TW201930374A - (meth)acrylic composition manufacturing method, (meth)acrylic composition-containing coating, and hardened product - Google Patents

Abstract

The present invention provides: a method for manufacturing a (meth)acrylic composition which has low viscosity, exhibits high refractive index when hardened, and is less susceptible to yellowing after undergoing an environmental test at high temperature and high humidity; and a coating containing such a (meth)acrylic composition. The method according to one embodiment of the present invention comprises mixing, within a prescribed temperature range, a (meth)acrylate represented by general formula (1) with a multivalent (meth)acrylic monomer represented by general formula (2).

Description

Method for producing (meth)acrylic composition, coating containing (meth)acrylic composition, and hardened body

The present invention relates to a method for producing a (meth)acrylic composition, and a coating comprising a (meth)acrylic composition. Further, the present invention is also a hardened body relating to the composition.

In recent years, resin materials have been widely used in optical overcoat agents, hard coating agents, antireflection films, spectacle lenses, optical fibers, optical waveguides, holograms, etc., because of their excellent processing and productivity. Optical parts. Further, in the field of optical parts, the tendency to be smaller and thinner is increased, and accordingly, a material having a high refractive index is required. Further, for such a requirement, a coating material containing a resin composition having a high refractive index at the time of hardening is widely used. On the other hand, such a coating generally has a relatively high viscosity characteristic, and thus it is difficult to apply it thinly. Thus, the proposal has a low viscosity composition that improves this point.

For example, in Patent Document 1, an o-phenyl benzyl acrylate (OPBA; or 2-phenylbenzyl acrylate) as an isomer of phenyl benzyl acrylate and p-phenylbenzyl acrylate (PPBA; Or 4-phenylbenzyl acrylate) is mixed in a specific ratio, and a composition having a high refractive index and a low viscosity is proposed. Further, Patent Document 2 discloses that a composition having a high refractive index and a low viscosity is obtained by mixing phenyl benzyl acrylate with a difunctional (meth) acrylate or a diphenyl derivative.

Patent Documents 3 to 7 describe mixing of phenoxybenzyl (meth)acrylate and polyfunctional (meth)acrylate (fluorene bisphenol derivative or bisphenol A derivative) having a high refractive index. A resin composition for an optical material was obtained.

[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-82387
[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-82386
[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-248358
[Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-126991
[Patent Document 5] Japanese Patent Laid-Open Publication No. 2012-219205
[Patent Document 6] Japanese Patent Laid-Open Publication No. 2013-53310
[Patent Document 7] Japanese Patent Laid-Open Publication No. 2014-185337

[Questions to be solved by the invention]

As described above, various high refractive index and low viscosity compositions have been proposed so far. However, low-viscosity monofunctional (meth) acrylates are mostly low in refractive index. In other respects, high-refractive-index monofunctional (meth) acrylates cannot sufficiently obtain polyfunctional (meth)acrylic acid having a high refractive index. The effect of the viscosity reduction of the ester. Due to such a situation, a monofunctional (meth) acrylate having a high refractive index and a low viscosity has been developed. As an example thereof, phenoxybenzyl (meth)acrylate represented by the chemical formula (C) has been newly discovered and studied (for example, Patent Document 4, (B) Component 1, etc.).

However, it has been found that if the phenoxybenzyl (meth)acrylate represented by the chemical formula (C) is used, the yellow film is applied in an environmental test under high temperature and high humidity (specifically, 85 ° C / 85% RH). Becomes intense. Thus, a (meth)acrylic composition having a low viscosity of the composition, a high refractive index at the time of curing, and a yellowing reduction in an environmental test under high temperature and high humidity was sought.

The present invention provides a method for producing a (meth)acrylic composition having a low viscosity of a composition, a high refractive index at the time of curing, and a yellowing reduction in an environmental test under high temperature and high humidity, And a coating material containing the (meth)acrylic composition is intended for the purpose. Further, the present invention has an object of providing a cured body of the above composition.

[Means for solving the problem]

As a result of intensive studies to solve the above problems, the inventors of the present invention found that the (meth) acrylate of the following general formula (1) is in a predetermined temperature range and the plural of the following general formula (2) ( The present invention can be accomplished by mixing a methyl group-based acrylic monomer to solve the above problems.

That is, the present invention has the features described below.
[1] A method for producing a liquid composition, wherein the liquid composition comprises (A) a (meth) acrylate represented by the following formula (1), and (B) a plural represented by the following formula (2); (meth)acrylic monomer;
The method includes mixing a (meth) acrylate represented by the following formula (1) and a polyvalent (meth)acrylic monomer represented by the following formula (2) at a temperature of from 35 ° C to 120 ° C;

[in the formula (1),
X is selected from a single bond, -C(R ₂ )(R ₃ )-, -C(=O)-, -O-,
-OC(=O)-, -OC(=O)O-, -S-, -SO-, -SO ₂ - and the divalent group in the group formed by any combination of these (here, R ₂ and R ₃ are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a carbon number of 1 to 10 a linear alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group; or R ₂ and R ₃ may be mutually Linking and forming a cyclic alkyl group having a carbon number of 3 to 10 together with the carbon atoms bonded thereto,
Y is a branched alkyl group having 2 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an extended aryl group having 6 to 10 carbon atoms.
R ₁ is a hydrogen atom or a methyl group,
R ₄ and R ₅ are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a straight carbon having 1 to 10 carbon atoms. a chain alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group;
m is an integer from 0 to 10,
n is an integer from 1 to 2,
p is an integer from 0 to 4,
q is an integer from 0 to 5];

[in formula (2),
R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkane having 5 to 20 carbon atoms. An oxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom,
R ₁₂ is a hydrogen atom or a methyl group,
X represents any one of a group consisting of a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, and the following general formulae (3) to (6),
Y and Z are each independently a branched alkyl group having 2 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an extended aryl group having 6 to 10 carbon atoms;
p and q are each independently an integer from 0 to 4];

[in equation (3),
R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, and may have a substituent. Any one of a group of an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent,
Each of the above substituents is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.
c represents an integer from 1 to 20];

In the formula (4), R ₁₅ and R ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 5 carbon atoms which may have a substituent. a group of an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent Either R ₁₅ and R ₁₆ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms.
Each of the above substituents is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms;

In the formula (5), R ₁₇ to R ₂₀ each independently represent a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 5 carbon atoms which may have a substituent. An aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent Or, R ₁₇ and R ₁₈ and R ₁₉ and R ₂₀ are each bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms;
The above substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms;

In the formula (6), R ₂₁ to R ₃₀ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
[2] The method according to [1], wherein in the above formula (1), both p and q are 0.
[3] The method according to [1] or [2], wherein in the above formula (1), n is 1, and m is 0.
[4] The method according to any one of [1] to [3] wherein the (meth) acrylate represented by the above formula (1) and the poly (meth) acrylate series represented by the above formula (2) The content of the body is from 1:10 to 10:1 by mass ratio.
[5] The method according to any one of [1] to [4] wherein the (meth) acrylate represented by the above formula (1) is a blend of two or more kinds of compounds.
[6] The method according to any one of [1] to [5] wherein, in the above formula (2), X has a structure represented by the formula (4).
[7] The method according to any one of [1] to [6] wherein the liquid composition is an active energy ray-curable composition.
[8] A coating comprising the composition obtained by the method according to any one of [1] to [7].
[9] A hardened body obtained by hardening a composition obtained by the method according to any one of [1] to [7].
[10] A method of producing a hardened body, and comprising:
The step of obtaining a composition by the method according to any one of [1] to [7], and the step of hardening the above composition.

[Effects of the Invention]

According to the present invention, a method for producing a (meth)acrylic composition having a low viscosity of a composition, a high refractive index at the time of curing, and a yellowing reduction in an environmental test under high temperature and high humidity can be provided, and A coating of an acrylic composition. Further, according to the present invention, a hardened body of the above composition can be provided.

Hereinafter, embodiments of the present invention will be described in detail.

<Manufacturing method>
The method for producing the liquid composition of the present invention comprises: including
(A) a (meth) acrylate represented by the following formula (1), and

[in the formula (1),
X is selected from a single bond, -C(R ₂ )(R ₃ )-, -C(=O)-, -O-,
-OC(=O)-, -OC(=O)O-, -S-, -SO-, -SO ₂ - and the divalent group in the group formed by any combination of these (here, R ₂ and R ₃ are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a carbon number of 1 to 10 a linear alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group; or R ₂ and R ₃ may be mutually Linking and forming a cyclic alkyl group having a carbon number of 3 to 10 together with the carbon atoms bonded thereto;
Y is a branched alkyl group having 2 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an extended aryl group having 6 to 10 carbon atoms;
R ₁ is a hydrogen atom or a methyl group;
R ₄ and R ₅ are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a straight carbon having 1 to 10 carbon atoms. a chain alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group;
m is an integer from 0 to 10;
n is an integer from 1 to 2;
p is an integer from 0 to 4;
q is an integer from 0 to 5]
(B) a polyvalent (meth)acrylic monomer represented by the following formula (2);

[in formula (2),
R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkane having 5 to 20 carbon atoms. An oxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom,
R ₁₂ is a hydrogen atom or a methyl group;
X represents any one of a group consisting of a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, and the following general formulae (3) to (6);
Y and Z are each independently a branched alkyl group having 2 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an extended aryl group having 6 to 10 carbon atoms;
p and q are each independently an integer of 0-4. ]
a method of producing a liquid composition;
Further, the (meth)acrylate represented by the formula (1) and the polybasic (meth)acrylic monomer represented by the formula (2) are mixed at a temperature of from 35 ° C to 120 ° C.

As described above, a liquid obtained by mixing a (meth) acrylate having a structure of the formula (1) and a poly (meth) acryl monomer having a structure of the formula (2) in a predetermined temperature range The composition has a low viscosity and a high refractive index when hardened, and the yellowing is reduced in an environmental test under high temperature and high humidity. Although not limited by theory, the reason for the yellowing of the inference is that the glass transition temperature is low. Further, it is considered that the (meth) acrylate having the structure of the general formula (1) is usually a solid at normal temperature, and it is not possible to reduce the high refractive index and high viscosity of the general formula (2) poly(meth)acrylic acid. It is used for the purpose of viscosity of the monomer. For example, in Patent Document 1, p-phenylbenzyl (meth)acrylate which is one of the (meth) acrylates having the structure of the general formula (1) is a solid at normal temperature (mp: 32 ° C), and therefore It cannot be used for this purpose. Further, Patent Document 1 obtains a liquid composition by mixing o-phenylbenzyl (meth)acrylate and p-phenylbenzyl (meth)acrylate at a specific ratio in a specific ratio.

Under such circumstances, the inventors of the present invention have found that (meth) acrylate having the structure of the formula (1) is heated to a predetermined temperature range, and has a structure of the formula (1) (methyl group). The acrylate is liquefied, and by mixing with a polyvalent (meth)acrylic monomer having a structure of the formula (2) in this state, a liquid composition can be obtained. And surprisingly, it is known that after the (meth) acrylate having the structure of the general formula (1) is liquefied, it is mixed with a polyvalent (meth)acrylic monomer having a structure of the general formula (2). In the case of the liquid composition obtained, even if it is cooled, crystals or the like are not precipitated, and it becomes a stable liquid composition. Further, the liquid composition thus obtained has a low viscosity, a high refractive index at the time of curing, and a yellow color in an environmental test under high temperature and high humidity. The present invention is based on the above findings.

In the production method of the present invention, the temperature at which the (meth) acrylate having the structure of the formula (1) is mixed with the poly (meth)acrylic monomer having the structure of the formula (2) is 35 ° C or more and 120 ° C Hereinafter, it is preferably 40° C. or higher and 100° C. or lower, and more preferably 45° C. or higher and 80° C. or lower. When the temperature at the time of mixing is 35° C. or more, the (meth) acrylate having the structure of the formula (1) is sufficiently liquefied, and when it is 120° C. or lower, polymerization of the monomer can be prevented. At the time of mixing, at least the temperature of the (meth) acrylate having the structure of the general formula (1) may be adjusted to the above temperature range, and the poly (meth)acrylic monomer having the structure of the general formula (2) may be used. Can be mixed directly at room temperature.

The viscosity of the liquid composition of the present invention is less than 10,000 mPa·s, preferably 5,000 mPa·s or less, measured at a measurement temperature of 25 ° C using an E-type viscometer (TV-22 type). Good for 5~2,000 mPa·s.

Hereinafter, each component contained in the composition obtained by the production method of the present invention will be described in order.

1. (Meth) acrylate The (meth) acrylate used for the composition obtained by the manufacturing method of this invention has the structure represented by following General formula (1).

In the formula (1), X is selected from a single bond, -C(R ₂ )(R ₃ )-,
-C(=O)-, -O-, -OC(=O)-, -OC(=O)O-, -S-, -SO-, -SO ₂ - and any combination of these The divalent group in the group is preferably a divalent group selected from the group consisting of a single bond, -C(R ₂ )(R ₃ )-, -O-, and any combination thereof. Here, R ₂ and R ₃ each independently represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and carbon. A linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group. Alternatively, R ₂ and R ₃ may be bonded to each other and form a cyclic alkyl group having 3 to 10 carbon atoms together with the carbon atoms bonded thereto. Preferably, both R ₂ and R ₃ are a hydrogen atom.

Y is a branched alkyl group having 2 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an extended aryl group having 6 to 10 carbon atoms.

R ₁ is a hydrogen atom or a methyl group, preferably a hydrogen atom.
R ₄ and R ₅ are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a straight carbon having 1 to 10 carbon atoms. a chain alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group.

m is an integer of 0 to 10, preferably an integer of 0 to 5, more preferably 0.
n is an integer of 1 to 2, preferably 1.
Further preferably, n is 1 and m is 0.
p is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0.
q is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0.
Further preferably, both p and q are zero. The case where p and q are 0 means that the hydrogen of the benzene ring is not substituted by the functional groups of R ₄ or R ₅ .

Examples of the (meth) acrylate represented by the above formula (1) include 4-phenylbenzyl (meth)acrylate, 3-phenylbenzyl (meth)acrylate, and 2-(meth)acrylate. Phenylbenzyl ester, 4-biphenylbenzyl (meth)acrylate, 3-biphenylbenzyl (meth)acrylate, 2-biphenylbenzyl (meth)acrylate, (meth)acrylic acid 4 -benzylbenzyl ester, 3-benzylbenzyl (meth)acrylate, 2-benzylbenzyl (meth)acrylate, 4-phenylethylbenzyl (meth)acrylate, 3-(meth)acrylate Phenylethyl benzyl ester, 2-phenylethyl benzyl (meth) acrylate, 4-phenylethyl phenethyl (meth) acrylate, 3-phenylethyl phenyl (meth) acrylate, (methyl) ) 2-Phenylethyl phenethyl acrylate, 4-(4-methylphenyl)benzyl (meth) acrylate, 3-(4-methylphenyl) benzyl (meth) acrylate, (methyl) ) 2-(4-methylphenyl)benzyl acrylate, 4-(4-methoxyphenyl)benzyl (meth)acrylate, 3-(4-methoxyphenyl) (meth)acrylate Benzyl ester, 2-(4-methoxyphenyl)benzyl (meth)acrylate, 4-(4-bromophenyl)benzyl (meth)acrylate, 3-(4-bromo)(meth)acrylate Phenyl)benzyl ester, 2-(4-bromophenyl)(meth)acrylate Benzyl ester, 4-benzylidene benzyl (meth)acrylate, 3-benzylidene benzyl (meth)acrylate, 2-benzylidene benzyl (meth)acrylate, (methyl) 4-(phenylsulfinyl)benzyl acrylate, 3-(phenylsulfinyl)benzyl (meth)acrylate, 2-(phenylsulfinyl)benzyl (meth)acrylate, (methyl) ) 4-(phenylsulfonyl)benzyl acrylate, 3-(phenylsulfonyl)benzyl (meth)acrylate, 2-(phenylsulfonyl)benzyl (meth)acrylate, (meth)acrylic acid 4-((phenoxycarbonyl)oxy)benzyl ester, 3-((phenoxycarbonyl)oxy)benzyl (meth)acrylate, 2-((phenoxycarbonyl)oxy (meth)acrylate Benzyl ester, 4-(((meth)propenyloxy)methyl)phenyl benzoate, 3-(((meth)propenyloxy)methyl)phenyl benzoate, benzoic acid 2 -(((Methyl)propenyloxy)methyl)phenyl ester, 4-(((meth)propenyloxy)methyl)benzoate phenyl, 3-(((meth)propeneoxy) Phenyl (meth) phenyl benzoate, phenyl 2-(((meth)propenyloxy)methyl)benzoate, 4-(1-phenylcyclohexyl)benzyl (meth)acrylate, ( 3-(1-phenylcyclohexyl)benzyl (meth)acrylate, 2-(1-phenylcyclohexyl)(meth)acrylate Benzyl ester, 4-phenoxybenzyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, 2-phenoxybenzyl (meth)acrylate, 4-(meth)acrylate Phenylthio)benzyl ester, 3-(phenylthio)benzyl (meth)acrylate, 2-(phenylthio)benzyl (meth)acrylate and 3-methyl-4-(2-methacrylate) Methylphenyl) benzyl ester. These may be used alone or in combination of two or more. For example, a blend of a compound of two or more kinds of (meth) acrylates may be used. In this case, at least one type of methacrylate may be a (meth) acrylate represented by the above formula (1). Among the above (meth) acrylates, preferred are 2-phenylbenzyl (meth)acrylate, 4-phenylbenzyl (meth)acrylate, 4-phenoxybenzyl (meth)acrylate and ( 4-Benzylbenzyl methacrylate, more preferably 2-phenylbenzyl acrylate, 4-phenylbenzyl acrylate, 4-phenoxybenzyl acrylate and 4-benzyl benzyl acrylate.

The amount of the (meth) acrylate to be contained in the composition obtained by the production method of the present invention is not particularly limited as long as it does not deviate from the gist of the present invention, but (meth) acrylate and The content of the polyvalent (meth)acrylic monomer represented by the formula (2) is preferably from 1:9 to 9:1, more preferably from 2:8 to 8:2, and still more preferably from 3:7 by mass ratio. ~7:3, especially good for 4:6~6:4. Further, the higher the ratio of the monofunctional (meth) acrylate, the more desirable it is to prevent peeling in a high-temperature and high-humidity environment. Although not limited by theory, it is inferred that the water absorption rate is large because the adhesion between the substrate and the hardened body is low.

3. The composition of the poly(meth)acrylic monomer by the production method of the present invention further comprises the following general formula (2) copolymerizable with the (meth) acrylate represented by the above formula (1). A polyvalent (meth)acrylic monomer represented.

In the formula (2), R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a carbon number. The cycloalkyloxy group of 5 to 20, the aryl group having 6 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms, and a halogen atom are preferably a hydrogen atom.
R ₁₂ is a hydrogen atom or a methyl group.
X represents any one of a group consisting of a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, and the following general formulae (3) to (6).
Y and Z are each independently a branchable alkyl group having 2 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an extended aryl group having 6 to 10 carbon atoms.
p and q are each independently an integer of 0 to 4, and preferably both p and q are 0.

In the following formula (3),

R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, and may have a substituent. Any one of a group of an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, here The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. Preferably, both R ₁₃ and R ₁₄ are a hydrogen atom.
c represents an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.

In the following formula (4),

R ₁₅ and R ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, and may have a substituent. Any one of the group consisting of an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or R ₁₅ and R ₁₆ are each bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, and the substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. Preferably, both R ₁₅ and R ₁₆ are a hydrogen atom.

In the following formula (5),

R ₁₇ to R ₂₀ each independently represent a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, and a carbon which may have a substituent Any of a group of 6 to 12 aryl groups, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or R ₁₇ and R ₁₈ and R ₁₉ and R ₂₀ are each bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, and the substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms or a carbon number of 6 to 12 Aryl. Preferably, R ₁₇ to R ₂₀ are each a hydrogen atom.

In the following formula (6),

R ₂₁ to R ₃₀ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Preferably, R ₂₁ to R ₃₀ are each a hydrogen atom.

In the above formula (2), X preferably has a structure represented by the formula (4).

Examples of the polyvalent (meth)acrylic monomer represented by the above formula (2) include 9,9-bis[4-(2-(methyl)acryloxyethoxyethoxy)phenyl]anthracene. 4,4'-isopropylidenediphenol di(meth)acrylate, 2,2'-bis[4-(2-(methyl)propenyloxyethoxy)phenyl]propane, double [ 4-(2-(Methyl)acryloxyethoxyethoxy)phenyl]methane, 1,1'-bis[4-(2-(methyl)propenyloxyethoxy)phenyl]methane , bis[4-(2-(methyl)acryloxyethoxyethoxy)phenyl]ether, bis[4-(2-(methyl)acryloxyethoxy)phenyl]anthracene, Bis[4-(2-(methyl)acryloxyethoxyethoxy)phenyl] sulfide, bis(4-(2-(methyl)(methyl)propenyloxyethoxy)phenyl)碸, bis(4-(2-(methyl) propylene methoxy ethoxy) phenyl] ketone, ethoxylated bisphenol A diacrylate and 4,4'-di(meth) propylene oxime Oxybiphenyl, etc. Among them, preferred are 9,9-bis[4-(2-(methyl)acryloxyethoxy)phenyl]anthracene, 4,4'-isopropylidenediphenol (meth) acrylate, ethoxylated bisphenol A diacrylate and 2,2'-bis[4-(2-(methyl) propylene oxyethoxy) phenyl] propane, more preferably Ethoxygen Bisphenol A diacrylate and 9,9-bis[4-(2-(methyl) propylene oxyethoxy)phenyl] fluorene. Further, as the plural represented by the above formula (2) For example, ABE-300 or A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd., A-BPEF, and Light Acrylate BP manufactured by Kyoritsu Chemical Co., Ltd. -4EAL, Viscoat #700HV manufactured by Shin-Nakamura Chemical Co., Ltd., FA-324A manufactured by Hitachi Chemical Co., Ltd., etc., but not limited thereto.

3. Any of the components obtained by the production method of the present invention may contain various optional additives in addition to the above-described constituent components, as long as they do not deviate from the gist of the present invention. As such an additive, at least one additive selected from the group consisting of a thermal stabilizer, an antioxidant, a flame retardant, a flame retardant auxiliary, an ultraviolet absorber, a release agent, and a coloring agent can be exemplified. The amount of the additive is preferably 0.005 parts by mass based on 100 parts by mass of the total of the (meth) acrylate represented by the above formula (1) and the poly(meth)acrylic monomer represented by the above formula (2). ~0.1 parts by mass, more preferably 0.01 parts by mass to 0.05 parts by mass.

The composition obtained by the method of the present invention can be hardened by various methods. Although it will be described later in detail, the composition obtained by the method of the present invention is preferably an active energy ray-curable composition.

<paint>
The coating of the present invention comprises a composition obtained by the method of the present invention. The coating of the present invention can be mainly used for coating agents, hard coating agents and the like for optical members.

When the coating material of the present invention is applied to a general substrate such as a plastic, a wetting agent such as a hydrogen peroxide polymer or an acrylic compound may be added to the coating material in order to contribute to the wetting of the surface of each of the substrates. As a suitable wetting agent, there are BYK331, BYK333, BYK340, BYK347, BYK348, BYK378 obtained from BYK Chemical Co., Ltd.
BYK380, BYK381, etc. When these are added, it is preferably in the range of 0.01 to 2.0% by mass based on the total mass of the coating material.

Moreover, in order to improve the adhesion to various materials, an adhesion-imparting agent such as a xylene resin, a terpene resin, a phenol resin, or a rosin resin may be added to the coating as needed. When these are added, it is preferably in the range of 0.01 to 2.0% by mass based on the total mass of the coating material.

In order to improve the adhesion to various materials, a coupling agent such as a decane coupling agent or a titanium coupling agent may be added to the coating material. When these are added, it is preferably in the range of 0.01 to 5.0% by mass based on the total mass of the coating material.

Further, in order to improve various properties such as impact resistance, an inorganic filler such as cerium oxide, alumina, mica, talc, aluminum flake, or glass flake may be added to the coating material. When these are added, it is preferably in the range of 0.01 to 10.0% by mass based on the total mass of the coating material.

Further, when the coating material of the present invention is applied to a general substrate such as metal, concrete or plastic, a helium oxide polymer system may be added to the coating material in order to facilitate the disappearance of bubbles generated during stirring or coating. Or an antifoaming agent made of an acrylic compound. As a suitable antifoaming agent, BYK019, BYK052, BYK065, BYK066N, BYK067N, BYK070, BYK080, etc., which are obtained from BYK Chemical Co., Ltd., may be mentioned, but it is particularly preferable to be BYK065. When these are added, it is preferably in the range of 0.01 to 3.0% by mass based on the total mass of the coating material.

Anti-rust additives such as zinc phosphate, iron phosphate, calcium molybdate, vanadium oxide, water-dispersed cerium oxide, fumed silica, etc., indigo organic pigments, condensed polycyclic organic pigments may also be used as needed. The organic pigment such as titanium oxide, zinc oxide, calcium carbonate, barium sulfate, aluminum oxide or carbon black is added to the coating material of the present invention in an essential amount.

As a coating form when the coating material of the present invention is applied to various substrates, for example, bar coater coating, meyer bar coating, air knife coating, gravure coating, and reverse can be used. Gravure coating, micro gravure coating, micro reverse gravure coater coating, die coater coating, slot die coater coating, vacuum die coater coating, dip coating Any one of the coating forms generally used for cloth, spin coating, spray coating, brush coating, and the like. It is preferably roll coated or spray coated.

<hardened body>
The hardening system of the present invention is a hardened body obtained by hardening a composition obtained by the method of the present invention. The hardened body of the present invention has a high refractive index of 1.580 or more, and yellowing is reduced in an environmental test under high temperature and high humidity. Further, the cured body of the present invention preferably has a high refractive index of 1.585 or more, more preferably a high refractive index of 1.590 or more. Further, the cured product of the present invention has a yellowness (YI) of preferably 4.0 or less when stored in an environment of 85 ° C / 85% RH for 350 hours, and is yellow when stored in an environment of 85 ° C / 85% RH for 1,000 hours. The degree (YI) is preferably 6.5 or less.

The hardened body of the present invention comprises:
(A) a constituent unit derived from a (meth) acrylate represented by the formula (1), and

a constituent unit derived from a polyvalent (meth)acrylic monomer represented by the general formula (2)
.

Here, X, Y, R ₁ , R ₄ , R ₅ , m, n, p and q in the formula (1) are respectively the same as those in the composition obtained by the method of the present invention. Further, R ₁₀ , R ₁₁ , R ₁₂ , X, Y, Z, p and q in the formula (2) are also the same as those in the composition obtained by the method of the present invention, respectively.

In addition, the constituent unit derived from the (meth) acrylate represented by the formula (1) represents a constituent unit having a structure of the following formula (1a).

The constituent unit derived from the polyvalent (meth)acrylic monomer represented by the formula (2) represents a constituent unit having a structure of the following formula (2a).

Here, X, Y, R ₁ , R ₄ , R ₅ , m, n, p and q in the formula (1a) each correspond to R ₁₀ in the formula (1), R ₁₀ in the formula (2a), R ₁₁ , R ₁₂ , X, Y, Z, p and q correspond to those in the formula (2).

The method for producing a cured body of the present invention comprises the steps of obtaining a composition by the method of the present invention, and the step of hardening the composition. Here, the method of hardening is not specifically limited, and it can carry out by various well-known methods. For example, the composition of the present invention can be cured by photopolymerization by irradiation of an active energy ray. In the present specification, "active energy ray" means ultraviolet rays, electron beams, ion beams, X-rays, and the like.

When the composition obtained by the method of the present invention is hardened by an active energy ray, a photopolymerization initiator is not necessarily required. However, when a photopolymerization initiator is added, for example, Irgacure (registered trademark) 2959 (1-[4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2- which can be obtained from Ciba Corporation can be mentioned. Methyl-1-propan-1-one, Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, diphenylmethyl) Ketone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethan-1-one), Irgacure (registered trademark) 369 (2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)butanone-1), Irgacure (registered trademark) 907 (2-methyl-1[4-methylthiophenyl]-2-morpholinylpropane- 1-ketone, Irgacure (registered trademark) 819 (bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, Irgacure (registered trademark) 1800 (bis(2,6-dimethoxy) Benzhydryl)-2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-one), Irgacure (registered trademark) 1800 (double (2,6-dimethyl) Oxylbenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure (Registered trademark ) OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzylidene), Darocur (registered trademark) 1173 (2-hydroxyl) 2-methyl-1-phenyl-1-propan-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1020, CGI242 (ethanone), 1-[9-ethyl- 6-(2-Methylbenzylidene)-9H-carbazol-3-yl]-1-(O-ethylindenyl), LucirinTPO (2,4,6-Third) available from BASF Benzyl indenyl diphenylphosphine oxide), Lucirin TPO-L (2,4,6-trimethylbenzhydrylethoxyphenylphosphine oxide), ESACURE 1001M available from Siber Hegner, Japan ( 1-[4-Benzylnonylphenylsulfanyl]phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, obtainable from Asahi Chemical Co., Ltd. ADEKA OPTOMER (registered trademark) N-1414 (carbazole and benzophenone), ADEKA OPTOMER (registered trademark) N-1717 (acridine), ADEKA OPTOMER (registered trademark) N-1606 (triazine), Sanwa Chemically prepared TFE-triazine (2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine), tri-chemical TME-triazine (2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine), tris Chemically prepared MP-triazine (2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine), TAZ-113 manufactured by Midori Kagaku (2) -[2-(3,4-dimethoxy) Vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine), TAZ-108 (2-(3,4-dimethoxyphenyl)-) manufactured by Midori Kagaku 4,6-bis(trichloromethyl)-1,3,5-triazine), diphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, methyl-2- Diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 4-phenyldiphenyl ketone, ethyl mitone, 2-chlorothioxanthone, 2- Methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2- Methyl thioxanthone, thioxanthone ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl di Methyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone, methyl orthophthalic acid benzoate, 2-benzylformamide Naphthyl, 4-benzylidenebiphenyl, 4-benzylidene diphenyl ether, 1,4-benzylidene benzene, diphenylethylenedione, 10-butyl-2-chloroacridine Ketone, [4-(methylphenylthio)phenyl]phenylmethane), 2-ethylhydrazine, 2,2-bis(2-chlorophenyl)4,5,4',5 '-肆(3,4,5-trimethoxyphenyl) 1,2'-biimidazole, 2,2-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1 , 2'-biimidazole, ginseng (4-dimethylaminophenyl)methane, ethyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzene Formate, butoxyethyl-4-(dimethylamino)benzoate, and the like. These photopolymerization initiators may be used singly or in combination of two or more. Further, the amount of the photopolymerization initiator to be added is in the range of 0.01% by mass to 15% by mass, preferably 0.1% by mass to 10% by mass in the composition.

[Examples]

Hereinafter, the present invention will be described in detail with reference to the embodiments, but the scope of the present invention is not limited thereto. The "parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively.

Further, the physical properties of the examples and comparative examples were measured in accordance with the following methods.

1. Composition Viscosity The viscosity of the composition obtained by the method described below was measured using an E-type viscometer (TV-22 type) at a measurement temperature of 25 °C.

2. Refractive index of the composition The composition obtained by the method described below was measured using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Aiko Co., Ltd.) at a measurement wavelength of 589 nm and a measurement temperature of 23 °C.

3. The refractive index of the cured product was measured using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Aiko Co., Ltd.) at a measurement wavelength of 589 nm, and at a measurement temperature of 23 ° C, and the composition obtained by the method described below was measured. Hardened material.

4. Yellowness (YI)
The yellowness (YI) was measured in accordance with JIS K 7373 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

5. Peelability The cured body of the composition obtained by the method described below was stored in an environment of 85 ° C and 85% RH. When the predetermined time elapsed, it was visually confirmed whether or not the cured body of the composition was peeled off from the PET film as the base film.

<Example 1: Preparation of composition and hardened body>
In order to investigate the viscosity and refractive index of a liquid composition containing a monofunctional (meth) acrylate and a polyvalent (meth)acrylic monomer represented by the general formula (2), a liquid composition was prepared by the composition of Table 1. Example 13. The polyvalent (meth)acrylic monomer represented by the formula (2) which is reduced in viscosity by heating at 60 ° C for 1 hour is blended with a monofunctional (meth) acrylate, and sufficiently stirred. A homogeneously dissolved liquid composition. Next, the temperature of the composition was 23 ° C by storage in an environment of 23 ° C for 12 hours. Thereafter, the viscosity and the refractive index were measured.

The following compounds were used as the compounds of the chemical formulae (A) to (D). OGSOL EA0200 manufactured by Osaka Gas Chemical Co., Ltd. is used as a compound of the chemical formula (A), and ALEN-10 manufactured by Shin-Nakamura Chemical Industry Co., Ltd. is used as a compound of the chemical formula (B), and is manufactured by Kyoeisha Chemical Co., Ltd. POB-A, as a compound of the formula (C), a compound of the formula (D) is synthesized by a known method.
The method for synthesizing the compound of the formula (D) is specifically as follows. First, 90 parts by weight of biphenylmethanol, 156 parts by weight of methyl acrylate, and 0.4 parts by weight of 4-methoxyphenol were placed in a round bottom flask, and after heating under air flow to remove moisture in the system, tetraisopropanol was added. The reaction was started by 0.82 parts by weight of titanium tetraisopropoxide. The reaction liquid was heated to 90 ° C to remove methanol generated by the reaction, and the reaction was carried out for 6 hours while appropriately adding methyl acrylate. After the reaction was terminated, the catalyst was hydrolyzed by adding 10 parts by weight of pure water. Further, it is purified by distillation and filtration to obtain a compound of the formula (D).

From the above results, it is understood that when a compound of the formula (D) is used, a liquid composition having a low viscosity and having a high refractive index upon curing can be obtained.

<Example 2: Physical properties of each liquid composition composition and hardened body>
Liquid compositions 14 to 16 containing a monofunctional (meth) acrylate and a polyvalent (meth)acrylic monomer represented by the formula (2) in a ratio of 50:50 were prepared, and the composition and the hardened body were measured. Various things. 20 parts by mass of a polyvalent (meth)acrylic monomer represented by the formula (2) which is reduced in viscosity by heating at 60 ° C for 1 hour, 20 parts by mass of a monofunctional (meth) acrylate, and photopolymerization 1.2 parts by mass of Irukacure 184 (manufactured by Ciba Specialty Chemicals) of the initiator was blended, and by sufficiently stirring, a uniformly dissolved liquid composition was obtained. Then, the liquid composition was applied to a corona-treated surface of a polyester film (manufactured by Toyobo Co., Ltd.; Toyobo Ester Film E5100) having a thickness of 50 μm as a base material using a bar coater No. 60, and was set to be used immediately. Conveyor type ultraviolet irradiation device U-0303 of 300 mJ/cm ² ultraviolet irradiation amount (manufactured by GS Yuasa Co., Ltd., using high-pressure mercury lamp, lamp output: 80 W/cm, conveying speed: 4.8 m/min The ultraviolet ray is irradiated to obtain a film of a cured body in which a liquid composition is formed on the polyester film. The results are shown in Table 2.

The physical properties described in Table 2 were measured by the following methods.

[pencil hardness]
The pencil hardness was measured in accordance with JIS K5600-5-4. Specifically, the surface of the polyester film on which the hardened body of the liquid composition is formed is pressed with a pencil from the lower hardness of the surface of the dried coating film at an angle of 45 degrees and a load of 750 g, and no scratch is generated. The hardest pencil hardness was evaluated as the pencil hardness. The pencil hardness is expressed in order from low order to 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H and 7H.

[elongation]
20 parts by mass of a polyvalent (meth)acrylic monomer represented by the formula (2) which is reduced in viscosity by heating at 60 ° C for 1 hour, 20 parts by mass of a monofunctional (meth) acrylate, and photopolymerization 1.2 parts by mass of Irukacure 184 (manufactured by Ciba Specialty Chemicals) of the initiator was blended, and the liquid composition was obtained by sufficiently stirring and uniformly dissolving. Then, the liquid composition was applied to a non-corona treated surface of a polyester film (manufactured by Toyobo Co., Ltd.; Toyobo Ester Film E5100) having a thickness of 50 μm as a substrate, using a bar coater No. 60, and then the setting was used. Ultraviolet irradiation device U-0303 (manufactured by GS Yuasa Co., Ltd., using high-pressure mercury lamp, lamp output: 80 W/cm, conveying speed: 4.8 m/min) in an ultraviolet irradiation amount of 300 mJ/cm ² The film of the hardened body in which the liquid composition was formed on the polyester film was obtained by ultraviolet irradiation. The hardened body of the liquid composition was peeled off from the surface of the polyester film, and the tensile test was carried out in accordance with JIS K7161-1.

[Haze (HAZE)]
The HAZE was measured in accordance with JIS K 7136 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

[total light transmittance]
The total light transmittance (TT) was measured in accordance with JIS K 7375 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

[saturated water absorption rate]
A hardened body of the liquid composition was prepared as described above, and a sample piece of 5 cm × 5 cm was prepared, and dried at 50 ° C for 24 hours. Next, the weight of the sample after drying was measured, and after immersing in water of 23 ° C, after a predetermined period of time, the test piece was taken out from the water, the water was wiped off, and the mass was measured. This operation was continued until the water absorption rate was saturated, and the weight of the test piece at the time of saturation was taken as the weight at the time of saturation, and the saturated water absorption rate was measured by the following formula.
Saturated water absorption (%) = weight of test piece at saturation / weight of sample after drying × 100

[glass transition temperature]
The glass transition temperature was measured in accordance with JIS-K-7121 using DSC6200 (manufactured by Seiko Instruments Inc.).

From the above results, it is understood that when a monofunctional (meth) acrylate of the formula (D) is used, a cured body having a high refractive index, a low water absorption rate, and a high Tg can be obtained.

<Example 3: Evaluation of coloring of each liquid composition and its hardened body under high temperature and high humidity>
Liquid compositions 17 to 25 containing a monofunctional (meth) acrylate and a polyvalent (meth)acrylic monomer represented by the formula (2) in the ratios shown in Table 3 were prepared, and the respective high temperature and high humidity were used. The next color is evaluated. At the time of preparation, the polyvalent (meth)acrylic monomer represented by the formula (2) and the monofunctional methacrylate represented by the formula (2) which is reduced in viscosity by heating at 60 ° C for 1 hour are used in the ratios shown in Table 3. mixing. In addition, the occurrence of peeling under high temperature and high humidity was confirmed. The polyester film in which the hardened body of the liquid composition was formed was stored in a constant temperature and humidity machine set to an environment of 85 ° C / 85% RH, and the yellowness (YI) was measured by the above measurement method after 350 hours and 1000 hours passed. ).

From the above results, it is understood that when a monofunctional (meth) acrylate of the formula (D) is used, coloring can be suppressed even under high temperature and high humidity, and the amount of the monofunctional methacrylate added is set to 75 wt. %, which can effectively inhibit peeling.

<Example 4: Evaluation of crystallization>
The liquid composition examples 26 to 49 in which the monofunctional (meth) acrylate and the polyvalent (meth) acryl monomer represented by the formula (2) are contained in the ratios shown in Tables 4 to 6 are prepared, and whether or not it is borrowed at this time. Evaluation was made by changing the blending temperature to affect the generation of crystals. The results are shown in Tables 4 to 7. The compound of the chemical formulas (A), (C), and (D) which are tempered at the temperature indicated in the table is blended by the formulation and method shown in the table, and thoroughly stirred to obtain a uniform dissolution. Liquid composition. Further, the chemical formula (D) / (C) means a mixture of the compound of the formula (D) and the compound of the formula (C) in a weight ratio of 1:1. Next, the storage was carried out under the storage conditions shown in the table, and when a predetermined period of time elapsed, it was visually confirmed whether or not crystal precipitation occurred. In addition, "keeping at 23 ° C / 1 day → 5 ° C" means storing at 23 ° C for 1 day and then storing at 5 ° C. "Crystalization (5 ° C / 5 day)" means storage at 5 ° C for 5 days.

From the results of Examples 26 and 27, it was found that by setting the blending temperature to 40 ° C, crystallization was more effectively suppressed than when blending at 23 ° C.

From the above results, it is understood that crystallization is further suppressed by setting the blending temperature to 60 ° C or higher, and no crystal is formed in the liquid composition after storage at 5 ° C / 30 days or more. Further, even when only the monofunctional (meth) acrylate was heated to 60 ° C, no crystal was generated when the obtained liquid composition was stored at 5 ° C / 30 days or more. Further, the same result was obtained also when the A-BPEF manufactured by Shin-Nakamura Chemical Co., Ltd. was used as the compound of the chemical formula (A). Further, when blending at a temperature exceeding 120 ° C, the monomer (meth) acrylate was polymerized, so the test was carried out until 120 ° C.

<Example 5: Solubility of polyvalent (meth)acrylic monomer represented by the general formula (2) which crystallized>
When the polybasic (meth)acrylic monomer represented by the general formula (2) has been crystallized before being blended with the monofunctional (meth) acrylate, it is evaluated by heating with a monofunctional (meth) acrylate. Blending is carried out to determine if the crystals are dissolved. At this time, a monofunctional (meth) acrylate and a polyvalent (meth)acrylic monomer were mixed at each blending temperature, and then kept at 60 ° C to evaluate whether or not the crystallized poly (meth)acrylic monomer was dissolved. . The results are shown in Table 8. In addition, "solubility (60 ° C / Nday)" in the table means the degree of dissolution at the time of storage at 60 ° C for N days.

From the above results, it is understood that even if the polybasic (meth)acrylic monomer represented by the general formula (2) is crystallized by using the monofunctional (meth) acrylate of the formula (D), it can be dissolved well.

Claims (10)

A method for producing a liquid composition comprising: (A) a (meth) acrylate represented by the following formula (1), and (B) a polyvalent (methyl) represented by the following formula (2) The acrylic monomer; the method comprises: mixing the (meth) acrylate represented by the following general formula (1) with the polyvalent (methyl) represented by the following general formula (2) at a temperature of from 35 ° C to 120 ° C; ) an acrylic monomer; [In the formula (1), X is selected from a single bond, -C(R ₂ )(R ₃ )-, -C(=O)-, -O-, -OC(=O)-, -OC(= O) a divalent group in the group formed by O-, -S-, -SO-, -SO ₂ - and any combination thereof (here, R ₂ and R ₃ are each independently a hydrogen atom, carbon a linear alkyl group having 1 to 10, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, and a carbon number of 3~ a branched alkoxy group of 10, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group; or R ₂ and R ₃ may be bonded to each other and to the carbon atom to which the bond is bonded Together, a cyclic alkyl group having a carbon number of 3 to 10 is formed, and Y is a branched alkyl group having 2 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an extended aryl group having 6 to 10 carbon atoms. R ₁ is a hydrogen atom or a methyl group, and R ₄ and R ₅ are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, and a cyclic alkyl group having 3 to 10 carbon atoms. a base, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group; m is an integer from 0 to 10, n is an integer from 1 to 2, p is an integer from 0 to 4, and q is an integer from 0 to 5] ; In the formula (2), R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and carbon. 5 to 20 cycloalkyloxy groups, 6 to 20 carbon atoms aryl groups, 6 to 20 carbon atoms aryloxy groups and halogen atoms, R ₁₂ is a hydrogen atom or a methyl group, and X represents a single bond, -O- , -S-, -SO-, -SO ₂ -, -CO-, and any of the groups of the following general formulae (3) to (6), wherein Y and Z are each independently a branchable carbon a number of 2 to 6 alkylene, a carbon number of 6 to 10 cycloalkyl or a carbon number of 6 to 10 aryl; p and q are each independently an integer of 0 to 4]; In the formula (3), R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 5 carbon atoms which may have a substituent. a group of an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent In any one of the above, each of the substituents is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and c is an integer of 1 to 20]; In the formula (4), R ₁₅ and R ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 5 carbon atoms which may have a substituent. a group of an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent Either R ₁₅ and R ₁₆ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, and the substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms or a carbon number of 6 ~12 aryl]; In the formula (5), R ₁₇ to R ₂₀ each independently represent a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 5 carbon atoms which may have a substituent. An aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent Or, R ₁₇ and R ₁₈ and R ₁₉ and R ₂₀ are each bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, and the above substituents are each independently a halogen atom and an alkyl group having 1 to 20 carbon atoms. Base or carbon number 6~12 aryl]; In the formula (6), R ₂₁ to R ₃₀ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The method of claim 1, wherein in the above formula (1), both p and q are 0. The method of claim 1 or 2, wherein in the above formula (1), n is 1 and m is 0. The method of claim 1 or 2, wherein the content of the (meth) acrylate represented by the above formula (1) and the poly (meth) acrylate monomer represented by the above formula (2) is in terms of mass ratio It is 1:10~10:1. The method of claim 1 or 2, wherein the (meth) acrylate represented by the above formula (1) is a blend of two or more kinds of compounds. The method of claim 1 or 2, wherein in the above formula (2), X has a structure represented by the formula (4). The method of claim 1 or 2, wherein the liquid composition is an active energy ray-curable composition. A coating comprising the composition obtained by the method of any one of claims 1 to 7. A hardened body obtained by hardening a composition obtained by the method of any one of claims 1 to 7. A method of manufacturing a hardened body, and comprising: The step of obtaining a composition by the method of any one of claims 1 to 7, and A step of hardening the aforementioned composition.