Curable composition, cured product, and laminate

Abstract

Provided are a curable composition, a cured product, and a laminate which are capable of producing a cured product in which curl is suppressed and changes in hardness are suppressed when applied in a high-humidity environment. The curable composition comprises a non-cyclic siloxane containing an alicyclic epoxy group, a compound containing a radical polymerizable group, and a borate salt.

Description

Technical Field

[0001] The present invention relates to a curable composition, a cured product, and a laminate. Background Art

[0002] Active energy ray-curable compositions have been used in various fields such as coating agents (for example, Patent Document 1).

[0003] [Prior art literature]

[0004] [Patent Document]

[0005] [Patent Document 1] Japanese Patent Publication No. 62-021815 Summary of the Invention

[0006] [Problems to be solved by the invention]

[0007] An object of the present invention is to provide a curable composition capable of producing a cured product that is suppressed from curling and exhibits a suppressed change in hardness when applied under a high-humidity environment.

[0008] [Technical means to solve the problem]

[0009] According to the present disclosure, the following items are provided.

[0010] (Item 1)

[0011] A curable composition comprises: a non-cyclic siloxane containing an alicyclic epoxy group, a compound containing a free radical polymerizable group, and a borate.

[0012] (Item 2)

[0013] The curable composition described in the above item comprises a compound containing a hindered phenol group.

[0014] (Item 3)

[0015] A cured product of the curable composition according to any one of the above items.

[0016] (Item 4)

[0017] A laminate comprising the hardened article according to the above item.

[0018] In the present disclosure, one or more features may be provided in further combinations other than the explicit combinations.

[0019] [Effects of the Invention]

[0020] The cured product of the present invention is prevented from curling and from changing in hardness when applied under a high-humidity environment. DETAILED DESCRIPTION

[0021] Throughout the present disclosure, the ranges of the values ​​of various physical property values, contents, etc. can be appropriately set (for example, selected from the values ​​described in the following items). Specifically, regarding the numerical value α, when A3, A2, A1 (assuming A3>A2>A1) and the like can be listed as the numerical value α, the range of the numerical value α can be exemplified by A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A3, greater than A2 and less than A3, greater than A2 and less than A3, greater than A3 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, etc.

[0022] As long as the problems to be solved by the present invention can be solved, the components, conditions, numerical values, etc. are not particularly limited.

[0023] "αβ Amount (A / B)" refers to the β amount (α) of A relative to 100α of B. Examples of α include mass %, mole %, and parts by mass. Examples of β amount include content and usage amount. "Mass % Content (A / B)" refers to the content (mass %) of A relative to 100% of B.

[0024] "γ ratio (A / B)" refers to the γ ratio calculated by the formula "A÷B". Examples of the γ ratio include mass ratio and molar ratio.

[0025] The term "non-volatile matter" refers to the total mass of components other than the organic solvent and water. In one embodiment, the term "non-volatile matter of A" refers to the total mass of components remaining when 1 g of A is heated at 105°C to a constant weight.

[0026] “(Meth)acrylic acid” means “acrylic acid and / or methacrylic acid.” “(Meth)acrylate” means “acrylate and / or methacrylate.” “(Meth)acryloyl” means “acryloyl and / or methacryloyl.”

[0027] "C..." means "carbon number..." For example, "C1-6 alkyl" means an alkyl group having 1 to 6 carbon atoms. "C6 alkyl" means an alkyl group having 6 carbon atoms.

[0028] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cycloalkyl group.

[0029] Examples of the linear alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0030] Examples of the branched alkyl group include isopropyl, sec-butyl, isobutyl, tert-butyl, 2-ethylhexyl, diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

[0031] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a cross-linked cycloalkyl group, a condensed cycloalkyl group, etc. Furthermore, a cycloalkyl group in which at least one hydrogen atom is substituted by an alkyl group is also considered to be a cycloalkyl group.

[0032] "Monocyclic" refers to a ring structure formed by covalent carbon bonds with no internal bridging structure. "Fused ring" refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., they share (fuse) only one side of each ring). "Cross-linked ring" refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0033] Examples of the monocyclic cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl.

[0034] Examples of the cross-linked cycloalkyl group include tricyclodecanyl, adamantyl, and norbornyl.

[0035] Furthermore, the alkyl group also includes a combination of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. Examples of such a combination include a cycloalkylalkyl group and the like.

[0036] The aromatic group (aryl group, arylene group) may be substituted or unsubstituted. Examples of the substituent of the aryl group include an alkyl group, a thioalkyl group, a thioaryl group, and a carbonylaryl group.

[0037] Examples of the aryl group include a monocyclic aryl group and a condensed ring aryl group.

[0038] Examples of the monocyclic aryl group include phenyl, tolyl, and mesityl.

[0039] Examples of the fused ring aryl group include naphthyl and the like.

[0040] Examples of the arylene group include a monocyclic arylene group and a condensed ring arylene group.

[0041] Examples of the monocyclic arylene group include a phenylene group and a tolylene group.

[0042] Examples of the fused ring arylene group include naphthylene and the like.

[0043] [Curable composition]

[0044] The present disclosure relates to a curable composition comprising: a non-cyclic siloxane containing an alicyclic epoxy group, a compound containing a free radical polymerizable group, and a borate.

[0045] <Alicyclic Epoxy-Containing Non-Cyclic Siloxane>

[0046] The alicyclic epoxy group-containing non-cyclic siloxanes may be used alone or in combination of two or more.

[0047] "Cyclic siloxane" refers to a compound composed of silicon and oxygen atoms, SiO 2 / 2 It represents siloxane, which is a cyclic structure formed only by silicon atoms and oxygen atoms.

[0048] "Acyclic siloxane" refers to a siloxane that is not one of the cyclic siloxanes described above.

[0049] Examples of the alicyclic epoxy group include an epoxycyclohexyl group and the like.

[0050] Examples of the alicyclic epoxy group-containing non-cyclic siloxane include alicyclic epoxy group-containing non-cyclic siloxane and alicyclic epoxy group-containing non-cyclic alkylsiloxane.

[0051] (Acyclic siloxane containing alicyclic epoxy groups)

[0052] "Alkoxysiloxane" refers to a condensate of alkoxysilane.

[0053] Examples of the alkoxysilane include alkoxysilanes containing an alicyclic epoxy group and alkoxysilanes not containing an alicyclic epoxy group.

[0054] <Allicyclic epoxy group-containing alkoxysilane>

[0055] In one embodiment, the alicyclic epoxy group-containing alkoxysilane is represented by the following formula.

[0056] [Chemistry 1]

[0057] R sre1 -SiR sre2 s1 (OR sre3 ) 3-s1

[0058] (R sre1 represents an alicyclic epoxy-substituted alkyl group.

[0059] R sre2 Each independently represents a hydrogen atom, an alkyl group, an aryl group or an aryl-substituted alkyl group.

[0060] R sre3 Each independently represents a hydrogen atom or an alkyl group.

[0061] s1 represents an integer from 0 to 2.)

[0062] Examples of the alicyclic epoxy group-containing alkoxysilane include 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)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)methylmethyldimethoxysilane, 1-(3,4-epoxycyclohexyl)methyltriethoxysilane, 1-(3,4-epoxycyclohexyl)methylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)methylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)methylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)methylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)methylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)methyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)methylmethyldi ... 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 3-(3,4-epoxycyclohexyl)propylmethyl 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 silane, 6-(3,4-epoxycyclohexyl)hexyltriethoxysilane, 6-(3,4-epoxycyclohexyl)hexylmethyldiethoxysilane, 8-(3,4-epoxycyclohexyl)octyltrimethoxysilane, 8-(3,4-epoxycyclohexyl)octylmethyldimethoxysilane, 8-(3,4-epoxycyclohexyl)octyltriethoxysilane, 8-(3,4-epoxycyclohexyl)octylmethyldiethoxysilane, etc.

[0063] The mass % content (alicyclic epoxy group-containing alkoxysilane unit / alicyclic epoxy group-containing acyclic siloxane) can be, for example, 100 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, etc. In one embodiment, the content is preferably 10 to 100 mass %.

[0064] The mol% content (alicyclic epoxy group-containing alkoxysilane unit / alicyclic epoxy group-containing acyclic siloxane) can be, for example, 100 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, etc. In one embodiment, the content is preferably 10 mol% to 100 mol%.

[0065] <Alkoxysilanes containing no alicyclic epoxy group>

[0066] In one embodiment, the alkoxysilane not containing an alicyclic epoxy group is represented by the following formula.

[0067] [Chemistry 2]

[0068] R srn1 -SiR srn2 s2 (OR srn3 ) 3-s2

[0069] (R srn1 represents an alkyl group, a thiol-substituted alkyl group, an isocyanate-substituted alkyl group, a (meth)acryloyl-substituted alkyl group, an aryl-substituted alkyl group, a cyclohexyl-substituted alkyl group, a chloro-substituted alkyl group, an oxetanyloxy-substituted alkyl group, an alkenyl group, or an alkenyl-substituted aryl group.

[0070] R srn2 Each independently represents a hydrogen atom, an alkyl group, an aryl group or an aryl-substituted alkyl group.

[0071] R srn3 Each independently represents a hydrogen atom or an alkyl group.

[0072] s2 represents an integer from 0 to 2.)

[0073] Alkoxysilane without alicyclic epoxy group (R srn1 =alkyl) Examples include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethylmethyldimethoxysilane, ethyltriethoxysilane, ethylmethyldiethoxysilane, propyltrimethoxysilane, propylmethyldimethoxysilane, propyltriethoxysilane, propylmethyldiethoxysilane, butyltrimethoxysilane, butylmethyldimethoxysilane, butyltriethoxysilane, butylmethyldiethoxysilane, hexyltrimethoxysilane, hexylmethyldimethoxysilane, hexyltriethoxysilane, hexylmethyldiethoxysilane, octyltrimethoxysilane, octylmethyldimethoxysilane, octyltriethoxysilane, and octylmethyldiethoxysilane.

[0074] Alkoxysilane without alicyclic epoxy group (R srn1= thiol-substituted alkyl) Examples include 1-mercaptomethyltrimethoxysilane, 1-mercaptomethylmethyldimethoxysilane, 1-mercaptomethyltriethoxysilane, 1-mercaptomethylmethyldiethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyl Diethoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutylmethyldiethoxysilane, 6-mercaptohexyltrimethoxysilane, 6-mercaptohexylmethyldimethoxysilane, 6-mercaptohexyltriethoxysilane, 6-mercaptohexylmethyldiethoxysilane, 8-mercaptooctyltrimethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctyltriethoxysilane, 8-mercaptooctylmethyldiethoxysilane, etc.

[0075] Alkoxysilane without alicyclic epoxy group (R srn1 =isocyanate-substituted alkyl) Examples thereof include 1-isocyanatemethyltrimethoxysilane, 1-isocyanatemethylmethyldimethoxysilane, 1-isocyanatemethyltriethoxysilane, 1-isocyanatemethylmethyldiethoxysilane, 2-isocyanateethyltrimethoxysilane, 2-isocyanateethylmethyldimethoxysilane, 2-isocyanateethyltriethoxysilane, 2-isocyanateethylmethyldiethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyl 4-Isocyanatebutyltrimethoxysilane, 4-Isocyanatebutylmethyldimethoxysilane, 4-Isocyanatebutyltriethoxysilane, 4-Isocyanatebutylmethyldiethoxysilane, 6-isocyanatehexyltrimethoxysilane, 6-isocyanatehexylmethyldimethoxysilane, 6-isocyanatehexyltriethoxysilane, 6-isocyanatehexylmethyldiethoxysilane, 8-isocyanateoctyltrimethoxysilane, 8-isocyanateoctylmethyldimethoxysilane, 8-isocyanateoctyltriethoxysilane, 8-isocyanateoctylmethyldiethoxysilane, etc.

[0076] Alkoxysilane without alicyclic epoxy group (R srn1=(meth)acryloyl-substituted alkyl) Examples thereof include 1-(meth)acryloyloxymethyltrimethoxysilane, 1-(meth)acryloyloxymethylmethyldimethoxysilane, 1-(meth)acryloyloxymethyltriethoxysilane, 1-(meth)acryloyloxymethylmethyldiethoxysilane, 2-(meth)acryloyloxyethyltrimethoxysilane, 2-(meth)acryloyloxyethylmethyldimethoxysilane, 2-(meth)acryloyloxyethyltriethoxysilane, 2-(meth)acryloyloxyethylmethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropyl Methyldiethoxysilane, 4-(meth)acryloyloxybutyltrimethoxysilane, 4-(meth)acryloyloxybutylmethyldimethoxysilane, 4-(meth)acryloyloxybutyltriethoxysilane, 4-(meth)acryloyloxybutylmethyldiethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 6-(meth)acryloyloxyhexylmethyldimethoxysilane, 6-(meth)acryloyloxyhexyltriethoxysilane, 6-(meth)acryloyloxyhexylmethyldiethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, 8-(meth)acryloyloxyoctylmethyldiethoxysilane, and the like.

[0077] Alkoxysilane without alicyclic epoxy group (R srn1 =aryl-substituted alkyl) Examples include benzyltrimethoxysilane, benzyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-phenylpropyltrimethoxysilane, 3-phenylpropyltriethoxysilane, 4-phenylbutyltrimethoxysilane, 4-phenylbutyltriethoxysilane, 5-phenylpentyltrimethoxysilane, 5-phenylpentyltriethoxysilane, 6-phenylhexyltrimethoxysilane, and 6-phenylhexyltriethoxysilane.

[0078] Alkoxysilane without alicyclic epoxy group (R srn1 =cyclohexyl-substituted alkyl) Examples include cyclohexylmethyltrimethoxysilane, cyclohexylmethyltriethoxysilane, 2-cyclohexylethyltrimethoxysilane, 2-cyclohexylethyltriethoxysilane, 3-cyclohexylpropyltrimethoxysilane, 3-cyclohexylpropyltriethoxysilane, 4-cyclohexylbutyltrimethoxysilane, 4-cyclohexylbutyltriethoxysilane, 5-cyclohexylpentyltrimethoxysilane, 5-cyclohexylpentyltriethoxysilane, 6-cyclohexylhexyltrimethoxysilane, and 6-cyclohexylhexyltriethoxysilane.

[0079] Alkoxysilane without alicyclic epoxy group (R srn1 =chloro-substituted alkyl) Examples include chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 5-chloropentyltrimethoxysilane, 5-chloropentyltriethoxysilane, 6-chlorohexyltrimethoxysilane, and 6-chlorohexyltriethoxysilane.

[0080] Alkoxysilane without alicyclic epoxy group (R srn1 =oxetanyloxy-substituted alkyl) Examples thereof include 1-oxetanyloxymethyltrimethoxysilane, 1-oxetanyloxymethylmethyldimethoxysilane, 1-oxetanyloxymethyltriethoxysilane, 1-oxetanyloxymethylmethyldiethoxysilane, 2-oxetanyloxyethyltrimethoxysilane, 2-oxetanyloxyethylmethyldimethoxysilane, 2-oxetanyloxyethyltriethoxysilane, 2-oxetanyloxyethylmethyldiethoxysilane, 3-oxetanyloxypropyltrimethoxysilane, 3-oxetanyloxypropylmethyldimethoxysilane, 3-oxetanyloxypropyltriethoxysilane, 3-oxetanyloxypropyl Methyldiethoxysilane, 4-oxetanyloxybutyltrimethoxysilane, 4-oxetanyloxybutylmethyldimethoxysilane, 4-oxetanyloxybutyltriethoxysilane, 4-oxetanyloxybutylmethyldiethoxysilane, 6-oxetanyloxyhexyltrimethoxysilane, 6-oxetanyloxyhexylmethyldimethoxysilane, 6-oxetanyloxyhexyltriethoxysilane, 6-oxetanyloxyhexylmethyldiethoxysilane, 8-oxetanyloxyoctyltrimethoxysilane, 8-oxetanyloxyoctylmethyldimethoxysilane, 8-oxetanyloxyoctyltriethoxysilane, 8-oxetanyloxyoctylmethyldiethoxysilane, and the like.

[0081] Alkoxysilane without alicyclic epoxy group (R srn1 =alkenyl) Examples thereof include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyltriethoxysilane, and allylmethyldiethoxysilane.

[0082] Alkoxysilane without alicyclic epoxy group (R srn1 =alkenyl-substituted aryl) Examples thereof include p-phenylenediamine trimethoxysilane and p-phenylenediamine triethoxysilane.

[0083] The mass % content (alkoxysilane unit without alicyclic epoxy group / alicyclic epoxy group-containing acyclic siloxane) can be, for example, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 90 mass %.

[0084] The mol% content (alkoxysilane unit without alicyclic epoxy group / alicyclic epoxy group-containing acyclic siloxane) can be, for example, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 90 mol%.

[0085] <Production Method (Alicyclic Epoxy Group-Containing Non-cyclic Siloxane)>

[0086] Alicyclic epoxy group-containing non-cyclic siloxane is produced by subjecting alkoxysilane to a hydrolysis-condensation reaction.

[0087] The molar ratio (water / alkoxy group) is preferably 0.2 to 20, more preferably 0.4 to 3, and even more preferably 0.45 to 2.

[0088] The reaction solvent may be used alone or in combination of two or more. Examples of the reaction solvent include 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, and propylene glycol dimethyl ether.

[0089] The reaction temperature is preferably 40°C to 200°C, more preferably 50°C to 250°C, and even more preferably 60°C to 230°C.

[0090] The reaction time is preferably 0.5 hours to 10 hours, more preferably 1 hour to 5 hours.

[0091] (Acyclic alkylsiloxane containing alicyclic epoxy groups)

[0092] "Alkylsiloxane" refers to a siloxane containing dialkylsiloxane units.

[0093] The dialkylsiloxane unit is represented by the following formula.

[0094] [Chemistry 3]

[0095]

[0096] (R sk1 ~R sk2 are independently selected from alkyl or alicyclic epoxy-substituted alkyl.

[0097] In one embodiment, the alicyclic epoxy group-containing non-cyclic alkylsiloxane is represented by the following formula.

[0098] [Chemistry 4]

[0099]

[0100] (R sk1 ~R sk6 R is independently selected from a C1-6 alkyl group or an alicyclic epoxy-substituted alkyl group. sk7 ~R sk8 are independently selected from C1-4 epoxy groups. s represents an integer from 0 to 12.

[0101] In one embodiment, R sk1 ~R sk6 Preferred examples include methyl and ethylepoxycyclohexyl. sk7 ~R sk8 A preferred example of s is 0.

[0102] Examples of the epoxy equivalent weight (alicyclic epoxy group-containing acyclic siloxane) include 500 g / eq, 450 g / eq, 400 g / eq, 350 g / eq, 300 g / eq, 250 g / eq, 200 g / eq, and 150 g / eq. In one embodiment, the epoxy equivalent weight is preferably 150 g / eq to 500 g / eq.

[0103] Examples of the mass % content (alicyclic epoxy group-containing acyclic siloxane / curable composition non-volatile component) include 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, and 5 mass %. In one embodiment, the content is preferably 5 mass % to 70 mass %.

[0104] <Compounds containing a radically polymerizable group>

[0105] The radical polymerizable group-containing compound may be used alone or in combination of two or more.

[0106] Examples of the radical polymerizable group-containing compound include poly(meth)acrylates.

[0107] “Poly(meth)acrylate” refers to a compound having two or more (meth)acryloyl groups.

[0108] Examples of the poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, (poly)glycerol poly(meth)acrylate, and urethane poly(meth)acrylate.

[0109] Examples of the (poly)pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and tripentaerythritol octa(meth)acrylate.

[0110] Examples of the (poly)trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

[0111] Examples of the (poly)glycerol poly(meth)acrylate include glycerol di(meth)acrylate, glycerol tri(meth)acrylate, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, and diglycerol tetra(meth)acrylate.

[0112] (urethane poly(meth)acrylate)

[0113] Examples of the urethane poly(meth)acrylate include reaction products of a compound group consisting of a hydroxyl group-containing poly(meth)acrylate and polyisocyanate.

[0114] <Hydroxy-containing poly(meth)acrylate>

[0115] Examples of the hydroxyl group-containing poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, and (poly)glycerol poly(meth)acrylate.

[0116] The polyisocyanate may be used alone or in combination of two or more.

[0117] <Polyisocyanate>

[0118] “Polyisocyanate” refers to a compound having two or more isocyanate groups (—N═C═O).

[0119] Examples of the polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and biuret forms, isocyanurate forms, allophanate forms, and adduct forms thereof.

[0120] Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.

[0121] Examples of the branched aliphatic polyisocyanate include diethylpentamethylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0122] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, crosslinked alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

[0123] Examples of the monocyclic alicyclic polyisocyanate include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0124] Examples of the cross-linked cycloaliphatic polyisocyanate include tricyclodecene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0125] Examples of the condensed-ring alicyclic polyisocyanate include dicyclodecene diisocyanate.

[0126] Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and condensed-ring aromatic polyisocyanate.

[0127] Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0128] Examples of the condensed-ring aromatic polyisocyanate include 1,5-naphthalene diisocyanate.

[0129] Examples of the mass % content (radical polymerizable group-containing compound / curable composition non-volatile component) include 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, and 30 mass %. In one embodiment, the content is preferably 30 mass % to 95 mass %.

[0130] <Borate>

[0131] The borate may be used alone or in combination of two or more.

[0132] Examples of the borate include sulfonium borate, iodonium borate, diazonium borate, and pyridinium borate.

[0133] Examples of the borate include tetrakis(pentafluorophenyl)borate and tetrafluoroborate.

[0134] Examples of the sulfonium ion include bis(4-(diphenylsulfonium)phenyl)sulfide, diphenyl-4-(phenylthio)phenylsulfonium, triphenylsulfonium, and bis(4-(bis(4-(2-hydroxyethoxy))phenylsulfonium)phenyl)sulfide.

[0135] Examples of the sulfonium borate include bis(4-(diphenylsulfonium)phenyl)sulfide bistetrafluoroborate, bis(4-(diphenylsulfonium)phenyl)sulfide tetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis(4-(bis(4-(2-hydroxyethoxy))phenylsulfonium)phenyl)sulfide bistetrafluoroborate, and bis(4-(bis(4-(2-hydroxyethoxy))phenylsulfonium)phenyl)sulfide tetrakis(pentafluorophenyl)borate.

[0136] Examples of the iodonium ion include diphenyliodonium, bis(dodecylphenyl)iodonium, and 4-isopropylphenyl-4-methylphenyliodonium.

[0137] Examples of the iodonium borate salt include diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-isopropylphenyl-4-methylphenyliodonium tetrafluoroborate, and 4-isopropylphenyl-4-methylphenyliodonium tetrakis(pentafluorophenyl)borate.

[0138] Examples of the diazonium ion include phenyldiazonium.

[0139] Examples of the diazonium borate include phenyldiazonium tetrafluoroborate and phenyldiazonium tetrakis(pentafluorophenyl)borate.

[0140] Examples of the pyridinium ion include 1-benzyl-2-cyanopyridinium and 1-(naphthylmethyl)-2-cyanopyridinium.

[0141] Examples of the pyridinium borate salt include 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, and 1-(naphthylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate.

[0142] Examples of the mass % content (borate / curable composition non-volatile component) include 10 mass %, 9.5 mass %, 9 mass %, 8.5 mass %, 8 mass %, 7.5 mass %, 7 mass %, 6.5 mass %, 6 mass %, 5.9 mass %, 5.5 mass %, 5 mass %, 4.5 mass %, 4 mass %, 3.5 mass %, 3 mass %, 2.9 mass %, 2.5 mass %, 2 mass %, 1.5 mass %, 1 mass %, and 0.5 mass %. In one embodiment, the content is preferably 0.5 mass % to 10 mass %.

[0143] <Hindered Phenol Group-Containing Compounds>

[0144] In one embodiment, the curable composition may optionally contain a hindered phenol group-containing compound. The hindered phenol group-containing compound may be used alone or in combination of two or more.

[0145] Examples of the hindered phenol group-containing compound include a hindered phenol structure-containing compound, a semi-hindered phenol structure-containing compound, and a low-hindered phenol structure-containing compound.

[0146] The hindered phenol structure is represented by the following formula.

[0147] [Chemistry 5]

[0148]

[0149] Examples of the hindered phenol structure-containing compound include 3,5-di-tert-butyl-4-hydroxytoluene, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene.

[0150] The semi-hindered phenol structure is represented by the following formula.

[0151] [Chemistry 6]

[0152]

[0153] Examples of the compound containing a semi-hindered phenol structure include 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-hydroxy-m-tolyl)propionate], and triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0154] The low hindered phenol structure is represented by the following formula.

[0155] [Chemistry 7]

[0156]

[0157] Examples of the compound containing a low hindered phenol structure include 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane and 4,4'-butenebis(3-methyl-6-tert-butylphenol).

[0158] Examples of the mass % content (hindered phenol group-containing compound / non-volatile component of the curable composition) include 3 mass %, 2.5 mass %, 2 mass %, 1.5 mass %, 1 mass %, 0.5 mass %, 0.2 mass %, 0.15 mass %, 0.1 mass %, 0.05 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 3 mass %, more preferably 0.05 mass % to 1 mass %. The reason for this preference is, for example, to suppress changes in hardness during coating in a high-humidity environment.

[0159] <Free Radical Initiator>

[0160] In one embodiment, the curable composition may optionally contain a free radical initiator. The free radical initiators may be used alone or in combination of two or more.

[0161] Examples of the free radical initiator include free radical initiators containing an α-hydroxydimethylacetophenone group, α-hydroxycycloalkylphenones, α-aminoalkylphenones, benzyldimethylketal, unsubstituted or substituted alkylphenones, unsubstituted or substituted benzyl groups, unsubstituted or substituted benzophenones, acylphosphine oxides, substituted thioxanthones, and oxime esters.

[0162] Examples of the radical initiator containing an α-hydroxydimethylacetophenone group include 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1-one.

[0163] Examples of the α-hydroxyphenylcycloalkyl ketone include 1-hydroxycyclohexylphenyl ketone.

[0164] Examples of the α-aminoalkylphenone include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0165] Examples of benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0166] Examples of the unsubstituted or substituted alkyl phenone include benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonitropropiophenone, and 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0167] Examples of the unsubstituted or substituted benzyl group include benzyl and p-anisyl.

[0168] Examples of the unsubstituted or substituted benzophenone include benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 2-benzoylbenzoic acid methyl.

[0169] Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0170] Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0171] Examples of oxime esters include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyloxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one);

[0172] Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethan-1-one, and the like.

[0173] When electron beam hardening is performed, no free radical initiator is required.

[0174] In one embodiment, the radical initiator preferably includes acylphosphine oxide, and the reason for this preference is, for example, that the amount of precipitate after emulsification is small.

[0175] Examples of the mass % content (radical initiator / active energy ray-curable composition non-volatile component) include 10 mass %, 9.5 mass %, 9 mass %, 8.5 mass %, 8 mass %, 7.5 mass %, 7 mass %, 6.5 mass %, 6 mass %, 5.9 mass %, 5.5 mass %, 5 mass %, 4.5 mass %, 4 mass %, 3.5 mass %, 3 mass %, 2.9 mass %, 2.5 mass %, 2 mass %, 1.5 mass %, 1 mass %, 0.5 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 10 mass %.

[0176] <Organic Solvent>

[0177] In one embodiment, the active energy ray-curable composition may optionally contain an organic solvent. The organic solvents may be used alone or in combination of two or more.

[0178] Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, alkyl halide solvents, and amide solvents.

[0179] Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0180] Examples of the aromatic solvent include toluene and xylene.

[0181] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.

[0182] Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

[0183] Examples of the glycol ether solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-tert-butyl ether.

[0184] Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0185] Examples of the petroleum-based solvent include aromatic oil (SOLVESSO) #100 (manufactured by Exxon) and aromatic oil (SOLVESSO) #150 (manufactured by Exxon).

[0186] Examples of the halogenated alkyl solvent include chloroform.

[0187] Examples of the amide solvent include dimethylformamide.

[0188] In one embodiment, the organic solvent preferably includes an alcohol solvent and a glycol ether solvent, more preferably includes isopropyl alcohol, n-butanol, isobutyl alcohol, and propylene glycol monomethyl ether, further preferably includes a combination of isopropyl alcohol, propylene glycol monomethyl ether, isopropyl alcohol, and propylene glycol monomethyl ether, and particularly preferably includes a combination of isopropyl alcohol and propylene glycol monomethyl ether. The reasons for this preference include, for example, improved leveling properties.

[0189] The mass % content (organic solvent / active energy ray-curable composition) can be, for example, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, or 0 mass %. In one embodiment, the content is preferably 0 mass % to 80 mass %.

[0190] <Additives>

[0191] The curable composition may optionally contain any agent (additive) not specified in any of the above.

[0192] Examples of the additives include ultraviolet absorbers, defoaming agents, surface conditioners, antifouling agents, and pigments.

[0193] In one embodiment, the content (additive / curable composition) in parts by mass may preferably be less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass.

[0194] In one embodiment, the content in parts by mass (additive / acyclic siloxane containing alicyclic epoxy groups), the content in parts by mass (additive / compound containing free radical polymerizable groups), the content in parts by mass (additive / borate), the content in parts by mass (additive / compound containing hindered phenol groups), the content in parts by mass (additive / free radical initiator), and the content in parts by mass (additive / organic solvent) can preferably be less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc.

[0195] The curable composition can be produced by dispersing and mixing the above-mentioned reagents.

[0196] Examples of the dispersing and mixing means include an emulsifying disperser and an ultrasonic dispersing device.

[0197] Examples of the application (curable composition) include coating agents.

[0198] [Hardened material]

[0199] The present disclosure relates to a hardened product of the hardenable composition.

[0200] Examples of the curing conditions include the following conditions.

[0201] [Laminated material]

[0202] The present disclosure relates to a laminate comprising the hardened

[0203] In one embodiment, the production method (laminated product) may include, for example, a method including the following steps.

[0204] Coating step: A step of coating a curable composition on at least one side of a substrate

[0205] Active energy ray curing process: The process of forming a hardened layer by irradiating active energy rays

[0206] Examples of the substrate include polycarbonate films, acrylic films (such as polymethyl methacrylate films), polystyrene films, polyester films, polyolefin films, epoxy resin films, melamine resin films, triacetyl cellulose films, ABS films, AS films, norbornene-based resin films, cyclic olefin films, and polyvinyl alcohol films.

[0207] In one embodiment, the thickness (base material) is preferably 10 μm to 2000 μm.

[0208] In one embodiment, the thickness (hardened material layer) is preferably 0.1 μm to 20 μm.

[0209] (Coating process)

[0210] Examples of the coating method include rod coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coater coating, offset printing, flexographic printing, and screen printing.

[0211] (Active Energy Ray Irradiation Step)

[0212] Examples of active energy rays include ultraviolet rays and electron beams.

[0213] Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp.

[0214] When a high-pressure mercury lamp is used, preferred curing conditions include the following conditions.

[0215] Lamp output: 25W / cm2~160W / cm2

[0216] UV illumination: 10mW / cm 2 ~800mW / cm 2

[0217] Cumulative light intensity: 25mJ / cm 2 ~2000mJ / cm 2

[0218] Conveying speed: 1m / min~50m / min

[0219] When an electron beam is used, preferred curing conditions include the following conditions.

[0220] Accelerating voltage: 10kV~300kV

[0221] Conveying speed: 5m / min~50m / min

[0222] [Example]

[0223] The present invention is described in detail below using examples and comparative examples. However, the above description and the following examples are not intended to limit the present invention. The present invention is limited only by the scope of the claims. Unless otherwise specified, all values ​​such as parts and % are by mass.

[0224] Preparation Example 1: Non-cyclic siloxane containing alicyclic epoxy groups

[0225] In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube, and air inlet, 66 parts by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (product name "KBM-303," manufactured by Shin-Etsu Chemical Co., Ltd.), 7 parts by mass of methanol, and 7 parts by mass of water were mixed and reacted at 70°C for 2 hours. After the reaction system was cooled to room temperature, 20 parts by mass of 1-methoxy-2-propanol was added and mixed to obtain an alicyclic epoxy group-containing acyclic alkoxysiloxane (non-volatile content 66%).

[0226] Example

[0227] The substances listed in the table below were mixed as non-volatile components and then diluted to obtain a coating (the dilution solvent was methyl isobutyl ketone, non-volatile content 30%).

[0228] Unless otherwise specified, other embodiments are carried out in the same manner as above except for the changes shown in the following table.

[0229] [Table 1]

[0230]

[0231] X-40-2669: Made by Shin-Etsu Chemical Co., Ltd.

[0232] [Chemistry 8]

[0233]

[0234] KR-470: Made by Shin-Etsu Chemical Co., Ltd.

[0235] [Chemistry 9]

[0236]

[0237] X-40-2678: Alicyclic epoxy group-containing cyclic siloxane bifunctional oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.

[0238] Epoxy resin GT-401: Butanetetracarboxylic acid tetrakis (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, manufactured by Daicel Co., Ltd.

[0239] NK Ester A-9550: Dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0240] Aronix M305: Pentaerythritol polyacrylate, manufactured by Toa Gosei Co., Ltd.

[0241] Compound A: 4-isopropylphenyl-4-methylphenyliodonium tetrakis(pentafluorophenyl)borate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0242] CPI-110B: Diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate, manufactured by San Ai Fu Co., Ltd.

[0243] IK-1: 4-Isopropylphenyl (p-tolyl) iodonium tris(pentafluoroethyl) trifluorophosphate, manufactured by San Ai Fu Co., Ltd.

[0244] CPI-100P: 4-(Phenylthio)phenyl-diphenylsulfonium hexafluorophosphate, manufactured by San Ai Fu Co., Ltd. CPI-210S: 4-(Phenylthio)phenyl-diphenylsulfonium tris(pentafluoroethyl) trifluorophosphate, manufactured by San Ai Fu Co., Ltd.

[0245] OMNIRAD184: 1-Hydroxycyclohexyl-phenyl ketone, manufactured by IGM Regins

[0246] BHT: 3,5-di-tert-butyl-4-hydroxytoluene

[0247] The prepared coating was applied to the adhesive surface of a polyester film, Cosmoshine A4160 (manufactured by Toyobo Co., Ltd., thickness 100 μm), using a bar coater in a normal temperature and humidity environment (air temperature 23.0°C, relative humidity 50%) regulated in a humidity controlled chamber. The film thickness after drying was 10 μm. The film was then dried at 80°C for 60 seconds using a commercially available hot air dryer. Subsequently, the film was irradiated with a high-pressure mercury lamp at 900 mJ / cm2 in a nitrogen atmosphere. 2 of ultraviolet light to obtain a laminate.

[0248] curly

[0249] Each laminate was cut into 10 cm x 10 cm squares and placed on a horizontal surface. The vertical heights of the four corners of the cut laminate square from the surface were measured and the average value was calculated as the curl value and evaluated as follows.

[0250] ○: Curl value is less than 5 mm.

[0251] △: The curl value is 5 mm or more and 10 mm or less.

[0252] ×: The curl value is 10 mm or more. Alternatively, the cut laminate is in a cylindrical shape.

[0253] Changes in coating hardness under high humidity conditions

[0254] A laminate was prepared under a high-humidity environment (26.0°C, 70% relative humidity) maintained in a humidity-controlled chamber, using the same method as under normal temperature and humidity. The pencil hardness was measured. The pencil hardness values ​​measured under normal temperature and humidity were compared with those under high humidity, and the evaluation was performed as follows.

[0255] ◎: Compared with the normal temperature and humidity environment, there is no difference in the evaluation value of pencil hardness, including the difference in defects caused by plastic deformation.

[0256] ○: Although there is a slight difference due to differences in defects caused by plastic deformation, there is no difference in the evaluation value of the pencil hardness due to scratches compared to the normal temperature and humidity environment.

[0257] ×: The pencil hardness is significantly lower than that under normal temperature and humidity conditions.

[0258] Evaluation Example

[0259] [Table 2]

[0260]

[0261] Total light transmittance%

[0262] The measurement was performed using a haze meter manufactured by Suga Testing Instruments Co., Ltd.

[0263] Haze

[0264] The measurement was performed using a haze meter manufactured by Suga Testing Instruments Co., Ltd.

[0265] Pencil hardness

[0266] The pencil hardness of the cured product was measured in accordance with JIS K5600-5-4.

Claims

1. A hardening composition comprising: Non-cyclic siloxanes containing alicyclic epoxy groups; Compounds containing free radical polymerizable groups; and borate. 2 . The curable composition according to claim 1 , comprising a compound containing a hindered phenol group.

3. A cured product, which is a cured product of the curable composition according to claim 1 or 2. A laminate comprising the cured product according to claim 3 .

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