JPWO2019124190A1 - Method for producing (meth) acrylic composition, paint and cured product containing (meth) acrylic composition - Google Patents

Abstract

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

Description

The present invention relates to a method for producing a (meth) acrylic composition and a coating material containing the (meth) acrylic composition. The present invention also relates to a cured product of this composition.

In recent years, resin materials have been widely used for optical components such as optical overcoat agents, hard coat agents, antireflection films, spectacle lenses, optical fibers, optical waveguides, and holograms because of their excellent processing and productivity. Further, in the field of optical components, there is an increasing tendency for miniaturization and thinning, and along with this, a material having a high refractive index is required. To meet such demands, paints containing a resin composition having a high refractive index at the time of curing are widely used. On the other hand, since such paints are generally characterized by having a relatively high viscosity, it may be difficult to apply them thinly. Therefore, a composition having a low viscosity that improves this point has been proposed.

For example, in Patent Document 1, a specific ratio of o-phenylbenzyl acrylate (OPBA; or 2-phenylbenzyl acrylate) and p-phenylbenzyl acrylate (PPBA; or 4-phenylbenzyl acrylate), which are isomers of phenylbenzyl acrylate. A composition having a high refractive index and a low viscosity has been proposed by mixing with. Further, Patent Document 2 describes that a composition having a high refractive index and a low viscosity can be obtained by mixing a phenylbenzyl acrylate with a bifunctional (meth) acrylate or a diphenyl derivative.

Patent Documents 3 to 7 describe that a phenoxybenzyl (meth) acrylate and a polyfunctional (meth) acrylate having a high refractive index (fluorene-based bisphenol derivative or bisphenol A derivative) are mixed to obtain a resin composition for an optical material. Has been done.

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

As described above, various compositions having a high refractive index and a low viscosity have been proposed so far. However, monofunctional (meth) acrylates having a low refractive index often have a low refractive index, while monofunctional (meth) acrylates having a high refractive index have the effect of lowering the viscosity of a polyfunctional (meth) acrylate having a high refractive index. May not be obtained sufficiently. Under these circumstances, monofunctional (meth) acrylates having a high refractive index and low viscosity have been developed. As an example thereof, a phenoxybenzyl (meth) acrylate represented by the chemical formula (C) has been newly found and researched (for example, Patent Document 4, (B) component 1 and the like).

However, when phenoxybenzyl (meth) acrylate represented by the chemical formula (C) is used, yellowing of the coating film is severe in an environmental test under high temperature and high humidity (specifically, 85 ° C / 85% RH). Is known. For this reason, a (meth) acrylic composition having 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 is required.

The present invention addresses such a problem, and is a (meth) acrylic composition having a low viscosity of the composition, a high refractive index at the time of curing, and less yellowing in an environmental test under high temperature and high humidity. It is an object of the present invention to provide a manufacturing method and a coating material containing such a (meth) acrylic composition. It is also an object of the present invention to provide a cured product of the above composition.

As a result of diligent studies to solve the above problems, the present inventors have made the (meth) acrylate of the general formula (1) described later within a predetermined temperature range and the polyvalent (meth) of the general formula (2) described later. ) We have found that the above problems can be solved by mixing with an acrylic monomer, and have reached the present invention.

That is, the present invention has the features described below.
[1]
(A) The (meth) acrylate represented by the following general formula (1) and
[In equation (1),
X is a single bond, -C (R ₂ ) (R ₃ )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O) O-, -S- , -SO-, -SO _2-, and any combination thereof are divalent groups selected from the group (where R ₂ and R ₃ are independently hydrogen atoms and 1 to 1 carbon atoms, respectively. 10 linear alkyl groups, branched alkyl groups with 3 to 10 carbon atoms, cyclic alkyl groups with 3 to 10 carbon atoms, linear alkoxy groups with 1 to 10 carbon atoms, branched alkoxy groups with 3 to 10 carbon atoms A group, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group; or R ₂ and R ₃ are linked to each other and have ₃ carbon atoms together with the carbon atom to which they are bonded. 10 to 10 cyclic alkyl groups may be formed);
Y is 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;
R ₁ is a hydrogen atom or a methyl group;
R ₄ and R ₅ independently have 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 1 to 10 carbon atoms. 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 halogen atom, a phenyl group or a phenylphenyl group;
m is an integer from 0 to 10;
n is an integer of 1-2;
p is an integer from 0 to 4;
q is an integer from 0 to 5]
(B) With a multivalent (meth) acrylic monomer represented by the following general formula (2)
[In equation (2),
R ₁₀ and R ₁₁ independently have 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, and a cycloalkoxy group having 5 to 20 carbon atoms. Selected from groups, aryl groups with 6 to 20 carbon atoms, aryloxy groups with 6 to 20 carbon atoms, and halogen atoms.
R ₁₂ is a hydrogen atom or a methyl group;
X represents the structure of any of the single bond, -O-, -S-, -SO-, -SO _2- , -CO- and the group consisting of the following general formulas (3) to (6);
Y and Z are independently branched alkylene groups having 2 to 6 carbon atoms, cycloalkylene groups having 6 to 10 carbon atoms, or arylene groups having 6 to 10 carbon atoms;
p and q are independently integers from 0 to 4. ]
[In equation (3),
R ₁₃ and R ₁₄ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms which may have substituents, alkoxy groups having 1 to 5 carbon atoms which may have substituents, and substituents. An aryl group having 6 to 12 carbon atoms which may have a 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. Represents one of the groups consisting of;
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;
c represents an integer of 1 to 20. ]
[In the formula (4), R ₁₅ and R ₁₆ independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon number which may have a substituent. An alkoxy group of ~ 5, 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 a carbon number which may have a substituent. Represents any of the group consisting of 7 to 17 aralkyl groups, or R ₁₅ and R ₁₆ are each bonded to each other to form a carbocycle or heterocycle having 1 to 20 carbon atoms;
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. ]
[In formula (5), R _{17 to} R ₂₀ independently have a hydrogen atom, a Haguchigen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent. An alkoxy group of 1 to 5, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group which may have a substituent and a carbon having 2 to 5 carbon atoms, and a carbon which may have a substituent. Represents one of the groups consisting of aralkyl groups of numbers 7 to 17, or R ₁₇ and R ₁₈ and R ₁₉ and R ₂₀ are bonded to each other, respectively, to form a carbon ring or heterocycle having 1 to 20 carbon atoms. Form;
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. ]
[In formula (6), R _{21 to} R ₃₀ are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms. ]
A method for producing a liquid composition containing
The present invention comprises mixing the (meth) acrylate represented by the general formula (1) with the multivalent (meth) acrylic monomer represented by the general formula (2) at a temperature of 35 ° C. or higher and 120 ° C. or lower. ,Method.
[2]
The method according to [1], wherein both p and q are 0 in the formula (1).
[3]
The method according to [1] or [2], wherein n is 1 and m is 0 in the formula (1).
[4]
The contents of the (meth) acrylate represented by the general formula (1) and the multivalent (meth) acrylic monomer represented by the general formula (2) are 1:10 to 10: 1 in mass ratio. The method according to any one of [1] to [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 kinds of compounds.
[6]
The method according to any one of [1] to [5], wherein X has a structure represented by the general formula (4) in the above 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 containing 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]
It is a method of manufacturing a cured product.
The step of obtaining the composition by the method according to any one of [1] to [7], and
A method comprising a step of curing the composition.

According to the present invention, a method for producing a (meth) acrylic composition having a low viscosity, a high refractive index at the time of curing, and less yellowing in an environmental test under high temperature and high humidity, and such a method. A paint containing a (meth) acrylic composition can be provided. Further, according to the present invention, a cured product of the above composition can also be provided.

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

<Manufacturing method>
The method for producing a liquid composition of the present invention
(A) The (meth) acrylate represented by the following general formula (1) and
[In equation (1),
X is a single bond, -C (R ₂ ) (R ₃ )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O) O-, -S- , -SO-, -SO _2-, and any combination thereof are divalent groups selected from the group (where R ₂ and R ₃ are independently hydrogen atoms and 1 to 1 carbon atoms, respectively. 10 linear alkyl groups, branched alkyl groups with 3 to 10 carbon atoms, cyclic alkyl groups with 3 to 10 carbon atoms, linear alkoxy groups with 1 to 10 carbon atoms, branched alkoxy groups with 3 to 10 carbon atoms A group, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group; or R ₂ and R ₃ are linked to each other and have ₃ carbon atoms together with the carbon atom to which they are bonded. 10 to 10 cyclic alkyl groups may be formed);
Y is 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;
R ₁ is a hydrogen atom or a methyl group;
R ₄ and R ₅ independently have 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 1 to 10 carbon atoms. 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 halogen atom, a phenyl group or a phenylphenyl group;
m is an integer from 0 to 10;
n is an integer of 1-2;
p is an integer from 0 to 4;
q is an integer from 0 to 5]
(B) With a multivalent (meth) acrylic monomer represented by the following general formula (2)
[In equation (2),
R ₁₀ and R ₁₁ independently have 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, and a cycloalkoxy group having 5 to 20 carbon atoms. Selected from groups, aryl groups with 6 to 20 carbon atoms, aryloxy groups with 6 to 20 carbon atoms, and halogen atoms.
R ₁₂ is a hydrogen atom or a methyl group;
X represents a structure of any one of a group consisting of a single bond, -O-, -S-, -SO-, -SO _2- , -CO- and the general formulas (3) to (6) described later. ;
Y and Z are independently branched alkylene groups having 2 to 6 carbon atoms, cycloalkylene groups having 6 to 10 carbon atoms, or arylene groups having 6 to 10 carbon atoms;
p and q are independently integers from 0 to 4. ]
A method for producing a liquid composition containing
It comprises mixing the (meth) acrylate represented by the general formula (1) with the multivalent (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, it is obtained by mixing a (meth) acrylate having the structure of the general formula (1) with a polyvalent (meth) acrylic monomer having the structure of the general formula (2) in a predetermined temperature range. The liquid composition has a low viscosity, has a high refractive index when cured, and has a small yellowing in an environmental test under high temperature and high humidity. Although not bound by theory, the occurrence of yellowing is presumed to be due to the low glass transition temperature. In addition, many (meth) acrylates having the structure of the general formula (1) are always solid at room temperature, and the viscosity of the general formula (2) multivalent (meth) acrylic monomer having a high refractive index and high viscosity. It was thought that it could not be used for the purpose of reducing. For example, in Patent Document 1, p-phenylbenzyl (meth) acrylate, which is a kind of (meth) acrylate having the structure of the general formula (1), is solid (mp: 32 ° C.) at room temperature, and therefore, in this application. It is said that it cannot be used. Then, in Patent Document 1, a liquid composition is obtained by mixing o-phenylbenzyl (meth) acrylate, which is a liquid at room temperature, and p-phenylbenzyl (meth) acrylate in a specific ratio.

Under such circumstances, the present inventors heat the (meth) acrylate having the structure of the general formula (1) to a predetermined temperature range to liquefy the (meth) acrylate having the structure of the general formula (1). Then, it was found that a liquid composition can be obtained by mixing with a polyvalent (meth) acrylic monomer having the structure of the general formula (2) in that state. 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), it is obtained. It was found that even if the liquid composition was subsequently cooled, crystals and the like did not precipitate, resulting in a stable liquid composition. Further, 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 such findings.

The temperature at which the (meth) acrylate having the structure of the general formula (1) in the production method of the present invention is mixed with the multivalent (meth) acrylic monomer having the structure of the general formula (2) is 35 ° C. or higher. It is 120 ° C. or lower, 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 higher, the (meth) acrylate having the structure of the general formula (1) is sufficiently liquefied, and when the temperature 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 the general formula (1) may be adjusted to the above temperature range, and the polyvalent (meth) acrylic monomer having the structure of the general formula (2) may be used. May be mixed 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, when measured at a measurement temperature of 25 ° C. using an E-type viscometer (TV-22 type). It is s or less, more preferably 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. 1. (Meta) 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).

In formula (1), X is a single bond, -C (R ₂ ) (R ₃ )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O). A divalent group selected from the group consisting of O-, -S-, -SO-, -SO _2- and any combination thereof, preferably single bond, -C (R ₂ ) (R ₃ ). )-, -O-, and a divalent group selected from the group consisting of any combination thereof. Here, R ₂ and R ₃ are independently hydrogen atoms, linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, and the like. It is 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 linked to each other to form a cyclic alkyl group having 3 to 10 carbon atoms together with the carbon atom to which they are bonded. Preferably, both R ₂ and R ₃ are hydrogen atoms.

Y is an 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 which may be branched.

R ₁ is a hydrogen atom or a methyl group, preferably a hydrogen atom.
R ₄ and R ₅ independently have 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 1 to 10 carbon atoms. It is 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 halogen atom, a phenyl group or a phenylphenyl group.

m is an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably 0.
n is an integer of 1 to 2, preferably 1.
More preferably, n is 1 and m is 0.
p is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
q is an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0.
More preferably, both p and q are 0. When p and q are 0, it means that the hydrogen in the benzene ring is not substituted with the functional group of R ₄ or R ₅ .

Examples of the (meth) acrylate represented by the general formula (1) include 4-phenylbenzyl (meth) acrylate, 3-phenylbenzyl (meth) acrylate, 2-phenylbenzyl (meth) acrylate, and 4-biphenylbenzyl. (Meta) acrylate, 3-biphenylbenzyl (meth) acrylate, 2-biphenylbenzyl (meth) acrylate, 4-benzylbenzyl (meth) acrylate, 3-benzylbenzyl (meth) acrylate, 2-benzylbenzyl (meth) acrylate, 4-Phenetylbenzyl (meth) acrylate, 3-Phenetylbenzyl (meth) acrylate, 2-Phenetylbenzyl (meth) acrylate, 4-Phenetyl Penetyl (meth) acrylate, 3-Phenetyl Penetyl (meth) acrylate, 2-Phenetyl Penetyl Meta) 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) acrylate, 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 (Meta) 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) phenylbenzoate, 3-(((meth) acryloxy) ) Methyl) phenylbenzoate, 2-(((meth) acryloxy) methyl) phenylbenzoate, phenyl4-(((meth) acryloxy) methyl) benzoate, phenyl3-(((meth) acryloxy) methyl) benzoate, phenyl2 -(((Meta) acryloxy) methyl) benzoate, 4- (1-phenylcyclohexyl) benzyl (meth) acrylate, 3- (1-phenylcyclohexyl) benzyl (meth) acrylate, 2- (1-phenylcyclohexyl) benzyl ( Meta) acrylate, 4-phenoxybenzyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, 2-phenoxybenzyl (meth) acrylate, 4- (phenylthio) benzyl (meth) acrylate, 3- (phenylthio) benzyl (meth) ) Acrylic, 2- (phenylthio) benzyl (meth) acrylate and 3-methyl-4- (2-methylphenyl) benzyl methacrylate can be mentioned. These can be used alone or in combination of two or more. For example, the (meth) acrylate may be a blend of two or more kinds of compounds, and in that case, at least one kind of the (meth) acrylate may be a (meth) acrylate represented by the above general formula (1). Among the above (meth) acrylates, 2-phenylbenzyl (meth) acrylate, 4-phenylbenzyl (meth) acrylate, 4-phenoxybenzyl (meth) acrylate and 4-benzylbenzyl (meth) acrylate are preferable. More preferably, it is 2-phenylbenzyl acrylate, 4-phenylbenzyl acrylate, 4-phenoxybenzyl acrylate and 4-benzylbenzyl acrylate.

The blending 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 deviate 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 to be formed is preferably 1: 9 to 9: 1 in mass ratio, more preferably 2: 8 to 8: 2, and 3: 7. It is more preferably ~ 7: 3, and particularly preferably 4: 6 to 6: 4. Further, the higher the ratio of the monofunctional (meth) acrylate, the more preferable it is in that peeling in a high temperature and high humidity environment can be prevented. Although not bound by theory, it is presumed that the decrease in adhesion between the base material and the cured product is due to the large water absorption rate.

3. 3. Polyvalent (meth) acrylic monomer The composition obtained by the production method of the present invention can be copolymerized with the (meth) acrylate represented by the above general formula (1), and can be copolymerized with the following general formula (2). Further contains a polyvalent (meth) acrylic monomer represented by.

In formula (2), R ₁₀ and R ₁₁ independently have 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, and a carbon number of carbon atoms. It is selected from a cycloalkoxyl group of 5 to 20, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom, preferably a hydrogen atom.
R ₁₂ is a hydrogen atom or a methyl group.
X represents any structure in the group consisting of a single bond, -O-, -S-, -SO-, -SO _2- , -CO- and the following general formulas (3) to (6).
Y and Z are alkylene groups having 2 to 6 carbon atoms, cycloalkylene groups having 6 to 10 carbon atoms, or arylene groups having 6 to 10 carbon atoms, which may be branched independently of each other.
p and q are independently integers from 0 to 4, preferably both p and q are 0.

In the following formula (3),
R ₁₃ and R ₁₄ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms which may have substituents, alkoxy groups having 1 to 5 carbon atoms which may have substituents, and substituents. An aryl group having 6 to 12 carbon atoms which may have a 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. Represents any of the group consisting of, where the substituents are independently halogen atoms, alkyl groups with 1 to 20 carbon atoms, or aryl groups with 6 to 12 carbon atoms. Preferably R ₁₃ and R ₁₄ are both hydrogen atoms.
c represents an integer of 1 to 20, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

In the following formula (4),
R ₁₅ and R ₁₆ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms which may have substituents, alkoxy groups having 1 to 5 carbon atoms which may have substituents, and substituents. From an aryl group having 6 to 12 carbon atoms which may have a 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. Representing one of the groups, or R ₁₅ and R ₁₆ are bonded to each other to form a carbocycle or heterocycle having 1 to 20 carbon atoms, and the substituents are independently halogen atoms and carbons, respectively. It is an alkyl group having a number of 1 to 20 or an aryl group having 6 to 12 carbon atoms. Preferably, both R ₁₅ and R ₁₆ are hydrogen atoms.

In the following formula (5),
R _{17 to} R ₂₀ are independent hydrogen atoms, Haguchigen, 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. Representing any of the group consisting of, or R ₁₇ and R ₁₈ and R ₁₉ and R ₂₀ , respectively, are bonded to each other to form a carbocycle or heterocycle having 1 to 20 carbon atoms, the substituents being Each is 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 _{17 to} R ₂₀ are hydrogen atoms.

In the following formula (6),
R _{21 to} R ₃₀ are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms. Preferably, both R _{21 to} R ₃₀ are hydrogen atoms.

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

Examples of the polyvalent (meth) acrylic monomer represented by the above general formula (2) include 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 4,4. '-Isopropyridene diphenol di (meth) acrylate, 2,2'-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] propane, bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] Methan, 1,1'-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] methane, bis [4- (2- (meth) acryloyloxyethoxy) phenyl] ether, bis [4- (2) − (Meta) 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'-isopropyridene diphenol di (meth) acrylate, ethoxylated bisphenol A diacrylate and 2,2'-bis [4-( 2- (Meta) acryloyloxyethoxy) phenyl] propane is preferred, ethoxylated bisphenol A diacrylate and 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene are more preferred. Among the polyvalent (meth) acrylic monomers represented by the general formula (2), commercially available ones include, for example, ABE-300, A-BPE-4, and A manufactured by Shin-Nakamura Chemical Industry Co., Ltd. -BPEF, Light Acryloyl BP-4EAL manufactured by Kyoeisha Chemical Co., Ltd., Viscoat # 700HV manufactured by Shin-Nakamura Chemical Co., Ltd., FA-324A manufactured by Hitachi Kasei Co., Ltd., etc., but are not limited thereto. ..

3. 3. Optional Additives In addition to the above-mentioned constituent components, the composition obtained by the production method of the present invention may contain various arbitrary additives depending on the intended use without 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. To. The blending amount of the additive is 100 parts by mass in total of the (meth) acrylate represented by the general formula (1) and the multivalent (meth) acrylic monomer represented by the general formula (2). , 0.005 part by mass to 0.1 part by mass, more preferably 0.01 part by mass to 0.05 part by mass.

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

<Paint>
The paint of the present invention comprises the composition obtained by the method of the present invention. The coating material of the present invention can be mainly used for applications such as a coating agent for an optical member and a hard coating agent.

When the coating material of the present invention is applied to a general substrate such as plastic, a wetting agent such as a silicone or an acrylic compound may be added to the coating material in order to help wet the surfaces of various substrates. Suitable wetting agents include BYK331, BYK333, BYK340, BYK347, BYK348, BYK378, BYK380, BYK381 and the like, which are available from Big Chemie. When these are added, the range of 0.01 to 2.0% by mass is preferable based on the total mass of the coating material.

Further, in order to improve the adhesiveness to various materials, a tackifier such as xylene resin, terpene resin, phenol resin and rosin resin may be added to the paint as needed. When these are added, the range of 0.01 to 2.0% by mass is preferable based on the total mass of the coating material.

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

Further, in order to improve various performances such as impact resistance, inorganic fillers such as silica, alumina, mica, talc, aluminum flakes and glass flakes may be added to the paint. When these are added, the range is preferably 0.01 to 10.0% by mass based on the total mass of the coating material.

Furthermore, when the paint of the present invention is applied to a general base material such as metal, concrete, or plastic, in order to help the bubbles generated during stirring and mixing and application disappear, the paint may be made of a silicone-based or acrylic compound. Antifoaming agent may be added. Suitable antifoaming agents include BYK019, BYK052, BYK065, BYK066N, BYK067N, BYK070, BYK080, etc., which can be obtained from Big Chemie, but BYK065 is particularly preferable. When these are added, the range is preferably 0.01 to 3.0% by mass based on the total mass of the coating material.

The coating material of the present invention contains, if necessary, rust preventive additives such as zinc phosphate, iron phosphate, calcium molybdenate, vanadium oxide, water-dispersed silica, fumed silica, phthalocyanine-based organic pigment, and condensed polycyclic organic. A required amount of each component such as an organic pigment such as a pigment and an inorganic pigment such as titanium oxide, zinc oxide, calcium carbonate, barium sulfate, alumina, and carbon black may be added.

Examples of the coating format for applying the coating material of the present invention onto various substrates include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, and micro. Commonly used paint types such as reverse gravure coater coating, die coater coating, slot die coater coating, vacuum die coater coating, dip coating, spin coating coating, spray coating, brush coating, etc. Both can be used. Roll coating or spray coating is preferred.

<Hardened body>
The cured product of the present invention is a cured product 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. Further, the cured product of the present invention preferably has a high refractive index of 1.585 or more, and more preferably 1.590 or more. Further, the cured product of the present invention preferably has a yellowness (YI) of 4.0 or less when stored in an atmosphere of 85 ° C./85% RH for 350 hours, and 1 in an atmosphere of 85 ° C./85% RH. It is preferable that the yellowness (YI) after storage for 000 hours is 6.5 or less.

The cured product of the present invention is
(A) Constituent units derived from (meth) acrylate represented by the general formula (1)
Constituent units derived from a multivalent (meth) acrylic monomer represented by the general formula (2)
including.

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. Further, R ₁₀ , R ₁₁ , R ₁₂ , X, Y, Z, p and q in the general formula (2) are also the same as those of the composition obtained by the method of the present invention.

The structural unit derived from the (meth) acrylate represented by the general formula (1) indicates a structural unit having the structure of the following formula (1a).
The structural unit derived from the multivalent (meth) acrylic monomer represented by the general formula (2) indicates a structural unit having the structure of the following formula (2a).

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

The method for producing a cured product of the present invention includes a step of obtaining a composition by the method of the present invention and a step of curing the composition. Here, the method of curing is not particularly limited, and various known methods may be used. For example, the composition of the present invention may be cured by photopolymerization by irradiating with active energy rays. As used herein, the term "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 active energy rays, a photopolymerization initiator is not always necessary. However, when a photopolymerization initiator is added, for example, Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-, available from Ciba). Propane-1-one, Irgacure® 184 (1-hydroxycyclohexylphenylketone), Irgacure® 500 (1-hydroxycyclohexylphenylketone, benzoylene), Irgacure® 651 (2,2-dimethoxy) -1,2-diphenylethane-1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (registered trademark) 2-Methyl-1 [4-methylthiophenyl] -2-morpholinopropan-1-one, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® ) 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 (bis (2,6--) Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure® OXE01 (1,2-octane) Dione, 1- [4- (Phenylthio) phenyl] -2- (O-benzoyloxime), Darocur® 1173 (2-hydroxy-2-methyl-1-phenyl-1-propane-1-one), Darocur® 1116, 1398, 1174 and 1020, CGI242 (Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) , Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) available from BASF, Lucirin TPO-L (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), ESACURE1001M available from Siebel Hegner Japan 1- [4-benzoylphenyl sulfanyl] phenyl] -2-methyl-2- (4-methi Luphenylsulfonyl) propan-1-one, adecaoptomer (registered trademark) N-1414 (carbazole / phenone type), adecaoptomer (registered trademark) N-1717 (aclysin type), adeca available from Asahi Denka. Optomer (registered trademark) N-1606 (triazine type), TFE-triazine manufactured by Sanwa Chemical (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1, 3,5-Triazine), TME-Triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-" manufactured by Sanwa Chemical Co., Ltd. Triazine), MP-triazine manufactured by Sanwa Chemical (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-113 manufactured by Midori Chemical Co., Ltd. (2-[ 2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 (2- (3,4-dimethoxyphenyl)-" manufactured by Midori Chemical Co., Ltd. 4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4-phenyl Benzophenone, ethylmihillers ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium Salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosverone, o -Methyl benzoyl benzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacrydone, [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 Examples thereof include -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. The amount of these photopolymerization initiators 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.

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

In addition, the physical properties of Examples and Comparative Examples were measured by the following methods.

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

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

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

5. Peelability The cured product of the composition obtained by the method described below was stored in an environment of 85 ° C. and 85% RH. When a predetermined time had elapsed, it was visually confirmed whether the cured product of the composition had peeled off from the PET film which was 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 multivalent (meth) acrylic monomer represented by the general formula (2), the liquid composition according to the composition shown in Table 1 is used. Examples 1 to 13 were prepared. A polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity has been reduced by heating at 60 ° C. for 1 hour and a monofunctional (meth) acrylate are blended and stirred well. As a result, it was uniformly dissolved to obtain a liquid composition. Next, the temperature of the composition was adjusted to 23 ° C. by storing in an atmosphere of 23 ° C. for 12 hours. Then, the viscosity and the refractive index were measured.

The following compounds were used as the compounds of the chemical formulas (A) to (D). OGSOL EA0200 manufactured by Osaka Gas Chemical Co., Ltd. was used as the compound of chemical formula (A), ALEN-10 manufactured by Shin-Nakamura Chemical Industry Co., Ltd. was used as the compound of chemical formula (B), and Kyoeisha Chemical Co., Ltd. was used as the compound of chemical formula (C). The compound of the chemical formula (D) was synthesized by a known method using POB-A manufactured by the company.
Specifically, the method for synthesizing the compound of the chemical formula (D) is 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 heated under air flow to remove water in the system, and then titanium tetraiso. 0.82 parts by weight of propoxide was added to initiate the reaction. The reaction mixture was heated to 90 ° C. to remove methanol generated by the reaction, and the reaction was carried out for 6 hours while adding methyl acrylate as appropriate. After completion of the reaction, the catalyst was hydrolyzed by adding 10 parts by weight of pure water. Further, the mixture was purified by distillation and filtration to obtain a compound of the chemical formula (D).

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

<Example 2: Physical properties of each liquid composition composition and its cured product>
Liquid composition examples 14 to 16 containing a monofunctional (meth) acrylate and a multivalent (meth) acrylic monomer represented by the general formula (2) in a ratio of 50:50 were prepared, and the composition and the composition and the liquid composition Examples 14 to 16 were prepared. Various physical properties of the cured product were measured. 20 parts by mass of a polyvalent (meth) acrylic monomer represented by the general formula (2) and 20 parts by mass of a monofunctional (meth) acrylate whose viscosity was lowered by heating at 60 ° C. for 1 hour. And Irugacure184 (manufactured by Ciba Specialty Chemicals), which is a photopolymerization initiator, was blended with 1.2 parts by mass and stirred well to uniformly dissolve the liquid composition. Next, a liquid composition was applied to a corona-treated surface of a polyester film having a thickness of 50 μm (manufactured by Toyobo Co., Ltd .; Toyobo ester film E5100) as a base material, and a bar coater No. Conveyor-type UV irradiation device U-0303 (manufactured by GS Yuasa Co., Ltd., using a high-pressure mercury lamp, lamp output: 80 W / cm), which was applied using 60 and immediately set to an ultraviolet irradiation amount of 300 mJ / cm ^2. , Conveyor speed: 4.8 m / min) was irradiated with ultraviolet rays to obtain a film in which a cured product of a liquid composition was formed on a polyester film. The results are shown in Table 2.
Each physical property shown in Table 2 was measured by the following method.
[Pencil hardness]
Pencil hardness was measured according to JIS K5600-5-4. Specifically, a pencil is pressed against the surface of the polyester film on which the cured product of the liquid composition is formed at an angle of 45 degrees and a load of 750 g on the surface of the dry coating film in ascending order of hardness without causing scars. The hardness of the hardest pencil was evaluated as the pencil hardness. Pencil hardness is indicated by 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H and 7H in ascending order of rank.
[Growth]
20 parts by mass of a polyvalent (meth) acrylic monomer represented by the general formula (2) and 20 parts by mass of a monofunctional (meth) acrylate whose viscosity was lowered by heating at 60 ° C. for 1 hour. A liquid composition was obtained by blending 1.2 parts by mass of Irugacure 184 (manufactured by Ciba Specialty Chemicals), which is a photopolymerization initiator, and stirring well to uniformly dissolve it. Next, a liquid composition was applied to a non-corona-treated surface of a polyester film having a thickness of 50 μm (manufactured by Toyobo Co., Ltd .; Toyobo ester film E5100) as a base material, and a bar coater No. Conveyor-type UV irradiation device U-0303 (manufactured by GS Yuasa Co., Ltd., using a high-pressure mercury lamp, lamp output: 80 W / cm), which was applied using 60 and immediately set to an ultraviolet irradiation amount of 300 mJ / cm ^2. , Conveyor speed: 4.8 m / min) was irradiated with ultraviolet rays to obtain a film in which a cured product of a liquid composition was formed on a polyester film. The cured product of the liquid composition was peeled off from the polyester film surface, and a tensile test was performed according to JIS K7161-1.
[HAZE]
HAZE was measured according to 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 according to JIS K 7375 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
[Saturated water absorption rate]
A cured product 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 the test piece was taken out from the water after a predetermined time had passed after being immersed in water at 23 ° C., the water content was wiped off, and the mass thereof was measured. This work was continued until the water absorption rate was saturated, and the saturated water absorption rate was measured by the following formula as the weight of the test piece at the time of saturation as the weight at the time of saturation.
Saturated water absorption (%) = weight of test piece when saturated / weight of dried sample x 100
[Glass-transition temperature]
Using DSC6200 (manufactured by Seiko Instruments Inc.), the glass transition temperature was measured according to JIS-K-7121.

From the above results, it can be seen that a cured product having a high refractive index, a low water absorption rate, and a high Tg can be obtained by using the monofunctional (meth) acrylate of the chemical formula (D).

<Example 3: Coloring evaluation of each liquid composition and its cured product under high temperature and high humidity>
Examples 17 to 25 of liquid compositions containing a monofunctional (meth) acrylate and a polyvalent (meth) acrylic monomer represented by the general formula (2) in the proportions shown in Table 3 were prepared, and the respective high temperatures were prepared. -Evaluated coloring under high humidity. At the time of preparation, the polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity was reduced by heating at 60 ° C. for 1 hour was monofunctional at the ratio shown in Table 3. Mixed with metal acrylate. At the same time, 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 was formed was stored in a constant temperature and humidity chamber set to an 85 ° C./85% RH atmosphere, and after 350 hours and 1000 hours, the yellowness was measured by the above measurement method. (YI) was measured.

From the above results, when the monofunctional (meth) acrylate of the chemical formula (D) is used, coloring is suppressed even under high temperature and high humidity, and by setting the addition amount of the monofunctional methacrylate to 75 wt%, peeling is also effective. It turned out to be suppressed.

<Example 4: Evaluation of crystallization>
Examples of liquid compositions 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 are prepared. It was evaluated whether changing the blending temperature affects the generation of crystals. The results are shown in Tables 4-7. The liquid composition is prepared by blending the compounds of the chemical formulas (A), (C), and (D) adjusted to the temperatures shown in the table by the formulation and method shown in the table, stirring well, and dissolving them uniformly. Obtained. The chemical formula (D) / (C) means a mixture of the compound of the chemical formula (D) and the compound of the chemical formula (C) in a weight ratio of 1: 1. Next, storage was carried out under the storage conditions shown in the table, and when a predetermined time had passed, the presence or absence of crystal precipitation was visually confirmed. In addition, "23 ° C./1 day → 5 ° C. storage" means that the product is stored at 23 ° C. for 1 day and then stored at 5 ° C., and "crystallization (5 ° C./5 day)" is stored at 5 ° C. for 5 days. Means that.
From the results of Examples 26 and 27, it can be seen that setting the blending temperature to 40 ° C. has an effect of suppressing crystallization as compared with the case of blending at 23 ° C.

From the above results, it can be seen that crystallization is further suppressed by setting the blending temperature to 60 ° C. or higher, and no crystals are generated in the liquid composition even after storage at 5 ° C./30 days or longer. Further, even when only the monofunctional (meth) acrylate was heated to 60 ° C., no crystals were formed even when the obtained liquid composition was stored at 5 ° C./30 days or more. Further, the same result was obtained when A-BPEF manufactured by Shin Nakamura Chemical Industry Co., Ltd. was used as the compound of the chemical formula (A). When blended at a temperature exceeding 120 ° C., the (meth) acrylate of the monomer may polymerize, so the test was limited to 120 ° C.

<Example 5: Solubility of crystallized multivalent (meth) acrylic monomer represented by the general formula (2)>
If the polyvalent (meth) acrylic monomer represented by the general formula (2) has already crystallized before being blended with the monofunctional (meth) acrylate, it is blended with the heated monofunctional (meth) acrylate. It was evaluated whether the crystals would dissolve. At that time, the monofunctional (meth) acrylate and the polyvalent (meth) acrylic monomer were mixed at each blend temperature, and then the polyvalent (meth) acrylic monomer crystallized by holding at 60 ° C. It was evaluated whether it would dissolve. The results are shown in Table 8. In addition, "solubility (60 ° C./Nday)" in the table means the degree of dissolution when stored at 60 ° C. for N days.

From the above results, even if the multivalent (meth) acrylic monomer represented by the general formula (2) is crystallized by using the monofunctional (meth) acrylate of the chemical formula (D), it is good. It turns out that it is dissolved.

Claims (10)

(A) The (meth) acrylate represented by the following general formula (1) and
[In equation (1),
X is a single bond, -C (R ₂ ) (R ₃ )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O) O-, -S- , -SO-, -SO _2-, and any combination thereof are divalent groups selected from the group (where R ₂ and R ₃ are independently hydrogen atoms and 1 to 1 carbon atoms, respectively. 10 linear alkyl groups, branched alkyl groups with 3 to 10 carbon atoms, cyclic alkyl groups with 3 to 10 carbon atoms, linear alkoxy groups with 1 to 10 carbon atoms, branched alkoxy groups with 3 to 10 carbon atoms A group, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group; or R ₂ and R ₃ are linked to each other and have ₃ carbon atoms together with the carbon atom to which they are bonded. 10 to 10 cyclic alkyl groups may be formed);
Y is 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;
R ₁ is a hydrogen atom or a methyl group;
R ₄ and R ₅ independently have 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 1 to 10 carbon atoms. 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 halogen atom, a phenyl group or a phenylphenyl group;
m is an integer from 0 to 10;
n is an integer of 1-2;
p is an integer from 0 to 4;
q is an integer from 0 to 5]
(B) With a multivalent (meth) acrylic monomer represented by the following general formula (2)
[In equation (2),
R ₁₀ and R ₁₁ independently have 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, and a cycloalkoxy group having 5 to 20 carbon atoms. Selected from groups, aryl groups with 6 to 20 carbon atoms, aryloxy groups with 6 to 20 carbon atoms, and halogen atoms.
R ₁₂ is a hydrogen atom or a methyl group;
X represents the structure of any of the single bond, -O-, -S-, -SO-, -SO _2- , -CO- and the group consisting of the following general formulas (3) to (6);
Y and Z are independently branched alkylene groups having 2 to 6 carbon atoms, cycloalkylene groups having 6 to 10 carbon atoms, or arylene groups having 6 to 10 carbon atoms;
p and q are independently integers from 0 to 4. ]
[In equation (3),
R ₁₃ and R ₁₄ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms which may have substituents, alkoxy groups having 1 to 5 carbon atoms which may have substituents, and substituents. An aryl group having 6 to 12 carbon atoms which may have a 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. Represents one of the groups consisting of;
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;
c represents an integer of 1 to 20. ]
[In the formula (4), R ₁₅ and R ₁₆ independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 carbon number which may have a substituent. An alkoxy group of ~ 5, 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 a carbon number which may have a substituent. Represents any of the group consisting of 7 to 17 aralkyl groups, or R ₁₅ and R ₁₆ are each bonded to each other to form a carbocycle or heterocycle having 1 to 20 carbon atoms;
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. ]
[In formula (5), R _{17 to} R ₂₀ independently have a hydrogen atom, a Haguchigen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent. An alkoxy group of 1 to 5, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group which may have a substituent and a carbon having 2 to 5 carbon atoms, and a carbon which may have a substituent. Represents one of the groups consisting of aralkyl groups of numbers 7 to 17, or R ₁₇ and R ₁₈ and R ₁₉ and R ₂₀ are bonded to each other, respectively, to form a carbon ring or heterocycle having 1 to 20 carbon atoms. Form;
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. ]
[In formula (6), R _{21 to} R ₃₀ are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms. ]
A method for producing a liquid composition containing
The present invention comprises mixing the (meth) acrylate represented by the general formula (1) with the multivalent (meth) acrylic monomer represented by the general formula (2) at a temperature of 35 ° C. or higher and 120 ° C. or lower. ,Method. The method according to claim 1, wherein both p and q are 0 in the formula (1). The method according to claim 1 or 2, wherein n is 1 and m is 0 in the formula (1). The contents of the (meth) acrylate represented by the general formula (1) and the multivalent (meth) acrylic monomer represented by the general formula (2) are 1:10 to 10: 1 in mass ratio. The method according to any one of claims 1 to 3. The method according to any one of claims 1 to 4, wherein the (meth) acrylate represented by the general formula (1) is a blend of two or more kinds of compounds. The method according to any one of claims 1 to 5, wherein X has a structure represented by the general formula (4) in the above formula (2). The method according to any one of claims 1 to 6, wherein the liquid composition is an active energy ray-curable composition. A coating material containing the composition obtained by the method according to any one of claims 1 to 7. A cured product obtained by curing the composition obtained by the method according to any one of claims 1 to 7. It is a method of manufacturing a cured product.
The step of obtaining the composition by the method according to any one of claims 1 to 7.
A method comprising a step of curing the composition.