JP6935313B2 - Curable composition and cured film - Google Patents

Description

The present invention relates to curable compositions.

Conventionally, display devices such as liquid crystal displays (LCDs) and touch panel displays provided with a plastic film having a hard coat coating film as a protective layer on the surface, and electronic elements such as polarizers, optical fibers and optical disks in the LCD have been known. The hard coat coating film is used for surface protection purposes such as preventing surface scratches and dust adhesion. In recent years, electronic devices equipped with touch panels that are operated by directly touching the screen with a finger, a pen, or the like, such as smartphones and tablet terminals, have become remarkably widespread, and such devices are required to further improve the hardness of the touch panel surface.

Further, while the hardness is improved, there is an increasing demand for a curable composition that can be cured even with an ultraviolet irradiation device using an LED light source. The ultraviolet irradiation device using the LED light source has low power consumption and generates less ozone. Therefore, there is an advantage that the running cost and the influence on the natural environment can be reduced.

However, since the LED light source has a single wavelength, the total amount of ultraviolet energy is smaller than that of an ultraviolet lamp light source such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or a metal halide lamp that emits ultraviolet rays having a wide range of wavelengths, and is generated from a photopolymerization initiator. Since the amount of generated radicals is small, the curability of the conventional curable composition is lowered, and the resin strength after curing is lowered.
Therefore, the curable composition is required to have high curability so that curability can be exhibited even when the total amount of energy such as an LED light source is small.

Generally, as a measure for enhancing the surface protection function of a hard coat coating film, a method of blending a highly hard inorganic filler into a curable composition to form a hard coat layer is known (for example, Patent Document 1). However, this composition has poor curability with an LED light source, and the hardness is lowered.
Further, as a composition for improving curability, a hard coat coating liquid containing 5 to 50% by weight of a monomer or oligomer containing acrylate as a main component and a polythiol compound having two or more thiol groups is known (for example). Patent Document 2). However, since this composition has poor storage stability, it thickens during storage at room temperature.

Japanese Unexamined Patent Publication No. 2009-90523 Japanese Unexamined Patent Publication No. 2012-197383

The present invention has high storage stability, high adhesion to a substrate, and curability that gives a cured product having excellent curability and high surface hardness even in the case of ultraviolet rays having a small total amount of energy such as an LED light source. It is an object of the present invention to provide a composition.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention comprises a monomer (A) having an ethylenically polymerizable group (a) and having neither a phosphate group (b1), a sulfo group (b2) nor a thiol group (c), and a phosphoric acid. A compound (B) having a group (b1) and / or a sulfo group (b2) and an ethylenically polymerizable group (a), a phosphoric acid group (b1) and a sulfo group (b2) having a thiol group (c). The compound (C) containing none of the above, or the monomer (A), and the compound (B2) having a phosphate group (b1) and / or a sulfo group (b2) and a thiol group (c). Curable composition containing the above; a cured film obtained by curing the curable composition.

The curable composition of the present invention has high storage stability and excellent curability by an LED light source. Further, the cured product of the curable composition of the present invention has the effects of high adhesion to the substrate and high surface hardness.

The curable composition of the present invention is the following composition of the first invention or the composition of the second invention.
The first invention described above is a monomer (A) having an ethylenically polymerizable group (a) and having neither a phosphate group (b1), a sulfo group (b2) nor a thiol group (c). , Compound (B) having a phosphate group (b1) and / or sulfo group (b2), and an ethylenically polymerizable group (a), a phosphate group (b1) and a sulfo group having a thiol group (c). It is a curable composition containing the compound (C) which does not have any of (b2).

Further, the second invention of the present invention includes the above-mentioned monomer (A) and (B2) having a phosphoric acid group (b1) and / or a sulfo group (b2) and a thiol group (c). It is a curable composition.

In the present specification, "(meth) acrylate" means "acrylate and / or methacrylate", "(meth) acryloyl group" means "acryloyl group and / or methacryloyl group", and "(meth) acryloyloxy group". "" Means "acryloyloxy group and / or methacryloyloxy group".

First, the first invention will be described.
A monomer (A) having an ethylenically polymerizable group (a), which is an essential component in the first invention, and having neither a phosphate group (b1), a sulfo group (b2) nor a thiol group (c). ), Examples of the ethylenically polymerizable group (a) contained in the monomer (A) include a (meth) acryloyl group, an allyl group, a vinyl group and a maleimide group.
Of these, the ethylenically polymerizable group (a) preferable from the viewpoint of curability is a (meth) acryloyl group, an allyl group and a vinyl group, and more preferably a (meth) acryloyl group.

Examples of the monomer (A) include a (meth) acrylate monomer (A1) having a (meth) acryloyl group, an allyl monomer (A2) having an allyl group, a vinyl monomer (A3) having a vinyl group, and a monomer having a maleimide group. (A4) can be mentioned.
Of these, (A1), (A2) and (A3) are preferable from the viewpoint of curability, and (A1) is more preferable.
In the present invention, it is assumed that the vinyl monomer (A3) having a vinyl group does not include the allyl monomer (A2) having an allyl group.
The above-mentioned monomer (A) may be used alone or in combination of two or more.

The (meth) acrylate monomer (A1) having a (meth) acryloyl group is not particularly limited as long as it is a known (meth) acrylate, and is monofunctional (meth) acrylate (A11) or bifunctional (meth). ) Acrylate (A12), trifunctional (meth) acrylate (A13), 4-6 functional (meth) acrylate (A14) and the like.
For example, the bifunctional (meth) acrylate means that the number of (meth) acryloyl groups is 2, and the same description method is used below.

Examples of the monofunctional (meth) acrylate (A11) include monoesterides of alcohol having 2 to 30 carbon atoms and (meth) acrylic acid [isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. Mono (meth) acrylates of o-, m- or p-phenylphenol and mono (meth) acrylates of 3,3'-diphenyl-4,4'-dihydroxybiphenyl], alkylene oxides of alcohols with 2 to 30 carbon atoms Examples thereof include a monoesterified product of (2 to 4 carbon atoms of alkylene group) 1 to 30 mol additive and (meth) acrylic acid [nonylphenoxypolyethylene glycol (meth) acrylate or the like], (meth) acryloylmorpholine and the like.

Of (A11), (meth) acryloylmorpholin and phenoxyethyl (meth) acrylate are preferable from the viewpoint of curability.

The bifunctional (meth) acrylate (A12) is a diesterified product of a polyhydric (preferably 2-8 valent) alcohol having 2 to 30 carbon atoms and (meth) acrylic acid [1,6-hexanediol di (meth). Acrylate, etc.], a diesterate of an alkylene oxide (2-4 carbon atoms of an alkylene group) 1 to 30 molar adduct of a polyhydric (preferably 2-8 valent) alcohol having 2 to 30 carbon atoms and (meth) acrylic acid. [Di (meth) acrylate of ethylene oxide adduct of bisphenol A, di (meth) acrylate of ethylene oxide adduct of bisphenol fluorene, etc.] and both-terminal epoxy (meth) acrylate having an OH group can be mentioned.

Of (A12), a diesterated product of a dihydric alcohol having 4 to 10 carbon atoms and (meth) acrylic acid [1,6-hexanediol di (meth) acrylate or the like] is preferable from the viewpoint of hardness.

The trifunctional (meth) acrylate (A13) is a triester product of a trihydric or higher (preferably 3 to 8 valent) alcohol having 3 to 30 carbon atoms and (meth) acrylic acid [tri (meth) acrylate of glycerin, Tri (meth) acrylate of trimethylolpropane and tri (meth) acrylate of pentaerythritol], and alkylene oxides of trivalent or higher (preferably 3 to 8 valent) alcohols having 3 to 30 carbon atoms (the number of carbon atoms of the alkylene group). 2-4) Examples thereof include a triester product of a 1 to 30 molar adduct and (meth) acrylic acid [tri (meth) acrylate of an ethylene oxide adduct of trimethylolpropane] and the like.

The 4 to 6 functional (meth) acrylate (A14) is an esterified product of a tetravalent or higher (preferably 4 to 8 valent) alcohol having 5 to 30 carbon atoms and (meth) acrylic acid [tetra (meth) of pentaerythritol. Acrylate, penta (meth) acrylate of dipentaerythritol, hexa (meth) acrylate of dipentaerythritol, etc.], and alkylene oxide (alkylene group) of tetravalent or higher (preferably 4 to 8 valent) alcohol having 5 to 30 carbon atoms. 2-4) 1 to 30 molar additions of carbon number and (meth) acrylic acid [Tetra (meth) acrylate of ethylene oxide adduct of dipentaerythritol, penta (penta) of ethylene oxide adduct of dipentaerythritol Penta (meth) acrylate, etc., which is a propylene oxide adduct of meta) acrylate and dipentaerythritol] and the like.

Of (A13) and (A14), trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta are preferable from the viewpoint of hardness. Hexa (meth) acrylates of (meth) acrylate and dipentaerythritol.

Examples of the allyl monomer (A2) having an allyl group include allyl glycidyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, triallyl trimellitic acid, and tetraallyl pyromellitic acid.

Of (A2), triallyl trimellitic acid and tetraallyl pyromellitic acid are preferable from the viewpoint of hardness.

Examples of the vinyl monomer (A3) having a vinyl group include N-vinylpyrrolidone, N-vinylcaprolactam, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether and diethylene glycol divinyl ether.

Of (A3), N-vinylcaprolactam, 1,4-butanediol divinyl ether and cyclohexanedimethanol divinyl ether are preferable from the viewpoint of hardness.

Examples of the maleimide group-bearing monomer (A4) include N-phenylmaleimide, N-cyclohexylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, and N-carboxyphenylmaleimide. Examples thereof include N-nitrophenylmaleimide and N-benzylmaleimide.

The compound (B) having a phosphate group (b1) and / or a sulfo group (b2), which is an essential component in the first invention, has a phosphate group (b1) and / or a sulfo group (b2). Examples thereof include the compound (B1) having no thiol group (c); and the compound (B2) having a phosphate group (b1) and / or a sulfo group (b2) and a thiol group (c).
Further, as the compound (B1), a compound having a phosphoric acid group (b1) and / or a sulfo group (b2) and having neither an ethylenically polymerizable group (a) nor a thiol group (c). (B11);
Examples thereof include a compound (B12) having a phosphoric acid group (b1) and / or a sulfo group (b2) and an ethylenically polymerizable group (a) and not having a thiol group (c).
The compound (B2) having a phosphate group (b1) and / or a sulfo group (b2) and a thiol group (c) includes a phosphate group (b1) and / or a sulfo group (b2) and a thiol group (c). ) And not the ethylenically polymerizable group (a); and the phosphate group (b1) and / or the sulfo group (b2), the ethylenically polymerizable group (a) and the thiol group (c). ), And the like (B22).
The compound (B) may be used alone or in combination of two or more.
Further, the ethylenically polymerizable group (a) contained in the compound (B12) and the compound (B22) is preferably a (meth) acryloyl group or a vinyl group from the viewpoint of curability and hardness, and the (meth) acryloyl group is preferable. More preferred.

From the viewpoint of storage stability, the compound (B) is essential to have a phosphoric acid group (b1) and / or a sulfo group (b2), and preferably has a phosphoric acid group (b1).
Further, the compound (B) may have another acidic functional group (carboxy group or the like) in addition to the phosphoric acid group (b1) and the sulfo group (b2).

Among the compounds (B11) having the phosphoric acid group (b1) and / or the sulfo group (b2) and having neither the ethylenically polymerizable group (a) nor the thiol group (c), the phosphoric acid group. Examples of the compound having (b1) include mono or dialkyl (alkyl group having 1 to 15 carbon atoms) phosphate [mono or dimethyl phosphate ester, mono or diethyl phosphate ester, mono or diisopropyl phosphate ester, mono or dibutyl phosphorus. Acid ester, mono or di- (2-ethylhexyl) phosphate ester, mono or diisodecyl phosphate, etc.] and acrylic polymer with phosphate group [Compound (B12), compound with phosphate group (b1) [Preferably, a radical polymer or the like containing 2- (meth) acryloyloxyethyl acid phosphate] as an essential constituent monomer] and the like can be mentioned.
The radical polymer may be a copolymer with another (meth) acrylate monomer [(meth) methyl acrylate, etc.].

Among the above (B11), examples of the compound having a sulfo group (b2) include alkyl (1 to 15 carbon atoms) benzenesulfonic acid (p-toluenesulfonic acid, nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, etc.) and sulfo. Salicylic acid, methanesulfonic acid, methanesulfonic acid trifluoride and acrylic polymer having a sulfonic acid group [Among compound (B12), a compound having a sulfo group (b2) (preferably vinyl sulfonic acid) is an essential constituent monomer. Radical polymer, etc.] and the like.
The radical polymer may be a copolymer with another (meth) acrylate monomer [(meth) methyl acrylate, etc.].

Among the compounds (B12) having the phosphate group (b1) and / or the sulfo group (b2) and the ethylenically polymerizable group (a) and not the thiol group (c), the phosphate group (b1) Examples of the compound having 2- (meth) acryloyloxyethyl acid phosphate, bis [2-[(meth) acryloyloxy] ethyl] phosphate, caprolactone-modified bis [2-[(meth) acryloyloxyethyl]] phos Fate, caprolactone-modified [2-[(meth) acryloyloxyethyl]] acid phosphate, caprolactone-modified bis [2-[(meth) acryloyloxymethyl]] phosphate, caprolactone-modified bis [2-[(meth) cryloyl] Oxypropyl]] phosphate and caprolactone-modified bis [2-[(meth) cryoyloxybutyl]] phosphate and the like can be mentioned.

Among the above (B12), examples of the compound having a sulfo group (b2) include vinyl sulfonic acid, Nt-butyl (meth) acrylamide sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid and the like. Can be mentioned.

Among the compounds (B21) having the phosphate group (b1) and / or the sulfo group (b2) and the thiol group (c) and not the ethylenically polymerizable group (a), the phosphate group (b1) Among the above-mentioned (B12) compounds, the compound having a phosphate group (b1) [preferably 2- (meth) acryloyloxyethyl acid phosphate or the like] and the (meth) acrylate monomer having a hydroxy group. A radical polymer containing the above as an essential constituent monomer, mercapto organic acid [mercapto aliphatic monocarboxylic acid (mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, dimercaptosuccinic acid, etc.) and mercapto aromatic monocarboxylic acid. Acids (mercapto benzoic acid, etc.)] and esterified compounds can be mentioned.
Examples of the (meth) acrylate monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate.
The radical polymer may be a copolymer with another (meth) acrylate monomer [(meth) methyl acrylate, etc.].
Further, the esterified product with the above-mentioned mercapto organic acid may be esterified with another organic acid (p-toluenesulfonic acid or the like) in addition to the mercapto organic acid.

Among the above (B21), examples of the compound having a sulfo group (b2) include mercaptoethanesulfonic acid and mercaptopropanesulfonic acid.

Among the compounds (B22) having a phosphoric acid group (b1) and / or a sulfo group (b2), an ethylenically polymerizable group (a) and a thiol group (c), the compound having a phosphoric acid group (b1) In the above (B12), a compound having a phosphate group (b1) [preferably 2- (meth) acryloyloxyoxyethyl acid phosphate] and a (meth) acrylate monomer having a hydroxy group are essential constituents. Examples thereof include an esterified product of a radical polymer as a monomer, a mercapto organic acid, and a urethane product of 2- (meth) acryloyloxyethyl isocyanate.
The radical polymer may be a copolymer with another (meth) acrylate monomer [(meth) methyl acrylate, etc.].
Further, the esterified product with the above-mentioned mercapto organic acid may be esterified with another organic acid (p-toluenesulfonic acid or the like) in addition to the mercapto organic acid.

Among the above (B22), the compound having a sulfo group (b2) includes a compound having a sulfo group (b2) (preferably vinyl sulfonic acid or the like) and a hydroxy group among the above (B12) (preferably vinyl sulfonic acid or the like). Examples thereof include an esterified product of a radical polymer containing a meta) acrylate monomer as an essential constituent monomer, a mercapto organic acid, and a urethane product of 2- (meth) acryloyloxyethyl isocyanate.
The radical polymer may be a copolymer with another (meth) acrylate monomer [(meth) methyl acrylate, etc.].
Further, the esterified product with the above-mentioned mercapto organic acid may be esterified with another organic acid (p-toluenesulfonic acid or the like) in addition to the mercapto organic acid.

Further, in the first invention of the present invention, the compound (B) includes a phosphate group (b1) and / or a sulfo group (b2) and an ethylenically polymerizable group (a) from the viewpoint of curability and hardness. ), And the compound (B12) having no thiol group (c) is preferable.

The compound (C) having the essential component thiol group (c) in the first invention and having neither an ethylenically polymerizable group (a), a phosphoric acid group (b1) nor a sulfo group (b2) , A polymer chain or a three-dimensional network structure is formed by adding to the double bond of the monomer (A) having the ethylenically polymerizable group (a).

A curable resin composed of only a general (meth) acrylate monomer is susceptible to curing inhibition by oxygen, but has the above-mentioned thiol group (c), and has an ethylenically polymerizable group (a) and phosphorus. In the case of a curable resin containing a compound (C) having neither an acid group (b1) nor a sulfo group (b2), the curable resin is not hindered by oxygen, so that the curability is improved.

Further, the curable resin containing the compound (C) having the above-mentioned thiol group (c) and having neither an ethylenically polymerizable group (a), a phosphoric acid group (b1) nor a sulfo group (b2) Since the curing reaction is a stepwise sequential reaction by a radical chain and the molecular weight of the produced polymer increases with time with curing, curability composed only of a (meth) acrylate monomer that gives a high molecular weight substance from the initial stage of curing. Compared with resin, it has the property of reducing shrinkage due to curing, so that it has good substrate adhesion.

Among the compounds (C) having the above-mentioned thiol group (c) and having neither ethylenically polymerizable group (a), phosphoric acid group (b1) nor sulfo group (b2), the thiol group (c) Examples of the compound having one of the above include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like.

Among the above-mentioned compound (C), examples of the compound having two thiol groups (c) include 1,2-ethanedithiole, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, and the like. 1,5-Pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonandithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 2,3-dimercaptosuccinic acid, 1,2-benzenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedithiol, 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 3,4-dimercaptotoluene, 4 −Chloro-1,3-benzenedithiol, 2,4,6-trimethyl-1,3-benzenedimethanethiol, 2-hexylamino-4,6-dimercapto-1,3,5-triazine, 2-diethylamino- 4,6-Dimercapto-1,3,5-triazine, 2-cyclohexylamino-4,6-dimercapto-1,3,5-triazine, 2-di-n-butylamino-4,6-dimercapto-1, 3,5-Triazine, ethylene glycol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bisthioglycolate, 2,5-dimercapto-1,3,4-thiathiozol, 2,2' Examples thereof include − (ethylenedithio) dietanthiol, 2,2-bis (2-hydroxy-3-mercaptopropoxyphenylpropane) and 1,4-bis (3-mercaptobutylyloxy) butane.

Among the above compounds (C), examples of the compound having three thiol groups (c) include 1,2,6-hexanetriol trithioglycolate, 1,3,5-trithiocyanic acid, and trimethylolpropane tris (3). -Mercaptopropionate), trimethylolpropane tristhioglycolate and tris [(3-mercaptopropioniroxy) -ethyl] isocyanurate and the like.

Among the above compounds (C), examples of the compound having four thiol groups (c) include pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakisthioglycolate.

Among the above compounds (C), dipentaerythritol hexakis (3-mercaptopropionate) and a (meth) acrylate monomer having a hydroxy group are essential constituents of the compound having 5 or more thiol groups (c). Examples thereof include an esterified product of a radical polymer as a monomer and a mercapto organic acid.
The radical polymer containing the (meth) acrylate monomer having a hydroxy group as an essential constituent monomer may be a copolymer with another (meth) acrylate monomer [methyl (meth) acrylate, etc.]. ..
Further, the esterified product with the above-mentioned mercapto organic acid may be esterified with another organic acid (p-toluenesulfonic acid or the like) in addition to the mercapto organic acid.

Among the above compounds (C), a compound having two or more thiol groups (c) is preferable from the viewpoint of curability and storage stability, and a compound having three or more thiol groups (c) is more preferable. Compounds, particularly preferred are trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).
The compound (C) may be used alone or in combination of two or more.

The first invention has the following carboxy group (b') in addition to the above-mentioned monomer (A), compound (B) and compound (C), and has a phosphoric acid group (b1) and a sulfo group ( A compound (B') having neither of b2) may be contained within a range that does not impair the effects of the invention.
The compound (B') having the above-mentioned carboxy group (b') and having neither a phosphate group (b1) nor a sulfo group (b2) has a carboxy group (b') and is ethylenically. A compound (B'11) having neither a polymerizable group (a) nor a thiol group (c);
A compound (B'12) having a carboxy group (b') and an ethylenically polymerizable group (a) and no thiol group (c);
A compound (B'21) having a carboxy group (b') and a thiol group (c) and no ethylenically polymerizable group (a); and an ethylenically polymerizable group (a) and a carboxy group (b'). And the compound (B'22) having a thiol group (c) and the like.
Further, the ethylenically polymerizable group (a) contained in the compound (B'12) and the compound (B'22) is preferably a (meth) acryloyl group or a vinyl group from the viewpoint of curability and hardness, and (meth). ) Acryloyl groups are more preferred.

The compound (B'11) having the above-mentioned carboxy group (b') and neither the ethylenically polymerizable group (a) nor the thiol group (c) is a monocarboxylic acid having 1 to 30 carbon atoms. , A 2-tetravalent polycarboxylic acid having 2 to 15 carbon atoms and an acrylic polymer having a carboxy group [(meth) acrylic monomer having a carboxy group having 3 to 30 carbon atoms [(meth) acrylic acid, etc.] are essential constituents. Radical polymers used as monomers, etc.] and the like.
A radical polymer containing a (meth) acrylic monomer having a carboxy group having 3 to 30 carbon atoms as an essential constituent monomer is copolymerized with another (meth) acrylate monomer [methyl (meth) acrylate, etc.]. It may be a thing.
Examples of the monocarboxylic acid having 1 to 30 carbon atoms include aliphatic monocarboxylic acids (gilic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, uralylic acid, etc. Myristic acid, stearic acid, bechenic acid, glycolic acid, lactic acid, etc.), alicyclic monocarboxylic acid (cyclohexanecarboxylic acid, etc.) and aromatic monocarboxylic acid (benzoic acid, silicic acid, naphthoic acid, salicylic acid, mandelic acid, etc.) ) Etc. can be mentioned.
Examples of the 2- to 4-valent polycarboxylic acid having 2 to 15 carbon atoms include an aliphatic polycarboxylic acid (such as oxalic acid, malonic acid and thiodibropionic acid) and an alicyclic polycarboxylic acid (1,4-cyclohexanedicarboxylic acid). Etc.) and aromatic polycarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) and the like.

As the compound (B'12) having a carboxy group (b') and an ethylenically polymerizable group (a) and not having a thiol group (c), an unsaturated monocarboxylic acid having 3 to 30 carbon atoms [(meth). ) Acrylic acid, etc.], unsaturated polyvalent (2-4 valent) carboxylic acid with 4 to 30 carbon atoms [(anhydrous) maleic acid, esteric acid, fumaric acid, citraconic acid, etc.], unsaturated with 4 to 30 carbon atoms Alkyl (alkyl group with 1 to 10 carbon atoms) ester of polyvalent carboxylic acid [maleic acid monoalkyl ester, fumaric acid monoalkyl ester, citraconic acid monoalkyl ester, etc.], succinic acid adduct of pentaerythritol tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate succinic acid adduct, pentaerythritol tri (meth) acrylate maleic acid adduct, dipentaerythritol penta (meth) acrylate maleic acid adduct, dipentaerythritol tetra (meth) acrylate Dicarboxylic acid adduct, maleic acid adduct of EO6 molar addition pentaerythritol tri (meth) acrylate, cyclohexenylcarboxylic acid addition of EO10 molar addition dipentaerythritol penta (meth) acrylate and 2- (meth) acryloyloxyethyl- Examples include phthalic acid.

Examples of the compound (B'21) having a carboxy group (b') and a thiol group (c) and no ethylenically polymerizable group (a) include mercapto organic acids [mercapto aliphatic monocarboxylic acids (mercapto acetic acid, mercaptoacetic acid,). Mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid and dimercaptosuccinic acid, etc.) and mercapto aromatic monocarboxylic acids (mercaptobenzoic acid, etc.)] and hydroxy organic acids [hydroxyacetic acid, lactic acid, malic acid, ascorbic acid and glycolic acid] , And the above-mentioned compound (B'12) [preferably (meth) acetic acid, etc.] and a radical polymer or the like containing a (meth) acrylate monomer having a hydroxy group as an essential constituent monomer] and a mercapto organic acid. Examples include esterified products.
The radical polymer may be a copolymer with another (meth) acrylate monomer [(meth) methyl acrylate, etc.].
Further, the esterified product with the mercapto organic acid may be esterified with another organic acid (p-toluenesulfonic acid or the like) in addition to the mercapto organic acid.

Examples of the compound (B'22) having an ethylenically polymerizable group (a), a carboxy group (b') and a thiol group (c) include the above-mentioned compound (B'12) [preferably (meth) acrylic acid and the like. ] And a radical polymer containing a (meth) acrylate monomer having a hydroxy group as an essential constituent monomer, an esterified product of mercapto organic acid, and a urethane product of 2- (meth) acryloyloxyethyl isocyanate. Be done.
The radical polymer may be a copolymer with another (meth) acrylate monomer [(meth) methyl acrylate, etc.].
Further, the esterified product with the above-mentioned mercapto organic acid may be esterified with another organic acid (p-toluenesulfonic acid or the like) in addition to the mercapto organic acid.

From the viewpoint of hardness, the weight ratio of the monomer (A) in the curable composition in the first invention is preferably 5 to 92% by weight, more preferably 5 to 92% by weight, based on the weight of the curable composition. It is 10 to 92% by weight, particularly preferably 20 to 90% by weight, and most preferably 30 to 70% by weight.

The weight ratio of the compound (B) in the curable composition in the first invention is preferably 0.5 to 30% by weight based on the weight of the curable composition from the viewpoint of storage stability. It is more preferably 1 to 15% by weight, and particularly preferably 1 to 3% by weight.

From the viewpoint of curability, the weight ratio of the compound (C) in the curable composition in the first invention is preferably 1 to 60% by weight, more preferably 1 to 60% by weight, based on the weight of the curable composition. Is 3 to 30% by weight, particularly preferably 5 to 20% by weight, and most preferably 10 to 18% by weight.

Next, the second invention described above will be described.
A monomer (A) having an ethylenically polymerizable group (a), which is an essential component in the second invention, and having neither a phosphate group (b1), a sulfo group (b2), nor a thiol group (c). ) Can use the compound (A) exemplified in the above description of the first invention, and the same applies to the preferred compound.
Further, the compound (B2) having a phosphoric acid group (b1) and / or a sulfo group (b2) and a thiol group (c), which are essential components in the second invention, is described in the first invention. The exemplified compound (B2) can be used, and the same applies to the preferred compound.
The curable composition in the second invention may contain the above-mentioned compound (B1) and compound (B') in addition to the above-mentioned monomer (A) and compound (B2).

From the viewpoint of hardness, the weight ratio of the monomer (A) in the curable composition in the second invention is preferably 5 to 92% by weight, more preferably 5 to 92% by weight, based on the weight of the curable composition. It is 10 to 92% by weight, particularly preferably 20 to 90% by weight, and most preferably 30 to 70% by weight.
The weight ratio of the compound (B2) in the curable composition in the second invention is 1 to 90% by weight based on the weight of the curable composition from the viewpoint of curability and storage stability. It is preferable, more preferably 1 to 60% by weight, and particularly preferably 10 to 30% by weight.

Next, matters common to the first invention and the second invention (hereinafter, may be abbreviated as the present invention) will be described.
The acid value of the curable composition of the present invention is preferably 1 to 70 mgKOH / g, more preferably 1 to 50 mgKOH / g, and particularly preferably 1 to 30 mgKOH / g from the viewpoint of storage stability. , Most preferably 1 to 15 mgKOH / g.

The content of the thiol group in the curable composition of the present invention is preferably 0.1 to 5.0 mmol / g, more preferably 0.4 to 4.5 mmol / g, and particularly preferably 0.5. ~ 4.2 mmol / g.
When it is 0.1 mmol / g or more, the curability is good, and when it is 5.0 mmol / g or less, the storage stability is good.
The content of the thiol group can be quantified according to the method described in JP-A-62-187731.

In the curable composition of the present invention, the value obtained by dividing the acid value (mgKOH / g) by the thiol group content (mmol / g) [[acid value (mgKOH / g)] / [thiol group]. Content (mmol / g)]] is preferably 0.1 to 100, more preferably 0.4 to 80, and particularly preferably 0.4 to 10 from the viewpoint of curability. ..

The curable composition of the present invention preferably further contains a radical polymerization initiator (D) for the purpose of improving curability.
Examples of the radical polymerization initiator (D) include a phosphine oxide compound (D1), a benzoylformate compound (D2), a thioxanthone compound (D3), an oxime ester compound (D4), and a hydroxybenzoyl compound (D5). , Benzophenone-based compound (D6), Ketal-based compound (D7), α-aminoalkylphenone-based compound (D8) and the like.

Examples of the phosphine oxide compound (D1) include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Examples of the benzoylformate compound (D2) include methylbenzoylformate and the like.

Examples of the thioxanthone compound (D3) include isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone and the like.

Examples of the oxime ester compound (D4) include 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime) and ethanone-1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned.

Examples of the hydroxybenzoyl compound (D5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexylphenyl ketone.

Examples of the benzophenone compound (D6) include benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4,4'-bismethylaminobenzophenone and the like.

Examples of the ketal compound (D7) include acetophenone dimethyl ketal and benzyl dimethyl ketal.

Examples of the α-aminoalkylphenone compound (D8) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2- (dimethylamino) -2-[(4). -Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like can be mentioned.

Among these photopolymerization initiators (D), phosphine oxide-based compounds (D1) and α-aminoalkylphenone-based compounds (D8) are preferable from the viewpoint of curability and coloring of the cured product.
The above-mentioned photopolymerization initiator (D) may be used alone or in combination of two or more.

The weight ratio of the radical polymerization initiator (D) in the curable composition of the present invention is preferably 5 to 20% by weight based on the weight of the curable composition from the viewpoint of curability and transparency. More preferably, it is 5 to 15% by weight.

The curable composition of the present invention may contain various additives, if necessary, as long as the effects of the present invention are not impaired.
Examples of the additive include a plasticizer, an organic solvent, a dispersant, a defoaming agent, a thixotropy-imparting agent (thickening agent), a slip-improving agent, an antioxidant, a hindered amine-based light stabilizer, and an ultraviolet absorber. ..

The curable composition of the present invention uses, for example, a known mechanical mixing method (for example, a method using a mechanical stirrer or a magnetic stirrer) in a temperature range of 20 to 80 ° C. for the essential components and optional components of each invention. It can be manufactured by uniformly mixing with.

The curable composition of the present invention is diluted with a solvent (methyl ethyl ketone, etc.) if necessary, applied to at least a part of at least one side of the substrate, dried if necessary, and then activated energy rays (ultraviolet rays, electron beams and A hard coat coating having a cured film can be obtained by irradiating with X-rays or the like and curing.
At the time of coating, a coating machine [bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife coater, spin coater, blade coater, etc.] can be used.
The coating film thickness is preferably 0.5 to 300 μm as the film thickness after curing and drying. A more preferable upper limit is 250 μm from the viewpoint of drying property and curability, and a further preferable lower limit is 1 μm from the viewpoint of hardness.

Examples of the above-mentioned base material include those made of a glass base material and resins such as methyl methacrylate (co) polymer, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose and polycycloolefin.

When the curable composition of the present invention is diluted with a solvent and used, it is preferably dried after coating. Examples of the drying method include hot air drying (dryer, etc.).
The drying temperature is preferably 10 to 200 ° C., a more preferable upper limit is 150 ° C. from the viewpoint of smoothness and appearance of the coating film, and a further preferable lower limit is 30 ° C. from the viewpoint of drying speed.

The active energy rays in the present invention include ultraviolet rays, electron beams, X-rays, infrared rays and visible rays. Of these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoint of curability and suppression of resin deterioration.

When the active energy ray-curable composition of the present invention is cured by ultraviolet rays, an LED light source ultraviolet irradiation device [for example, LED light source ultraviolet irradiation device "FJ100 150 × 20 365, manufactured by phoseon TECHNOLOGY Co., Ltd."] can be used.
The LED light source has lower power consumption, less ozone generation, lower running cost, and less environmental load than other general ultraviolet light sources.
^{The irradiation amount of ultraviolet rays is preferably 50 to 10,000 mJ / cm 2} from the viewpoint of curability of the curable composition and flexibility of the cured product, and more preferably 200 to 5,000 mJ / cm ² . ..
The active energy ray-curable composition of the present invention can of course be applied to an ultraviolet irradiation device such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp that emits ultraviolet rays having a wide wavelength from an LED light source, and exhibits its performance.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% indicates a weight% and a part indicates a weight part. In the following, Examples 5 to 8 will be referred to as Reference Examples 1 to 4.

Production Example 1 [Production of compound (B21-1) having a thiol group and a phosphoric acid group]
60 parts of methyl methacrylate, 10 parts of 2-methacryloyloxyethyl acid phosphate, 30 parts of 2-hydroxyethyl methacrylate and 200 parts of toluene in a glass reaction vessel equipped with a heating / cooling / stirring device, a reflux condenser and a nitrogen introduction tube. Was prepared. After replacing the gas phase portion in the system with nitrogen, a solution prepared by dissolving 5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) in 50 parts of toluene was added, and the mixture was heated to 90 ° C., and the same. The reaction was carried out at temperature for 4 hours.
After completion of the reaction, the Dean-Stark apparatus and reflux condenser were mounted in a glass reaction vessel containing the reaction product, 20 parts of β-mercaptopropionic acid and 2 parts of p-toluenesulfonic acid were added, and 140 parts were added with stirring. The mixture was heated to ° C. and further reacted at the same temperature for 6 hours. After the reaction, the mixture was cooled, neutralized with a 10% aqueous sodium hydrogen carbonate solution, and filtered. After filtration, toluene and water were distilled off under reduced pressure to obtain a compound having a thiol group and a phosphoric acid group (B21-1). The acid value was 43 mgKOH / g, and the thiol group content was 1.51 mmol / g.

Comparative Production Example 1 [Production of Methyl Methacrylate / Methacrylic Acid Copolymer (B'11-1)]
70 parts of methyl methacrylate, 30 parts of methacrylic acid and 200 parts of toluene were charged into a glass reaction vessel equipped with a heating / cooling / stirring device, a reflux condenser and a nitrogen introduction tube. After replacing the gas phase portion in the system with nitrogen, a solution prepared by dissolving 5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) in 50 parts of toluene was added, and the mixture was heated to 90 ° C., and the same. The reaction was carried out at temperature for 4 hours. After completion of the reaction, toluene was distilled off under reduced pressure to obtain a methyl methacrylate / methacrylic acid copolymer (B'11-1) as a compound having a carboxy group. The acid value was 186 mgKOH / g.

Examples 1-8 and Comparative Examples 1-6
The compounding compositions (parts by weight) shown in Table 1 were uniformly mixed to obtain curable compositions of Examples 1 to 8 and comparative curable compositions of Comparative Examples 1 to 6.

The raw materials used in Table 1 are as follows.
(A-1): Acryloylmorpholine [Product name: ACMO, manufactured by KJ Chemicals Co., Ltd.]
(A-2): Isobornyl acrylate [Product name: IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.]
(A-3): 1,6-Hexanediol diacrylate [Product name: Viscoat # 230, manufactured by Osaka Organic Chemical Industry Co., Ltd.]
(A-4): Pentaerythritol tetraacrylate [Product name: Neomer EA-300, manufactured by Sanyo Chemical Industries, Ltd.]
(A-5): N-vinylcaprolactam [manufactured by BASF]
(A-6): Triallyl trimellitic acid [Product name: TRIAM-705, manufactured by Wako Pure Chemical Industries, Ltd.]
(A-7): Pentaerythritol triallyl ether [Product name: Neoallyl P-30, manufactured by Osaka Soda Co., Ltd.]
(B12-1): Mixture of 2-acryloyloxyethyl acid phosphate and bis [2- (acryloyoxy) ethyl] phosphate [trade name: KAYARAD PM-2, manufactured by Nippon Kayaku Co., Ltd., phosphate group Compound with, acid value 270 mgKOH / g]
(B12-2): 2-methacryloyloxyethyl caprolactam-modified acid phosphate [trade name: KAYARAD PM-21, manufactured by Nippon Kayaku Co., Ltd., compound having a phosphoric acid group, acid value 178 mgKOH / g]
(B12-3): Vinyl sulfonic acid [manufactured by Asahi Kasei Finechem Co., Ltd., compound having a sulfo group, acid value 519 mgKOH / g]
(B12-4): Nt-butylacrylamide sulfonic acid [trade name: ATBS, manufactured by Toa Synthetic Co., Ltd., compound having a sulfo group, acid value 271 mgKOH / g]
(B'12-1): 2-acryloyloxyethyl-phthalic acid [trade name: HOA-MPL (N), manufactured by Kyoeisha Chemical Co., Ltd., compound having a carboxy group, acid value 226 mgKOH / g]
(C-1): 1,4-bis (3-mercaptobutylyloxy) butane [Product name: Karenz MT BD1, manufactured by Showa Denko KK, 2 thiol groups, thiol group content 6.68 mmol / g]
(C-2): Pentaerythritol Tetrakis (3-mercaptobutyrate) [Product name: Karenz MT PE1, manufactured by Showa Denko KK, 4 thiol groups, thiol group content 7.34 mmol / g]
(C-3): Pentaerythritol tetrakis (3-mercaptopropionate) [Product name: PEMP, manufactured by SC Organic Chemistry Co., Ltd., 4 thiol groups, thiol group content 8.19 mmol / g]
(D-1): 2,4,6-trimethylbenzoyldiphenylphosphine oxide [trade name: Irgacure TPO, manufactured by BASF Corporation, acylphosphine oxide-based polymerization initiator]
(D-2): Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide [trade name: Irgacure 819, manufactured by BASF, acylphosphine oxide-based polymerization initiator]
(D-3): 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone [trade name: Irgacure 379, BASF, Inc. Alkylphenyl radical polymerization initiator]
Additive: alkylene oxide-modified polydimethylsiloxane [trade name "BYK-302", manufactured by Big Chemie Japan Co., Ltd .; slip property improver]

Regarding the curable compositions obtained in Examples 1 to 8 and the comparative curable compositions obtained in Comparative Examples 1 to 6, curability, pencil hardness, total light transmittance of the cured product, adhesion of the cured product, and the like. Storage stability was evaluated.

<Evaluation of curability>
Each curable composition is applied to a glass substrate [Eagle XG (thickness 0.7 mm) manufactured by Corning Inc.] with a spin coater so that the film thickness after curing is 20 μm, and an LED light source ultraviolet irradiation device [model number: FJ100]. 150 × 20 365, manufactured by phoseon TECHNOLOGY Co., Ltd., irradiation wavelength 365 nm], ultraviolet rays are irradiated at an irradiation intensity of 400 mW / cm ² for 5 seconds, and the curable composition is cured by an integrated exposure amount of 2,000 mJ / cm ^2. I let you.

The surface of the cured product was touched with a finger to check whether it was sticky, and evaluated according to the following criteria.
○: No stickiness at all ×: Stickiness remains

<Evaluation of pencil hardness>
The cured product obtained by the above evaluation of curability was measured for pencil hardness according to JIS K-5400. When used for hard coating, the pencil hardness needs to be 2H or more.

<Evaluation of total light transmittance>
The cured product obtained by the above evaluation of curability is subjected to the total light transmittance according to JIS-K7105 and using a total light transmittance measuring device [trade name "haze-garddual", manufactured by BYK gardener Co., Ltd.]. (%) Was measured.
When prepared under these sample preparation conditions and used for general hard coating applications, the total light transmittance needs to be 88% or more.

<Evaluation of adhesion>
This was done in accordance with JIS K5600-5-6.
The cured product obtained by the above evaluation of curability was allowed to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then a 1 mm wide cut was made with a cutter knife to make a grid (5 x 5 pieces). It was created.
A cellophane adhesive tape was attached on the grid, peeled at 90 degrees, and the peeled state of the cured product from the glass substrate was visually observed. The number of squares in 25 squares that were in close contact with each other without peeling was counted and evaluated.
Further, in the above evaluation of adhesion, instead of standing for 24 hours in an environment of 23 ° C. and a relative humidity of 50%, it was left to stand for 24 hours in an environment of 60 ° C. and a relative humidity of 90%. , The same as the above-mentioned evaluation of adhesion was carried out, and the evaluation of adhesion under more severe conditions was also carried out.

<Evaluation of storage stability>
Each curable composition is stored in a 40 ° C environment, taken out after 30 days, the viscosity is measured, and the rate of change from the initial viscosity (viscosity before starting storage in a 40 ° C environment) is calculated. Then, it was evaluated according to the following criteria.
The viscosity was measured with an E-type viscometer [trade name: TVE-35, manufactured by Toki Sangyo Co., Ltd.].
Rate of change (%) = (viscosity after 30 days-initial viscosity) / initial viscosity x 100
◯: Less than 10% ×: 10% or more

As shown in Table 1, the curable compositions of Examples 1 to 8 of the present invention are excellent in all aspects of curability by LED light source, pencil hardness, total light transmittance, adhesion and storage stability.
On the other hand, the curable composition of Comparative Example 1 containing no compound having a thiol group (c) has insufficient curability, pencil hardness and adhesion.
Further, the curable composition for comparison of Comparative Example 2 which does not contain any compound having an acidic functional group [phosphoric acid group (b1), sulfo group (b2), etc.] has insufficient adhesion and storage stability. be.
Further, a comparative example containing the compound (B') which does not contain the above-mentioned (B), has a carboxy group (b'), and has neither a phosphoric acid group (b1) nor a sulfo group (b2). The curable compositions for comparison of 3 to 6 have insufficient adhesion and storage stability.

Since the curable composition of the present invention has high storage stability and excellent adhesion to a substrate, curability, and hardness, it can be suitably used as a hard coat film.

Claims (5)

A monomer (A) having an ethylenically polymerizable group (a) and having neither a phosphoric acid group (b1), a sulfo group (b2) nor a thiol group (c), a phosphoric acid group (b1) and / Alternatively, it has a compound (B) having a sulfo group (b2) and a thiol group (c), and has neither an ethylenically polymerizable group (a), a phosphoric acid group (b1) nor a sulfo group (b2). It contains the compound (C), and the monomer (A) has at least one selected from the group consisting of isobornyl (meth) acrylate, (meth) acryloylmorpholine and phenoxyethyl (meth) acrylate, and the number of carbon atoms. Diester of 4 to 10 divalent alcohols and (meth) acrylic acid, tri (meth) acrylate of trimethylrolpropane, tri (meth) acrylate of pentaerythritol, tetra (meth) acrylate of pentaerythritol, penta of dipentaerythritol. In combination with at least one selected from the group consisting of (meth) acrylate and hexa (meth) acrylate of dipentaerythritol, the compound (B) is a phosphate group (b1) and a (meth) acryloyl group. A compound (B12) having a certain ethylenically polymerizable group (a) and not having a thiol group (c), which is 2- (meth) acryloyloxyethyl acid phosphate, bis [2-[(meth) acryloyl). Oxy] ethyl] phosphate, caprolactone-modified bis [2-[(meth) acryloyloxyethyl]] phosphate, caprolactone-modified [2-[(meth) acryloyloxyethyl]] acid phosphate, caprolactone-modified bis [2-[ (Meta) acryloyloxymethyl]] phosphate, caprolactone-modified bis [2-[(meth) cryloyloxypropyl]] phosphate and caprolactone-modified bis [2-[(meth) cryloyloxybutyl]] phosphate At least one selected from the group, the compound (C) is trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercapto). At least one selected from the group consisting of butylate), wherein the weight ratio of the monomer (A) is 30 to 90% by weight based on the weight of the curable composition, and the compound (B) has a weight ratio of 30 to 90% by weight. The weight ratio is 1 to 15% by weight, before A curable composition in which the weight ratio of the compound (C) is 5 to 20% by weight. The curable composition according to claim 1, wherein the thiol group content is 0.5 to 4.2 m mmol / g. The curable composition according to claim 1 or 2, which has an acid value of 1 to 50 mgKOH / g. The curable composition according to any one of claims 1 to 3, further comprising a radical polymerization initiator (D). A cured film obtained by curing the curable composition according to any one of claims 1 to 4.