JP6545482B2 - Photo- or thermosetting resin composition, cured product and laminate - Google Patents

Description

  The present invention relates to a curable composition, a cured product, and a laminate comprising a siloxane resin containing an epoxy structure-containing group and a compound having two or more (meth) acryloyl groups in one molecule.

  Conventionally, glass has been used for the front plate of smartphones and tablets, car windows and the like from the viewpoint of hardness and durability. However, in recent years, demands for weight reduction and easy processability have been increased due to further high added value, and resin glazing studies as a substitute for glass are actively conducted. Candidates for resin glass include acrylic resin, polycarbonate, and PET, which are typical transparent resins.

However, because they can not satisfy the required characteristics for hardness and scratch resistance, they can be highly crosslinked on the surface, which is called a hard coat (sometimes referred to as "HC") on the order of several microns to several tens of microns. By forming a dense thin film, a material having both light weight, easy processability, high hardness, and high scratch resistance has been developed (Patent Document 1).
In the examination, from the viewpoint of scratch resistance and durability, attention has been focused on siloxane bond whose bonding energy is larger than carbon-carbon bond, and “includes siloxane bond or forms siloxane bond in curing process. Many HC agents have been reported (Patent Document 2).

  As it is required to form a high crosslink density, as the curing form, polymerization type ultraviolet light (hereinafter sometimes referred to as “UV”) curing, in particular UV radical curing, is often selected. This is because the internal temperature of the locally cured film (hereinafter sometimes referred to as "cured film" or "film") largely exceeds the curing temperature (outside temperature) due to the heat of polymerization during curing. It is believed that this is because the curing reaction proceeds more easily than the addition reaction type heat curing.

  However, in UV radical curing, reduction in intermolecular distance accompanying chain addition polymerization of carbon-carbon double bond, that is, curing shrinkage often becomes a problem, such as moisture and heat at the time of curing and after curing. A crack may occur in the coating film due to environmental changes (Patent Document 3).

A polyfunctional radically polymerizable compound having two or more (meth) acryloyl groups in one molecule forms a crosslink in three dimensions and easily produces a cured product having high hardness and high scratch resistance, As described above, since curing shrinkage occurs easily and cracks are easily generated, curing shrinkage is often reduced by blending a compound having one (meth) acryloyl group contained in one molecule.
However, since the concentration of the (meth) acryloyl group in the coating agent decreases, physical properties such as hardness, abrasion resistance and chemical resistance of the resulting cured product may be deteriorated.

  The curing shrinkage is also reduced by blending a compound having a polyfunctional group having a curing form different from that of radical curing and having a small curing shrinkage, such as an epoxy group, to the polyfunctional radically polymerizable compound. There is a method (patent document 4). However, in this method, each other acts as a reactive diluent, so that the crosslink density in the cured product does not increase, and the hardness and the scratch resistance deteriorate more than when each is cured alone. There are many.

JP 9-53025 A JP-A-8-73771 JP 2012-180487 International Publication WO2007 / 126066

  The problem to be solved by the present invention is that, when curing a mixture of a polyfunctional radically polymerizable compound and a siloxane-based resin containing an epoxy structure-containing group, it is possible to increase the crosslink density in the cured product individually. It is to obtain a cured product having the same degree of hardness and scratch resistance as that of the cured product of the above and having improved crack resistance.

  As a result of investigations to solve the above-mentioned conventional defects, the present inventors found that the amount of epoxy groups in the siloxane-based resin containing the epoxy structure-containing group, the type of curing agent, etc. The present invention was accomplished by increasing the crosslink concentration resulting from the epoxy groups.

Below, this invention is shown.
[1] The following general formula (I):
R ^1- (SiR ² _a (OR ³ ) _3-a ) (I)
(Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, the terminal of which is substituted with an epoxy structure-containing group, and R ² is each independently a hydrogen atom or an alkyl group having 1 to 10 carbons, 6 carbon atoms A monovalent hydrocarbon group selected from an aryl group of 25 and an aralkyl group having 7 to 12 carbon atoms, R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is 0 A silane compound (I) having a hydrolyzable silyl group, which is an integer of -2),
The following general formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(Wherein R ⁴ is a group selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and a substituted aryl group and having no epoxy group. R ² is each independently) 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, and each R ³ independently represents a hydrogen atom Or a silane compound (II) having a hydrolyzable silyl group, which is an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2),
Obtained by hydrolysis / condensation using a neutral salt or a basic compound as a catalyst, wherein the molar ratio of silane compound (II) to silane compound (I) is 9 or less
A condensate (A) having a weight average molecular weight of 500 or more and 30,000 or less,
A compound (B) having two or more (meth) acryloyl groups in one molecule,
It contains a curing agent (C) to cure the epoxy group and a radical generator (D),
And directly bonded to the silicon atom of the condensate (A) relative to the number of moles X of the OR ³ group directly bonded to the silicon atom of the silane compounds (I) and (II) that are the raw materials of the condensate (A) Curable composition in which ratio Y / X of mole number Y of OR ³ group is 0.2 or less.
[2] A compound (B) having two or more (meth) acryloyl groups in one molecule, containing 1 to 9900 parts by weight with respect to 100 parts by weight of the condensate (A),
When the curing agent (C) is a curing agent that polymerizes an epoxy group, curing is achieved by adding 0.5 to 10 parts by weight to the epoxy group with respect to 100 parts by weight of the condensation product (A) 10 to 150 parts by weight in the case of
And 0.05 to 50 parts by weight of a radical generator (D) per 100 parts by weight of the compound (B) having two or more (meth) acryloyl groups in one molecule, The curable composition as described in 1].
[3] The curable composition according to [1] or [2], wherein the condensation product (A) is obtained using a neutral salt as a hydrolysis / condensation catalyst.
[4] Any one of the neutral salts selected from the group consisting of Group 1 element ion, Group 2 element ion, tetraalkyl ammonium ion and guanidinium ion as a cation,
Any one of [1] to [3], which is a salt in combination with any one selected from the group consisting of a Group 17 element ion excluding fluoride ion as a anion, a sulfate ion, a nitrate ion, and a perchlorate ion The curable composition as described in-.
[5] The neutral salt is any one selected from the group consisting of a first group element ion and a second group element ion as a cation, and any one selected from a group consisting of a chloride ion, a bromide ion and an iodide ion as an anion The curable composition in any one of [2]-[4] which is a salt which consists of a combination of these.
[6] The curing agent (C) for curing an epoxy group and the radical generator (D) are compounds that exhibit an effect by irradiation with an active energy ray, [1] to [5] The active energy ray-curable composition according to any one of the above.
[7] The curing agent (C) which cures an epoxy group is a cationically polymerizable acid generator, and is a compound containing a fluorophosphate group, a fluoroantimonate group and a fluoroborate group, [, The curable composition in any one of [1]-[6].
[8] A cured product obtained by curing the curable composition according to any one of [1] to [7].
[9] A method for producing a laminate, comprising the steps of applying the curable composition according to any one of [1] to [8] to a substrate, curing the curable composition, and forming a cured film. .
The laminated body obtained by the manufacturing method as described in [10] [9].

  According to the present invention, when curing a mixture of a polyfunctional radically polymerizable compound and a siloxane resin containing an epoxy group, curing of each alone is achieved by increasing the crosslink density resulting from the epoxy group in the cured product. It is possible to obtain a cured product having improved crack resistance by reducing the curing shrinkage more than when curing the polyfunctional acrylate compound alone, having hardness and abrasion resistance comparable to those of the product. .

  A curable composition comprising the multifunctional radically polymerizable compound of the present invention and a siloxane resin containing an epoxy structure-containing group is a silane having a hydrolyzable silyl group represented by the following general formulas (I) and (II) A condensation product (A) obtained by hydrolyzing and condensing a compound using a neutral salt or a basic compound as a catalyst, a compound (B) having two or more (meth) acryloyl groups in one molecule, and curing an epoxy group Containing a curing agent (C) and a radical generator (D).

General Formula (I):
R ^1- (SiR ² _a (OR ³ ) _3-a ) (I)
(Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, the terminal of which is substituted with an epoxy structure-containing group, and R ² is each independently a hydrogen atom or an alkyl group having 1 to 10 carbons, 6 carbon atoms A monovalent hydrocarbon group selected from an aryl group of 25 and an aralkyl group having 7 to 12 carbon atoms, R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is 0 It is an integer of ~ 2.)
General formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(Wherein, R ⁴ is a group selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and a substituted aryl group and having no epoxy structure-containing group. Each R ² is independently 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 each R 3 independently represents hydrogen It is an atom or a C1-C10 alkyl group, a is an integer of 0-2).

Furthermore, the silane compound (II) is hydrolyzed / condensed using a basic compound or neutral salt as a catalyst with the molar ratio of the silane compound (II) to the silane compound (I) being 9 or less, and the weight average molecular weight 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 A feature is that 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)
(Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, the terminal of which is substituted with an epoxy structure-containing group, and R ² is each independently a hydrogen atom or an alkyl group having 1 to 10 carbons, 6 carbon atoms A monovalent hydrocarbon group selected from an aryl group of 25 and an aralkyl group having 7 to 12 carbon atoms, R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is 0 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 group selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and a substituted aryl group and having no epoxy structure-containing group. Each R ² is independently 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 each R 3 independently represents hydrogen It is an atom or a C1-C10 alkyl group, a is an integer of 0-2).
Is represented by

As a specific example of the alkyl group by which the terminal in R ¹ of General formula (I) was substituted by the epoxy structure containing group, For example, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, a isobutyl group, an amyl group, Examples include isoamyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, and the like.
The epoxy structure-containing group in R ¹ of the general formula (I) may be any 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. As such a hydrocarbon group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, phenyl group, tolyl group, xylyl group, naphthyl group, A benzyl group and a phenethyl group are mentioned.

R ^{3 in the} general formulas (I) and (II) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. As an alkyl group, 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 are mentioned, for example. The carbon number of the alkyl group of R ³ is preferably 1 to 3, and most preferably 1 from the viewpoint of facilitating hydrolysis and condensation of the silane compound having a hydrolyzable silyl group.

R ^{4 in the} general formula (II) is a group selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and a substituted aryl group and having no epoxy group.
As the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, amyl group, isoamyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 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. As an alkenyl group, for example, vinyl group, allyl group, 1-methylethenyl group, 2-methylethenyl group, 2-propenyl group, 1-methyl-3-propenyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl Groups, cyclohexenyl group, bicyclohexenyl group, 6-heptenyl group, 7-octenyl group, decenyl group, pentadecenyl group, eicosenyl group, tricosenyl group and the like. As a substituted aryl group, a styryl group is mentioned.

Among them, from the viewpoints of good storage stability, fast curing speed, and suppressed cracking of the obtained coating film, R ⁴ is a non-substituted alkyl group having 3 to 10 carbon atoms. The alkyl group is preferably an alkyl group, and more preferably an alkyl group having 3 to 6 carbon atoms.
When R ⁴ is a substituted alkyl group, the alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and as the substituent, a phenyl group, a cyclohexyl group, and (Meth) acryloyl is preferred. When it is an alkenyl group, a vinyl group or an allyl group is preferred.
As R ^{4 a} substituted aryl group, a styryl group is preferable.
When the number of carbon atoms in an unsubstituted alkyl group is 2 or less, or when the substituent is not bulkier than a phenyl group, a cyclohexyl group, or a (meth) acryloyl group, a dense crosslinked structure is formed during crosslinking, resulting in gel May be In addition, when the carbon number of the alkyl group is 11 or more, or when the substituted alkyl group is bulkier than the phenyl group, the cyclohexyl group or the (meth) acryloyl group, the hydrophobicity is high and the hydrolysis rate is It may decrease extremely or the curing rate may decrease.

  A in the general formula (I) and the 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- Glycidyl oxyhexyl triethoxysilane, 6-glycidyl oxyhexyl methyldiethoxysilane, 8-glycidyl oxyoctyl trimethoxysilane, 8-glycidyl oxyoctyl methyl dimethoxysilane, 8-glycidyl oxyoctyl triethoxysilane, 8-glycidyl oxyoctyl methyl 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-epoxybutyl ester Rudimethoxysilane, 4-epoxybutyltriethoxysilane, 4-epoxybutylmethyldiethoxysilane, 6-epoxyhexyltrimethoxysilane, 6-epoxyhexylmethyldimethoxysilane, 6-epoxyhexyltriethoxysilane, 6-epoxyhexylmethyl Diethoxysilane, 8-epoxyoctyltrimethoxysilane, 8-epoxyoctylmethyldimethoxysilane, 8-epoxyoctyltriethoxysilane, 8-epoxyoctylmethyldiethoxysilane and the like can be mentioned.

As described above, the carbon number of the alkyl group of R ³ in the general formula (I) is preferably 1 to 3, and most preferably 1 from the viewpoint of easy hydrolysis and condensation of the silane compound having a hydrolyzable silyl group. It is. In addition, the carbon number of the alkylene group which bonds the epoxy group and the silicon atom is important from the viewpoint of the reactivity (mobility) of the epoxy group at the time of curing, and the carbon number is preferably 1 to 4 and more preferably 2 or more. It is three.

Combining the above viewpoints, as the silane compound (I), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 3- (3,4 (3,4) -Epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propylmethyldimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane And 3-glycidyl oxypropyl methyl dimethoxysilane is preferred. Among them, compounds in which R ¹ is a 2- (3,4-epoxycyclohexyl) ethyl group and a 3-glycidyloxypropyl group are preferable.

Among silane compounds (II), those in which R ⁴ in the general formula (II) is a non-substituted alkyl group include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and ethyltrimethylsilane Methoxysilane, ethylmethyldimethoxysilane, ethyltriethoxysilane, ethylmethyldiethoxysilane, propyltrimethoxysilane, propylmethyldimethoxysilane, propyltriethoxysilane, propylmethyldiethoxysilane, butyltrimethoxysilane, butylmethyldimethoxysilane, Butyltriethoxysilane, butylmethyldiethoxysilane, hexyltrimethoxysilane, hexylmethyldimethoxysilane, hexyltriethoxysilane, hexylmethyldiethoxysilane, Examples thereof include tiltly methoxysilane, oxethyl methyl dimethoxysilane, oxtilly ethoxy, and oxyl methyl diethoxysilane.

In addition, examples of those in which R ⁴ in the general formula (II) is a substituted alkyl group include the following. 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, and therefore, as a silane compound (I), It is preferable to select an epoxysilane compound having an epoxycyclohexyl group which is less susceptible to nuclear attack.
On the other hand, a silane compound having an amino group or an acid anhydride group as a substituent is highly likely to react with an epoxy group during the hydrolysis / condensation reaction of a hydrolyzable silyl group to a mercapto group or more. It is not preferable to use in this application.

As a compound in which R ⁴ is a thiol group-substituted alkyl group, 1-mercaptomethyltrimethoxysilane, 1-mercaptomethylmethyldimethoxysilane, 1-mercaptomethyltriethoxysilane, 1-mercaptomethylmethyldiethoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Triethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 4-mercaptobutyl 4-triethoxysilane, 4-mercaptobutylmethyldiethoxysilane, 6-mercaptohexyltrimethoxysilane, 6-mercaptohexylmethyldimethoxysilane, 6-mercaptohexyltriethoxysilane, 6-mercaptohexylmethyldiethoxysilane, 8-mercaptooctyl Trimethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctyltriethoxysilane, 8-mercaptooctylmethyldiethoxysilane and the like can be mentioned.

As a compound in which R ⁴ is an isocyanate group-substituted alkyl group, 1-isocyanatomethyltrimethoxysilane, 1-isocyanatemethylmethyldimethoxysilane, 1-isocyanatemethyltriethoxysilane, 1-isocyanatemethylmethyldiethoxysilane, 2-isocyanate Ethyltrimethoxysilane, 2-isocyanateethylmethyldimethoxysilane, 2-isocyanateethyltriethoxysilane, 2-isocyanateethylmethyldiethoxysilane, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propylmethyldimethoxysilane, 3-isocyanate propyl Triethoxysilane, 3-isocyanate propylmethyldiethoxysilane, 4-isocyanate butyltrimethoxysilane, 4- Isocyanate butylmethyldimethoxysilane, 4-isocyanatebutyltriethoxysilane, 4-isocyanatebutylmethyldiethoxysilane, 6-isocyanatohexyltrimethoxysilane, 6-isocyanatohexylmethyldimethoxysilane, 6-isocyanatohexyltriethoxysilane, 6-isocyanate Hexylmethyldiethoxysilane, 8-isocyanateoctyltrimethoxysilane, 8-isocyanateoctylmethyldimethoxysilane, 8-isocyanateoctyltriethoxysilane, 8-isocyanateoctylmethyldiethoxysilane, and the like can be mentioned.

As a compound in which R ⁴ is a (meth) acryloyl group substituted alkyl group, 1- (meth) acryloyloxymethyltrimethoxysilane, 1- (meth) acryloyloxymethylmethyldimethoxysilane, 1- (meth) acryloyloxymethyltrithiol 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 acid Royloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 4- (meth) acryloyloxybutylmethyldimethoxysilane, 4- (meth) acryloylyl Oxybutyltriethoxysilane, 4- (meth) acryloyloxybutylmethyldiethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 6- (meth) acryloyloxyhexylmethyldimethoxysilane, 6- (meth) acryloyloxy Hexyltriethoxysilane, 6- (Meth) acryloyloxyhexylmethyldiethoxysilane, 8- (Meth) acryloyloxyoctyltrimethoxysilane, 8- (Meth) acryloyloxy oc Methyl dimethoxysilane, 8- (meth) acryloyloxy octyltriethoxysilane, 8- (meth) acryloyloxyoctyl diethoxysilane and the like.
As a compound in which R ⁴ is a phenyl group-substituted alkyl group, benzyltrimethoxysilane, benzyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-phenylpropyltrimethoxysilane, 3-phenylpropylsilane Rutriethoxysilane, 4-phenylbutyltrimethoxysilane, 4-phenylbutyltriethoxysilane, 5-phenylpentyltrimethoxysilane, 5-phenylpentyltriethoxysilane, 6-phenylhexyltrimethoxysilane, 6-phenylhexyltriethoxysilane Silane, etc. may be mentioned.

As a compound in which R ⁴ is a cyclohexyl group-substituted alkyl group, cyclohexylmethyltrimethoxysilane, cyclohexylmethyltriethoxysilane, 2-cyclohexylethyltrimethoxysilane, 2-cyclohexylethyltriethoxysilane, 3-cyclohexylpropyltrimethoxysilane, 3-cyclohexylpropyltriethoxysilane, 4-cyclohexylbutyltrimethoxysilane, 4-cyclohexylbutyltriethoxysilane, 5-cyclohexylpentyltrimethoxysilane, 5-cyclohexylpentyltriethoxysilane, 6-cyclohexylhexyltrimethoxysilane, 6- And cyclohexylhexyl triethoxysilane.

As a compound in which R ⁴ is a chloro group substituted alkyl group, for example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxy Silane, 3-chloropropyltriethoxysilane, 4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 5-chloropentyltrimethoxysilane, 5-chloropentyltriethoxysilane, 6-chlorohexyltrimethoxysilane, 6-chlorohexyl triethoxysilane etc. are mentioned.

As a compound in which R ⁴ is an alkenyl group, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyltriethoxysilane, allylmethyldi Ethoxysilane, 1-oxetanyl oxymethyl trimethoxysilane, 1-oxetanyl oxymethyl methyldimethoxysilane, 1-oxetanyl oxymethyl triethoxysilane, 1-oxetanyl oxymethyl methyl diethoxysilane, 2-oxetanyl oxyethyl trimethoxysilane, 2 -Oxetanyl oxyethyl methyldimethoxysilane, 2-oxetanyl oxyethyl triethoxysilane, 2-oxetanyl oxyethyl methyl diethoxysilane, 3 -Oxetanyl oxypropyl trimethoxysilane, 3-oxetanyl oxypropyl methyldimethoxysilane, 3-oxetanyl oxypropyl triethoxysilane, 3-oxetanyl oxypropyl methyl diethoxysilane, 4-oxetanyl butyl trimethoxysilane, 4-oxetanyl oxybutyl Methyldimethoxysilane, 4-oxetanyl oxybutyl triethoxysilane, 4-oxetanyl oxybutyl methyl diethoxysilane, 6-oxetanyl oxyhexyl trimethoxysilane, 6-oxetanyl oxyhexyl methyldimethoxysilane, 6-oxetanyl oxyhexyl triethoxysilane, 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.

As a compound in which R ⁴ is a substituted aryl group, p-styryltrimethoxysilane, p-styryltriethoxysilane and the like can be mentioned.

  In the condensation product (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 abrasion resistance and chemical resistance are required as physical properties of the cured product, it is important that crosslinking of the epoxy group in the condensation product (A) sufficiently proceeds, and a silane compound It is obtained by hydrolysis and condensation under the condition that the molar ratio of silane compound (II) to (I) [= the number of moles of silane compound (II) / the number of moles of silane compound (I)] is 0 or more and 9 or less preferable.

Even if the molar ratio of functional groups other than the epoxy structure-containing group exceeds 9, it is possible to obtain a cured product with high abrasion resistance and chemical resistance, but when problems occur in other properties such as cure shrinkage. There is.
For example, when the molar ratio of (meth) acryloyl groups exceeds 9, a cured product having high abrasion resistance and high chemical resistance can be obtained, but curing shrinkage becomes larger compared to crosslinking with epoxy groups. Therefore, when an environmental load due to heat or humidity is applied, a crack may occur, or a warp may occur when the laminate is formed. The organic functional group R ⁴ in (meth) silane compound exhibit similarly curing shrinkage acryloyl group (II), there is an alkenyl group.
On the other hand, since curing with an epoxy structure-containing group involves a ring opening reaction, it is possible to obtain a cured product with little shrinkage and hardly causing cure shrinkage, and in some cases, a cured product which cures and expands It is also possible to get.

  Furthermore, in consideration of coexistence of hard coat properties (that is, hardness and scratch resistance) and crack resistance, the molar ratio is more preferably 0 or more and 5 or less, still more preferably 0 or more and 3 or less, It is particularly preferable that it is 0 or more and 1 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.
If the condensation degree of the condensation product (A) is smaller than that of the tetramer, there is a concern that the condensation product may volatilize at high temperature or under high pressure. However, when condensation product (A) contains silane compound (II), it is preferable that the average number of epoxy groups per molecule is 2 or more.
In addition, if the degree of condensation of the condensation product (A) is greater than 200, there is a concern that the compatibility with the acrylate compound, the organic solvent, the cured product, etc. may be significantly reduced.

500 or more are preferable, as for the weight average molecular weight of the condensate (A) of this invention, 1,000 or more are more preferable, and 2,000 or more are more preferable. Further, the weight average molecular weight is preferably 30,000 or less, more preferably 28,000 or less, and still more preferably 25,000 or less.
When the weight average molecular weight of the condensation product (A) is less than 500 (or less than 1,000), it is volatile, and some or all of it may evaporate before curing under high temperature or high pressure reduction. is there. When the weight average molecular weight exceeds 30,000, the compatibility with the acrylate compound, the organic solvent, the cured product, and the like is reduced, and there is a possibility that the film becomes cloudy at the time of coating film formation.
The weight average molecular weight is a weight average molecular weight measured by GPC.

  Here, the weight average molecular weight of the condensate (A) can be controlled by appropriately selecting the amount of water used for 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.

Silane compound (I) which is a raw material of condensation product (A) of the present invention and silicon atom which condensation product (A) has with respect to mole number X of OR ³ group directly bonded to silicon atom which silane compound (II) has The ratio Y / X of the mole number Y of the directly bonded OR ³ group is preferably 0.2 or less, more preferably 0.1 or less, still more preferably 0.05 or less, and substantially zero. Is most preferred.
When Y / X exceeds 0.2, the coating film may shrink with time after curing, causing cracks, or impairing the storage stability of the epoxy group.
In addition, Y / X can be calculated | required by measuring by < ¹ > H-NMR and < ²⁹ > Si-NMR.

  Here, Y / X can be 0.2 or less by appropriately selecting the amount of water used for the hydrolysis / condensation reaction, and the type and amount of the catalyst. For example, the greater the amount of water, the more accelerated the hydrolysis and the lower the value of Y / X.

  From the viewpoint of increasing the crosslink density caused by the epoxy groups in the cured product to improve the hardness and scratch resistance of the cured product, the residual ratio of the epoxy structure-containing group in the condensate (A), ie, the silane which is the raw material The ratio of the number of moles of the epoxy structure-containing group in the condensation product (A) to the number of moles of the epoxy structure-containing group in 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 still more preferably 60% or more.
The residual ratio of the epoxy structure-containing group can be determined by ¹ H NMR measurement.

In addition, even when the residual ratio of the epoxy structural group in the condensation product (A) and the number of epoxy structural groups in one molecule are small, when R ¹ , R ² and R ⁴ are not bulky groups, R ¹ , R ² , and R ⁴ are preferably non-bulky groups because they can increase the crosslink density resulting from the epoxy group in the cured product.

<Hydrolysis and condensation reaction>
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 performing a hydrolysis / condensation reaction using a neutral salt or a basic compound as a catalyst, it is possible to obtain a siloxane resin without deactivating the epoxy group before, after, or during the hydrolysis / condensation reaction.

  In addition, when the hydrolysis / condensation reaction is carried out using an acidic compound as a catalyst, the resulting condensate (A) becomes acidic. When the resulting condensate (A) is acidic, it tends to cause rust when the storage container is a metal, and when it is a resin, it tends to cause deterioration due to hydrolysis, so it is necessary 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.

<Neutral salt>
The neutral salt used in the present invention is a normal salt composed of a strong acid and a strong base, and, for example, from a cation of a first group element ion, a second group element ion, a tetraalkyl ammonium ion, a guanidinium ion as a cation It is a salt composed of a combination of any one selected from the group consisting of: a group 17 element ion excluding fluoride ion as an anion; a sulfate ion; a nitrate ion; and a group selected from the group consisting of perchlorate ions.

Specific examples of the neutral salt in the present invention include, 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, rubidium bromide, cesium bromide, francium bromide, beryllium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, radium bromide, bromide Tetramethyl ammonium, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, tetrapentyl ammonium bromide, tetrahexyl ammonium bromide, guanidinium bromide;
Lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, francium iodide, beryllium iodide, magnesium iodide, calcium iodide, calcium iodide, strontium iodide, barium iodide, radium iodide, iodide Tetramethyl ammonium, tetraethyl ammonium iodide, tetrapropyl ammonium iodide, tetrabutyl ammonium iodide, tetrapentyl ammonium iodide, tetrahexyl ammonium 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, nitrate Tetrabutylammonium, 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, tetramethyl ammonium perchlorate, tetraethyl ammonium perchlorate, tetrapropyl ammonium perchlorate, tetrabutyl ammonium perchlorate, tetrapentyl ammonium perchlorate, tetrahexyl ammonium perchlorate And guanidinium perchlorate. These neutral salts may be used alone or in combination of two or more.

  Among these neutral salts, from the viewpoint of using as a catalyst, a highly nucleophilic 17th group element ion is more preferable as an anion, and as a cation, it is not bulky so as not to inhibit the nucleophile action. It is determined, and Group 1 element ions and Group 2 element ions are more preferable.

  Furthermore, considering availability and safety in 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 and condensation reaction of the silane compound is promoted, but in consideration of the transparency of the condensation product and the purification step, the smaller the addition amount, the better. .

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

<Basic compound>
The basic compound used in the present invention is not particularly limited as long as it is basic, but, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, carbonate Hydrogen potassium, inorganic bases such as ammonia;
Organic bases such as triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, tetramethylammonium hydroxide can be used. These basic compounds may be used alone or in combination of two or more.
Among these, inorganic bases are preferable in consideration of the ease of removal from the condensation product (A).

  In the present invention, the hydrolysis / condensation reaction of the silane compound is promoted as the use amount of the basic compound increases, but in consideration of the transparency of the condensation product and the purification step, the addition amount is preferably as small as possible. .

  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, per 1 mol of the hydrolyzable silyl group of the silane compound. Preferably, 0.000005 to 0.05 mol is particularly preferable, and 0.000005 to 0.01 mol is the 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 corrosiveness of the condensate (A) to the storage container is lower In addition, neutral salts are preferred from the viewpoint that the adverse effects on the human body are often low in the process of handling.

The amount of water required for the hydrolysis and condensation reaction in the preparation of the condensate (A) of the present invention is preferably 0.4 to 20 equivalents relative to the OR ³ group directly bonded to a silicon atom, 3 equivalents are more preferable, and 0.45 to 2 equivalents are more preferable.
If the amount of water is less than 0.4 equivalents, part of the OR ³ groups may remain without hydrolysis. If the amount of water exceeds 20 equivalents, the rate of hydrolysis / condensation reaction is too high to form a high molecular weight condensate, which may lower the physical properties and transparency of the coating.

  In the production of the condensate (A) of the present invention, it is preferable to carry out while refluxing the dilution solvent and the alcohol and the like generated by hydrolysis, in consideration of production safety.

The diluting solvent used in the preparation of the condensate (A) of the present invention refers to an alcohol or an ether compound, and is preferably water soluble.
The reason is that many silane compounds (I) and (II) used in the present invention have low compatibility with neutral salts (A) and water used for hydrolysis, so the reaction can be promoted smoothly. Because the reaction solution is preferably compatible, it is preferable.
On the other hand, ketone and ester solvents are not suitable because they have a carbonyl group and tend to 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 more and 200 ° C. or less, more preferably 50 ° C. or more and 200 ° C. or less, and still more preferably 60 ° C. or more and 250 ° C. or less 60 ° C. or more and 230 ° C. or less are particularly preferable.
If the boiling point of the diluted solvent is less than 40 ° C, refluxing occurs at a low temperature, which tends to interfere with the reaction, and if it is more than 200 ° C, it is difficult to remove after the reaction, It may be necessary to incorporate the complicated process of

Specific examples of the dilution solvent used in the preparation 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- 2-propanol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether and the like.
These dilution solvents may be used alone or in combination of two or more.

The use amount of the dilution solvent in the condensation product (A) production of the present invention is preferably the total amount of the silane compound (I) and (II) is 90% by mass or less, as the total amount of water and the dilution solvent. % Or more and 80 mass% or less is more preferable, and 40 mass% or more and 80 mass% or less is particularly preferable.
If the amount of dilution solvent used is too large, there is a concern that the concentration of the silane compound in the reaction system may decrease and the reaction rate may decrease. On the other hand, it is important to select an appropriate amount, as it has the effect of improving the compatibility between water and the silane compound, and also suppressing the increase in viscosity in the system with the progress of the reaction and suppressing the decrease in reaction rate. It is.

The reaction temperature for producing 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 decreases and the reaction time tends to increase significantly, and when the reaction temperature is higher than 200 ° C., the organic substituent causes side reaction There is a concern that it will cause it to be deactivated.

<A compound having two or more (B) (meth)acryloyl groups in one molecule>
The compound having at least one radically polymerizable group, which is the component (B) in the present invention, increases the crosslink density immediately after curing by light or heat due to the reaction heat at the time of curing, and also improves the adhesion to the organic substrate It can be used for the purpose of
If it is a compound which has a (meth) acryloyl group used by normal radical hardening as (B) component, there will be no problem in particular.

Specific examples of the component (B) include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tri Di (meth) acrylates such as propylene glycol di (meth) acrylate;
Tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triisocyanurate tri (meth) acrylate and the like;
Tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate and tetramethylolmethane tetra (meth) acrylate;
Examples thereof include tetrafunctional or higher functional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate.

Furthermore, NK oligo UA-122P, NK oligo U-4 HA, NK oligo U-6 LPA [above, Shin-Nakamura Chemical Co., Ltd. product made as a commercial item, AT-600, UA-306H, UA-510H [above, Kyoeisha Chemical Multi-functional urethane acrylates such as EBECRYL220, EBECRYL 8210, EBECRYL 8311 [above, Daicel-Cytec Co., Ltd.]; NK oligo EA-1020, NK oligo EA-6310, NK oligo EA-7120 [or more, Listed are multifunctional epoxy acrylates such as Shin-Nakamura Chemical Co., Ltd.], epoxy ester 70PA and epoxy ester 3002A [above, Kyoeisha Chemical Co., Ltd.], EBECRYL 600 and EBECRYL 6040 [above, Daicel Cytech Co., Ltd.]. be able to.
These compounds (B) having two or more (meth) acryloyl groups in one molecule may be used alone, or two or more kinds may be used in combination.

The mixing ratio of the compound (B) having two or more (meth) acryloyl groups in one molecule to the condensate (A) in the curable composition of the present invention is 100 parts by weight of the condensate (A), 1 to 9900 parts by weight is preferable, 3 to 1900 parts by weight is more preferable, 5 to 900 parts by weight is further preferable, and 10 to 200 parts by weight is particularly preferable.
If the mixing ratio of the component (B) to the condensation product (A) is less than 1 part by weight, crosslinking by radical polymerization tends not to proceed sufficiently, and if it exceeds 9900 parts by weight, crosslinking by epoxy groups can not proceed sufficiently Tend.

When the cured product is used as a transparent member such as a resin window, the condensate (A) and the compound (B) having two or more (meth) acryloyl groups in one molecule are required to be compatible with each other.
When it is not compatible before curing, a cloudy cured product is obtained, and it is difficult to use as a transparent member. When the cured product is cloudy, the cured products of the condensation product (A) and the compound (B) having two or more (meth) acryloyl groups in one molecule are not bonded to each other, and There is a possibility that intrusion network (IPN) can not be formed so much, and physical properties such as hardness, abrasion resistance and chemical resistance tend to be slightly deteriorated.
When mutually compatible and a transparent cured product is obtained, dispersion / IPN is formed in nanoscale, and high hardness, high scratch resistance, and high chemical resistance can be developed even if they are not bonded to one another. is there.
On the other hand, in the case where the cured product is not bonded to each other and the cured product is not three-dimensionally cross-linked or polymerized, even if it is transparent immediately after curing, the IPN is loosened due to heat and humidity and the cured product Phase separation progresses in the inside, and it may become cloudy.

  From this point of view, the compound (B) having two or more (meth) acryloyl groups in one molecule is preferably a low molecule. More specifically, the molecular weight of the compound (B) having two or more (meth) acryloyl groups in one molecule in the present invention is preferably 30,000 or less, more preferably 25,000 or less, and 20,000 or less It is further preferred that

2 or more and less than 200 are preferable, and, as for the functional group number of the compound (B) which has 2 or more of (meth) acryloyl groups in 1 molecule in this invention, 3 or more and less than 100 are more preferable.
When the number of (meth) acryloyl groups is less than 2, the cured product may not be three-dimensionally cross-linked / high molecular weight, and even if it is transparent immediately after curing, it may become cloudy by application of heat or humidity. . When the number of functional groups is more than 200, the molecular weight of the compound (B) having two or more (meth) acryloyl groups in one molecule is too large, and there is a concern that the compound may not be compatible before curing.

<(C) Curing agent for curing epoxy group>
The curing agent (C) for curing the epoxy group to the epoxy group-containing siloxane condensate (A) of the present invention is not particularly limited, and any of those generally known as epoxy resin curing agents can be used. .

  Examples of preferable curing agents include acid anhydride curing agents, cationic polymerization initiators, organic phosphorus compounds, amine curing agents, tertiary amines and the like.

In the case where the curing agent (C) is a curing agent that promotes the polymerization of the epoxy group 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 it is more than 10 parts by weight The polymerization degree of the epoxy group may not progress sufficiently due to the increase of the polymerization initiation point. Moreover, it may remain in a coating film as a plasticizer, without acting as a polymerization start point.

In the case where the curing agent (C) has active hydrogen and is a curing agent that undergoes an addition reaction with the epoxy group in the condensation product (A) (hereinafter sometimes referred to as "addition type curing agent"), 10 to 150 parts by weight is preferable, and 30 to 150 parts by weight is more preferable.
If the compounding amount of the curing agent (addition type curing agent) which causes an addition reaction with the epoxy group is less than 10 parts by weight, curing may not proceed sufficiently, and if it is more than 150 parts by weight, the curing agent is excessive Although the crosslinking of the epoxy group proceeds sufficiently, the remaining curing agent (C) may be a plasticizer and the crosslinking density may not be sufficiently high.

  Hereinafter, the details of the acid anhydride curing agent, the cationic polymerization initiator, the organic phosphorus compound, and other usable curing agents will be described.

(C-1) Acid Anhydride-Based Curing Agent From the viewpoint of heat resistance, an acid anhydride-based curing agent is preferable as the curing agent that cures the epoxy group in the present invention. The acid anhydride curing agent is classified into a polymerization type / addition type composite curing agent.

As an acid anhydride type curing agent, for example, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic acid anhydride, polyadipic acid anhydride, polyazelaic acid anhydride , Polysebacic anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride Acid anhydride, methylhymic 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 anhydride, methyl nadic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy -1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride etc. are mentioned.
These acid anhydride curing agents may be used alone, or two or more thereof may be used in any combination and amount.

  When using an acid anhydride type curing agent, it is preferable to use it so that the equivalent ratio of the functional group in a curing agent with respect to the epoxy group in a condensate (A) becomes the range of 0.5-10. It is preferable that the equivalent ratio is in the range of 0.5 to 110 because unreacted epoxy groups and functional groups of the curing agent hardly remain.

(C-2) Cationic polymerization initiator As a curing agent which cures the epoxy group in the present invention, a cationic polymerization initiator is preferable from the viewpoint of physical properties such as abrasion resistance and chemical resistance of a cured product to be obtained. The cationic polymerization initiator is classified as a polymerization type curing agent.

  Examples of the cationic polymerization initiator include a thermal cationic polymerization initiator which generates a cationic species and / or a Lewis acid by heat, and a cationic light polymerization initiator which generates a cationic species and / or a Lewis acid by light. There is no clear division between the thermal cationic polymerization initiator and the photo cationic polymerization initiator, and some of them act as a curing agent for both heat and light.

Examples of the thermal cationic polymerization initiator include onium salt cationic polymerization initiators such as sulfonium salts, ammonium salts, pyridinium salts phosphonium salts, iodonium salts and the like;
Examples thereof include a combination of an aluminum complex and a silanol compound, an aluminum complex composite cationic polymerization initiator such as a combination of an aluminum complex and bisphenol S, and the like.
As a photocationic polymerization initiator, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene type compound etc. are mentioned, for example.

The cationic polymerization initiator can be obtained as a commercial product. For example, FC-520 [or more, 3M company], UVR-6990, UVR-6974 [or more, Union Carbide company], UVE-1014, UVE-1016 [or more, General Electric company], KI-85 [ As described above, manufactured by Degussa, SP-15, SP-170 (above, manufactured by Asahi Denka Co., Ltd.), SI-60L, SI-80L, SI-100L (above, manufactured by Sanshin Kagaku Kogyo Co., Ltd.), CPI -100P, CPI-101A, CPI-200K, CPI-200S (above, San-Apro Ltd. made), WPI-124, WPI-113, WPI-116, WPI-169, WPI-170, WPI-124 [or more, Wako Pure Chemical Industries, Ltd.], Rhodesil 2074 [above, Rhodia company make], etc. are mentioned.
Among these cationic polymerization initiators, onium salts are preferable from the viewpoint of handleability. Further, among the 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 thereof may be used in combination in any combination amount.

The addition amount of the cationic polymerization initiator needs to be adjusted according to the generation amount of the acid to be generated and the generation rate, but 0.5 to 10 parts by weight per 100 parts by weight of the condensate (A) Preferably, 0.5 to 5 parts by weight is more preferable, and 0.1 to 5 parts by weight is further preferable.
When the addition amount of the cationic polymerization initiator is in the range of 0.01 to 15 parts by mass, it is preferable because the abrasion resistance and the chemical resistance of the cured epoxy resin product become good.

  Furthermore, when curing is carried out by cationic ring-opening polymerization using super strong acids such as fluorophosphates, fluoroantimonates, fluoroborates, etc., polymerization of epoxy groups proceeds rapidly due to the high acid strength. A cured product with high abrasion resistance and chemical resistance can be obtained.

  Furthermore, a cured product obtained using a cationic polymerization initiator as a curing agent (C) for curing an epoxy group specifically has a property of expanding upon curing.

(C-3) Organophosphorus Compound As the curing agent for curing the epoxy group in the present invention, an organophosphorus compound is preferable from the viewpoint of promoting the effective reaction. Organic phosphorus compounds are classified as polymerization type curing agents.

Organic phosphorus compounds include, for example, organic phosphines such as tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, diphenyl phosphine, phenyl phosphine and the like; methyl tributyl phosphonium dimethyl phosphate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium ethyl Examples thereof include phosphonium salts such as triphenyl borate and tetrabutyl phosphonium tetrabutyl borate.
These organic phosphorus compounds may be used alone, or two or more of them may be used in any combination and amount.
The addition amount of the organophosphorus compound needs to be adjusted according to the generation amount and generation rate of the acid to be generated, but preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the condensate (A) (solid content) And 0.5 to 5 parts by weight are more preferable.

(C-4) Amine-Based Curing Agent From the viewpoint of availability and cost, an amine-based curing agent (but excluding a tertiary amine) is preferable as a curing agent for curing the epoxy group in the present invention. Amine curing agents are classified as addition curing agents.

  Examples of the amine curing agent (but excluding tertiary amines) include aliphatic amines, polyether amines, alicyclic amines, aromatic amines and the like.

Examples of aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, Bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine and the like can be mentioned.
Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines and the like.
As alicyclic amines, for example, isophorone diamine, metacene diamine, N-aminoethyl piperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3) -Aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornene diamine 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-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl Sulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ) Ethylamine, diamino di Ethyl dimethyl diphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene and the like can be mentioned.
These amine curing agents may be used alone, or two or more thereof may be used in any combination and amount.

  10-150 weight part is preferable with respect to 100 mass parts of condensate (A) (solid content), and, as for an amine-type hardening | curing agent, 30-150 weight part is more preferable.

(C-5) Tertiary Amine As a curing agent for curing the epoxy group in the present invention, a tertiary amine is preferable from the viewpoint of availability and cost. Tertiary amines are classified as polymerization type curing agents.

Examples of tertiary amines include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, etc. It can be mentioned.
These tertiary amines may be used alone, or two or more of them may be used in any combination and amount.

  0.5-10 parts by weight is preferable, and 0.5-5 parts by weight is more preferable with respect to 100 parts by weight of the condensate (A) (solid content).

(C-6) Other curing agents As a curing agent for curing the epoxy group in the present invention, acid anhydride curing agents, cationic polymerization initiators, organic phosphorus compounds, amine curing agents (excluding tertiary amines) Other than tertiary amines, for example, amide-based curing agents, phenol-based curing agents, imidazoles, tetraphenylboronic salts, organic acid dihydrazides, halogenated boron amine complexes, polymercaptan-based curing agents, isocyanates Examples of the curing agent include blocked curing agents and blocked isocyanate curing agents.
These other curing agents may be used alone, or two or more of them may be used in any combination and amount.

<(D) Radical generator>
The curing agent used for the compound (B) having two or more (meth) acryloyl groups in one molecule according to the present invention is not particularly limited, and generally, a radical is generated by giving light or heat energy. Any compound known to be used can be used.

Although there are carbon radicals, oxygen radicals, thiyl radicals, etc. which can be used as radical species to be generated, compounds which generate thiyl radicals have poor storage stability and it is difficult to inhibit polymerization using a general polymerization inhibitor . From these viewpoints, as a radical source, one that generates carbon radicals or oxygen radicals is preferable. As a radical generator, for example, a photo radical generator, a thermal radical generator, etc. can be used.
The specific examples are given below.

(D-1) Photo radical initiator The photo radical initiator (d-1) in the present invention is a compound which generates a radical when exposed to active energy rays, and acts as a polymerization initiator for the component (B). Do.

Specific examples of the photo radical initiator (d-1) include, for example, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxy benzophenone, diethoxy acetophenone, benzyl dimethyl ketone , 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. A carbonyl compound of
Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide;
Acyl phosphine oxides such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide can be mentioned.
These photo radical initiators (d-1) may be used alone or in combination of two or more in consideration of the curing rate and the like.

  The photo radical initiator can be obtained as a commercial product. For example, IRGACURE series such as IRGACURE 184 and IRGACURE 819, DAROCUR series such as DAROCUR 1173 and DAROCUR TPO [above, made by BASF Corporation], KAYACURE series such as KAYACURE DETX-S, KAYACURE CTX [above, Nippon Kayaku Co., Ltd. made], TAZ TAZ series [above, Midori Chemical Co., Ltd. product] etc., such as -101 and TAZ-110, etc. are marketed.

The addition amount of the photo radical initiator (d-1) needs to be adjusted according to the amount of generated radicals and the target molecular weight, but a compound (B) having two or more (meth) acryloyl groups in one molecule The amount is preferably 0.05 to 50 parts by weight, and more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight.
If the addition amount of the photo radical initiator (d-1) is less than 0.05 parts by weight, the generated radicals run short, and the compound (B) having two or more (meth) acryloyl groups in one molecule is sufficiently cured. If the amount is more than 50 parts by weight, problems such as deterioration of coloration and weatherability tend to occur.

(D-2) Thermal Radical Generator The thermal radical initiator (d-2) in the present invention is a compound which generates a radical by heating and acts as a polymerization initiator for the component (B).

Specific examples of the thermal radical initiator (d-2) include typical polymerization initiators. Examples of the thermal polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl and the like. Peroxides, diacyl peroxides such as acetyl peroxide;
peroxy esters such as t-butyl peroxy-2-ethylhexanate, t-butyl peroxy neodecanate, cumyl peroxy neodecanate, t-butyl peroxybenzoate and the like;
Percarbonates such as diisopropyl peroxy dicarbonate and di-sec-butyl peroxy dicarbonate; azo compounds such as azobisisobutyronitrile etc. can be mentioned.
These thermal radical initiators (d-2) 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 thermal radical initiator (d-2) needs to be adjusted according to the amount of generated radicals and the target molecular weight, but a compound (B) having two or more (meth) acryloyl groups in one molecule 0.05 to 50 parts by weight is preferable to 100 parts by weight, and 0.1 to 30 parts by weight is more preferable.
If the addition amount of the thermal radical initiator (d-2) is less than 0.05 parts by weight, the generated radicals run short, and the compound (B) having two or more (meth) acryloyl groups in one molecule is sufficiently cured If the amount exceeds 50 parts by weight, problems such as deterioration of coloration and weatherability tend to occur.

  Also, the photo radical initiator (d-1) and the thermal radical initiator (d-2) may be mixed and used. When using a photo radical initiator (d-1), well-known polymerization accelerators, such as a tertiary amine, can be used together.

<(E) Metal oxide fine particles>
In the curable composition of the present invention, metal oxide fine particles (E) can be used, if necessary. By blending the metal oxide particles (E), the abrasion resistance of the coating may be further improved.

As metal oxide fine particles (E), silica (SiO ₂ ), alumina (Al ₂ O ₃ ), tin oxide (SnO ₂ ), zirconia (ZrO ₂ ), zinc oxide (ZnO), titania (TiO ₂ ), ITO Examples thereof include (tin / indium oxide), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ), and composite fine particles of these.
These metal oxide fine particles may be used alone or in combination of two or more.

  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 in view of availability, cost, surface hardness and the like, and silica fine particles are particularly preferable.

  The metal oxide fine particles in the present invention are preferably in the form of powder 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 viewpoint of compatibility with other components and dispersibility.
As such an organic solvent, for example, alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;
Esters such as ethyl acetate, butyl acetate, ethyl lactate and δ-butyrolactone;
Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether;
Aromatic hydrocarbons such as benzene, toluene and xylene;
Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be mentioned.
These metal oxide fine particles (E) may be used alone or in combination of two or more.
Among 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 in the present invention is preferably 100 nm or less, more preferably 40 nm or less, and still more preferably 20 nm or less.
When the average particle size 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, as colloidal silica, methanol silica sol, IPA-ST, MEK-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, Nissan Chemical Industries, Ltd. made], OSCAL series, ELECOM series [above, JGC Catalysts] Chemical conversion Co., Ltd. product] etc. can be mentioned.

  As powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT 600, Aerosil OX 50, etc. [above, Nippon Aerosil Co., Ltd. product], Sildex H 31, H 32, H 51, H 52, H 121, H 122, etc. [above, Asahi Glass Made by Co., Ltd., E220A, E220, etc. [above, made by Nippon Silica Kogyo Co., Ltd.], SYLYSIA 470 [manufactured by Fuji Silysia Co., Ltd.], SG flake [manufactured by Nippon Sheet Glass Co., Ltd.], etc. .

  As alumina fine particle dispersed products, NANOBYK-3601, NANOBYK-3602, NANOBYK-3610, etc. [as described above, manufactured by BIC Chemie Japan Ltd.], as an alumina dispersion of isopropanol, AS-150I, etc. [Sumitomo Osaka Cement Co., Ltd. Made as a toluene dispersion of alumina; AS-150T (Sumitomo Osaka Cement Co., Ltd.); As a toluene dispersion of zirconia: HXU-110JC (Sumitomo Osaka Cement Co., Ltd.), alumina, titania, oxidized Examples of powders and solvent dispersions of tin, indium oxide, zinc oxide and the like include Nanotech (manufactured by CI Kasei Co., Ltd.) and the like.

  Among these, ELECOM V-8802 and ELECOM V-8804 [manufactured by JGC Catalysts Chemical Co., Ltd.] have high dispersibility of the fine particles in the coating solution, and the transparency, hardness, and abrasion resistance of the resulting coating film are obtained. Is preferable because it improves.

The use amount of the metal oxide particles (E) in the present invention is preferably 0 to 100 parts by weight, and more preferably 0 to 50 parts by weight with respect to 100 parts by weight of the condensate (A).
When the amount of the metal oxide particles (E) used exceeds 100 parts by weight, the coating may not be formed or the transparency of the coating may be reduced.

In the present invention, the metal oxide fine particles (E) do not adversely affect the strength of the coating film, and therefore, they may be present together with the condensate (A). However, some metal hydroxides have high acidity due to silanol groups on the surface of silica particles, and they may cationically polymerize oxirane rings such as epoxy groups, vinyl ethers, etc. [The sum of the compound (B) having two or more condensates (A) and (meth) acryloyl groups in one molecule and the metal oxide fine particles (E) divided by the total weight of the curable composition] Needs to be adjusted to 0.1 to 0.6.
If the concentration to be a matrix in the curable composition is lower than 0.1, the viscosity of the coating liquid tends to be too low, making it difficult to adjust the thickness of the coating. If the concentration to be the matrix in the curable composition is higher than 0.6, there is a concern of gelling during storage.

  By the way, when it is desired to increase the concentration, chemical modification such as alkoxylation of the surface of the metal hydroxide (E) or sealing of silanol groups is effective. In addition, the above-mentioned ELECOM V-8802, ELECOM V-8804, etc. are products which improved the dispersion | distribution in the organic component by sealing a silanol group, and are effective.

The total solid concentration of the condensate (A), the compound (B) having two or more (meth) acryloyl groups in one molecule and the metal oxide fine particles (E) is 60% by weight or more of the total weight of the curable composition 70% by weight or more is more preferable, 80% by weight or more is even more preferable, 90% by weight or more is particularly preferable, and 95% by weight or more is most preferable.
However, since the solvent is also important for adhesion to the substrate, the total solid concentration of the condensate (A) and the metal oxide fine particles (C) is 30 weight when considering the adhesion. % Or more and 80% by weight or less are preferable, 40% by weight or more and 80% by weight or less are more preferable, 50% by weight or more and 80% by weight or less are further more preferable, and 60% by weight or more and 80% by weight or less are particularly preferable. If it exceeds 80% by weight, the adhesion to the substrate may be reduced.

<(F) Photosensitizer>
In the curable composition of the present invention, when the curing agent (C) that cures an epoxy group and the radical generator (D) exhibit performance by irradiating active energy rays, their photosensitivity is improved. A photosensitizer (F) can be used, if necessary, for the purpose of
The photosensitizer (F) which can absorb light in a wavelength range which can not be absorbed by the photoacid generator to be used is more efficient, and therefore, it is preferable that the overlap in the absorption wavelength range is small.

The photosensitizer (F) is not particularly limited, and examples thereof include anthracene derivative, benzophenone derivative, thioxanthone derivative, anthraquinone derivative, benzoin derivative and the like.
Among these, those having low oxidation potential and high singlet or triplet excitation energy involved in electron transfer are ideal, and from the viewpoint of photoinduced electron donating property, anthracene derivatives, thioxanthone derivatives, and benzophenones. Derivatives are preferred. More specifically, 9,10-dialkoxyanthracene, 2-alkylthioxanthone, 2,4-dialkylthioxanthone, 2-alkylanthraquinone, 2,4-dialkylanthraquinone, p, p'-aminobenzophenone, 2-hydroxy-4-hydroxybenzophenone Alkoxy benzophenone, benzoin ether, etc. are mentioned. More specifically, anthrone, anthracene, 9,10-diphenylanthracene, 9-ethoxyanthracene, pyrene, perylene, corylene, 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-isopropyl thioxanthone, 2,4-diethyl Thioxanthone, phenothiazine, acridine orange, benzoflavin, cetoflavin-T, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nit Aniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1,2-benzanthraquinone , 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3'-carbonyl-bis (5,7-dimethoxycarbonyl coumarin), 9,10 And -dibutoxyanthracene, 9,10-dipropoxyanthracene and the like.
These photosensitizers (F) may be used alone or in combination of two or more.

Although the addition amount in the case of using a photosensitizer (F) may be suitably adjusted according to the target hardening speed, 0.1 weight part or more is preferable with respect to 100 weight part of photo-acid generators. 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.
When the addition amount of the photosensitizer (F) is less than 0.1 parts by weight, the effect of the desired photosensitizer tends to be hardly obtained, and when it exceeds 10 parts by weight, the coating film is colored or It tends to lead to cost increase.

<Curable composition>
The curable composition of the present invention contains the above components (A), (B), (C) and (D), and optionally contains (E) and (F). However, in order to adjust physical properties, various additives may be added appropriately. For example, additives generally used in paints such as inorganic fillers, inorganic pigments / organic pigments, plasticizers, dispersants, wetting agents, thickeners, antifoaming agents, etc. can be added.

A solvent can be blended with the curable composition of the present invention.
The solvent used in the present invention is not particularly limited, but when the substrate used is a plastic, since the solvent resistance of the substrate is often low, ketones such as methyl isobutyl ketone and diisobutyl ketone, butanol And alcohols such as isopropyl alcohol, esters such as butyl acetate and isopropyl acetate, and ethers such as diethylene glycol methyl ether and propylene glycol methyl ether. In particular, it is preferable to use an ether-based solvent in an amount of 30% by weight or more based on the total solvent from the viewpoint of not damaging the substrate.

The compounding amount of the solvent is, based on 100 parts by weight of the total of (A) component, (B) component, (C) component, (D) component and, if necessary, (E) component and (F) component, 0 to 400 parts by weight is preferable, and 0 to 200 parts by weight is more preferable.
If the blending amount of the solvent is more than 400 parts by weight, the base material may be damaged as described above, which is not preferable.

There is no particular limitation on the method of preparing the linear curable composition of the present invention.
Mix the above components, block if necessary, and mix with a hand mixer or static mixer;
Knead at normal temperature or under heating using a planetary mixer, a disper, a roll, a kneader, etc .;
Conventional methods such as dissolving and mixing the components using a small amount of a suitable solvent and the like can be mentioned.

<Cured product>
The cured product of the present invention includes those obtained by curing an active energy ray-curable composition.

As the active energy ray to be irradiated at the time of curing, visible light, ultraviolet ray, infrared ray, X ray, α ray, β ray, δ ray and the like can be mentioned, but the reaction rate is fast and the active energy ray generator compares Ultraviolet light is the most preferable in that it is inexpensive.
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.
If the dose of active energy ray is less than 50 mJ / cm ² , curing may take time because the amount of light is small, and productivity may deteriorate. On the other hand, when the irradiation amount of the active energy ray exceeds 10,000 mJ / cm ² , it may not be cured beautifully or the substrate may be damaged.

  The cured products of the present invention also include those obtained by curing a thermosetting composition. In that case, there is no limitation in particular in curing temperature, Usually, 200 degrees C or less is preferable, 150 degrees C or less is more preferable, 120 degrees C or less is still more preferable. In the case of curing at a temperature higher than 200 ° C., there is a concern that the organic component in the condensate may be decomposed.

<Laminate>
A laminate can be produced using the curable composition of the present invention.
The laminate of the present invention is obtained by a manufacturing method including the steps of applying the curable composition of the present invention to a substrate, and curing the active composition using an active energy ray or a heat source to form a cured film.
In the present invention, the substrate is not particularly limited, and various substrates described later can be used.

The laminate of the present invention can be suitably used for a front plate of a personal computer, a smartphone, a tablet or the like, a window glass of a car or the like, a protective material of a lamp of a car or the like, a film or the like.
The curable composition of the present invention is used, for example, for coating of buildings made of metal, ceramics, glass, cement, ceramic base materials, plastics, films, sheets, wood, paper, fibers, etc., household appliances, industrial equipment, etc. It can be used suitably.

  In active energy ray irradiation curing, a resinous substrate is preferable from the viewpoint of taking advantage of not requiring high heat at the time of curing, and for example, acrylic resin, polycarbonate resin, polyethylene terephthalate (hereinafter referred to as "PET") resin, And substrates such as plastics, films, and sheets.

As an acrylic resin base material, for example, Sumipex, Technoroy [above, manufactured by Sumika Acrylics Co., Ltd.], acriprene, akrylite [above, Mitsubishi Rayon Co., Ltd.], Paragrass, Como Glass [above, Kuraray Co., Ltd. And dela glass, dera prism [above, made by Asahi Kasei Techno Plus Co., Ltd.], cannacerite [manufactured by Kanase Kogyo Co., Ltd.] and the like.
As a polycarbonate resin base material, for example, Carboglass [Asahi Glass Co., Ltd. product], Iris Polyca Sheet [Iris Shinyo Co., Ltd. product], Iupilon [Mitsubishi Gas Chemical Co., Ltd. product], Panlite [Teijin Kasei Co., Ltd. Products), polycarbonate plates (manufactured by Takiron Co., Ltd.), Polycaace (manufactured by Sumitomo Bakelite Co., Ltd.), polycarbonate plates (manufactured by Sekisui Molding Industry Co., Ltd.), PC mirrors (manufactured by Ribosui Co., Ltd.), etc. .

  Examples of PET resin substrates include Pet Ace (Sumitomo Bakelite Co., Ltd.), Estella, Estela Super (Sekisui Molding Industry Co., Ltd.), Peters (Mitsubishi Resins Co., Ltd.), Petek (Takiron Co., Ltd.) Made, Mineron [Mineron Chemical Industry Co., Ltd.], Polytech A-PET sheet [Polytech Co., Ltd.], A-PET resin sheet [Teijin Kasei Co., Ltd.], Lumirror [Toray Co., Ltd.], Cosmo Shine [made by Toyobo Co., Ltd.] etc. are mentioned.

It is preferable that it is 1-100 micrometers as a coating-film thickness in this invention.
If the coating 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 sufficient hardness tends not to be obtained. The curing tends to be delayed without reaching the deep part.
However, in the case where the coating film thickness is 100 μm or more, it is preferable to adopt a method of repeating coating and irradiation of active energy rays in several times.

  In the curable composition of the present invention, a cationic polymerization initiator as a curing agent (C) for curing the epoxy group with respect to the condensate (A) containing the silane compound (I) containing an epoxy group The hardened | cured material by this condensate (A) obtained by using has the property to expand | swell at the time of hardening. Therefore, the curing of the curable composition offsets the property of shrinking at the time of curing of the cured product by the compound (B) having two or more (meth) acryloyl groups in one molecule, and the entire cured product at the time of curing It hardly shrinks. Therefore, when the said curable composition is coated with respect to the base material which curvature does not generate | occur | produce by heat or moisture absorption, the laminated body which curvature hardly generate | occur | produces can be obtained at the time of hardening.

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

The substances used in Examples and Comparative Examples are as follows.
○ Silane compounds having hydrolyzable silyl group (I)
A-186: 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane [Momentive Performance Materials Japan Ltd. molecular weight 246.3]
A-187: 3-glycidyloxypropyltrimethoxysilane [Momentive Performance Materials Japan KK, molecular weight 236.3]
○ Silane compounds having hydrolyzable silyl group (II)
A-174: 3-methacryloxypropyl trimethoxysilane [Momentive Performance Materials Japan Ltd. molecular weight 248.4]
A-171: Vinyltrimethoxysilane [Momentive Performance Materials Japan Ltd. molecular weight 148.2]
A-1630: Methyltrimethoxysilane [Momentive Performance Materials Japan Ltd. molecular weight 136.2]
A-189: 3-Mercaptopropyltrimethoxysilane [Momentive Performance Materials Japan KK, molecular weight 196.3]
○ Neutral salt magnesium chloride (manufactured by Wako Pure Chemical Industries, Ltd., special grade, molecular weight 95.2)
Sodium chloride [manufactured by Wako Pure Chemical Industries, Ltd., special grade, molecular weight 58.4]
○ Basic compound TEA: triethylamine [manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 101.2]
○ Acid catalyst HCl: Hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., 0.01 mol / L)
○ Compounds having two or more (meth) acryloyl groups in one molecule (B)
DPHA: dipentaerythritol hexaacrylate [Shin-Nakamura Chemical Co., Ltd. product, molecular weight 578]
TMPTA: trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 296)
HDDA: 1,6-Hexanediol diacrylate [Shin Nakamura Chemical Industry Co., Ltd., molecular weight 226]
○ Radical polymerizable functional group ○ Epoxy curing agent (C)
Pyrrolitic anhydride [manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 218.2]
CPI-101A (San-Apro Co., Ltd., triarylsulfonium · SbF ₆ salt)
Hexamethylene diamine (made by Tokyo Chemical Industry Co., Ltd., molecular weight 116.2)
Benzyldimethylamine [manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 135.1]
○ Radical generator (D)
2-hydroxy-2-methylpropiophenone [manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 164.2]
BPO: benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 242.2)
○ Dilution solvent PGME: 1-methoxy-2-propanol [made by Daicel Corporation, molecular weight 90]
Methanol [Mitsubishi Gas Chemical Co., Ltd., molecular weight 32]
○ Others Bisphenol A diglycidyl ether [Tokyo Chemical Industry Co., Ltd., molecular weight 340.4]
MMA: methyl methacrylate [manufactured by Kuraray Co., Ltd.]
GMA: Glycidyl methacrylate [Nippon Yushi Co., Ltd. product]
AA: acrylic acid [Kanto Chemical Co., Ltd. product]
V59: 2,2'-azobis (2-methyl butyronitrile) [manufactured by Wako Pure Chemical Industries, Ltd.]

  The evaluation for the condensate obtained in the synthesis example is as follows.

(Quantification of OR group directly bonded to silicon)
The Y / X ratio was calculated by measuring the OR group directly bonded to silicon in the silane compound before and after the reaction according to the following method.
¹ H-NMR and ²⁹ Si-NMR measurements were carried out using heavy acetone as a solvent, using JNM-LA400 manufactured by JEOL.

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

(Evaluation of residual property of epoxy group)
The obtained condensate was subjected to ¹ H-NMR measurement using heavy acetone as a solvent using JNM-LA400 manufactured by JEOL.

  Physical-property evaluation with respect to the test piece obtained by the Example and the comparative example is as follows. In addition, evaluation with respect to a test piece measured after leaving still for 7 days at room temperature after hardening. (However, only the initial adhesion was measured immediately after curing.)

(Adhesiveness)
Make a cut with a cutter so that the resulting cured coating film becomes 100 squares of crosscut 10 × 10 at 1 mm intervals, stick Nichiban Cellophane Tape (registered trademark) on the cut, and vigorously peel it upward at 90 ° It was observed visually whether the cured coating film was peeled off from the substrate. 100 points were completely adhered, 0 points were completely peeled off, and the points were evaluated at 1 point per square.
The adhesion to boiling water was immersed in boiling water for 1 hour, taken out, lightly wiped moisture, and measured quickly.

(Abrasion resistance)
The abrasion test (500 gf load 500 rotation) of the cured film is performed using a Maze testing machine-made taber type ablation tester (using wear wheel CS-10F), and the turbidity of the cured film before and after the abrasion test is measured using a haze meter It measured and made the value of [the turbidity after an abrasion test-the turbidity before an abrasion test] into (DELTA) Haze ((DELTA) Haze is 15 or less in abrasion resistance being favorable).

(hardness)
The hardness of the cured coating was evaluated in accordance with JIS K5600, pencil hardness.

(Alkali resistance)
After spotting 0.5 mL of a 0.05 N aqueous solution of sodium hydroxide on the cured coating, capping it so that the water does not evaporate, heat at 55 ° C. for 4 hours, wipe off the aqueous solution of sodium hydroxide, The following criteria were evaluated.
○: There is no spot mark.
Fair: Spot marks slightly remain, but the smoothness of the coating is not impaired.
X: The coating film is affected, melted or cracked.

(Heat resistant crack)
After heating at 110 ° C. for 24 hours using a hot air drier, the coating film was visually observed for cracks, and evaluated as ××.

(warp)
The obtained coating liquid was coated on a PET film (150 × 100 × 0.25 mm) using a bar coater # 40 so that the dry film thickness was about 20 μm, and was cured to prepare a laminate. .
After the coating was cured, it was heated at 120 ° C. for 30 minutes for accelerated curing, and then cooled to room temperature, and the laminate was placed on a horizontal table so that the coating was on top.
For each of the four vertices on the top of the stack, the vertical distance from the top of the platform was measured and the average value was calculated. A positive value was obtained when the laminate warped to the painted side (a corner of the lower surface of the laminate floated from the surface of the table), and a negative value in the opposite case.
In addition, the result of the curvature evaluated on the same conditions by PET film base-material alone was 0 mm.

<Synthesis Examples 1 to 14 of Condensate (A)>
The compound described in Table 1 (units of compounding amounts are parts by weight) is charged into a reactor equipped with a stirrer, 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 evaporated under reduced pressure using an evaporator, concentrated, and adjusted to a 50% solution using PGME.
The evaluation results for the obtained condensate are shown in Table 1.

Synthesis Example 15 of Compound (B) Having Two or More (Meth) Acryloyl Groups in One Molecule>
50 parts by mass of PGME is charged into a reactor equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping rod, and the temperature is raised to 110 ° C. while introducing nitrogen gas, then 86.4 parts by mass of MMA ( A mixture of 0.864 mol), 13.6 parts by mass (0.096 mol) of GMA, 1.0 parts by mass of the initiator V59 and 30 parts by mass of PGME was dropped at a constant speed over 5 hours from the dropping funnel. Subsequently, a mixture of 0.5 parts by mass of an initiator V59 and 10 parts by mass of PGME was dropped at a constant speed over 1 hour. Thereafter, the mixture was further stirred at 110 ° C. for 2 hours. Then, after adding 8.6 parts by weight (0.119 mol) of AA and stirring for 5 hours to react with the epoxy group, it is cooled to room temperature and has an acryloyl group in one molecule with a weight average molecular weight of 21000. An acrylic polymer having an average of 20 was obtained.
The polymer was adjusted to have a solid content concentration of 50% by PGME.

Example 1
[Preparation of coating solution]
It has two or more (meth) acryloyl groups in one molecule per 100 parts by weight of a condensation product (50% solution) of Synthesis Example 1 [A-187 (3-glycidyl oxypropyl trimethoxysilane)] as a condensation product. 5.6 parts by weight of DPHA as a compound, 32.6 parts by weight of pyromellitic anhydride as a curing agent of epoxy group, and 0.28 parts by weight of BPO as a radical generator were mixed to prepare a coating liquid. The coating solution was diluted with 81.9 parts by weight of PGME (1-methoxy-2-propanol) as a dilution solvent so as to have a nonvolatile content of 40%.

[Preparation of laminate]
Using a bar coater # 20, the obtained coating liquid was coated on a Takilon polycarbonate (PC-1600, 2.0 mm thick) so that the dry film thickness would be about 12 μm.
Then, the removal of the dilution solvent and the curing reaction were simultaneously completed using a hot air dryer at 120 ° C. for 1 hour (hereinafter, referred to as “heat curing”) to obtain a test piece.
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 2
[Preparation of Coating Liquid] Example 1 except that the amount of DPHA was changed to 21.4 parts by weight, the amount of radical generator BPO to 1.08 parts by weight, and the amount of PGME to 105 parts by weight. By the same operation as in the above, a coating liquid was obtained, and a test piece was obtained by heat curing.
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 3
[Preparation of coating solution]
2.5 parts by weight of CPI 101A for the type and amount of curing agent curing the epoxy group, 0.19 parts by weight of 2-hydroxy-2-methylpropiophenone for the type and amount of radical generator, 37.4 parts by weight of PGME The coating liquid was obtained by the same operation as Example 1 except having changed into a part.
[Preparation of laminate]
Using a bar coater # 20, the obtained coating liquid was coated on a Takilon polycarbonate (PC-1600, 2.0 mm thick) so that the dry film thickness would be about 12 μm.
Next, after heating at 120 ° C. for 2 minutes using a hot air dryer to remove the dilution solvent, using a high pressure mercury lamp in the air, the integrated light quantity of wavelength 310 to 390 nm becomes 1000 mJ / cm ^{2 at} 240 mW. As described above, the sample was cured by irradiation with ultraviolet light (hereinafter referred to as "ultraviolet light curing") to obtain a test piece.
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 4
In [Preparation of coating liquid], the amount of DPHA was changed to 21.4 parts by weight, the amount of 2-hydroxy-2-methylpropiophenone to 0.73 parts by weight, and the amount of PGME to 62.0 parts by weight A coating liquid was obtained by the same operation as Example 3 except for the above, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 5
[Preparation of Coating Liquid] Example 2 except that the type and amount of the curing agent for curing the epoxy group were changed to 6.9 parts by weight of hexamethylene diamine, and PGME as the dilution solvent was changed to 66.5 parts by weight. The coating liquid was obtained by the same operation as the above, and a test piece was obtained by heat curing.
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 6
In [Preparation of Coating Liquid], the kind and amount of the curing agent for curing the epoxy group were changed to 32.3 parts by weight of benzyldimethylamine and the amount of the dilution solvent PGME to 104.5 parts by weight with respect to Example 2 A coating liquid was obtained by the same operation as Example 2 except having carried out, and a test piece was obtained by thermosetting.
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 7
[Preparation of Coating Liquid] A coating liquid is obtained by the same operation as Example 4, except that the type of the compound having two or more (meth) acryloyl groups in one molecule is changed to TMPTA, and the ultraviolet curing is performed. A test piece was obtained by
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 8
[Preparation of Coating Liquid] A coating liquid is obtained by the same operation as in Example 3 except that the type of the compound having two or more (meth) acryloyl groups in one molecule is changed to HDDA, and the ultraviolet curing is performed. A test piece was obtained by
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 9
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the kind of condensate was changed to Synthesis Example 2, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 10
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the kind of condensate was changed to Synthesis Example 3, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 11
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the type of condensate was changed to Synthesis Example 4, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 3.

Example 12
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the type of condensate was changed to Synthesis Example 5, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 2.

Example 13
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 3 except that the type of condensate was changed to Synthesis Example 6, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 3.

Example 14
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the type of condensate was changed to Synthesis Example 7, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 3.

Example 15
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the type of condensate was changed to Synthesis Example 8, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 3.

Example 16
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 3 except that the kind of condensate was changed to Synthesis Example 9, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 3.

Example 17
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the type of condensate was changed to Synthesis Example 10, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 3.

Example 18
In [Preparation of Coating Liquid], the kind and the amount of the compound having a (meth) acryloyl group, the amount of the compound having a (meth) acryloyl group, the amount of the synthesis example 15 / 42.9 parts by weight, and the amount of the dilution solvent PGME are 39.7 parts by weight. A coating liquid was obtained by the same operation as in Example 4 except that the above was changed to and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 3.

Example 19
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the type of condensate was changed to Synthesis Example 11, and a test piece was obtained by ultraviolet curing.
The physical property evaluation results for the obtained test pieces are shown in Table 3.

Comparative Example 1
[Preparation of Coating Liquid] A coating liquid is obtained by the same operation as in Example 2 except that the kind of condensate is changed to Synthesis Example 12 and the amount of pyrrolimate anhydride is changed to 65.2 parts by weight. The test piece was obtained by heat curing.
The evaluation results of the physical properties of the obtained test pieces are shown in Table 4.

Comparative Example 2
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the type of condensate was changed to Synthesis Example 12, and a test piece was obtained by ultraviolet curing.
The evaluation results of the physical properties of the obtained test pieces are shown in Table 4.

Comparative Example 3
[Preparation of coating liquid], except that the kind of condensate is changed to Synthesis Example 12, the amount of hexamethylenediamine is changed to 13.9 parts by weight, and the amount of dilution solvent PGME is changed to 79.6 parts by weight, A coating liquid was obtained by the same operation as in Example 5, and a test piece was obtained by heat curing.
The evaluation results of the physical properties of the obtained test pieces are shown in Table 4.

Comparative Example 4
[Preparation of coating solution], except that the kind of condensate is changed to Synthesis Example 12, the amount of benzyldimethylamine is changed to 64.6 parts by weight, and the amount of dilution solvent PGME is changed to 155.7 parts by weight The coating liquid was obtained by the same operation as Example 6, and the test piece was obtained by thermosetting.
The evaluation results of the physical properties of the obtained test pieces are shown in Table 4.

Comparative Example 5
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the type of condensate was changed to Synthesis Example 13, and a test piece was obtained by ultraviolet curing.
The evaluation results of the physical properties of the obtained test pieces are shown in Table 4.

Comparative Example 6
[Preparation of Coating Liquid] A coating liquid was obtained by the same operation as in Example 4 except that the type of condensate was changed to Synthesis Example 14, and a test piece was obtained by ultraviolet curing.
The evaluation results of the physical properties of the obtained test pieces are shown in Table 4.

Comparative Example 7
[Preparation of a coating liquid] In the kind and amount of compound having an epoxy group to 100 parts by weight of bisphenol A diglycidyl ether, the kind and amount of a curing agent for curing an epoxy group: CPI-101A 5.0 parts by weight, diluted A coating liquid was obtained by the same operation as in Example 4 except that the amount of the solvent PGME was changed to 190.7 parts by weight, and a test piece was obtained by ultraviolet curing.
The evaluation results of the physical properties of the obtained test pieces are shown in Table 4.

Comparative Example 8
[Preparation of Coating Liquid] The DPHA 100 does not use a condensation agent (A) and a curing agent (B) for curing an epoxy group, and a kind and amount of a compound having two or more (meth) acryloyl groups in one molecule. By the same operation as in Example 3 except that the amount by weight, the amount of radical generator 2-hydroxy-2-methylpropiophenone was changed to 3.4 parts by weight, and the amount of dilution solvent PGME was changed to 155.1 parts by weight A coating liquid was obtained, and a test piece was obtained by ultraviolet curing.
The evaluation results of the physical properties of the obtained test pieces are shown in Table 4.

In Examples 1 to 8, each of Synthesis Example 1, a compound having two or more (meth) acryloyl groups in one molecule, and different curing agents were variously blended and cured. In each of Examples 1 to 8, a cured coating film excellent in adhesion, scratch resistance, and crack resistance was obtained. Further, in Examples 3, 4, 7 and 8 cured with the cationic polymerization initiator, the warping of the PET film laminate hardly occurred due to the offset action due to the curing expansion.
However, in Examples 3 and 8, the compounding amount of the compound (B) having two or more (meth) acryloyl groups in one molecule is small, and the initial adhesion immediately after curing is the same as in Examples 1 to 8. The value was lower than that of the example. Moreover, the thing which used the photocation generator as a hardening agent of an epoxy group had the highest abrasion resistance.

In Examples 9 to 17, a compound having two or more (meth) acryloyl groups in one molecule and a curing agent were fixed, and the type of the condensation product (A) was changed to Synthesis Examples 2 to 10 for curing. In each of Examples 9 to 17, a cured coating film excellent in adhesion, scratch resistance, and crack resistance was obtained.
In Examples 9 and 10, the condensate (A) is synthesized using methyltrimethoxysilane having a nonreactive organic group as the silane compound (II). In Example 10, the amount of methyltrimethoxysilane is large, so the wear resistance is slightly reduced compared to Example 3 using Synthesis Example 1.
In Examples 11 to 13, the condensate (A) is synthesized using a silane compound having two or more (meth) acryloyl groups in one molecule as the silane compound (II). In these, although the co-condensation amount of the silane compound (II) is increased, that is, although the molar amount of the epoxy group by the silane compound (I) is decreased, the initial adhesion, scratch resistance, crack resistance It is high enough. It is believed that this is due to the increase of (meth) acryloyl groups instead of epoxy groups.

  In Examples 9 to 13, although the cationic polymerization initiator is used, the condensation product (A) contains the silane compound (II) having an unsaturated double bond which is a curing shrinkage component, so Compared to 3, 4, 7 and 8, although the warpage is slightly large, the PET film laminate is sufficiently reduced in warpage.

  In Example 16, a mercapto group is used as the organic group of the silane compound (II), but also in this case, a thiyl radical is formed along with the generation of a radical by the photo radical generator, so the same results as in Examples 11 to 13 Is obtained. Moreover, Example 16 did not contain a cure shrinkage component as silane compound (II), and almost no warpage of the PET film laminate occurred.

  In Examples 14, 15, and 17, the epoxy structure-containing group in the silane compound (I) is changed from a glycidyl ether group to an epoxycyclohexyl group which is an alicyclic epoxy, and all of them have adhesion, scratch resistance and crack resistance. An excellent cured coating was obtained. The hardness was slightly improved over the other examples due to the high cation reactivity of the epoxycyclohexyl group. Further, in Examples 14, 15, and 17, since the cationic polymerization initiator was used, almost no warpage of the laminate occurred.

  In Example 18, a high molecular weight compound (molecular weight 21000, functional group equivalent 1050) was used as a compound (B) having two or more (meth) acryloyl groups in one molecule. Due to the fact that the functional group equivalent of the radically reactive compound is a little high and the crosslink density does not become high enough, and it has a high molecular weight, the compatibility with the condensate (A) is a little low, and clouding Alkali resistance test results were slightly worse due to phase separation), but sufficiently good results were obtained for other evaluations.

  In Example 19, in the synthesis of the condensation product (A), a basic compound was used as a catalyst, and a compound having an alicyclic epoxy group as a silane compound (I) was used. Boiling water adhesion and alkali resistance tend to decrease compared to other examples due to a slight decrease in the residual ratio of epoxy groups after condensation product (A) synthesis, but initial adhesion and resistance With respect to the abrasion resistance and hardness, a cured coating film sufficiently good was obtained, no cracks were observed after the heat test, and the warp of the PET film was hardly found.

In Comparative Examples 1 to 4, Synthesis Example 12 in which hydrochloric acid is used as a catalyst as the condensation product (A) is used, but the boiling water adhesion and the alkali resistance decrease with the decrease of the remaining amount of epoxy group after synthesis. Was confirmed.
In Comparative Example 5, the condensation product (A) was synthesized without a catalyst, but the residual epoxy group amount was low as in Comparative Examples 1 to 4, and the boiling water adhesion and the alkali resistance were also lowered.
Further, in Comparative Examples 2 and 5, since the condensation product (A) synthesized under the acid catalyst and without the catalyst is used, the residual epoxy group is reduced, but the curing expansion by the residual epoxy group and the radical polymerization initiator The warpage of the PET film laminate is small due to the nature.

  In Comparative Example 6, as the condensate (A), a condensate obtained by using 19 moles of the silane compound (II) having a methacryloyl group with respect to 1 mole of the silane compound (I) having an epoxy structure-containing group is used. When the curing by the methacryloyl group occurs excessively, the curing shrinkage becomes large, and the adhesion to boiling water, the alkali resistance, and the anti-cracking property due to heat decrease.

  In Comparative Example 7, curing was performed using bisphenol A diglycidyl ether, which is a difunctional product of an epoxy compound, instead of the condensate (A). Due to the fact that the number of epoxy groups in one molecule is as small as 2, and the silicon film is not contained, the crosslink density in the cured coating does not increase, and the adhesion to boiling water, alkali resistance, and crack resistance A good coating film was not obtained. Moreover, before curing, it was compatible with the compound (B) having two or more (meth) acryloyl groups in one molecule, and it was a transparent coating liquid, but after curing, the coating gradually became cloudy, and the crosslink density was Since it is not sufficient, it is presumed that phase separation has progressed after curing.

In Comparative Example 8, only DPHA was cured, but although scratch resistance and hardness were high, curing shrinkage was large, resulting in a coating film having insufficient boiling water adhesion and crack resistance.

Claims (9)

The following general formula (I):
R ^1- (SiR ² _a (OR ³ ) _3-a ) (I)
(Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, the terminal of which is substituted with an epoxy structure-containing group, and R ² is each independently a hydrogen atom or an alkyl group having 1 to 10 carbons, 6 carbon atoms A monovalent hydrocarbon group selected from an aryl group of 25 and an aralkyl group having 7 to 12 carbon atoms, R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is 0 A silane compound (I) having a hydrolyzable silyl group, which is an integer of -2),
The following general formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(Wherein, R ⁴ is a group selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, and a substituted aryl group and having no epoxy structure-containing group. Each R ² is independently 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 each independently A hydrogen atom or an alkyl group having 1 to 10 carbon atoms, wherein a is an integer of 0 to 2. a silane compound having a hydrolyzable silyl group (II)
And the molar ratio of the silane compound (II) to the silane compound (I) is 9 or less and contains a neutral salt as a hydrolysis / condensation catalyst, and has a weight average molecular weight of 30 The silicon atom which the condensate (A) has relative to the number of moles X of the OR ³ group directly bonded to the silicon atom which the silane compounds (I) and (II) which are the raw materials of the condensate (A) have A condensate (A) in which the ratio Y / X of the mole number Y of OR ³ groups directly bonded to
A compound (B) having two or more (meth) acryloyl groups in one molecule,
A curable composition comprising a curing agent (C) for curing an epoxy group and a radical generator (D). (1) to 9900 parts by weight of a compound (B) having two or more (meth) acryloyl groups in one molecule, relative to 100 parts by weight of the condensate (A),
When the curing agent (C) is a curing agent that polymerizes an epoxy group, curing is achieved by adding 0.5 to 10 parts by weight to the epoxy group with respect to 100 parts by weight of the condensation product (A) 10 to 150 parts by weight in the case of
And 0.05 to 50 parts by weight of the radical generator (D) with respect to 100 parts by weight of the compound (B) having two or more (meth) acryloyl groups in one molecule. The curable composition according to Item 1. Any of the neutral salts selected from the group consisting of Group 1 element ion, Group 2 element ion, tetraalkyl ammonium ion and guanidinium ion as a cation;
The curability according to claim 1 or 2, wherein the salt is a salt in combination with any one selected from the group consisting of Group 17 element ions other than fluoride ions, sulfate ions, nitrate ions and perchlorate ions as anions. Composition.   From the combination of any one selected from the group consisting of a first group element ion and a second group element ion as a cation, and any one selected from a group consisting of a chloride ion, a bromide ion and an iodide ion as an anion The curable composition according to any one of claims 1 to 3, which is a salt of Curing agent of curing an epoxy group (C) and radical generator (D), characterized in that a compound which exhibit the effect by irradiating an active energy ray, according to claim 1 Curable composition. The curing agent (C) which cures an epoxy group is a cationically polymerizable acid generator, and is a compound containing a fluorophosphate group, a fluoroantimonate group and a fluoroborate group. The curable composition in any one of -5.   Hardened | cured material obtained by hardening the curable composition in any one of Claims 1-6. The manufacturing method of the laminated body containing the process of apply | coating the curable composition in any one of Claims 1-6 to a base material, making it harden | cure, and forming a cured film.   The laminated body obtained by the manufacturing method of Claim 8.