JP2019163421A - Resin composition and cured product thereof - Google Patents

Abstract

To provide a resin composition capable of forming a cured product with a good balance between the tensile strength at break and the elongation at break at room temperature and low temperature; and a cured product thereof.SOLUTION: A resin composition comprises (A) a monomer having a (meth)acryloyl group, (B) at least one polymer selected from the group consisting of acrylic polymers and (meth)acryloyl group-containing polymers, and (C) a compound represented by the formula (I) in the figure, where Rand Rare each independently a C1-20 alkyl group.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a cured product thereof.

A resin composition (such as road paint, civil engineering paint, repair material, joint material, etc.) used in civil engineering and construction may be mixed with a plasticizer for the purpose of plasticizing the cured product. The following are known as civil engineering resin compositions or architectural resin compositions containing a plasticizer.
A syrup composition containing an acrylic monomer, a polymer soluble in the acrylic monomer, a plasticizer (eg, chlorinated paraffin, phthalate ester, tributyl acetylcitrate) and a wax (Patent Document 1).
A resin composition containing an acrylic monomer, an acrylic polymer, and a plasticizer (alkyl sulfonic acid phenyl ester, phthalic acid ester, etc.) (Patent Document 2).

JP 2008-207182 A JP2015-0985527A

  A cured product obtained by curing the syrup composition described in Patent Document 1 and a cured product obtained by curing the resin composition described in Patent Document 2 are obtained at room temperature in a tensile test according to JIS K 6251: 2010. Although it has an excellent balance between tensile strength at cutting and elongation at cutting, the elongation at cutting is low at low temperatures.

  The present invention provides a resin composition capable of obtaining a cured product having a good balance between tensile strength at break and elongation at break at room temperature and low temperature, and a cured product thereof.

ただし、Ｒ^１およびＲ^２は、それぞれ独立に炭素数が１〜２０のアルキル基である。
＜２＞前記化合物（Ｃ）の含有量が、前記単量体（Ａ）の含有量および前記重合体（Ｂ）の含有量の合計１００質量部に対して５〜３０質量部である、前記＜１＞の樹脂組成物。
＜３＞下記作製方法にて前記樹脂組成物から得られた試験片が、下記条件（ａ）を満足する、前記＜１＞または＜２＞の樹脂組成物。
（試験片の作製方法）
温度２３℃、湿度５０％の雰囲気下、硬化剤未配合の樹脂組成物１００質量部に過酸化ベンゾイル（純度５０％）２部を加えて硬化剤入り樹脂組成物を調製する。硬化剤入り樹脂組成物を型に注入し、温度２３℃の雰囲気下、２時間かけて硬化させ、厚さ３ｍｍの硬化物を得る。打ち抜き具を用いて硬化物からＪＩＳ Ｋ ６２５１：２０１０に準拠したダンベル状１号形試験片を採取する。
（条件（ａ））
試験片について、ＪＩＳ Ｋ ６２５１：２０１０に準拠し、引張速度２００ｍｍ／ｍｉｎで測定した０℃における切断時引張強さおよび２３℃における切断時引張強さが、下記式（１）を満足する。
０．６≦（Ｋ０−Ｋ２３）／Ｋ２３≦１．５ （１）
ただし、Ｋ０は、０℃における切断時引張強さ（Ｎ／ｍｍ^２）であり、Ｋ２３は、２３℃における切断時引張強さ（Ｎ／ｍｍ^２）である。
＜４＞下記作製方法にて前記樹脂組成物から得られた試験片が、下記条件（ｂ）を満足する、前記＜１＞〜＜３＞のいずれかの樹脂組成物。
（試験片の作製方法）
温度２３℃、湿度５０％の雰囲気下、硬化剤未配合の樹脂組成物１００質量部に過酸化ベンゾイル（純度５０％）２部を加えて硬化剤入り樹脂組成物を調製する。硬化剤入り樹脂組成物を型に注入し、温度２３℃の雰囲気下、２時間かけて硬化させ、厚さ３ｍｍの硬化物を得る。打ち抜き具を用いて硬化物からＪＩＳ Ｋ ６２５１：２０１０に準拠したダンベル状１号形試験片を採取する。
（条件（ｂ））
試験片について、ＪＩＳ Ｋ ６２５１：２０１０に準拠し、引張速度２００ｍｍ／ｍｉｎで測定した０℃における切断時引張強さ、２３℃における切断時引張強さおよび２３℃における切断時伸びが、下記式（２）を満足する。
１８０≦（Ｋ０−Ｋ２３）×Ｓ２３／Ｋ２３≦２７０ （２）
ただし、Ｋ０は、０℃における切断時引張強さ（Ｎ／ｍｍ^２）であり、Ｋ２３は、２３℃における切断時引張強さ（Ｎ／ｍｍ^２）であり、Ｓ２３は、２３℃における切断時伸び（％）である。
＜５＞土木用樹脂組成物または建築用樹脂組成物である、前記＜１＞〜＜４＞のいずれかの樹脂組成物。
＜６＞前記＜１＞〜＜５＞のいずれかの樹脂組成物を硬化させてなる硬化物。 The present invention has the following aspects.
<1> a monomer (A) having a (meth) acryloyl group, an acrylic polymer, and at least one polymer (B) selected from the group consisting of a polymer having a (meth) acryloyl group; A resin composition comprising a compound (C) represented by the following formula (I).

However, R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms.
<2> The content of the compound (C) is 5 to 30 parts by mass with respect to 100 parts by mass in total of the content of the monomer (A) and the content of the polymer (B). <1> The resin composition.
<3> The resin composition according to <1> or <2>, wherein a test piece obtained from the resin composition by the following production method satisfies the following condition (a).
(Test piece preparation method)
In an atmosphere of a temperature of 23 ° C. and a humidity of 50%, 2 parts of benzoyl peroxide (purity 50%) is added to 100 parts by mass of the resin composition containing no curing agent to prepare a resin composition containing a curing agent. A resin composition containing a curing agent is poured into a mold and cured in an atmosphere at a temperature of 23 ° C. for 2 hours to obtain a cured product having a thickness of 3 mm. A dumbbell-shaped No. 1 specimen according to JIS K 6251: 2010 is collected from the cured product using a punching tool.
(Condition (a))
Regarding the test piece, the tensile strength at break at 0 ° C. and the tensile strength at break at 23 ° C. measured at a tensile speed of 200 mm / min in accordance with JIS K 6251: 2010 satisfy the following formula (1).
0.6 ≦ (K0−K23) /K23≦1.5 (1)
However, K0 is the tensile strength at break (N / mm ² ) at 0 ° C., and K23 is the tensile strength at break (N / mm ² ) at 23 ° C.
<4> The resin composition according to any one of <1> to <3>, wherein the test piece obtained from the resin composition by the following production method satisfies the following condition (b).
(Test piece preparation method)
In an atmosphere of a temperature of 23 ° C. and a humidity of 50%, 2 parts of benzoyl peroxide (purity 50%) is added to 100 parts by mass of the resin composition containing no curing agent to prepare a resin composition containing a curing agent. A resin composition containing a curing agent is poured into a mold and cured in an atmosphere at a temperature of 23 ° C. for 2 hours to obtain a cured product having a thickness of 3 mm. A dumbbell-shaped No. 1 specimen according to JIS K 6251: 2010 is collected from the cured product using a punching tool.
(Condition (b))
For the test piece, the tensile strength at break at 0 ° C., the tensile strength at break at 23 ° C., and the elongation at break at 23 ° C. measured at a tensile speed of 200 mm / min in accordance with JIS K 6251: 2010 are expressed by the following formula ( Satisfy 2).
180 ≦ (K0−K23) × S23 / K23 ≦ 270 (2)
However, K0 is the tensile strength at the time of cutting at 0 ° C. (N / mm ² ), K23 is the tensile strength at the time of cutting at 23 ° C. (N / mm ² ), and S23 is at the time of cutting at 23 ° C. Elongation (%).
<5> The resin composition according to any one of <1> to <4>, which is a civil engineering resin composition or a building resin composition.
<6> A cured product obtained by curing the resin composition according to any one of <1> to <5>.

According to the resin composition of the present invention, a cured product having a good balance between tensile strength at break and elongation at break at room temperature and low temperature can be obtained.
The cured product of the present invention has a good balance between tensile strength at break and elongation at break at room temperature and low temperature.

The following definitions of terms apply throughout this specification and the claims.
“(Meth) acryl” is a general term for acrylic and methacrylic.
“(Meth) acrylate” is a general term for acrylate and methacrylate.
“(Meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group.
“˜” indicating a numerical range means that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.

<Resin composition>
The resin composition of the present invention includes at least one polymer selected from the group consisting of a monomer (A) having a (meth) acryloyl group, an acrylic polymer, and a polymer having a (meth) acryloyl group. (B) and the compound (C) represented by the following formula (I) are included.

However, R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms.

(Monomer (A))
The monomer (A) is a monomer having a (meth) acryloyl group.
The monomer (A) is a monofunctional (meth) acrylate having only one (meth) acryloyl group in one molecule, or a polyfunctional (meth) having two or more (meth) acryloyl groups in one molecule. An acrylate is mentioned.
The monomer (A) may contain either one of monofunctional (meth) acrylate and polyfunctional (meth) acrylate, or may contain both.

As monofunctional (meth) acrylate, the following are mentioned, for example.
-Alkyl (meth) acrylate: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate and the like.
-Hydroxyl group-containing (meth) acrylate: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
Nitrogen-containing (meth) acrylate: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.
-Heterocycle-containing (meth) acrylate: glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholyl (meth) acrylate, and the like.
-Alicyclic ring-containing (meth) acrylate: isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclotentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and the like.
-Alkyl group terminal (poly) alkylene glycol mono (meth) acrylate: 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, and the like.
Aromatic ring-containing (meth) acrylate: benzyl (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, and the like.
A monofunctional (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.

As polyfunctional (meth) acrylate, the following are mentioned, for example.
Alkylene glycol di (meth) acrylate: ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.
・ Polyalkylene glycol di (meth) acrylate: diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate etc.
Alkoxy bisphenol A di (meth) acrylate: bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, and the like.
Trifunctional (meth) acrylate: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.
A polyfunctional (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.

  As the monomer (A), among the above-described monofunctional (meth) acrylates, methyl methacrylate, ethyl (meth) acrylate, n-butyl are used because the tensile strength at the time of cutting of the cured product and the elongation at the time of cutting increase. (Meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclotentanyl methacrylate, dicyclopentenyl (meth) acrylate are preferred. . Among these, methyl methacrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) can be used because the viscosity of the resin composition can be reduced. An acrylate and tetrahydrofurfuryl (meth) acrylate are more preferable.

  As the monomer (A), among the above-described polyfunctional (meth) acrylates, ethylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) ) Acrylate is preferred.

(Polymer (B))
The polymer (B) is an acrylic polymer (hereinafter also referred to as “polymer (B1)”) and a polymer having a (meth) acryloyl group (hereinafter also referred to as “polymer (B2)”). At least one polymer selected from the group consisting of

  The polymer (B1) is a homopolymer or copolymer having a monomer unit derived from a monomer having a (meth) acryloyl group. Examples of the polymer (B1) include (meth) acrylic acid (co) polymers, (meth) acrylate (co) polymers, copolymers of (meth) acrylic acid and (meth) acrylates, A (meth) acrylic polymer having a heavy bond is exemplified.

  The (meth) acrylic acid (co) polymer is a homopolymer or copolymer having a monomer unit derived from (meth) acrylic acid. Examples of (meth) acrylic acid (co) polymers include acrylic acid homopolymers, methacrylic acid homopolymers, copolymers of acrylic acid and methacrylic acid, (meth) acrylic acid and other single quantities. And a copolymer with a body (excluding (meth) acrylate). Examples of other monomers include vinyl group-containing monomers such as styrene, α-methylstyrene, acrylonitrile, and vinyl acetate. When using other monomers, two or more kinds may be used in combination.

The (meth) acrylate (co) polymer is a homopolymer or copolymer having a monomer unit derived from (meth) acrylate. As the (meth) acrylate (co) polymer, for example, a polymer obtained by polymerizing only one or more (meth) acrylates, one or more (meth) acrylates and other monomers (however, (meth) acrylic) And a copolymer with an acid. Examples of other monomers include vinyl group-containing monomers such as styrene, α-methylstyrene, acrylonitrile, and vinyl acetate. When using other monomers, two or more kinds may be used in combination.
As (meth) acrylate, the monofunctional (meth) acrylate illustrated previously in description of a monomer (A) is mentioned. Among them, alkyl (meta) such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. ) Acrylate is preferred.

The (meth) acrylic polymer having a polymerizable double bond has a monomer unit derived from a monomer having a (meth) acryloyl group and has a polymerizable double bond.
The method for producing the (meth) acrylic polymer having a polymerizable double bond is not particularly limited. A preferred example of a method for producing a (meth) acrylic polymer having a polymerizable double bond is shown below.
As a first stage reaction, a monomer (b1) having one or more (meth) acryloyl groups, a first functional group involved in an esterification reaction described later, and a monomer having a (meth) acryloyl group (B2) is copolymerized to obtain a precursor copolymer (B1 ′) having a first functional group.
As the second stage reaction, a monomer (b3) having a second functional group and a polymerizable double bond that are esterified with the first functional group to form a bond is converted into a precursor copolymer (B1 ′ ). Thereby, the first functional group of the precursor copolymer (B1 ′) and the second functional group of the monomer (b3) are reacted to form an ester. After the ester formation, the polymerizable double bond derived from the monomer (b3) remains. Therefore, a polymerizable double bond can be introduced into the precursor copolymer (B1 ′) by an ester forming reaction, and a (meth) acrylic polymer having a polymerizable double bond can be obtained.

  Specific examples of the monomer (b1) include monofunctional (meth) acrylates exemplified above in the description of the monomer (A). Examples of the combination of the first functional group and the second functional group include a combination of a carboxy group and a glycidyl group, and a combination of a hydroxyl group and an isocyanate group. When the combination of the first functional group and the second functional group is a combination of a carboxy group and a glycidyl group, (meth) acrylic acid is used as the monomer (b2) and glycidyl is used as the monomer (b3). It is preferable to use (meth) acrylate.

  The glass transition temperature (hereinafter referred to as “Tg”) of the polymer (B1) is preferably 0 ° C. or higher, and more preferably 20 to 105 ° C. As the Tg is higher, the solubility in the monomer (A) is improved, and as the Tg is lower, the tensile strength at the time of cutting the cured product of the resin composition tends to be improved. Tg is determined by measurement with a differential scanning calorimeter (DSC).

The weight average molecular weight (Mw) of the polymer (B1) is preferably 5,000 to 200,000, and more preferably 10,000 to 180,000. As the weight average molecular weight is higher, the tensile strength at the time of cutting the cured product of the resin composition is improved, and as the weight average molecular weight is lower, the solubility in the monomer (A) tends to be improved.
The weight average molecular weight was 100 μL of a 0.4 mass% tetrahydrofuran solution of the polymer (B1) injected into a gel permeation chromatography (GPC) apparatus, flow rate: 1 mL / min, eluent: tetrahydrofuran, column temperature: 40 ° C. The molecular weight measured under these conditions is converted to standard polystyrene.

  Examples of the polymer (B2) include urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and epoxy (meth) acrylate oligomers. However, since the acrylic polymer having a (meth) acryloyl group is included in the polymer (B1) as a (meth) acrylic polymer having a polymerizable double bond, it is excluded from the polymer (B2). . A polymer (B2) may be used individually by 1 type, and may use 2 or more types together.

  A urethane (meth) acrylate oligomer is a compound having a (meth) acryloyl group and a plurality of urethane bonds. The urethane (meth) acrylate oligomer is produced, for example, by reacting a urethane oligomer having an isocyanate group (—NCO) obtained by reacting a polyol and an isocyanate with a compound having a hydroxyl group and a (meth) acryloyl group. Can do.

As a polyol used for manufacture of a urethane oligomer, the following are mentioned, for example.
-Polyalkylene glycol: polyethylene glycol, polypropylene glycol, polybutylene glycol, polyhexamethylene glycol, and the like.
-Addition reaction product of dihydric phenol (bisphenol A, bisphenol F, bisphenol S, etc.) and alkylene oxide (ethylene oxide, propylene oxide, etc.).
・ Polyhydric alcohols (ethylene glycol, propylene glycol, butanediol, butylene glycol, methylpentanediol, etc.) and polybasic acids (phthalic acid, isophthalic acid, tetrahydrophthalic acid, succinic acid, maleic acid, fumaric acid, adipic acid, A polyester polyol obtained by reaction of sebacic acid, trimellitic acid, etc.) with an acid anhydride.
-Polylactone diol obtained from alkylene glycol and lactone.
Polycarbonate diol obtained by reaction of a diol (butanediol, pentanediol, hexanediol, heptanediol, octanediol, cyclohexanedimethanol, etc.) and a carbonating agent (phosgene, dimethylcarbonate, etc.).
A polyol may be used individually by 1 type and may use 2 or more types together.

As isocyanate used for manufacture of a urethane oligomer, the following are mentioned, for example.
Diisocyanate: 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, phenylene diisocyanate, Xylylene diisocyanate, tetramethyl xylylene diisocyanate, isophorone diisocyanate and the like.
An adduct compound of isocyanate and water, trimethylolpropane or the like.
-Trimeric cyclized compound of isocyanate.
Isocyanate may be used individually by 1 type and may use 2 or more types together.

  Examples of the compound having a hydroxyl group and a (meth) acryloyl group used in the production of the urethane (meth) acrylate oligomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) And hydroxyl group-containing (meth) acrylates such as 4-hydroxybutyl (meth) acrylate. The compound containing a hydroxyl group and a (meth) acryloyl group may be used alone or in combination of two or more.

  In the production of a urethane (meth) acrylate oligomer, a compound having a hydroxyl group and a (meth) acryloyl group may be used in combination with a compound having a vinyl group other than the hydroxyl group and the (meth) acryloyl group (such as an allyl group-containing alcohol). . In this case, the urethane (meth) acrylate oligomer has a vinyl group derived from a compound having a hydroxyl group and a vinyl group in addition to the (meth) acryloyl group.

  Examples of the allyl group-containing alcohol include allyl alcohol, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, glycerin mono Examples include allyl ether, glyceryl diallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, and pentaerythritol triallyl ether.

  The weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer is preferably 30,000 or less from the viewpoint of the viscosity of the resin composition. The higher the weight average molecular weight, the better the elongation at break of the cured product of the resin composition, and the lower the weight average molecular weight, the more the urethane (meth) acrylate oligomer dissolved in the monomer (A) when the resin composition is produced. Tend to improve. The weight average molecular weight of the urethane (meth) acrylate oligomer is measured in the same manner as in the case of the polymer (B1).

  The polyester (meth) acrylate oligomer is a compound having a (meth) acryloyl group and a plurality of ester bonds. Polyester (meth) acrylate oligomer is a compound having, for example, a polyester obtained by reacting a polybasic acid and a polyhydric alcohol, a functional group capable of ester bonding with the terminal hydroxyl group or carboxy group, and a (meth) acryloyl group Can be made to react.

  Examples of the polybasic acid used for the production of polyester include hexahydrophthalic anhydride, hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, methylhexahydrophthalic acid, maleic acid, and anhydride. Examples thereof include dibasic acids such as maleic acid, fumaric acid, itaconic acid, and adipic acid. A polybasic acid may be used individually by 1 type, and may use 2 or more types together.

  Examples of the polyhydric alcohol used in the production of the polyester include neopentyl glycol, hydrogenated bisphenol A, hydrogenated bisphenol F, 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1 , 4-cyclohexanediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol. A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

The epoxy (meth) acrylate oligomer is a reaction product of an epoxy resin and a monomer component containing (meth) acrylic acid.
Examples of the epoxy resin used for the production of the epoxy (meth) acrylate oligomer include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like. It is done. As an epoxy resin, various things, such as a solid thing and a liquid thing, can be used. An epoxy resin may be used individually by 1 type, and may use 2 or more types together.

  Other monomers other than (meth) acrylic acid may be contained in the monomer component used for the production of the epoxy (meth) acrylate oligomer, if necessary. The other monomer is not particularly limited as long as it can be copolymerized with (meth) acrylic acid, and examples thereof include monofunctional (meth) acrylates exemplified above in the description of the monomer (A).

  As the polymer (B), acrylic acid (co) polymer, (meth) acrylate (co) polymer, copolymer of (meth) acrylic acid and (meth) acrylate, urethane (meth) acrylate oligomer, polyester One selected from the group consisting of (meth) acrylate oligomers and epoxy (meth) acrylate oligomers may be used alone, or two or more may be used in combination.

(Compound (C))
Compound (C) is an alicyclic dibasic ester plasticizer represented by the following formula (I).

However, R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms.
Examples of the compound (C) include 1,2-cyclohexanedicarboxylic acid diisopentyl ester, 1,2-cyclohexanedicarboxylic acid diisononyl ester, 1,2-cyclohexanedicarboxylic acid diisodecyl ester, 1,2-cyclohexanedicarboxylic acid di ( 2-ethylhexyl) ester, 1,2-cyclohexanedicarboxylic acid dialkyl ester having an alkyl group having 7 to 11 carbon atoms, 1,2-cyclohexanedicarboxylic acid dialkyl ester having an alkyl group having 9 to 11 carbon atoms, alkyl group 1,2-cyclohexanedicarboxylic acid dialkyl ester having 7 to 9 carbon atoms.

Specific product names of the compound (C) include, for example, Hexamol DINCH (1,2-cyclohexanedicarboxylic acid diisononyl ester, manufactured by BASF Japan Ltd.).
The number of carbon atoms of R ¹ and R ² is preferably 1 to 20, and more preferably 3 to 16, since the balance between the tensile strength at break and the elongation at break at room temperature and low temperature of the cured product is good.

(Polymerization initiator (D))
The resin composition of the present invention further includes one or both of a reducing agent (D1) and a curing agent (D2) that constitute a redox polymerization initiator (hereinafter also referred to as a polymerization initiator (D)). You may go out.
In the resin composition of the present invention, a curing reaction proceeds by radicals generated from the redox polymerization initiator, and a cured product can be obtained.
The redox polymerization initiator is a polymerization initiator in which a reducing agent (D1) and a curing agent (D2) are used in combination. Examples of the combination of the reducing agent (D1) and the curing agent (D2) include the following (i) to (iv).

(I) Combination of reducing agent (D1): aromatic tertiary amine and curing agent (D2): dibenzoyl peroxide.
Examples of aromatic tertiary amines include the following.
N, N-dimethyl-p-toluidine, N, N-diethylaniline, N, N-diethyl-p-toluidine, N- (2-hydroxyethyl) N-methyl-p-toluidine, N, N-di ( 2-hydroxyethyl) -p-toluidine, N, N-di (2-hydroxypropyl) -p-toluidine and the like.
-N, N-di (2-hydroxyethyl) -p-toluidine or N, N-di (2-hydroxypropyl) -p-toluidine ethylene oxide or propylene oxide adduct, etc.
The aromatic tertiary amine is not limited to the p (para) isomer, and may be an o (ortho) isomer or an m (meth) isomer.

(Ii) A combination of a reducing agent (D1): metal soap and a curing agent (D2): hydroperoxide.
Examples of metal soaps include cobalt naphthenate, copper naphthenate, manganese naphthenate, cobalt octylate, nickel octylate, cobalt acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, iron acetylacetonate, and vanadylacetyl. Examples include acetonate and vanadium acetylacetonate.
Examples of the hydroperoxide include cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-butyl hydroperoxide, t- Examples include hexyl hydroperoxide, t-amyl hydroperoxide, and 2,5-dimethylhexane-2,5-dihydroperoxide.

(Iii) Combination of reducing agent (D1): thiourea compound and curing agent (D2): hydroperoxide.
Examples of thiourea compounds include thiourea, ethylene thiourea, N, N′-dimethylthiourea, N, N′-diethylthiourea, N, N′-dipropylthiourea, N, N′-di-n-butylthiourea, N, N′-dilaurylthiourea, N, N′-diphenylthiourea, trimethylthiourea, 1-acetyl-2-thiourea, 1-benzoyl-2-thiourea can be mentioned.

(Iv) A combination of a reducing agent (D1): a thiourea compound and a curing agent (D2): a monocarbonate type peroxide.
Examples of the monocarbonate type peroxide include t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-butyl peroxyallyl monocarbonate, 1 , 6-bis (t-butylperoxycarbonyloxy) hexane.

A reducing agent (D1) and a hardening | curing agent (D2) may each be used individually by 1 type, and may use 2 or more types together.
As the combination of the reducing agent (D1) and the curing agent (D2), the combination of (i) is particularly preferable from the viewpoint of improving the productivity by shortening the gel time of the resin composition. In terms of the balance between the tensile strength at break and the elongation at break of the cured product of the resin composition, aromatic tertiary amines in the combination (i) include N, N-dimethyl-p-toluidine, N, N- Particularly preferred are diethyl-p-toluidine, N, N-di (2-hydroxyethyl) -p-toluidine, and N, N-di (2-hydroxypropyl) -p-toluidine.
In the present invention, before the curing reaction, the monomer (A), the polymer (B), the compound (C) and the reducing agent (D1) are included, and the curing agent not containing the curing agent (D2) is not blended. It is preferable to add a curing agent (D2) immediately before the curing reaction to obtain a curing agent-containing resin composition.

(Other ingredients)
The resin composition of the present invention is a component other than the monomer (A), the polymer (B), the compound (C) and the polymerization initiator (D) as necessary, as long as the effects of the present invention are not impaired. Hereinafter, it may be further described as “other components”.
Examples of other components include plasticizers other than the compound (C) (hereinafter also referred to as “other plasticizers”), paraffin wax, rubber, antioxidants, ultraviolet absorbers, thixotropic agents, and antifoaming agents. , Polymerization inhibitors, silane coupling agents, various additives, radical polymerization initiators (thermal polymerization initiators, photopolymerization initiators, etc.) other than the polymerization initiator (D).

In view of compatibility with the polymer (B), other plasticizers other than the compound (C) may be added to the resin composition of the present invention. Examples of other plasticizers include the following.
-Phthalate esters: dibutyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, etc.
Adipic acid ester: di-2-ethylhexyl adipate, octyl adipate, etc.
Sebacate: dibutyl sebacate, di-2-ethylhexyl sebacate, etc.
-Azelain ester: di-2-ethylhexyl azelate, octyl azelate and the like.
Paraffin (excluding the following paraffin wax): Chlorinated paraffin, etc.

Paraffin wax may be added to the resin composition of the present invention in order to suppress curing inhibition by oxygen.
The melting point of the paraffin wax is preferably 40 to 80 ° C. If melting | fusing point is 40 degreeC or more, when hardening a resin composition, sufficient air blocking effect will be acquired and surface curability will become favorable. If melting | fusing point is 80 degrees C or less, when preparing a resin composition, the solubility to the resin composition of paraffin wax will become favorable.

  It is preferable to use two or more paraffin waxes having different melting points. By using paraffin waxes having different melting points in combination, even when the temperature changes, a sufficient air blocking action can be obtained and the surface curability can be improved. When using together, it is preferable to use together that whose melting | fusing point difference is about 5-20 degreeC.

  As the paraffin wax, a wax dispersed in an organic solvent may be used in terms of improving surface curability. Since the wax is in a dispersed state in an organic solvent and the particle diameter of the dispersed wax is finely divided to 0.1 to 50 μm, an air blocking action is effectively expressed. Dispersed paraffin wax is commercially available and can be added as it is.

  Specific product names of paraffin wax include, for example, paraffin 115 (melting point described in catalog: 47 ° C, manufactured by Nippon Seiwa Co., Ltd.), paraffin 130 (melting point described in catalog: 55 ° C, manufactured by Nippon Seiwa Co., Ltd.) ), Paraffin 150 (melting point described in the catalog: 66 ° C., manufactured by Nippon Seiwa Co., Ltd.).

  Rubber may be added to the resin composition of the present invention in order to improve the tensile fracture strength and tensile fracture elongation of the cured product. Examples of the rubber include (meth) acrylic acid ester-butadiene copolymer, (meth) acrylic acid ester-butadiene-styrene copolymer, polybutadiene rubber, chloroprene rubber, and acrylonitrile butadiene rubber.

An antioxidant may be added to the resin composition of the present invention in order to prevent oxidative degradation of the cured product. Examples of the antioxidant include the following.
Phenolic antioxidants: n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3 ′, 5′-di- t-butyl-4′-hydroxyphenyl) propionate] methane, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like.
Phosphorous antioxidants: triphenyl phosphite, trisisodecyl phosphite, tristridecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, etc.
Sulfur-based antioxidants: dihexyl sulfide, dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3 , 3′-thiodipropionate, pentaerythritol tetrakis (β-lauryl thiopropionate).

An ultraviolet absorber may be added to the resin composition of the present invention in order to suppress photodegradation of the cured product. As an ultraviolet absorber, the following are mentioned, for example.
Derivatives of 2-hydroxybenzophenone: 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy -4,4'-dibutoxybenzophenone and the like.
-2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) benzotriazole, or a halide thereof.
-Phenyl salicylate, p-tertiary butyl phenyl salicylate, etc.

A thixotropic agent may be added to the resin composition of the present invention in order to suppress sedimentation when an aggregate described later is added to the resin composition. Examples of the thixotropic agent include the following.
Organic thixotropic agent: urethane urea type thixotropic agent, fatty acid amide, organic bentonite, oxidized polyethylene wax, organically modified sepiolite, etc.
Inorganic thixotropic agent: fine particle silica and the like.

An antifoaming agent may be added to the resin composition of the present invention in order to remove bubbles in the resin composition. Examples of the antifoaming agent include an acrylic antifoaming agent obtained by dissolving a special acrylic polymer in a solvent, and a vinyl antifoaming agent obtained by dissolving a special vinyl polymer in a solvent.
Specific examples of the product name of the antifoaming agent include the following.
-Disparon series manufactured by Enomoto Kasei Co., Ltd .: OX-880EF, OX-881, OX-883, OX-77EF, OX-710, OX-8040, 1922, 1927, 1950, P-410EF, P-420, P-425, PD-7, 1970, 230, 230HF, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985 and the like.
-BYK-052, BYK-1752, etc. manufactured by Big Chemie Japan Co., Ltd.

  A polymerization inhibitor may be added to the resin composition of the present invention in order to improve the storage stability of the resin composition. Examples of the polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-t-butyl-4-methylphenol.

  A silane coupling agent may be added to the resin composition of the present invention in order to improve the adhesion between the resin composition and the aggregate described later. Examples of the silane coupling agent include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (glycidoxypropyl) trimethoxysilane, and 3-mercaptopropyltri Examples include methoxysilane and 3-aminopropyltriethoxysilane.

A thermal polymerization initiator may be added to the resin composition of the present invention in order to improve the curability of the resin composition. Examples of the thermal polymerization initiator include peroxides and azo compounds.
As a peroxide, the following are mentioned, for example.
Ketone peroxide: methyl ethyl ketone peroxide and the like.
Peroxyketal: 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butyl Peroxy) cyclohexane and the like.
Dialkyl peroxide: dicumyl peroxide, di-t-butyl peroxide, etc.
-Diacyl peroxide: Dilauroyl peroxide and the like.
Peroxydicarbonate: di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, and the like.
Peroxyester: t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2- Ethyl hexanoate etc.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis- (2- Amidinopropane) dihydrochloride.

In order to improve the curability of the resin composition, a photopolymerization initiator may be added to the resin composition of the present invention. As a photoinitiator, the following are mentioned, for example.
Benzophenone type compounds: benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, etc.
Anthraquinone type compounds: t-butylanthraquinone, 2-ethylanthraquinone, etc.
Alkylphenone type compounds: 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, benzyl Dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one and the like.
Thioxanthone type compounds: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diethylthioxanthone, isopropylthioxanthone and the like.
Acylphosphine oxide type compounds: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide and the like.
Phenyl glyoxylate type compounds: phenyl glyoxylic acid methyl ester and the like.

(Content of each component)
The content of the monomer (A) is preferably from 30 to 90% by mass, preferably from 35 to 85% by mass, in the total of 100% by mass of the content of the monomer (A) and the content of the polymer (B). Is more preferable, and 55-80 mass% is further more preferable. As the monomer (A) content increases, the viscosity of the resin composition decreases, and as the monomer (A) content decreases, the viscosity of the resin composition tends to increase.

  When the polyfunctional (meth) acrylate is included as the monomer (A), the content of the polyfunctional (meth) acrylate is 100 in total of the content of the monomer (A) and the content of the polymer (B). In mass%, 1-20 mass% is preferable and 1.5-15 mass% is more preferable. The higher the content of the polyfunctional (meth) acrylate, the higher the tensile strength when cutting the cured product of the resin composition, and the lower the content of the polyfunctional (meth) acrylate, the longer the elongation when cutting the cured product of the resin composition. Can be suppressed.

  When the polymer (B1) is included as the polymer (B), the content of the polymer (B1) is 100% by mass in total of the content of the monomer (A) and the content of the polymer (B). 10-50 mass% is preferable, and 15-40 mass% is more preferable. There exists a tendency for the tensile strength at the time of cutting | disconnection of the hardened | cured material of a resin composition to improve, so that there is much content of a polymer (B1), and the viscosity of a resin composition becomes low, so that there is little content of a polymer (B1).

  When the polymer (B) includes the urethane (meth) acrylate oligomer of the polymer (B2), the content of the urethane (meth) acrylate oligomer is the content of the monomer (A) and the content of the polymer (B). 10-70 mass% is preferable in total 100 mass% with quantity, and 15-65 mass% is more preferable. As the content of the urethane (meth) acrylate oligomer is larger, the elongation at break of the cured product of the resin composition is improved, and as the content of the urethane (meth) acrylate oligomer is smaller, the viscosity of the resin composition tends to be lower.

  When the polymer (B) contains the polyester (meth) acrylate oligomer of the polymer (B2), the content of the polyester (meth) acrylate oligomer is the content of the monomer (A) and the content of the polymer (B). 10-70 mass% is preferable in total 100 mass% with quantity, and 15-65 mass% is more preferable. As the content of the polyester (meth) acrylate oligomer is larger, the elongation at break of the cured product of the resin composition is improved, and as the content of the polyester (meth) acrylate oligomer is smaller, the viscosity of the resin composition tends to be lower.

  When the polymer (B) contains the epoxy (meth) acrylate oligomer of the polymer (B2), the content of the epoxy (meth) acrylate oligomer is the content of the monomer (A) and the content of the polymer (B). 10-70 mass% is preferable in total 100 mass% with quantity, and 15-65 mass% is more preferable. As the content of the epoxy (meth) acrylate oligomer increases, the elongation at the time of cutting of the cured product of the resin composition improves, and as the content of the epoxy (meth) acrylate oligomer decreases, the viscosity of the resin composition tends to decrease.

  When using 2 or more types of polymers (B) together, the total content of the polymer (B) is 100% by mass of the content of the monomer (A) and the content of the polymer (B). Among them, 10 to 70% by mass is preferable, and 15 to 65% by mass is more preferable. There exists a tendency for the elongation at the time of cutting | disconnection of the hardened | cured material of a resin composition to improve, so that there is much content of a polymer (B), and the viscosity of a resin composition becomes low, so that there is little content of a polymer (B).

  The content of the compound (C) is preferably 5 to 30 parts by mass with respect to 100 parts by mass in total of the content of the monomer (A) and the content of the polymer (B), and 10 to 25 parts by mass. Is more preferable. The elongation at the time of cutting of the cured product of the resin composition is improved as the content of the compound (C) is increased, and the decrease in the tensile strength at cutting is suppressed as the content of the compound (C) is decreased.

  When other plasticizers are used in combination, the content of the compound (C) is 5 to 25 masses with respect to a total of 100 mass parts of the content of the monomer (A) and the content of the polymer (B). Part is preferable, and 10 to 20 parts by mass is more preferable. The elongation at the time of cutting of the cured product of the resin composition is improved as the content of the compound (C) is increased, and the decrease in the tensile strength at cutting is suppressed as the content of the compound (C) is decreased.

  When the reducing agent (D1) is included, the content of the reducing agent (D1) is 0.1% with respect to 100 parts by mass in total of the content of the monomer (A) and the content of the polymer (B). -10 mass parts is preferable, 0.2-5 mass parts is more preferable, 0.3-3 mass parts is further more preferable. Since the curability becomes better as the content of the reducing agent (D1) is larger, the tensile strength at break and the elongation at break of the cured product of the resin composition are improved. The smaller the content of the reducing agent (D1), the longer the gelation time, and it becomes easier to perform operations such as stirring and pouring of the resin composition.

  When the curing agent (D2) is included, the content of the curing agent (D2) is 0.1 with respect to a total of 100 parts by mass of the content of the monomer (A) and the content of the polymer (B). -10 mass parts is preferable, 0.2-5 mass parts is more preferable, 0.3-3 mass parts is further more preferable. The higher the content of the curing agent (D2), the better the curability, so that the tensile strength at break and the elongation at break of the cured product of the resin composition are improved. The smaller the content of the curing agent (D2), the longer the gelation time and the easier the operations such as stirring and pouring of the resin composition.

In the resin composition of the present invention, the test piece obtained from the resin composition by the following production method preferably satisfies the following condition (a).
(Test piece preparation method)
In an atmosphere of a temperature of 23 ° C. and a humidity of 50%, 2 parts of benzoyl peroxide (purity 50%) is added to 100 parts by mass of the resin composition containing no curing agent to prepare a resin composition containing a curing agent. A resin composition containing a curing agent is poured into a mold and cured in an atmosphere at a temperature of 23 ° C. for 2 hours to obtain a cured product having a thickness of 3 mm. A dumbbell-shaped No. 1 specimen according to JIS K 6251: 2010 is collected from the cured product using a punching tool.
(Condition (a))
Regarding the test piece, the tensile strength at break at 0 ° C. and the tensile strength at break at 23 ° C. measured at a tensile speed of 200 mm / min in accordance with JIS K 6251: 2010 satisfy the following formula (1).
0.6 ≦ (K0−K23) /K23≦1.5 (1)
However, K0 is the tensile strength at break (N / mm ² ) at 0 ° C., and K23 is the tensile strength at break (N / mm ² ) at 23 ° C.

According to the resin composition satisfying the condition (a), a cured product is obtained in which the difference between the tensile strength at break at 23 ° C. and the tensile strength at break at 0 ° C. is small, and the temperature dependence of the tensile strength at break is small. be able to.
(K0-K23) / K23 is more preferably 0.7 or more, and further preferably 0.8 or more. (K0-K23) / K23 is more preferably 1.4 or less, and further preferably 1.35 or less.

As for the resin composition of this invention, it is preferable that the test piece obtained from the resin composition with the said preparation method satisfies the following conditions (b).
(Condition (b))
For the test piece, the tensile strength at break at 0 ° C., the tensile strength at break at 23 ° C., and the elongation at break at 23 ° C. measured at a tensile speed of 200 mm / min in accordance with JIS K 6251: 2010 are expressed by the following formula ( Satisfy 2).
180 ≦ (K0−K23) × S23 / K23 ≦ 270 (2)
However, K0 is the tensile strength at the time of cutting at 0 ° C. (N / mm ² ), K23 is the tensile strength at the time of cutting at 23 ° C. (N / mm ² ), and S23 is at the time of cutting at 23 ° C. Elongation (%).

According to the resin composition satisfying the condition (b), the difference between the tensile strength at break at 23 ° C. and the tensile strength at break at 0 ° C. is small, the temperature dependence of the tensile strength at break is small, and 0 ° C. A cured product having a good elongation at break can be obtained.
(K0-K23) × S23 / K23 is more preferably 185 or more, and further preferably 195 or more. (K0-K23) × S23 / K23 is more preferably 250 or less, and further preferably 245 or less.

(Preparation of resin composition)
As a method for preparing the resin composition of the present invention, a monomer (A), a polymer (B), a compound (C), a reducing agent (D1), and other components as necessary are mixed with a curing agent. A method of preparing a resin composition containing a curing agent by preparing an unblended resin composition and blending a curing agent (D2) with a resin composition not blended with a curing agent immediately before performing a curing reaction is preferable.
In preparing the resin composition, other components may be mixed as necessary.

  Examples of the method of mixing the components include a method of stirring and mixing at room temperature, and a method of stirring and mixing while heating. The temperature at the time of heating is preferably 40 to 100 ° C. from the viewpoint of good compatibility and more uniform mixing. The stirring time for mixing is preferably 0.1 to 5 hours.

(Use of resin composition)
Applications of the resin composition of the present invention include, for example, paints, casting materials, binder materials, adhesives, repair materials, and joint materials.

Examples of the paint include the following.
Road paint: Non-slip paint, drainage paint, thermal barrier paint, road marking paint, floor slab waterproofing paint, etc.
Civil and architectural paints: Wall paints, floor paints, roof paints, bridge paints, plant paints, iron structure paints, concrete paints, etc.
・ Furniture paints, decorative paints, electronic equipment paints, mobile equipment paints, home appliance paints, waterproof paints, automotive paints, motorcycle paints, heavy machinery paints, railway vehicle paints, marine paints, etc.

  Examples of the molded product obtained when used as a casting material include films, sheets, lenses, optical waveguides, and sealing materials. Molded articles are, for example, light emitting diode modules, mobile phones, smartphones, tablet terminals, personal computers, cameras, organic electroluminescence (organic EL) devices, flat panel displays, touch panels, electronic paper, photodiodes, phototransistors, solar cells, Used for projectors and the like. The molded product can also be used as an optical member.

Examples of the binder material include binders such as artificial marble, fiber reinforced plastic, and Braille tile.
Examples of the adhesive include glass adhesives, resin adhesives, metal adhesives, and second-generation acrylic adhesives (SGA).
Examples of the repair material include a concrete repair material and a road repair material.
Examples of joint materials include tile joint materials, stone joint materials, concrete joint materials, and asphalt joint materials.

(Resin composition for civil engineering or resin composition for construction)
Among these uses, the use of the resin composition of the present invention is preferably a civil engineering resin composition or a building resin composition (road paint, civil engineering paint, repair material, joint material, etc.).
The resin composition for civil engineering or the resin composition for construction preferably further contains an aggregate as another component for the purpose of suppressing curing shrinkage during molding, improving strength, and improving durability such as wear resistance. .

  As the aggregate, for example, sand, dredged sand, river sand, emery stone, emery, marble, calcium carbonate, kaolin, bentonite, mica, talc, silicon carbide powder, silicon nitride powder, boron nitride powder, alumina, slag, glass powder, Examples include ceramic aggregates, ceramic scraps, and colored aggregates. These aggregates may be used alone or in combination of two or more.

  Although the particle size of the aggregate depends on the thickness of the cured product of the resin composition, the particle size by sieving is preferably 5 mm or less, more preferably 3 mm or less, and even more preferably 2 mm or less. When the aggregate particle size is 5 mm or less, the flexibility of the cured product is easily obtained. The particle size distribution of the aggregate is not particularly defined because it is caused by the viscosity of the curable resin composition, the shape of the aggregate, the thickness of the cured product to be molded, and the like, and may be adjusted as appropriate.

  The aggregate content is preferably 50 to 400 parts by mass and more preferably 75 to 350 parts by mass with respect to 100 parts by mass in total of the content of the monomer (A) and the content of the polymer (B). Preferably, 100-300 mass parts is further more preferable. As the aggregate content increases, the strength and wear resistance of the cured product can be improved. The smaller the aggregate content, the harder the cracking of the cured product.

The resin composition for civil engineering or the resin composition for construction may contain a pigment as another component for coloring. Examples of the pigment include organic pigments (azo pigments, phthalocyanine pigments, etc.) and inorganic pigments (ceramic pigments, iron oxide, titanium oxide, etc.). A pigment may be used individually by 1 type and may use 2 or more types together.
The content of the pigment is preferably 0 to 40 parts by mass, and 0.5 to 35 parts by mass with respect to 100 parts by mass in total of the content of the monomer (A) and the content of the polymer (B). More preferably, 1-30 mass parts is further more preferable.

<Hardened product>
The cured product of the present invention is obtained by curing the resin composition of the present invention.
As a method for producing the cured product of the present invention, the monomer (A), the polymer (B), the compound (C), the reducing agent (D1), and other components as necessary are mixed and the curing agent is not used. Prepare a compounded resin composition and immediately before the curing reaction, the curing agent (D2) is blended with a resin composition not containing the curing agent to prepare a resin composition containing a curing agent and start the curing reaction and cure. A method for obtaining a product is preferred.
When using the resin composition of this invention as a casting material, the hardened | cured material (molded article) which has an unevenness | corrugation and a specific shape is obtained by methods, such as pouring the resin composition containing a hardening | curing agent in a type | mold.

The curing temperature after blending the curing agent (D2) is preferably -10 to 65 ° C, more preferably 10 to 60 ° C, and further preferably 15 to 55 ° C. By setting the curing temperature to −10 to 65 ° C., the curing reaction of the resin composition containing a curing agent proceeds sufficiently, and the properties of the cured product are improved. The curing time varies depending on the curing temperature, but is preferably 10 minutes to 24 hours.
In order to suppress bubbles in the cured product, vacuum defoaming, vibration defoaming, or the like may be performed on the resin composition containing the curing agent after additionally blending the curing agent (D2).

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these examples. In each example and comparative example, “part” means “part by mass”.

(viscosity)
The liquid temperature of the resin composition was 23 ° C., and the viscosity was measured using a B-type viscometer at 60 rpm.

(Tensile test)
Add 2 parts of benzoyl peroxide (manufactured by Kayaku Akzo, Parkardox CH-50L, purity 50%) to 100 parts of a resin composition containing no curing agent in an environment variable room with an indoor temperature of 23 ° C. and a humidity of 50%. , Stirred and mixed to obtain a resin composition containing a curing agent. This was poured into a mold and cured in an atmosphere at a temperature of 23 ° C. for 2 hours, and then the cured product was taken out to obtain a cast plate having a thickness of 3 mm. A dumbbell-shaped No. 1 test piece conforming to JIS K 6251: 2010 was collected from the casting plate using a punching tool.

  The test piece was subjected to a tensile test at 23 ° C., 0 ° C., and 40 ° C. in accordance with JIS K 6251: 2010, and the tensile strength at break and the elongation at break were measured. The tensile strength at the time of cutting is one of the indicators of the mechanical strength of the cured product.

(Synthesis Example 1)
In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 135 parts of deionized water and 0.4 part of polyvinyl alcohol (degree of saponification 80 mol%, degree of polymerization 1,700) as a dispersant were added and stirred. Then, after the polyvinyl alcohol was completely dissolved, the stirring was once stopped. 92.5 parts of methyl methacrylate, 7.5 parts of n-butyl acrylate, 0.2 part of 2,2′-azobis-2-methylbutyronitrile as a polymerization initiator, and 0.8 part of n-dodecyl mercaptan as a chain transfer agent Then, 0.1 parts of sodium carbonate as an electrolyte was added and stirred again, and the temperature was raised to 75 ° C. and reacted for 2.5 hours. Further, the temperature was raised to 98 ° C. and maintained for 1.5 hours, and then the reaction was terminated.
After cooling to 40 ° C., the obtained aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water and dehydrated. It dried at 40 degreeC for 16 hours, and obtained the granular acrylic polymer (polymer P-1). Polymer T-1 had a Tg of 100 ° C. and a weight average molecular weight of 73,000.

(Synthesis Example 2)
92.5 parts of methyl methacrylate and 7.5 parts of n-butyl acrylate were changed to 40 parts of methyl methacrylate and 40 parts of n-butyl methacrylate, and the amount of n-dodecyl mercaptan used was changed from 0.8 parts to 0.5 parts. Except having changed, it carried out similarly to the synthesis example 1, and obtained the granular acrylic polymer (polymer P-2). Polymer T-2 had a Tg of 65 ° C. and a weight average molecular weight of 160,000.

(Abbreviation)
MMA: methyl methacrylate,
2-EHA: 2-ethylhexyl acrylate,
PDE-150: Triethylene glycol dimethacrylate (manufactured by NOF Corporation),
RUA-012: Urethane acrylate oligomer (Asia Kogyo Co., Ltd.),
EBECRYL810: Polyester acrylate oligomer (manufactured by Daicel Ornex Co., Ltd.)
DINCH: 1,2-cyclohexanedicarboxylic acid diisononyl ester (manufactured by BASF Japan Ltd.),
P-115, P-130, P-150: Paraffin wax (manufactured by Nippon Seiwa Co., Ltd.),
PTEO: N, N-di (2-hydroxyethyl) -p-toluidine,
Toyoparax A50: Chlorinated paraffin (manufactured by Tosoh Corporation),
Vinicizer 85: Phthalate ester plasticizer (manufactured by Kao Corporation),
Adeka Sizer P300: Adipic acid polyester plasticizer (manufactured by ADEKA),
JF-77: UV absorber (manufactured by Johoku Chemical Industry Co., Ltd.)
HQ: Hydroquinone.

(Examples 1-8, Comparative Examples 1-3)
Into a 1 L flask equipped with a stirrer, a thermometer, and a cooling tube, each component other than the polymer P-1 or the polymer P-2 was added at the blending amount shown in Table 1 or Table 2, and then stirred, Polymer P-1 or polymer P-2 was added in the amount shown in 1 or Table 2, and dissolved by heating at 75 ° C. for 2 hours. After confirming the dissolution of the polymer P-1 or the polymer P-2, it was cooled to obtain resin compositions (S-1 to S-11) containing no curing agent.
Tables 1 and 2 show the viscosities of the resin compositions not containing the curing agent. Table 1 or Table 2 shows the results of the tensile test of the cured product.

In Examples 1 to 8, the viscosity of the resin composition is within an appropriate range, and the tensile strength at break and the elongation at break of the cured product in the tensile test conducted at 23 ° C. and 0 ° C. are the conditions (a), Satisfying (b), the balance between tensile strength at break and elongation at break was good at room temperature and low temperature.
The resin compositions of Comparative Examples 1 to 3 do not contain the compound (C) blended in Example 1, but instead blend the same amount of another plasticizer. The cured product of Comparative Example 1 had a low elongation at break at 23 ° C., and as a result, did not satisfy the conditions (a) and (b). The cured product of Comparative Example 2 had a low value of tensile strength at break at 23 ° C., and as a result, did not satisfy the condition (b). The cured product of Comparative Example 3 had a low elongation at break at 23 ° C., and as a result, did not satisfy the conditions (a) and (b).

  The resin composition of the present invention is useful as a civil engineering resin composition or an architectural resin composition (road paint, civil engineering paint, repair material, joint material, etc.) and the like.

Claims (6)

A monomer (A) having a (meth) acryloyl group;
At least one polymer (B) selected from the group consisting of an acrylic polymer and a polymer having a (meth) acryloyl group;
A resin composition comprising: a compound (C) represented by the following formula (I):

However, R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms.   The content of the compound (C) is 5 to 30 parts by mass with respect to a total of 100 parts by mass of the content of the monomer (A) and the content of the polymer (B). The resin composition as described. The resin composition according to claim 1 or 2, wherein a test piece obtained from the resin composition by the following production method satisfies the following condition (a).
(Test piece preparation method)
In an atmosphere of a temperature of 23 ° C. and a humidity of 50%, 2 parts of benzoyl peroxide (purity 50%) is added to 100 parts by mass of the resin composition containing no curing agent to prepare a resin composition containing a curing agent. A resin composition containing a curing agent is poured into a mold and cured in an atmosphere at a temperature of 23 ° C. for 2 hours to obtain a cured product having a thickness of 3 mm. A dumbbell-shaped No. 1 specimen according to JIS K 6251: 2010 is collected from the cured product using a punching tool.
(Condition (a))
Regarding the test piece, the tensile strength at break at 0 ° C. and the tensile strength at break at 23 ° C. measured at a tensile speed of 200 mm / min in accordance with JIS K 6251: 2010 satisfy the following formula (1).
0.6 ≦ (K0−K23) /K23≦1.5 (1)
However, K0 is the tensile strength at break (N / mm ² ) at 0 ° C., and K23 is the tensile strength at break (N / mm ² ) at 23 ° C. The resin composition according to any one of claims 1 to 3, wherein a test piece obtained from the resin composition by the following production method satisfies the following condition (b).
(Test piece preparation method)
In an atmosphere of a temperature of 23 ° C. and a humidity of 50%, 2 parts of benzoyl peroxide (purity 50%) is added to 100 parts by mass of the resin composition containing no curing agent to prepare a resin composition containing a curing agent. A resin composition containing a curing agent is poured into a mold and cured in an atmosphere at a temperature of 23 ° C. for 2 hours to obtain a cured product having a thickness of 3 mm. A dumbbell-shaped No. 1 specimen according to JIS K 6251: 2010 is collected from the cured product using a punching tool.
(Condition (b))
For the test piece, the tensile strength at break at 0 ° C., the tensile strength at break at 23 ° C., and the elongation at break at 23 ° C. measured at a tensile speed of 200 mm / min in accordance with JIS K 6251: 2010 are expressed by the following formula ( Satisfy 2).
180 ≦ (K0−K23) × S23 / K23 ≦ 270 (2)
However, K0 is the tensile strength at the time of cutting at 0 ° C. (N / mm ² ), K23 is the tensile strength at the time of cutting at 23 ° C. (N / mm ² ), and S23 is at the time of cutting at 23 ° C. Elongation (%).   The resin composition according to any one of claims 1 to 4, which is a civil engineering resin composition or an architectural resin composition.   Hardened | cured material formed by hardening the resin composition as described in any one of Claims 1-5.