KR20200090791A - Method for manufacturing (meth)acrylic composition, paint and cured body comprising (meth)acrylic composition - Google Patents

Abstract

The present invention provides a method for producing a (meth)acrylic composition having a low viscosity of the composition, a high refractive index upon curing, and having less yellowing in an environmental test under high temperature and high humidity, and a paint containing such a (meth)acrylic composition. Is to do. According to one embodiment, there is provided a method of mixing the (meth)acrylate of the general formula (1) with the poly(meth)acrylic monomer of the general formula (2) in a predetermined temperature range.

Description

Method for manufacturing (meth)acrylic composition, paint and cured body comprising (meth)acrylic composition

The present invention relates to a method for producing a (meth)acrylic composition and a coating material comprising a (meth)acrylic composition. Moreover, this invention also relates to the hardened|cured material of this composition.

In recent years, resin materials have been widely used in optical parts such as optical overcoats, hard coats, antireflection films, spectacle lenses, optical fibers, optical waveguides, and holograms because of their excellent processing and productivity. Further, in the field of optical components, the tendency to downsizing and thinning is increasing, and accordingly, materials having a high refractive index are required. In addition, for these demands, paints containing a resin composition having a high refractive index during curing are widely used. On the other hand, these paints are generally characterized by having a relatively high viscosity, so it may be difficult to apply thinly. Accordingly, a composition having a low viscosity that improved this point has been proposed.

For example, in Patent Document 1, o-phenylbenzyl acrylate (OPBA; or 2-phenylbenzylacrylate) and p-phenylbenzylacrylate (PPBA; or 4-phenylbenzylacrylate), isomers of phenylbenzylacrylate. ) By mixing in a specific ratio, a composition having a high refractive index and a low viscosity has been proposed. In addition, Patent Document 2 describes that a composition having a high refractive index and a low viscosity is obtained by mixing phenylbenzyl acrylate and a difunctional (meth)acrylate or diphenyl derivative.

In Patent Documents 3 to 7, mixing of phenoxybenzyl (meth)acrylate and polyfunctional (meth)acrylate having high refractive index (fluorene-based bisphenol derivatives or bisphenol A derivatives) to obtain a resin composition for optical materials It is described.

Japanese Patent Publication 2012-82387 Japanese Patent Publication 2012-82386 Japanese Patent Publication 2010-248358 Japanese Patent Publication No. 2011-126991 Japanese Patent Publication 2012-219205 Japanese Patent Publication No. 2013-53310 Japanese Patent Publication 2014-185337

As described above, various compositions having a high refractive index and a low viscosity have been proposed so far. However, a monofunctional (meth)acrylate having a low viscosity has many low refractive indexes, while a monofunctional (meth)acrylate having a high refractive index has an effect of lowering the viscosity of a polyfunctional (meth)acrylate having a high refractive index. It may not be sufficiently obtained. In this situation, development of a monofunctional (meth)acrylate having a high refractive index and a low viscosity has been conducted. As an example, a phenoxybenzyl (meth)acrylate represented by the formula (C) is newly discovered, and research is underway (for example, Patent Document 4, (B) component 1, etc.).

[Formula 1]

However, when the phenoxybenzyl (meth)acrylate represented by the formula (C) is used, in environmental tests under high temperature and high humidity (specifically 85°C/85%RH), it has been found that the yellowing of the coating film is severe. In this respect, a (meth)acrylic composition having a low viscosity of the composition, a high refractive index during curing, and a small yellowing in an environmental test under high temperature and high humidity is required.

The present invention relates to these problems, the composition has a low viscosity, has a high refractive index upon curing, and further, a method for producing a (meth)acrylic composition having little yellowing in an environmental test under high temperature and high humidity, and such a (meth)acrylic composition It is an object to provide a paint containing a. It is also an object of the present invention to provide a cured body of the composition.

The present inventors conducted extensive investigations to solve the above problems, and as a result, the (meth)acrylate of the general formula (1) described later was mixed with the poly(meth)acrylic monomer of the general formula (2) described later in a predetermined temperature range. It has been found that the above problems can be solved by mixing, and the present invention has been reached.

That is, the present invention has the characteristics described below.

[One]

(A) (meth) acrylate represented by the following general formula (1),

[Formula 2]

[In formula (1),

X is a single bond, -C(R ₂ )(R ₃ )-, -C(=O)-, -O-, -OC(=O)-, -OC(=O)O-, -S- , -SO-, -SO ₂ -and a divalent group selected from the group consisting of any combination thereof (where R ₂ and R ₃ are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms) , C3-C10 branched alkyl group, C3-C10 cyclic alkyl group, C1-C10 linear alkoxy group, C3-C10 branched alkoxy group, C3-C10 cyclic alkoxy group, phenyl group or phenyl Or a phenyl group, or R ₂ and R ₃ may be interconnected to form a cyclic alkyl group having 3 to 10 carbon atoms as one of the carbon atoms to which they are attached);

Y is a C2-C6 alkylene group which may be branched, a C6-C10 cycloalkylene group, or a C6-C10 arylene group;

R ₁ is a hydrogen atom or a methyl group;

R ₄ and R ₅ are, each independently, a straight-chain 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, a straight-chain alkoxy group having 1 to 10 carbon atoms, 3 to 10 carbon atoms. A branched alkoxy group of 10, a cyclic alkoxy group of 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group;

m is an integer of 0-10;

n is an integer of 1 to 2;

p is an integer of 0-4;

q is an integer from 0 to 5]

(B) a polyvalent (meth) acrylic monomer represented by the following general formula (2) and

[Formula 3]

[In formula (2),

R ₁₀ and R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, or 6 to 20 carbon atoms. Is selected from an aryl group, 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 a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO- and any one of the groups consisting of the following formulas (3) to (6);

Y and Z are each independently a branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;

p and q are each independently an integer of 0-4.]

[Formula 4]

[In formula (3),

R ₁₃ and R ₁₄ are each independently 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, or 6 to 12 carbon atoms which may have a substituent. An aryl group, 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 group;

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;

c represents the integer of 1-20.]

[Formula 5]

[In formula (4), R ₁₅ and R ₁₆ each independently have 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 a substituent 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 group, or R ₁₅ and R ₁₆ are each bonded to each other to form a carbon ring having 1 to 20 carbon atoms or a heterocycle;

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.]

[Formula 6]

[In the formula (5), R ₁₇ to R ₂₀ may each independently have 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, or a substituent. 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 group, or R ₁₇ and R ₁₈ and R ₁₉ and R ₂₀ are each bonded to each other to form a carbon ring having 1 to 20 carbon atoms or a heterocycle;

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.]

[Formula 7]

[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.]

A method of manufacturing a liquid composition comprising:

A method comprising mixing the (meth)acrylate represented by the general formula (1) with a poly(meth)acrylic monomer represented by the general formula (2) at a temperature of 35°C or higher and 120°C or lower.

[2]

The method according to [1], in which p and q are both 0 in the formula (1).

[3]

In the formula (1), the method according to [1] or [2], wherein n is 1 and m is 0.

[4]

The content of the (meth)acrylate represented by the general formula (1) and the polyvalent (meth)acrylic monomer represented by the general formula (2) is 1:10 to 10:1 in mass ratio, [1] to [ The method according to any one of 3].

[5]

The method according to any one of [1] to [4], wherein the (meth)acrylate represented by the general formula (1) is a blend of two or more types of compounds.

[6]

The method according to any one of [1] to [5], wherein X has a structure represented by General Formula (4) in Formula (2).

[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 material comprising the composition obtained by the method according to any one of [1] to [7].

[9]

A cured product obtained by curing the composition obtained by the method according to any one of [1] to [7].

[10]

As a method of manufacturing a cured body,

The process of obtaining a composition by the method in any one of [1]-[7],

Process of curing the composition

Including, method.

According to the present invention, the composition has a low viscosity, has a high refractive index upon curing, and further provides a method for producing a (meth)acrylic composition having little yellowing in an environmental test under high temperature and high humidity, and a coating material containing such a (meth)acrylic composition Can provide. Further, according to the present invention, it is also possible to provide a cured body of the composition.

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

<Manufacturing method>

Method of manufacturing a liquid composition of the present invention,

(A) (meth) acrylate represented by the following general formula (1),

[Formula 8]

[In formula (1),

X is a single bond, -C(R ₂ )(R ₃ )-, -C(=O)-, -O-, -OC(=O)-, -OC(=O)O-, -S- , -SO-, -SO ₂ -and a divalent group selected from the group consisting of any combination thereof (where R ₂ and R ₃ are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms) , C3-C10 branched alkyl group, C3-C10 cyclic alkyl group, C1-C10 linear alkoxy group, C3-C10 branched alkoxy group, C3-C10 cyclic alkoxy group, phenyl group or phenyl Or a phenyl group, or R ₂ and R ₃ may be interconnected to form a cyclic alkyl group having 3 to 10 carbon atoms as one of the carbon atoms to which they are attached);

Y is a C2-C6 alkylene group which may be branched, a C6-C10 cycloalkylene group, or a C6-C10 arylene group;

R ₁ is a hydrogen atom or a methyl group;

R ₄ and R ₅ are, each independently, a straight-chain 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, a straight-chain alkoxy group having 1 to 10 carbon atoms, 3 to 10 carbon atoms. A branched alkoxy group of 10, a cyclic alkoxy group of 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group;

m is an integer of 0-10;

n is an integer of 1 to 2;

p is an integer of 0-4;

q is an integer from 0 to 5]

(B) Polyhydric (meth)acrylic monomer represented by the following general formula (2)

[Formula 9]

[In formula (2),

R ₁₀ and R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, or 6 to 20 carbon atoms. Is selected from an aryl group, 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 a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO- and any one of the groups consisting of general formulas (3) to (6) described below;

Y and Z are each independently a branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;

p and q are each independently an integer of 0-4.]

A method of manufacturing a liquid composition comprising:

And mixing the (meth)acrylate represented by the general formula (1) with a polyvalent (meth)acrylic monomer represented by the general formula (2) at a temperature of 35°C or higher and 120°C or lower.

As described above, the liquid composition obtained by mixing the (meth)acrylate having the structure of the general formula (1) with the polyvalent (meth)acrylic monomer having the structure of the general formula (2) at a predetermined temperature range has a low viscosity. , It has a high refractive index at the time of curing, and further, has little yellowing in an environmental test under high temperature and high humidity. Without being bound by theory, it is presumed that the occurrence of yellowing is caused by a low glass transition temperature. In addition, the (meth)acrylate having the structure of the general formula (1) is often solid at room temperature, and is used for the purpose of lowering the viscosity of the polyvalent (meth)acrylic monomer of the general formula (2) with high refractive index and high viscosity. It was thought that I could not. For example, in Patent Document 1, p-phenylbenzyl (meth)acrylate, one of the (meth)acrylates having the structure of Formula (1), is a solid (mp: 32°C) at room temperature, and thus Is not available. And in patent document 1, the liquid composition is obtained by mixing the liquid o-phenylbenzyl (meth)acrylate and p-phenylbenzyl (meth)acrylate in a specific ratio at normal temperature.

Under these circumstances, the present inventors heat the (meth)acrylate having the structure of the general formula (1) to a predetermined temperature range, thereby liquefying the (meth)acrylate having the structure of the general formula (1) and the state thereof. It was found that a liquid composition was obtained by mixing with a polyvalent (meth)acrylic monomer having the structure of formula (2). And surprisingly, when the (meth)acrylate having the structure of the general formula (1) is liquefied and then mixed with the polyvalent (meth)acrylic monomer having the structure of the general formula (2), the obtained liquid composition is then cooled even after cooling. It has been found that the back does not precipitate and becomes a stable liquid composition. Furthermore, the liquid composition thus obtained had a low viscosity, a high refractive index at the time of curing, and a small yellowing in an environmental test under high temperature and high humidity. The present invention is based on this knowledge.

The temperature at the time of mixing the (meth)acrylate having the structure of the general formula (1) with the polyvalent (meth)acrylic monomer having the structure of the general formula (2) in the production method of the present invention is 35°C to 120 ℃ or less, preferably 40 to 100°C, and more preferably 45 to 80°C. If the temperature at the time of mixing is 35°C or higher, (meth)acrylate having the structure of formula (1) is sufficiently liquefied, and if it is 120°C or lower, polymerization of the monomer can be prevented. When mixing, at least the temperature of the (meth)acrylate having the structure of Formula (1) may be adjusted to the above temperature range, and the polyvalent (meth)acrylic monomer having the structure of Formula (2) remains at room temperature. You may mix.

The viscosity of the liquid composition of the present invention is less than 10,000 mPa·s when measured at a measurement temperature of 25° C. using an E-type viscometer (TV-22 type), preferably 5,000 mPa·s or less, More preferably, it is 5 to 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 in the composition obtained by the production method of the present invention has a structure represented by the following general formula (1).

[Formula 10]

In formula (1), X is a single bond, -C(R ₂ )(R ₃ )-, -C(=O)-, -O-, -OC(=O)-, -OC(=O) O-, -S-, -SO-, -SO ₂ -and a divalent group selected from the group consisting of any combination thereof, preferably a single bond, -C(R ₂ )(R ₃ )- , -O-, and any combination thereof. 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, a linear alkoxy having 1 to 10 carbon atoms. 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. Alternatively, R ₂ and R ₃ may be interconnected to form one of the carbon atoms to which they are attached to form a cyclic alkyl group having 3 to 10 carbon atoms. Preferably, R ₂ and R ₃ are both hydrogen atoms.

Y is a C2-C6 alkylene group which may be branched, a C6-C10 cycloalkylene group, or a C6-C10 arylene group.

R ₁ is a hydrogen atom or a methyl group, and preferably a hydrogen atom.

R ₄ and R ₅ are, each independently, a straight-chain 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, a straight-chain alkoxy group having 1 to 10 carbon atoms, 3 to 10 carbon atoms. It is a branched alkoxy group of 10, 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 0-10, Preferably it is an integer of 0-5, More preferably, it is 0.

n is an integer of 1-2, Preferably it is 1.

More preferably, n is 1 and m is 0.

p is an integer of 0-4, Preferably it is an integer of 0-2, More preferably, it is 0.

q is an integer of 0-5, Preferably it is an integer of 0-2, More preferably, it is 0.

More preferably, both p and q are 0. When p and q are 0, it means that the hydrogen of the benzene ring is not substituted with a functional group of R ₄ or R ₅ .

As the (meth)acrylate represented by the general formula (1), for example, 4-phenylbenzyl (meth)acrylate, 3-phenylbenzyl (meth)acrylate, 2-phenylbenzyl (meth)acrylate , 4-biphenylbenzyl(meth)acrylate, 3-biphenylbenzyl(meth)acrylate, 2-biphenylbenzyl(meth)acrylate, 4-benzylbenzyl(meth)acrylate, 3-benzylbenzyl(meth) )Acrylate, 2-benzylbenzyl(meth)acrylate, 4-phenethylbenzyl(meth)acrylate, 3-phenethylbenzyl(meth)acrylate, 2-phenethylbenzyl(meth)acrylate, 4-phenene Tilphenethyl(meth)acrylate, 3-phenethylphenethyl(meth)acrylate, 2-phenethylphenethyl(meth)acrylate, 4-(4-methylphenyl)benzyl(meth)acrylate, 3-(4-methylphenyl )Benzyl (meth)acrylate, 2-(4-methylphenyl)benzyl (meth)acrylate, 4-(4-methoxyphenyl)benzyl (meth)acrylate, 3-(4-methoxyphenyl)benzyl (meth) )Acrylate, 2-(4-methoxyphenyl)benzyl (meth)acrylate, 4-(4-bromophenyl)benzyl (meth)acrylate, 3-(4-bromophenyl)benzyl (meth)acrylic Rate, 2-(4-bromophenyl)benzyl (meth)acrylate, 4-benzoylbenzyl (meth)acrylate, 3-benzoylbenzyl (meth)acrylate, 2-benzoylbenzyl (meth)acrylate, 4- (Phenylsulfinyl)benzyl (meth)acrylate, 3-(phenylsulfinyl)benzyl (meth)acrylate, 2-(phenylsulfinyl)benzyl (meth)acrylate, 4-(phenylsulfonyl)benzyl (meth) )Acrylate, 3-(phenylsulfonyl)benzyl (meth)acrylate, 2-(phenylsulfonyl)benzyl (meth)acrylate, 4-((phenoxycarbonyl)oxy)benzyl (meth)acrylate, 3-((phenoxycarbonyl)oxy)benzyl (meth)acrylate, 2-((phenoxycarbonyl)oxy)benzyl (meth)acrylate, 4-(((meth)acryloxy)methyl)phenylbenzo Eight, 3-((((meth)acryloxy)methyl)phenylbenzoate, 2-(((meth)acryloxy)methyl)phenylbenzoate, phenyl4-(((meth)acryloxy)methyl)benzoate, Phenyl3-((((meth)acryloxy)methyl)benzoate, phenyl2-(((meth)acryloxy)methyl)benzoate, 4-(1-phenylcyclohexyl)benzyl(meth) arc Relate, 3-(1-phenylcyclohexyl)benzyl (meth)acrylate, 2-(1-phenylcyclohexyl)benzyl (meth)acrylate, 4-phenoxybenzyl (meth)acrylate, 3-phenoxy Benzyl (meth)acrylate, 2-phenoxybenzyl (meth)acrylate, 4-(phenylthio)benzyl (meth)acrylate, 3-(phenylthio)benzyl (meth)acrylate, 2-(phenylthio) And benzyl (meth)acrylate and 3-methyl-4-(2-methylphenyl)benzyl methacrylate. These can be used individually by 1 type or in combination of 2 or more type. For example, (meth)acrylate may be a blend of two or more types of compounds, and in this case, at least one methacrylate may be a (meth)acrylate represented by the general formula (1). Among the above (meth)acrylates, preferably, 2-phenylbenzyl (meth)acrylate, 4-phenylbenzyl (meth)acrylate, 4-phenoxybenzyl (meth)acrylate and 4-benzylbenzyl (meth) )Acrylates, more preferably 2-phenylbenzyl acrylate, 4-phenylbenzylacrylate, 4-phenoxybenzylacrylate and 4-benzylbenzylacrylate.

The amount of the (meth)acrylate contained in the composition obtained by the production method of the present invention is not particularly limited as long as it does not depart from the gist of the present invention, but is represented by the (meth)acrylate and the general formula (2). The content of the polyvalent (meth)acrylic monomer is preferably 1:9 to 9:1 by mass ratio, more preferably 2:8 to 8:2, even more preferably 3:7 to 7:3, It is especially preferable that it is 4:6-6:4. In addition, the higher the proportion of the monofunctional (meth)acrylate, the more preferable is that it can prevent peeling under a high temperature and high humidity environment. Although not being bound by theory, it is presumed that the decrease in the adhesion between the substrate and the cured body is caused by a large water absorption.

3. Polyvalent (meth)acrylic monomer

The composition obtained by the production method of the present invention further comprises a polyvalent (meth)acrylic monomer represented by the following general formula (2) capable of copolymerization with the (meth)acrylate represented by the general formula (1). do.

[Formula 11]

In formula (2), R ₁₀ and R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkyl having 5 to 20 carbon atoms. It is selected from an actual group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom, and is preferably a hydrogen atom.

R ₁₂ is a hydrogen atom or a methyl group.

X represents a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, and any one of the groups consisting of the following general formulas (3) to (6).

Y and Z are each independently a branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.

p and q are each independently integers of 0 to 4, and preferably p and q are both 0.

In the following formula (3),

[Formula 12]

R ₁₃ and R ₁₄ are each independently 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, or 6 to 12 carbon atoms which may have a substituent. An aryl group, 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 group, wherein the substituents are each independently a halogen atom or a carbon number It is an alkyl group of 1 to 20 or an aryl group having 6 to 12 carbon atoms. Preferably, R ₁₃ and R ₁₄ are both hydrogen atoms.

c represents the integer of 1-20, Preferably it represents the integer of 1-10, More preferably, it represents the integer of 1-5.

In the following formula (4),

[Formula 13]

R ₁₅ and R ₁₆ are each independently 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, or 6 to 12 carbon atoms which may have a substituent. An aryl group, 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 group, or R ₁₅ and R ₁₆ are each bonded to each other , To form a carbon ring having 1 to 20 carbon atoms or a heterocycle, 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, R ₁₅ and R ₁₆ are both hydrogen atoms.

In the following formula (5),

[Formula 14]

R ₁₇ to R ₂₀ are each independently a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbons which may have a substituent, an alkoxy group having 1 to 5 carbons which may have a substituent, or aryl having 6 to 12 carbons which may have a substituent. Group, 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 group, or R ₁₇ and R ₁₈ and R ₁₉ and R ₂₀ Silver, respectively, combines with each other to form a carbon ring having 1 to 20 carbon atoms or a heterocycle, 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, R ₁₇ to R ₂₀ are all hydrogen atoms.

In the following formula (6),

[Formula 15]

R ₂₁ to R ₃₀ are each independently a hydrogen atom or a C 1 to C 3 alkyl group. Preferably, R ₂₁ to R ₃₀ are all hydrogen atoms.

In the formula (2), it is preferable that X has a structure represented by the formula (4).

As the polyvalent (meth)acrylic monomer represented by the general formula (2), for example, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 4, 4'-isopropylidene diphenol di(meth)acrylate, 2,2'-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]propane, bis[4-(2-(meth) )Acryloyloxyethoxy)phenyl]methane, 1,1'-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]methane, bis[4-(2-(meth)acrylo Iloxyethoxy)phenyl]ether, bis[4-(2-(meth)acryloyloxyethoxy)phenyl]sulfoxide, bis[4-(2-(meth)acryloyloxyethoxy)phenyl] Sulfide, bis(4-(2-(meth)(meth)acryloyloxyethoxy)phenyl]sulfone, bis(4-(2-(meth)acryloyloxyethoxy)phenyl]ketone, ethoxylated bisphenol A diacrylate and 4,4'-di(meth)acryloyloxybiphenyl, etc. Among them, 9,9-bis[4-(2-(meth)acryloyloxyethoxy) Phenyl]fluorene, 4,4'-isopropylidene diphenol di(meth)acrylate, ethoxylated bisphenol A diacrylate and 2,2'-bis[4-(2-(meth)acryloyloxye Thoxy)phenyl]propane is preferable, and ethoxylated bisphenol A diacrylate and 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene are more preferable. Among the polyvalent (meth)acrylic monomers represented by the general formula (2), commercially available ones are, for example, ABE-300, A-BPE-4, A-BPEF, and Kyoeisha Chemical, manufactured by Shin-Nakamura Chemical Industries, Ltd. Light acrylate BP-4EAL manufactured by Co., Ltd., Biscot #700HV manufactured by Shin-Nakamura Chemical Industries, Ltd., and FA-324A manufactured by Hitachi Chemical Co., Ltd.

3. Random additives

The composition obtained by the production method of the present invention may contain, in addition to the above-described components, various optional additives depending on the use, within a range not departing from the gist of the present invention. Examples of such additives include at least one additive selected from the group consisting of heat stabilizers, antioxidants, flame retardants, flame retardants, UV absorbers, mold release agents and colorants. The blending amount of the additive is 0.005 parts by mass to 0.1 parts by mass based on 100 parts by mass of the (meth)acrylate represented by the general formula (1) and the polyvalent (meth)acrylic monomer represented by the general formula (2). It is preferable, and it is more preferable that it is 0.01 mass parts-0.05 mass parts.

The composition obtained by the method of the present invention can be cured by various methods. As 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 material of the present invention comprises a composition obtained by the method of the present invention. The paint of the present invention can be mainly used for applications such as a coating agent for an optical member or a hard coat agent.

In the case where the paint of the present invention is applied to a general substrate such as plastic, a wetting agent such as a silicone or acrylic compound may be added to the coating in order to help wet the surfaces of various substrates. Suitable wetting agents include BYK331, BYK333, BYK340, BYK347, BYK348, BYK378, BYK380, BYK381, etc., available from Big Chemical. When adding these, the range of 0.01 to 2.0 mass% is preferable based on the total mass of the paint.

In addition, in order to improve the adhesion to various materials, an tackifier such as xylene resin, terpene resin, phenol resin, or rosin resin may be added to the coating material as necessary. When adding these, the range of 0.01 to 2.0 mass% is preferable based on the total mass of the paint.

In order to improve the adhesion to various materials, a coupling agent such as a silane coupling agent or a titanium coupling agent may be added to the coating material. When adding these, the range of 0.01 to 5.0 mass% is preferable based on the total mass of the paint.

In addition, inorganic fillers such as silica, alumina, mica, talc, aluminum flakes, and glass flakes may be added to the coating material in order to improve performances such as impact resistance. When adding these, the range of 0.01-10.0 mass% is preferable based on the total mass of a coating material.

Furthermore, in the case of applying the paint of the present invention to a general substrate such as metal, concrete, or plastic, even if an antifoaming agent composed of a silicone-based or acrylic-based compound is added to the paint to assist in the mixing of agitation and the loss of bubbles generated during application, do. Suitable antifoaming agents include BYK019, BYK052, BYK065, BYK066N, BYK067N, BYK070, BYK080, etc., which are available from Big Chemical, but BYK065 is particularly preferred. When adding these, the range of 0.01 to 3.0 mass% is preferable based on the total mass of the paint.

In the paint of the present invention, if necessary, anti-rust additives such as zinc phosphate, iron phosphate, calcium molybdate, vanadium oxide, water-dispersed silica, fumed silica, organic pigments such as phthalocyanine-based organic pigments and condensed polycyclic organic pigments, oxidation Each component such as inorganic pigments such as titanium, zinc oxide, calcium carbonate, barium sulfate, alumina, and carbon black may be added in required amounts.

As a coating form when the coating material of the present invention is applied on various substrates, for example, bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, microgravure coating, microreverse Gravure coater coating, die coater coating, slot die coater coating, versatile die coater coating, dip coating, spin coating coating, spray coating, or any of commonly used coating types such as brushing can be used. Roll coating or spray coating is preferred.

<cured body>

The cured body of the present invention is a cured body obtained by curing the composition obtained by the method of the present invention. The cured product of the present invention has a high refractive index of 1.580 or more, and has little yellowing in an environmental test under high temperature and high humidity. Moreover, it is preferable that the hardened|cured material of this invention has a high refractive index of 1.585 or more, and it is more preferable to have a high refractive index of 1.590 or more. The cured product of the present invention preferably has a yellowness (YI) of 4.0 or less when stored in an 85°C/85%RH atmosphere for 350 hours, and a yellowness when stored in an 85°C/85%RH atmosphere for 1,000 hours. It is preferable that (YI) is 6.5 or less.

The cured body of the present invention,

(A) the structural unit derived from (meth)acrylate represented by the general formula (1) and

[Formula 16]

The structural unit derived from a poly(meth)acrylic monomer represented by the general formula (2) and

[Formula 17]

It includes.

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

On the other hand, the structural unit derived from the (meth)acrylate represented by the general formula (1) represents a structural unit having the structure of the following formula (1a),

[Formula 18]

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

[Formula 19]

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

The manufacturing method of the hardened|cured material of this invention contains the process of obtaining a composition by the method of this invention, and the process of hardening the composition. Here, the method of curing is not particularly limited, and may be performed by various known methods. For example, the composition of the present invention may be cured by photopolymerization upon irradiation with active energy rays. 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 cured by an active energy ray, a photopolymerization initiator is not necessary. However, when a photopolymerization initiator is added, for example, Irgacure (registered trademark) 2959 (1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl- which is available from Ciba Corporation. 1-propan-1-one, Irgacure (registered trademark) 184 (1-hydroxycyclohexylphenylketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexylphenylketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethan-1-one), Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone -1), Irgacure(registered trademark) 907(2-methyl-1[4-methylthiophenyl]-2-morpholinopropan-1-one, Irgacure(registered trademark) 819(bis(2,4,6- Trimethylbenzoyl)-phenylphosphine oxide, Irgacure(registered trademark) 1800(bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide,1-hydroxy-cyclohexyl-phenyl- Ketone), Irgacure (registered trademark) 1800 (bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide,2-hydroxy-2-methyl-1-phenyl-1-propane -1-one), Irgacure(trademark) OXE01(1,2-octanedione,1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), Darocur(trademark) 1173(2- Hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur® 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), available from BASF, Lucirin TPO-L (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), ESACURE 1001M(1-[4-benzoylphenylsulfanyl]phenyl]-2-methyl-2-(4, available from Sieber Hegner, Japan) -Methylphenylsulfonyl)propan-1-one, Adeka Optomer (registered trademark) N-1414 (carbazole-phenone system), Adeka Optomer (registered trademark) N-1717 (acridine system available from Adeca Corporation) ), adeka optomer (registered trademark) N-1606 (triazine series), TFE-triazine (2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloro) from Sanwa Chemical Methyl)-1,3,5-triazine), TME-triazine (2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl) from Sanwa Chemical -1,3,5-triazine), MP-triazine (2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine made by Sanwa Chemical) , Midori Chemical TAZ-113 (2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine), Midori Chemical TAZ-108 (2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzo Phenone, methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4-phenylbenzophenone, ethylmihilazketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-iso Propyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxyxanthoxone, 2-methylthioxanthone, thioxanthoneammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxy aceto Phenone and dibenzosuberone, o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyl diphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone , [4-(methylphenylthio)phenyl]phenylmethane), 2-ethylanthraquinone, 2,2-bis(2-chlorophenyl)4,5,4',5'-tetrakis(3,4,5- Trimethoxyphenyl)1,2'-biimidazole, 2,2-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-biimidazole, tris(4 -Dimethylaminophenyl)methane, ethyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzoate, butoxyethyl-4-(dimethylamino)benzoate, and the like. These photopolymerization initiators may be used alone or in combination of two or more. Moreover, the addition amount of these photoinitiators is 0.01 mass%-15 mass% in a composition, Preferably it is the range of 0.1 mass%-10 mass %.

Example

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

In addition, the measurement of each physical property in an Example and a comparative example was performed according to the following method.

1. Composition viscosity

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

2. The refractive index of the composition

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

3. Refractive index of cured product

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

4. Yellowness (YI)

The yellowness (YI) was measured according to JIS K 7373 using a haze meter NDH4000 (manufactured by Nippon Color Industries, Ltd.).

5. Peelability

The cured product of the composition obtained by the method described below was stored in an 85° C. 85% RH environment. When the predetermined time elapsed, it was visually confirmed whether the cured body of the composition was peeled from the PET film as the base film.

<Example 1: Preparation of composition and cured product thereof>

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), liquid compositions Examples 1 to 13 were prepared with the composition of Table 1. Did. The polyhydric (meth)acrylic monomer represented by the general formula (2) having a reduced viscosity by heating at 60° C. for 1 hour and a monofunctional (meth)acrylate were blended and stirred well to uniformly dissolve to obtain a liquid composition. . Next, the temperature of the composition was set to 23°C by storing in an atmosphere at 23°C for 12 hours. Thereafter, viscosity and refractive index were measured.

[Table 1]

As the compounds of the formulas (A) to (D), the following compounds were used. OGSOL EA0200 manufactured by Osaka Gas Chemical Co., Ltd. is used as the compound of formula (A), and ALEN-10 manufactured by Shin-Nakamura Chemical Industry Co., Ltd. is used as the compound of formula (B), and Kyoeisha as compound of formula (C) POB-A manufactured by Chemical Co., Ltd. was used, and the compound of formula (D) was synthesized according to a known method.

The method for synthesizing the compound of formula (D) is specifically as follows. First, 90 parts by weight of biphenyl methanol, 156 parts by weight of methyl acrylate, and 0.4 parts by weight of 4-methoxyphenol were put into a round bottom flask, and heated under air circulation to remove moisture in the system, and then 0.82 weight of titanium tetraisopropoxide. The reaction was initiated by adding parts. The reaction solution was heated to 90°C to remove methanol generated by the reaction, and reacted for 6 hours while suitably adding methyl acrylate. After completion of the reaction, the catalyst was hydrolyzed by adding 10 parts by weight of pure water. The mixture was further purified by distillation and filtration to obtain a compound of formula (D).

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

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

<Example 2: Physical properties of each liquid composition and its cured body>

Liquid compositions examples 14 to 16 containing monofunctional (meth)acrylate and poly(meth)acrylic monomers represented by the general formula (2) at a ratio of 50:50 are prepared, and the properties of the composition and cured body are measured. Did. Irugacure 184 (photopolymerization initiator) with 20 parts by mass of polyvalent (meth)acrylic monomer represented by the general formula (2) with reduced viscosity by heating at 60° C. for 1 hour, 20 parts by mass of monofunctional (meth)acrylate, Chiba specialty chemicals) 1.2 mass parts were blended and stirred well to dissolve uniformly to obtain a liquid composition. Subsequently, a liquid composition was applied to a corona-treated surface of a polyester film having a thickness of 50 μm (Toyobo Co., Ltd.; manufactured by Toyobo Ester Film E5100) using a bar coater No. 60, and immediately, it was 300 mJ/cm ² Ultraviolet rays are irradiated by using a conveyor type ultraviolet ray irradiation device U-0303 (made by GS Yua, high pressure mercury lamp, lamp output: 80 W/cm, conveyor speed: 4.8 m/min) set to a UV irradiation amount, and poly A film on which a cured product of the liquid composition was formed was obtained on the ester film. Table 2 shows the results.

[Table 2]

Each physical property described in Table 2 was measured by the following method.

[Pencil hardness]

The pencil hardness was measured according to JIS K5600-5-4. Specifically, with respect to the surface of the polyester film on which the cured product of the liquid composition is formed, the pencil is pressed in order from the lowest hardness on the surface of the dry film at an angle of 45 degrees and a load of 750 g, and the hardness of the hardest pencil that is not scratched. Was evaluated as the pencil hardness. The pencil hardness is 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H and 7H in the order of the lowest rank.

[Stretching]

20 parts by weight of polyvalent (meth)acrylic monomer represented by the general formula (2) with reduced viscosity by heating at 60° C. for 1 hour, and 20 parts by weight of monofunctional (meth)acrylate, Irugacure 184 (Chiba, photopolymerization initiator) A liquid composition was obtained by blending 1.2 parts by mass of Specialty Chemicals) and stirring well to dissolve uniformly. Next, a liquid composition was applied to a non-corona treated surface of a polyester film having a thickness of 50 μm (Toyobo Co., Ltd.; manufactured by Toyobo Ester Film E5100) using a bar coater No. 60, and immediately, 300 mJ/cm ² UV light is irradiated using U-0303 (a high-pressure mercury lamp manufactured by GS Infant Co., Ltd., lamp output: 80 W/cm, conveyor speed: 4.8 m/min), which is set to the UV irradiation amount of A film having a cured product of a liquid composition formed on a polyester film was obtained. The cured body of the liquid composition was removed from the polyester film surface, and a tensile test was performed according to JISK7161-1.

[HAZE]

HAZE was measured according to JIS K 7136 using a haze meter NDH4000 (manufactured by Nippon Electric Industries, Ltd.).

[All light transmittance]

The total light transmittance (T.T.) was measured according to JIS K 7375 using a haze meter NDH4000 (manufactured by Nippon Electric Industries, Ltd.).

[Saturation absorption rate]

A cured body of the liquid composition was prepared as described above, a sample piece of 5 cm×5 cm was prepared, and dried at 50° C. for 24 hours. Next, the weight of the dried sample was measured, and then immersed in water at 23° C., and after a predetermined time elapsed, the test piece was taken out from the water, and the mass was measured by wiping off moisture. This operation was continued until the absorption rate was saturated, and the saturated absorption rate was measured by the following formula using the weight of the test piece when saturated as the weight when saturated.

Saturation Absorption Rate (%) = Weight of test piece when saturated/Weight of dried sample x 100

[Glass transition temperature]

The glass transition temperature was measured according to JIS-K-7121 using DSC6200 (manufactured by Seiko Instruments Co., Ltd.).

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

<Example 3: Color evaluation of each liquid composition and its cured body under high temperature and high humidity>

Liquid compositions Examples 17 to 25 containing monofunctional (meth)acrylates and polyvalent (meth)acrylic monomers represented by the general formula (2) in the ratios shown in Table 3 were prepared, and the coloring under each high temperature and high humidity was evaluated. Did. At the time of preparation, the polyfunctional (meth)acrylic monomer represented by the general formula (2), whose viscosity was lowered by heating at 60° C. for 1 hour, was mixed with the monofunctional methacrylate in the ratio shown in Table 3. In addition, the occurrence of peeling under high temperature and high humidity was also confirmed. The polyester film on which the cured product of the liquid composition is formed is stored in a thermo-hygrostat set at 85°C/85%RH atmosphere, and after 350 hours and 1000 hours, the yellowness (YI) is measured by the above measuring method. Did.

[Table 3]

From the above results, when monofunctional (meth)acrylate of the formula (D) is used, coloring is suppressed even at high temperature and high humidity, and peeling is also effectively suppressed by setting the amount of monofunctional methacrylate to be 75 wt%. Could know.

<Example 4: Evaluation of crystallization>

By preparing a liquid composition examples 26 to 49 containing a monofunctional (meth) acrylate and a polyvalent (meth) acrylic monomer represented by the general formula (2) in the ratios shown in Tables 4 to 6, and changing the blend temperature at that time It was evaluated whether it affects the occurrence of crystals. The results are shown in Tables 4-7. Using the compounds of formulas (A), (C), and (D) heated to the temperatures shown in the table, blending was carried out by the formulations and methods shown in the table, stirred well, and uniformly dissolved to obtain a liquid composition. Meanwhile, the 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, storage was performed under the storage conditions shown in the table, and the presence or absence of precipitation of crystals was visually confirmed when a predetermined time had elapsed. On the other hand, "23°C/1day→5°C storage" means storage at 23°C for 1 day, then storage at 5°C, and "crystallization (5°C/5day)" means storage at 5°C for 5 days. do.

[Table 4]

From the results of Examples 26 and 27, it can be seen that by setting the blend temperature to 40°C, there is an effect of suppressing crystallization than when blended at 23°C.

[Table 5]

[Table 6]

[Table 7]

From the above results, it can be seen that by setting the blend temperature to 60°C or higher, crystallization is further suppressed and crystals do not occur in the liquid composition even after storage for 5°C/30 days or longer. Further, even when only the monofunctional (meth)acrylate was heated to 60°C, crystals did not occur even if the obtained liquid composition was stored for 5°C/30 days or longer. Moreover, the same result was obtained also when A-BPEF manufactured by Shin-Nakamura Chemical Co., Ltd. was used as the compound of formula (A). On the other hand, when blending at a temperature exceeding 120°C, the (meth)acrylate of the monomer may be polymerized, so the test was made to 120°C.

<Example 5: Solubility of the polyvalent (meth)acrylic monomer represented by crystallized general formula (2)>

If the polyfunctional (meth)acrylic monomer represented by the general formula (2) is crystallized before blending with the monofunctional (meth)acrylate, whether the crystal is dissolved by blending with the heated monofunctional (meth)acrylate. Was evaluated. At this time, at each blend temperature, the monofunctional (meth)acrylate and the poly(meth)acrylic monomer were mixed, and then, the crystallized poly((meth)acrylic monomer) was dissolved at 60°C to evaluate whether it was dissolved. Table 8 shows the results. On the other hand, "solubility (60°C/Nday)" in the table means the degree of dissolution when stored at 60°C for N days.

[Table 8]

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

Claims (10)

(A) (meth) acrylate represented by the following general formula (1),
[Formula 1]

[In formula (1),
X is a single bond, -C(R ₂ )(R ₃ )-, -C(=O)-, -O-, -OC(=O)-, -OC(=O)O-, -S- , -SO-, -SO ₂ -and a divalent group selected from the group consisting of any combination thereof (where R ₂ and R ₃ are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms) , C3-C10 branched alkyl group, C3-C10 cyclic alkyl group, C1-C10 linear alkoxy group, C3-C10 branched alkoxy group, C3-C10 cyclic alkoxy group, phenyl group or phenyl Or a phenyl group, or R ₂ and R ₃ may be interconnected to form a cyclic alkyl group having 3 to 10 carbon atoms as one of the carbon atoms to which they are attached);
Y is a C2-C6 alkylene group which may be branched, a C6-C10 cycloalkylene group, or a C6-C10 arylene group;
R ₁ is a hydrogen atom or a methyl group;
R ₄ and R ₅ are, each independently, a straight-chain 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, a straight-chain alkoxy group having 1 to 10 carbon atoms, 3 to 10 carbon atoms. A branched alkoxy group of 10, a cyclic alkoxy group of 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group;
m is an integer of 0-10;
n is an integer of 1 to 2;
p is an integer of 0-4;
q is an integer from 0 to 5]
(B) a polyvalent (meth) acrylic monomer represented by the following general formula (2) and
[Formula 2]

[In formula (2),
R ₁₀ and R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, or 6 to 20 carbon atoms. Is selected from an aryl group, 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 a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO- and any one of the groups consisting of the following formulas (3) to (6);
Y and Z are each independently a branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;
p and q are each independently an integer of 0-4.]
[Formula 3]

[In formula (3),
R ₁₃ and R ₁₄ are each independently 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, or 6 to 12 carbon atoms which may have a substituent. An aryl group, 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 group;
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;
c represents the integer of 1-20.]
[Formula 4]

[In formula (4), R ₁₅ and R ₁₆ each independently has 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 a substituent 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 group, or R ₁₅ and R ₁₆ each bond with each other to form a carbon ring having 1 to 20 carbon atoms or a heterocycle;
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.]
[Formula 5]

[In the formula (5), R ₁₇ to R ₂₀ may each independently have 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, or a substituent. An aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms which may have a substituent group, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent group, or R ₁₇ and R ₁₈ and R ₁₉ and R ₂₀ are each bonded to each other to form a carbon ring having 1 to 20 carbon atoms or a heterocycle;
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.]
[Formula 6]

[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.]
A method of manufacturing a liquid composition comprising:
A method comprising mixing the (meth)acrylate represented by the general formula (1) with a poly(meth)acrylic monomer represented by the general formula (2) at a temperature of 35°C or higher and 120°C or lower. According to claim 1,
In the formula (1), p and q are both 0. The method according to claim 1 or 2,
In the formula (1), n is 1 and m is 0. The method according to any one of claims 1 to 3,
The method in which the content of the (meth)acrylate represented by the general formula (1) and the polyvalent (meth)acrylic monomer represented by the general formula (2) is 1:10 to 10:1 by mass ratio. The method according to any one of claims 1 to 4,
The (meth)acrylate represented by the general formula (1) is a blend of two or more types of compounds, a method. The method according to any one of claims 1 to 5,
In said formula (2), X has a structure represented by general formula (4). The method according to any one of claims 1 to 6,
The method, wherein the liquid composition is an active energy ray-curable composition. A coating material comprising the composition obtained by the method according to claim 1. A cured product obtained by curing the composition obtained by the method according to any one of claims 1 to 7. As a method of manufacturing a cured body,
A process for obtaining a composition by the method according to any one of claims 1 to 7, and
Process of curing the composition
Including, method.