the condensate (A). The ultraviolet absorber content in the condensate (A) is more preferably 0.02 to 2.5% by weight, particularly preferably 0.03 to 2.2% by weight, based on the condensate (A). is there.

<Curable composition>
The curable composition of the present invention necessarily contains the component (A) and further contains the components (B) to (H) as necessary. In order to adjust the physical properties, various additives are appropriately added. You may mix | blend. For example, additives generally used in paints such as inorganic fillers, inorganic pigments / organic pigments, plasticizers, dispersants, wetting agents, thickeners, antifoaming agents, and the like can be added.

A solvent can be mix | blended with the curable composition of this invention.
The solvent is not particularly limited. For example, ketones such as methyl isobutyl ketone and diisobutyl ketone; alcohols such as butanol and isopropyl alcohol; esters such as butyl acetate and isopropyl acetate; diethylene glycol methyl ether and propylene glycol methyl ether These ethers are preferred from the viewpoint of availability.
As a compounding quantity of a solvent, 0-400 weight part is preferable with respect to 100 weight part of total amounts of (A)-(H) component, and 0-100 weight part is more preferable.
When the amount of the solvent is more than 400 parts by weight, the substrate may be damaged as described above, which is not preferable.
In particular, when the base material is a resin, it is preferable to use an ether or alcohol solvent in an amount of 30% by weight or more based on the total amount of the solvent because the base material is not damaged.

  The method for preparing the curable composition of the present invention is not particularly limited, and the above components are blended, and if necessary, shaded and mixed with a hand mixer or a static mixer, a planetary mixer, a disper, a roll, Examples of the conventional method include kneading using a kneader or the like at room temperature or under heating, and using a small amount of a suitable solvent to dissolve and mix the components.

<Hardened product>
The cured product of the present invention includes those obtained by curing the active energy ray-curable composition. Examples of active energy rays irradiated when curing include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, δ rays, etc., but the reaction rate is fast, and active energy ray generators are compared. Ultraviolet rays are most preferable from the viewpoint of low cost.

The irradiation amount of the active energy ray is preferably integrated quantity of light 50~10,000mJ / cm ^2, accumulated light quantity of 100~2,000mJ / cm ² is more preferable.
When the irradiation amount of the active energy ray is less than 50 mJ / cm ² , since the amount of light is small, it takes time to cure and the productivity may be deteriorated. On the other hand, when the irradiation amount of an active energy ray exceeds 10,000 mJ / cm < ² >, decomposition | disassembly of a curable composition may be caused and it may not harden | cure neatly.

  The cured product of the present invention includes those obtained by curing a thermosetting composition. In that case, there is no limitation in particular in hardening temperature, Usually, 300 degrees C or less is preferable, 200 degrees C or less is more preferable, 150 degrees C or less is still more preferable. When curing at a temperature higher than 300 ° C., there is a concern that the organic component in the condensate is decomposed.

<Laminate>
A laminate can be produced using the curable composition of the present invention.

  The laminate of the present invention is a laminate obtained by applying and curing a heat and photocurable resin composition (L2) on an organic resin substrate (L1) having a thickness of 1 μm to 1 mm.

  The laminate of the present invention is a step of applying the curable composition of the present invention to a substrate and is cured using an active energy ray or a heat source, and a cured film (hereinafter sometimes referred to as “coating film”). It is obtained by a manufacturing method including a forming step.

In the present invention, the substrate is not particularly limited, and various substrates described later can be used. The curable composition of the present invention can be used, for example, for the coating of metals, ceramics, glass, cement, ceramic base materials, plastics, films, sheets, wood, paper, fibers, etc., home appliances, industrial equipment, etc. It can be used suitably.
In the active energy ray irradiation curing, an organic resin base material is preferable from the viewpoint of not requiring high heat at the time of curing, for example, acrylic resin, polycarbonate resin, polyethylene terephthalate (hereinafter referred to as “PET”) resin, Examples of the base material include films and sheets such as triacetyl cellulose resin and cycloolefin resin.

  As an acrylic resin base material, for example, Sumipex, Technoloy (above, manufactured by Sumika Acrylic Sales Co., Ltd.), Acryprene, Acrylite (above, manufactured by Mitsubishi Rayon Co., Ltd.), Paragrass, Comoglass (above, manufactured by Kuraray Co., Ltd.) Examples include Delagrass, Delaprism (manufactured by Asahi Kasei Technoplus Co., Ltd.), Kanaselite (manufactured by Kanase Kogyo Co., Ltd.) and the like.

  Examples of the polycarbonate resin substrate include Carbograss (Asahi Glass Co., Ltd.), Iris Polyca Sheet (Iris Shinyo Co., Ltd.), Iupilon (Mitsubishi Gas Chemical Co., Ltd.), Panlite (Teijin Chemicals Co., Ltd.), Polycarbonate Examples thereof include plates (made by Takiron Co., Ltd.), polycarbonate ace (made by Sumitomo Bakelite Co., Ltd.), polycarbonate plates (made by Sekisui Molding Co., Ltd.), PC mirrors (made by Hishijo Co., Ltd.), and the like.

  Examples of the PET resin base material include Pet Ace (manufactured by Sumitomo Bakelite), Estella, Estella Super (manufactured by Sekisui Molding Industry Co., Ltd.), Peters (manufactured by Mitsubishi Plastics Co., Ltd.), Petek (manufactured by Takiron Co., Ltd.), Mineron ( Mineron Kasei Kogyo Co., Ltd.), Polytech A-PET sheet (Polytech Co., Ltd.), A-PET resin sheet (Teijin Kasei Co., Ltd.), Lumirror (Toray Industries, Inc.), Cosmo Shine (Toyobo Co., Ltd.), etc. Is mentioned.

In particular, a thin substrate is preferable from the viewpoint of utilizing the low curing shrinkage of the present invention.
The thickness of the organic resin substrate in the present invention is preferably 1 μm to 1 mm, more preferably 1 μm to 300 μm, and still more preferably 1 μm to 200 μm.
When the thickness of the organic resin base material is less than 1 μm, the organic resin base material may be damaged by stress applied during coating or by a solvent contained in the coating liquid. On the other hand, when the thickness of the organic resin substrate is more than 1 mm, the rigidity of the substrate itself is increased, and it is difficult to be affected by stress such as curing shrinkage received from the cured product applied to the surface, which is called low curing shrinkage. The benefits are lost. That is, even if the cured product has a large curing shrinkage, warping often does not occur.

The cured film thickness (coating film thickness) in the present invention is preferably 1 to 100 μm.
If the coating film thickness is less than 1 μm, it tends to be affected by the hardness of the substrate itself such as plastic, film, sheet, etc., and there is a tendency that sufficient hardness cannot be obtained. Hardening tends to be slow without reaching the deep part.
However, when the thickness of the coating film is 100 μm or more, it is preferable to adopt a method of repeating application and irradiation with active energy rays in several steps.

  The laminate of the present invention can be suitably used for a front plate such as a personal computer, a smartphone, or a tablet, a liquid crystal member, a window glass of an automobile, a protective material for a lamp of an automobile, a building material, a home appliance, or the like.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.

Substances used in Examples and Comparative Examples are as follows.
-Silane compounds having hydrolyzable silyl groups (I)
A-186: Momentive Performance Materials Japan GK, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, molecular weight 246.3
A-187: Momentive Performance Materials Japan GK, 3-glycidyloxypropyltrimethoxysilane, molecular weight 236.3
-Silane compounds having hydrolyzable silyl groups (II)
A-174: Momentive Performance Materials Japan GK, 3-methacryloxypropyltrimethoxysilane, molecular weight 248.4
A-171: Momentive Performance Materials Japan GK, vinyltrimethoxysilane, molecular weight 148.2
A-1630: Momentive Performance Materials Japan GK, methyltrimethoxysilane, molecular weight 136.2
○ Neutral magnesium chloride (Wako Pure Chemical Industries, special grade, molecular weight 95.2)
○ Basic compound TEA: Triethylamine (Wako Pure Chemical Industries, Ltd., molecular weight 101.2)
○ (Meth) acrylate compound (D)
DPHA: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 578)
TMPTA: trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 296)
HDDA: hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 226)
○ Curing agent that cures epoxy group (B)
CPI-101A: manufactured by San Apro Co., Ltd., triarylsulfonium / SbF ₆ salt ALCH-TR: Kawaken Fine Chemical Co., Ltd., aluminum trisethyl acetoacetate ○ radical generator (G)
2-hydroxy-2-methylpropiophenone: Tokyo Chemical Industry Co., Ltd., molecular weight 164.2
○ Dilution solvent PGME: 1-methoxy-2-propanol (manufactured by Daicel Corporation, molecular weight 90)
Methanol (Mitsubishi Gas Chemical Co., Ltd., molecular weight 32)
○ Organic substrate PET (polyethylene terephthalate) film [Toyobo Co., Ltd., Cosmo Shine A4300, 150 μm × 100 μm × 250 μm thickness]
Acrylic film [Sumitomo Chemical Co., Ltd., Technoloy S001G, 150 μm × 100 μm × 250 μm thickness]
TAC (triacetyl cellulose) film [150 μm × 100 μm × 50 μm thickness]
PC (polycarbonate) sheet [Takiron Co., Ltd., PC-1600, 150 μm × 100 μm × 0.8 mm thickness]

  Evaluation of the condensate obtained in the synthesis example is as follows.

(Quantification of OR group directly bonded to silicon)
By the following method, the OR group directly bonded to silicon in the silane compound before and after the reaction was measured, and the Y / X ratio was calculated.
JH-LA400 manufactured by JEOL Ltd. was used for ¹ H-NMR and ²⁹ Si-NMR measurements using heavy acetone as a solvent.

(Measurement of weight average molecular weight)
The weight average molecular weight was measured by GPC. That is, it calculated in polystyrene conversion using Tosoh Co., Ltd. HLC-8220GPC as a liquid feeding system, using Tosoh Co., Ltd. TSK-GEL H type as a column, using THF as a solvent.

(Evaluation of epoxy group survivability)
¹ H-NMR measurement was performed on the obtained condensate using JNM-LA400 manufactured by JEOL Ltd. using heavy acetone as a solvent.
Evaluation of physical properties of the laminate test pieces obtained in Examples and Comparative Examples is as follows. In addition, the evaluation with respect to a test piece was measured after standing for 7 days at room temperature after hardening.

(Alkali resistance)
After spotting 0.5 mL of 0.05N sodium hydroxide aqueous solution on the cured coating film of the obtained laminate, capping so that moisture does not volatilize, heating at 55 ° C. for 4 hours, and then wiping off the sodium hydroxide aqueous solution. The presence or absence of spot marks was evaluated according to the following criteria.
○: No spot mark is attached.
Δ: Some spot marks remain, but the smoothness of the coating film is not impaired.
X: The coating film was affected and melted or cracked.

(Acetone resistance)
0.5 mL of acetone is spotted on the cured coating film of the obtained laminate, and the mixture is allowed to stand until the acetone volatilizes at room temperature. After volatilization, evaluation was made based on the presence or absence of acetone spot marks.
○: No spot mark is attached.
Δ: Some spot marks remain, but the smoothness of the coating film is not impaired.
X: The coating film was affected and melted or cracked.

(Abrasion resistance)
Using an eraser abrasion tester [manufactured by Mitsumoto Seisakusho Co., Ltd.], a load of 500 g / cm ² was applied to steel wool # 0000, and the resulting laminate was reciprocated 100 times on the coating surface to create a coating film. I checked if there was a scratch.

(warp)
The laminate was placed on a horizontal table so that the coating surface of the obtained laminate was the upper surface.
For each of the four vertices on the top surface of the laminate, the vertical distance from the top surface of the table was measured, and the average value was calculated. When the laminate warps on the coated surface side (the corner of the bottom surface of the laminate floats from the surface of the table), the positive value is set, and in the opposite case, the negative value is set.
In addition, the result of the curvature evaluated on the same conditions with PET film single, acrylic film single, TAC film single, and PC sheet single was 0 mm.

<Synthesis Examples 1-10 of Condensate (A)>
The compound shown in Table 1 (the unit of the compounding amount is parts by weight) is charged into a reactor equipped with a stirrer, a thermometer, and a reflux condenser, and stirred at the reaction temperature and reaction time shown in Table 1 for condensation. I got a thing. The resulting condensate was devolatilized and concentrated under reduced pressure using an evaporator, and adjusted to a 50% solution using PGME.
Table 1 shows the evaluation results for the obtained condensate.

<Example 1>
[Preparation of coating solution]
As a condensate, 100 parts by weight of Synthesis Example 1 [A-186 (condensate of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) (50% solution)] as an epoxy group curing agent, ALCH- TR1.5 parts by weight were blended to prepare a coating solution. The coating solution used was diluted with 27.3 parts by weight of PGME (1-methoxy-2-propanol) as a diluent solvent so that the nonvolatile content was 40%.
[Production of laminate]
The obtained coating solution was applied onto a PET film (150 μm × 100 μm × 250 μm thickness) using a bar coater # 20 so that the dry film thickness was about 10 μm.
Next, the removal of the diluting solvent and the curing reaction were simultaneously completed using a hot air dryer at 120 ° C. for 1 hour to obtain a laminate (hereinafter referred to as “thermal curing”).
Table 2 shows the physical property evaluation results for the obtained test pieces.

<Example 2>
A coating solution was obtained in the same manner as in Example 1 except that the epoxy group curing agent was changed to 0.5 parts by weight of CPI-101A and the amount of PGME was changed to 25.8 parts by weight. After heating at 80 ° C. for 3 minutes using a hot air drier to remove the UV light, the UV light was applied in air using a high-pressure mercury lamp at 240 mW so that the integrated light quantity at a wavelength of 310 to 390 nm would be 1000 mJ / cm ^2. It was cured by irradiation (hereinafter referred to as “ultraviolet ray curing”) to obtain a laminate.
Table 2 shows the physical property evaluation results for the obtained laminate.

<Example 3>
A laminate was obtained in the same manner as in Example 2, except that the condensate (A) was changed to Synthesis Example 2.
Table 2 shows the physical property evaluation results for the obtained laminate.

<Example 4>
A laminate was obtained in the same manner as in Example 2, except that the condensate (A) was changed to Synthesis Example 3.
Table 2 shows the physical property evaluation results for the obtained laminate.

<Example 5>
A laminate was obtained in the same manner as in Example 2, except that the condensate (A) was changed to Synthesis Example 4.
Table 2 shows the physical property evaluation results for the obtained laminate.

<Example 6>
A laminate was obtained in the same manner as in Example 2, except that the condensate (A) was changed to Synthesis Example 5.
Table 2 shows the physical property evaluation results for the obtained laminate.

<Example 7>
A laminate was obtained in the same manner as in Example 2, except that the condensate (A) was changed to Synthesis Example 6.
Table 2 shows the physical property evaluation results for the obtained laminate.

<Example 8>
A laminate was obtained in the same manner as in Example 2, except that the condensate (A) was changed to Synthesis Example 7.
Table 2 shows the physical property evaluation results for the obtained laminate.

<Example 9>
A laminate was obtained in the same manner as in Example 2, except that the condensate (A) was changed to Synthesis Example 8.
Table 2 shows the physical property evaluation results for the obtained laminate.

< Reference Example 1 >
A laminate was obtained in the same manner as in Example 2, except that the condensate (A) was changed to Synthesis Example 9.
Table 2 shows the physical property evaluation results for the obtained laminate.

<Example 11>
A laminate was obtained in the same manner as in Example 2, except that the condensate (A) was changed to Synthesis Example 10.
Table 2 shows the physical property evaluation results for the obtained laminate.

<Example 12>
The same procedure as in Example 2 except that DPHA was added to 21.4 parts by weight and 2-hydroxy-2-methylpropiophenone 0.73 parts by weight, and the amount of PGME was changed to 59.0 parts by weight. Thus, a laminate was obtained.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 13>
In Example 12 , the condensate was changed to Synthesis Example 5, DPHA 12.5 parts by weight, 2-hydroxy-2-methylpropiophenone 0.43 parts by weight, and PGME 45.1 parts by weight. Other than that obtained the laminated body by the same operation.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 14>
For Example 2, the coated substrate was changed to an acrylic film (250 μm thick), and a laminate was obtained in the same manner except that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 15>
For Example 6, the coated substrate was changed to an acrylic film (250 μm thick), and a laminate was obtained by the same operation except that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 16>
A laminate was obtained by the same operation as in Example 12 except that the coating substrate was changed to an acrylic film (250 μm thick).
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 17>
For Example 13, the coated substrate was changed to an acrylic film (250 μm thick), and a laminate was obtained by the same operation except that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 18>
The coated substrate was changed to a TAC film (50 μm thickness) with respect to Example 2, and a laminate was obtained by the same operation except that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 19>
For Example 6, the coated substrate was changed to a TAC film (50 μm thick), and a laminate was obtained in the same manner except for that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 20>
For Example 12, the coated substrate was changed to a TAC film (50 μm thick), and a laminate was obtained by the same operation except that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 21>
For Example 13, the coated substrate was changed to a TAC film (50 μm thickness), and a laminate was obtained by the same operation except for that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 22>
The coated substrate was changed to a PC sheet (0.8 mm thickness) with respect to Example 2, and a laminate was obtained by the same operation except that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 23>
For Example 6, the coated substrate was changed to a PC sheet (0.8 mm thickness), and a laminate was obtained by the same operation except that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 24>
For Example 12, the coated substrate was changed to a PC sheet (0.8 mm thickness), and a laminate was obtained by the same operation except that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Example 25>
For Example 13, the coated substrate was changed to a PC sheet (0.8 mm thickness), and a laminate was obtained by the same operation except that.
Table 3 shows the physical property evaluation results for the obtained laminate.

<Comparative Example 1>
In [Preparation of coating solution], a coating solution was obtained by the same operation as in Example 2 using 100 parts by weight of DPHA, 3 parts by weight of 2-hydroxy-2-methylpropiophenone, and 154.5 parts by weight of PGME, and ultraviolet rays were obtained. A laminate was obtained by curing.
Table 4 shows the physical property evaluation results for the obtained laminate.

<Comparative Example 2>
A coating solution was obtained in the same manner as in Comparative Example 1 except that the (meth) acrylate compound (D) was changed to TMPTA, and a laminate was obtained by ultraviolet curing.
Table 4 shows the physical property evaluation results for the obtained laminate.

<Comparative Example 3>
A coating solution was obtained in the same manner as in Comparative Example 1 except that the (meth) acrylate compound (D) was changed to HDDA, and a laminate was obtained by ultraviolet curing.
Table 4 shows the physical property evaluation results for the obtained laminate.

<Comparative Example 4>
A coating solution was obtained in the same manner as in Comparative Example 1 except that the (meth) acrylate compound (D) was changed to 20 parts by weight of DPHA and 80 parts by weight of HDDA, and a laminate was obtained by ultraviolet curing.
Table 4 shows the physical property evaluation results for the obtained laminate.

<Comparative Example 5>
Compared to Comparative Example 1, the curable resin composition is changed to a condensate 11 having both an epoxy group and a methacryloyl group, and 1 part by weight of CPI-101A and 1.5 parts by weight of radical initiator (G) are used as the curing agent (B). A coating solution was obtained by the same operation except that it was changed to, and a laminate was obtained by ultraviolet curing.
Table 4 shows the physical property evaluation results for the obtained laminate.

In Examples 1 to 9, Reference Example 1 and Example 11 , laminates were obtained by cationic polymerization curing of epoxy groups using Synthesis Examples 1 to 10, and all were cured while being excellent in chemical resistance and scratch resistance. Almost no warpage of the laminate due to shrinkage occurred.
Examples 12 and 13 use Synthesis Examples 1 and 5 to further blend (meth) acrylate compound (D) to obtain a laminate, both of which are excellent in chemical resistance and scratch resistance, and are laminated by curing shrinkage. There was almost no warping of the body.
In Examples 14 to 25, the base material was changed with respect to Examples 2, 6, 12, and 13 to create a laminate, and even if the base material was changed, both were excellent in chemical resistance and scratch resistance, Almost no warpage of the laminate due to curing shrinkage occurred.

In Comparative Examples 1 and 2, a laminate was obtained using a polyfunctional acrylate compound, and a high crosslink density due to an acryloyl group was formed, and although scratch resistance and organic solvent resistance were excellent, the alkali resistance was poor and the warp was large. I'm stuck. In Comparative Examples 3 and 4, warpage is suppressed by using a bifunctional acrylate compound, but the scratch resistance is deteriorated compared to Comparative Examples 1 and 2 due to a decrease in the crosslinking density, and the warpage is also sufficient. It is a value that cannot be said. In Comparative Example 5, the condensate itself has both an epoxy group and a methacryloyl group, but the ratio of the methacryloyl group is large, and the warpage is large.

Claims (4)

A laminate obtained by applying and curing a heat and photocurable resin composition on an organic resin substrate having a thickness of 1 μm to 1 mm,
The laminated body characterized by satisfying the following conditions (1) and (2).
Condition (1) The curable resin composition has the following general formula (I):
_{^{R 1 - (SiR 2 a (}} OR 3) 3-a) (I)
(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms whose terminal is substituted with an epoxy structure-containing group, and R ² is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or 6 carbon atoms. A monovalent hydrocarbon group selected from an aryl group having ˜25 and an aralkyl group having 7 to 12 carbons, and R ³ is each independently a hydrogen atom or an alkyl group having 1 to 10 carbons. A silane compound (I) having a hydrolyzable silyl group represented by:
The following general formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(Wherein, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and is selected from substituted aryl group, .R ² are each independently a group having no epoxy structure-containing group And a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and R ³ is independently A hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2.), and a silane compound (II) having a hydrolyzable silyl group is represented by Consists of a condensate (A) obtained by hydrolysis and condensation with a silane compound (II) molar ratio of 9 or less and a curing agent (B) for curing the epoxy group.
Condition (2) The condensate (A) uses a neutral salt (C) as a hydrolysis / condensation catalyst, and the neutral salt is selected from the group consisting of group 1 element ions and group 2 element ions as cations. Or a salt selected from the group consisting of chloride ion, bromide ion and iodide ion as an anion. Regarding the condensate (A), the OR directly bonded to the silicon atom of the condensate (A) with respect to the mole number X of the OR ³ group directly bonded to the silicon atom of the silane compounds (I) and (II) as the raw materials ^2. The laminate according to claim 1, wherein the ratio Y / X of the number of moles Y of the ^three groups is 0.5 or less.   The laminate according to claim 1 or 2, wherein the curing agent (B) for curing the epoxy group is a cationic polymerization initiator. The laminate according to claim 3, wherein the cationic polymerization initiator is at least one selected from the group consisting of a fluorophosphoric acid type, a fluoroantimonic acid type, and a fluorophenylboronic acid type.