JP2000129068A - Emulsion composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an emulsion composition being excellent in polymerization stability and mechanical stability and not emitting a pungent odor by incorporating a homopolymer of an epoxy-containing acrylic acid derivative or a copolymer of this monomer with a copolymerizable monomer. SOLUTION: This composition contains 0.1-50.0 pts.wt. homopolymer of an epoxy-containing acrylic acid derivative represented by the formula and 50.0-99.9 pts.wt. copolymer of this derivative with a copolymerizable vinyl monomer such as acrylic acid. The epoxy-containing acrylic acid derivative is obtained by combining an epoxy-containing alicyclic compound such as vinylcyclohexene monoepoxide with a copolymerizable monomer such as acrylic acid through a ring opening addition reaction and epoxidizing the double bond of the vinyl group bonded to the alicyclic skeleton of the cyclohexyl group. In the formula, any one of R14 to R17 is 1-epoxyethyl or the like; R1 to R3, R8 to R10, and R14 to R17 are each hydrogen, phenyl, or the like; R11 is hydrogen, methyl, or the like; X is methylene or the like; and n is 1-10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion composition and a method for producing the same, and more particularly, to a method for crosslinking an epoxy group-containing acrylic acid derivative homopolymer or copolymer with an epoxy group as a crosslinking component. The present invention relates to an emulsion composition which is useful for an emulsion type paint, an adhesive, a sealing agent, an ink binder, a fiber treating agent, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art As an emulsion composition used for paints, adhesives, sealing agents, fiber treatment agents, etc., it contains an epoxy group of a polymer or copolymer such as glycidyl methacrylate or N-methylolacrylamide as a crosslinking component. Emulsion compositions have been put to practical use. However, in an emulsion composition containing a glycidyl methacrylate constituent unit as a crosslinking component, the reactivity of glycidyl methacrylate during emulsion polymerization is high, and the polymerization stability of the obtained emulsion composition may be poor. On the other hand, in an emulsion composition containing an N-methylolacrylamide structural unit as a cross-linking component, formaldehyde is released from the N-methylolacrylamide structural unit during the curing reaction after the application of the emulsion. May be irritating. From this situation,
It is desired to develop an emulsion composition which has excellent polymerization stability and does not generate irritants such as formalin when used, and which is highly safe in a working environment.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an emulsion composition which is excellent in polymerization stability and mechanical stability and which does not generate irritants such as formalin when used and which has high environmental safety. It is in.

[0004]

Means for Solving the Problems The present inventors have found that when a specific epoxy group-containing acrylic acid derivative having an alicyclic structure and an epoxy group is used, an emulsion composition containing a large amount of a crosslinkable component can be produced. In addition, the present inventors have found that the polymerization stability of the emulsion composition during emulsion polymerization is good, no irritants such as formalin are generated in the use environment, and the environmental safety is high. Thus, the present invention has been completed.

That is, the present invention provides an emulsion composition containing a homopolymer of an epoxy group-containing acrylic acid derivative represented by the following formula (1) or a copolymer of a monomer copolymerizable with the derivative. provide. Further, the present invention provides an emulsion composition wherein the monomer copolymerizable with the derivative is a vinyl monomer in the above invention and 0.1 to 50.0 parts by weight of an epoxy group-containing acrylic acid derivative and the derivative. Copolymerizable vinyl monomer 50.0-9
An emulsion composition comprising 9.9 parts by weight of the copolymer is provided. The present invention further provides the emulsion characterized in that an epoxy group-containing acrylic acid derivative alone or an epoxy group-containing acrylic acid derivative and a monomer copolymerizable with the derivative are emulsion-polymerized in an aqueous medium. A method of making the composition is provided.

[0006]

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[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The emulsion composition of the present invention is an emulsion composition containing a polymer obtained by polymerizing or copolymerizing the epoxy group-containing acrylic acid derivative represented by the formula (1). Use of this epoxy group-containing acrylic acid derivative can provide an emulsion composition having good polymerization stability even when producing an emulsion composition having a high content of a crosslinking component.

The epoxy group-containing acrylic acid derivative of the present invention has, for example, the following formula (2):
An epoxy group-containing alicyclic compound represented by -vinylbicyclo [2.2.1] heptomonoepoxide), (2-2; vinylcyclohexene monoepoxide), (2-3; limonene monoepoxide)} and acrylic acid , Methacrylic acid, α-ethylacrylic acid or the like (hereinafter referred to as acrylic acid or the like) with a copolymerizable monomer by a ring-opening addition reaction of an epoxy group, and then a cyclohexyl group or It can be produced by epoxidizing a double bond of a vinyl group or a 1-methylvinyl group bonded to an alicyclic skeleton such as a bicyclohexyl group.

[0009]

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The method of the addition reaction between the epoxy group-containing alicyclic compound and acrylic acid is carried out in the presence or absence of a solvent at a reaction temperature of 60 to 140 ° C., particularly 70 to 120 ° C.
The reaction is preferably carried out. The solvent used in the reaction is not particularly limited, but hexane, cyclohexane, toluene, benzene, ethyl acetate, carbon tetrachloride, chloroform and the like can be used, and glycol ethers and glycol acetates can also be used. The charging ratio of the epoxy group-containing alicyclic compound to acrylic acid or the like is preferably equimolar to or greater than the epoxy group of the alicyclic compound. Usually, it is about 1.0 to 1.5 times mol.

At the time of the reaction, a catalyst can be used.
For example, phosphorus compounds such as triphenylphosphine, quaternary amine compounds such as diazabicycloundecene and tetraethylammonium, 2-methyl-imidazole and 2-
Imidazole compounds such as methyl-4-ethyl-imidazole can be used. Further, boric acid esters, Lewis acids, organic metal compounds, metal salts of organic acids and the like can also be used. The use amount of these catalysts is preferably 0.03 to 5% by weight, particularly preferably 0.05 to 3% by weight, based on the total weight of the epoxy group-containing alicyclic compound and acrylic acid.

In the reaction, commonly used polymerization inhibitors such as methoquinone (p-methoxyphenol), hydroquinone, and phenothiazine can be used to prevent polymerization of acryloyl groups and the like. The amount of the polymerization inhibitor used is 0.03 to 5% by weight, particularly 0.05%, based on the total weight of acrylic acid or the like and the epoxy group-containing alicyclic compound.
It is preferably about 3% by weight.

Next, a double bond of a vinyl group or a 1-methylvinyl group bonded to the cyclo ring of the obtained compound is epoxidized with an epoxidizing agent. As the epoxidizing agent, peracids and hydroperoxides can be used. Examples of the peracids include organic acids such as formic acid, peracetic acid, perbenzoic acid, and trifluoroperacetic acid, and examples of the hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, and cumene hydroperoxide. Etc. can be exemplified. Among them, it is particularly preferable to use peracetic acid. This is because peracetic acid is industrially available at low cost and has high stability. The amount of the epoxidizing agent can be appropriately selected depending on the particular epoxidizing agent used, the desired degree of epoxidation, the particular epoxidized compound used, and the like.

It is preferable that the molar ratio of the epoxidizing agent to be added is equal to or greater than 1 mol per 1 mol of the vinyl group or 1-methylvinyl group bonded to the cyclo ring. However, it is usually disadvantageous to exceed 2 moles from the viewpoints of economy and the side reaction described below. When peracetic acid is used as the epoxidizing agent, it is preferable to use 1 to 1.5 moles. .

In the epoxidation reaction, an inert solvent can be used. As the inert solvent, the viscosity of the raw material decreases,
It can be used for the purpose of stabilization by dilution of the epoxidizing agent, etc., such as aliphatic compounds such as hexane and cyclohexane, aromatic compounds such as toluene and benzene, esters such as ethyl acetate, carbon tetrachloride, and chloroform. Halogenated hydrocarbon compounds can be exemplified. In particular, when peracetic acid is used as the epoxidizing agent, it is preferable to use esters such as ethyl acetate.

[0016] The temperature of the epoxidation reaction is preferably from 0 to 70 ° C when peracetic acid is used as the epoxidizing agent. If the temperature is 0 ° C. or lower, the reaction is slow, and if it is 70 ° C., decomposition of peracetic acid may occur. In addition, when a tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate-based compound, which is one example of hydroperoxide, is used, the temperature is increased to 20 ° C. for the same reason.
150 ° C. is preferred. No special operation is required during the reaction. For example, the mixture may be stirred for 2 to 8 hours. Thereby, an epoxy group-containing acrylic acid derivative can be produced.

The acrylic acid derivative containing an epoxy group is prepared by, for example, a method of precipitating a poor solvent from the reaction solution, a method of putting an epoxidized product into hot water with stirring and distilling off the solvent, and a direct desolvation method. Can be isolated.

The epoxy group-containing acrylic acid derivative obtained in this manner can be prepared by the following procedure: the charge ratio of acrylic acid and epoxy group-containing alicyclic compound in the acryloylation reaction; It can be obtained as a mixture of derivatives having a plurality of alicyclic structures depending on the epoxidation reaction conditions such as the charging ratio and the reaction temperature. Further, by changing the reaction conditions, a mixing ratio of a different number of derivatives having an alicyclic structure, that is, a monomer having one alicyclic structure, a dimer having two, a trimer having three, Products having different ratios of the above polymers can be obtained.

In the present invention, an epoxy group-containing acrylic acid derivative obtained by epoxidizing an adduct of acrylic acid, methacrylic acid or ethacrylic acid and vinylcyclohexene monoepoxide, that is, a chemical structural formula (3)
-1) or epoxidized adducts of acrylic acid, methacrylic acid or ethacrylic acid and limonene monoepoxide, that is, those of the chemical structural formula (3-2) are generally easily available industrial materials. Is preferred.

[0020]

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The emulsion composition of the present invention has the formula (1)
Is produced by copolymerizing an epoxy group-containing acrylic acid derivative represented by the following formula with another monomer capable of homopolymerization or copolymerization. In the emulsion composition of the present invention, in the case of homopolymerization in which only an epoxy group-containing acrylic acid derivative is radically polymerized, a very hard and transparent film having a large number of cyclic aliphatic structures and a coating agent are produced. The resulting emulsion composition is obtained.

Examples of monomers copolymerizable with the epoxy group-containing acrylic acid derivative represented by the formula (1) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, and acrylic acid esters. And unsaturated carboxylic acid esters such as methacrylic acid esters, and vinyl monomers such as vinyl ethers and styrene derivatives. These vinyl monomers are preferably used. These monomers may be used as a mixture of two or more kinds.

The emulsion composition is prepared by emulsion polymerization of a homopolymer of an epoxy group-containing acrylic acid derivative represented by the formula (1) or a monomer copolymerizable with the derivative. Emulsion polymerization is carried out by charging water and an emulsifier in a reactor in advance, and stirring and copolymerizing with an epoxy group-containing acrylic acid derivative homopolymer or a derivative represented by the formula (1), which is a polymerizable monomer. A pre-emulsified mixture of both possible monomers with an emulsifier and water is added dropwise. Pre-emulsification is based on 2 times the total amount of polymerizable monomers.
Good pre-emulsions are obtained with up to 8% by weight of emulsifier. The amount of the polymerizable monomer added is preferably such that the final solid concentration is 75% by weight or less, particularly 70 to 10% by weight. If the solid content exceeds 75%, coarse particles are easily formed during the polymerization, and stable polymerization is hardly performed.

In the polymerization, a polymerization initiator is used. For example, sodium persulfate, persulfates such as ammonium persulfate,
Known polymerization initiators such as peroxides such as hydrogen peroxide, organic peroxides such as cumene hydroperoxide, and redox polymerization initiators obtained by combining these peroxides with a reducing agent are usually used. Can be used. The polymerization initiator may be dropped in parallel with the dropping of the polymerizable monomer, or may be mixed in the pre-emulsion.

The polymerization temperature can be appropriately selected depending on the polymerization initiator used, but is generally 100 ° C. or lower, particularly 50 to 100 ° C.
Preferably, the temperature is in the range of 90 ° C. If the temperature exceeds 100 ° C., the water boils, so that coarse particles are easily formed.
If the temperature is lower than 0 ° C., the polymerization reaction is slowed and the polymerization requires a long time. As the emulsifier, various nonionic surfactants that can be generally added to the emulsion composition can be used alone or in combination with an anionic surfactant. Also,
The amount used may be in the range used for producing a general emulsion composition. The reaction time is 2 to 5 hours at the same temperature as the polymerization temperature after the addition of a small amount of the polymerization initiator after the completion of the dropping of the pre-emulsion and the polymerization initiator. This is because the polymerization reaction proceeds sufficiently within this range.

The emulsion composition of the present invention can be prepared by emulsion polymerization in an aqueous medium as described above, or by polymerizing a polymerizable monomer in a solvent and dispersing the obtained polymer in an aqueous medium. Can be manufactured. For example, a solvent such as acetone, methyl ethyl ketone, toluene, xylene, butanol, or 2- (1-methoxypropyl) acetate is charged into a reactor and heated to 40 to 90 ° C. While stirring the solvent, the polymerizable monomer and the polymerization initiator are added dropwise thereto. The polymerization is preferably terminated when the residual monomer concentration becomes less than 1%. Next, the emulsifier aqueous solution adjusted to a temperature of 50 to 90 ° C. is added to the polymer solution while stirring. Addition of the aqueous emulsifier solution to the polymer solution
From the viewpoint of the stability of the emulsion composition, the dropping method is preferable. As for the type and amount of the polymerization initiator and the emulsifier, the same ones as in the emulsion polymerization can be used. The solvent may be removed under reduced pressure to reduce the content of the solvent.

The emulsion composition of the present invention can be directly used as an emulsion type paint, adhesive, sealing agent, ink binder, fiber treating agent, etc. by blending pigments, antioxidants, stabilizers, fillers and the like. .

[0028]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. "Parts" and "%" in the examples are "parts by weight" and "% by weight", respectively.
Represents In addition, NMR is “GXS270W” manufactured by JEOL Ltd.
B ", IR is JASCOFT / IR-5300, G is
PC was manufactured by Shimadzu Corporation “HPLC LC-6A SYS”
TEM "(column: polystyrene column, solvent: TH
F) was used. The evaluation was performed as follows. (1) Polymerization stability: The polymerization stability was indicated by the amount of grit at the end of polymerization (the weight of a 200-mesh filtration residue in 1 kg of emulsion). (2) Mechanical stability: Mechanical stability was measured by placing 50 g of a sample for 15 minutes in a Marlon measuring instrument under the conditions of 15 kg / cm ² and 1000 rpm, and then measuring the amount of grit in the sample under the same conditions as in the measurement of polymerization stability. It was measured.

(Synthesis Example 1) 5-vinylbicyclo [2.2.1] hept-2 was placed in a 0.5-liter jacketed flask.
-Ene (product name: VBH, manufactured by San Apro Co.) was charged with 100 g and ethyl acetate (50 g), and while blowing nitrogen, the reaction system was brought to a temperature of 50 ° C. in about 1 hour so that the temperature in the reaction system was raised to 257. 2 g (peracetic acid concentration; 29.
5%) was added dropwise. After completion of the dropwise addition of the peracetic acid solution, the mixture was aged at 50 ° C. for 4 hours to complete the reaction. Further, the crude liquid was washed with water at 50 ° C., and deboiled at 70 ° C./10 mmHg to obtain 97.3 g of epoxidized VBH. The properties of the product are oxirane oxygen concentration 10.6%, viscosity 12cp / 25 ° C, ¹
From H-NMR, a peak derived from an internal double bond in the vicinity of δ 4.5 to 5 ppm disappeared, and generation of a proton peak derived from an epoxy group was confirmed in the vicinity of δ 2.9 to 3.1 ppm.

(Synthesis Example 2) 180 g of vinylcyclohexene monoepoxide ("Celoxide 2000" manufactured by Daicel Chemical Industries, Ltd.) was placed in a 1-liter jacketed flask.
1.36 g of triphenylphosphine, 1.3 of methoquinone
6 g and 245 g of toluene as a solvent were charged. While blowing air into the liquid, the temperature in the reaction system was raised to 80 ° C., and then 100 g of acrylic acid was added dropwise over about 1 hour.
After the completion of the dropwise addition, the temperature in the system was set to 100 ° C., and the reaction was further performed. The reaction was terminated when the oxirane oxygen in the system became 0.2%. After the completion of the reaction, the resultant was washed with 500 g of water, and then 1.36 g of methoquinone was added. The reaction solution was deboiled at 70 ° C./10 mmHg to obtain 271 g of an unsaturated acrylate (A) having an alicyclic skeleton. ¹ H
From -NMR, it was confirmed that (A) was produced because the peak derived from the epoxy group disappeared in the vicinity of δ 2.9 to 3.1. Analysis by GPC showed that the alicyclic structure was 1
A monomer having a molecular weight of 196 (A-1), a dimer having a molecular weight of 320 having two alicyclic structures (A-2), a trimer having a molecular weight of 444 having three alicyclic structures, and More than that (A-3) are A-1: A-2: A-3 = 84.
It was confirmed that they were produced at a ratio of 7: 13.8: 1.5 (area% of GPC).

100 g of this reaction product and 50 g of ethyl acetate were charged, and while blowing nitrogen into the gas phase, 156.7 g of a solution of peracetic acid in ethyl acetate was taken over about 1 hour so that the temperature in the reaction system became 50 ° C. (Peracetic acid concentration: 29.5%) was added dropwise. After completion of the dropwise addition of the peracetic acid solution, the reaction was aged at 50 ° C. for 5 hours to complete the reaction. Further, the crude liquid was washed with water at 50 ° C.
Epoxy acrylate (B) having an alicyclic skeleton (hereinafter referred to as "EA-B") 9
1.7 g were obtained. The properties of the product, an oxirane oxygen concentration of 8.29%, a viscosity of 773cp / 25 ℃, ¹
From H-NMR, a peak derived from a double bond in the vicinity of δ 4.5 to 5 almost disappeared, and generation of a proton peak derived from an epoxy group in the vicinity of δ 2.9 to 3.3 was confirmed. G
Analysis by PC revealed that a monomer having a molecular weight of 212 having one alicyclic structure (B-1), a dimer having a molecular weight of 352 having two alicyclic structures (B-2), and an alicyclic structure were obtained. A trimer having a molecular weight of 492 having three structures and a trimer having a molecular weight of 492 or more (B-3) are respectively B-1: B-2: B-3 = 82.2: 15.
It was confirmed that they were produced at a ratio of 7: 2.1 (GPC area%).

Synthesis Example 3 limonene monoepoxide (195 g of limonene monoxide manufactured by Elfasatochem Co., Ltd., 195 g of diazabicycloundecene octylate, 0.3 g of methoquinone) was placed in a 1-liter jacketed flask.
g, methoxypropanol acetate 300 as a solvent
g. While blowing air into the liquid, the temperature in the reaction system was raised to 80 ° C., and 108 g of methacrylic acid was added to about 1
It was dropped over time. After completion of the dropping, the temperature in the system is set to 100
° C and further reacted. The reaction was terminated when the oxirane oxygen in the system became 0.23%. This reaction solution was deboiled at 70 ° C./10 mmHg to obtain 293 g of an unsaturated acrylate (C) having an alicyclic skeleton. ¹ H
Since the peak derived from the epoxy group near δ 2.9 to 3.1 disappeared from -NMR, the formation of (C) was confirmed. When analyzed by GPC, a monomer (C-1) having a molecular weight of 238 and having one alicyclic structure,
The dimer having a molecular weight of 390 (C-2), the trimer having a molecular weight of 542 having three alicyclic structures and the higher one (C-3) are C-1: C-2: C, respectively. -3 = 80.
It was confirmed that they were produced at a ratio of 6: 17.8: 1.6 (GPC area%).

100 g of this reaction product and 50 g of ethyl acetate were charged, and the temperature in the reaction system was raised to 50 while blowing nitrogen.
116.2 g (peracetic acid concentration: 29.5%) of a solution of peracetic acid in ethyl acetate was added dropwise over about one hour so that the temperature became ° C.
After completion of the addition of the peracetic acid solution, the reaction was aged at 50 ° C. for 4 hours to complete the reaction. Further, the crude liquid was washed with water at 50 ° C.
96.6 g of an epoxy acrylate (D) having an alicyclic skeleton (hereinafter referred to as "EA-D") after deboiling at mHg.
I got The properties of the obtained product were oxirane oxygen concentration 6.23%, viscosity 1590 cp / 25 ° C., and ¹ H-
From NMR, a peak derived from a double bond in the vicinity of δ 4.5 to 5 almost disappeared, and generation of a proton peak derived from the epoxy group in the vicinity of 2.9 to 3.3 was confirmed. Analysis by GPC revealed a molecular weight of 254 with one alicyclic structure.
Monomer (D-1) having a molecular weight of 42 having two alicyclic structures
2 dimer (D-2), molecular weight 5 having three alicyclic structures
90 trimers and higher (D-3) were D-1: D-2: D-3 = 80.1: 18.2: 1.7, respectively.
(GPC area%).

(Synthesis Example 4) Epoxidized VBH215 synthesized in Synthesis Example 1 was placed in a 1-liter jacketed flask.
g, triphenylphosphine 0.33 g, methoquinone 0.33 g, and 350 g of toluene as a solvent.
While blowing air into the liquid, raise the temperature in the reaction system to 80 ° C.
After that, 114 g of acrylic acid was added dropwise over about 1 hour. After the completion of the dropwise addition, the temperature in the system was set to 100 ° C., and the reaction was further performed. The reaction was terminated when the oxirane oxygen in the system became 0.22%. This reaction solution is deionized water 5
After washing with 00 g, 0.33 g of metoquinone was charged,
Low boiling was performed at 70 ° C./10 mmHg to obtain 321 g of an unsaturated acrylate (E) having an alicyclic skeleton. ¹ H-N
The generation of (E) was confirmed from the disappearance of the peak derived from the epoxy group in the vicinity of δ2.9 to 3.2 from MR. When analyzed by GPC, a monomer having a molecular weight of 208 (E-1) having one alicyclic structure, a dimer having a molecular weight of 344 having two alicyclic structures (E-2), and an alicyclic structure were obtained. And three or more (E-3) having a molecular weight of 480 having three of the following: E-1: E-2: E-3 = 83.9: 14.2:
It was confirmed that they were produced at a ratio of 1.9 (area% of GPC).

100 g of this reaction product and 50 g of ethyl acetate were charged, and the temperature in the reaction system was raised to 50 while blowing nitrogen.
123.7 g of a solution of peracetic acid in ethyl acetate (concentration of peracetic acid: 29.5%) was added dropwise over about 1 hour so that the temperature became ° C.
After completion of the addition of the peracetic acid solution, the reaction was aged at 50 ° C. for 4 hours to complete the reaction. Further, the crude liquid was washed with water at 50 ° C.
Deboiling at mHg, epoxy acrylate (F) having an alicyclic skeleton (hereinafter referred to as “EA-F”) 96.0
g was obtained. The properties of the obtained product were as follows: oxirane oxygen concentration 7.44%, viscosity 880 cp / 25 ° C., and ¹ H-N
From MR, a peak derived from a double bond near δ 4.5 to 5 almost disappeared, and generation of a peak of a proton derived from an epoxy group near δ 2.9 to 3.3 was confirmed. Analysis by GPC revealed a molecular weight of 224 with one alicyclic structure.
Monomer (F-1) having a molecular weight of 37 having two alicyclic structures
6 dimer (F-2), molecular weight 5 with 3 alicyclic structures
28 trimers and higher (F-3) were F-1: F-2: F-3 = 81.2: 15.7: 3.1, respectively.
(GPC area%).

(Synthesis Example 5) Vinylcyclohexene monoepoxide 241 was placed in a 1-liter jacketed flask.
g, triphenylphosphine 0.36 g, and methoquinone 0.36 g. While blowing air into the liquid,
100 g of acrylic acid after the temperature in the reaction system is raised to 80 ° C
Was added dropwise over about 1 hour. After completion of the dropwise addition, the temperature in the system was set to 100 ° C., and the reaction was further performed. When the oxirane oxygen in the system became 0.18%, the reaction was terminated to obtain 340 g of an unsaturated acrylate (G) having an alicyclic skeleton. ¹ H-
From NMR, the peak derived from the epoxy group almost disappeared in the vicinity of δ 2.9 to 3.2, and thus the formation of (G) was confirmed. Analysis by GPC revealed that the alicyclic structure was 1
A monomer having a molecular weight of 196 (G-1), a dimer having a molecular weight of 320 having two alicyclic structures (G-2), a trimer having a molecular weight of 444 having three alicyclic structures, and More than that
(G-3) is G-1: G-2: G-3 = 41.
It was confirmed that they were produced at a ratio of 2: 48.6: 10.2 (area% of GPC).

100 g of this reaction product and 50 g of ethyl acetate were charged, and the temperature in the reaction system was raised to 50 while blowing nitrogen.
125.8 g of a solution of peracetic acid in ethyl acetate (concentration of peracetic acid: 29.5%) was added dropwise over about 1 hour so that the temperature became ° C.
After completion of the dropwise addition of peracetic acid, the mixture was aged at 50 ° C. for 5 hours to complete the reaction. Further, the crude liquid is washed with water at 50 ° C.
g was removed to obtain 80.4 g of an epoxy acrylate (H) having an alicyclic skeleton (hereinafter referred to as “EA-H”). The properties of the obtained product were oxirane oxygen concentration 7.3.
9%, viscosity 8620 cp / 25 ° C., ¹ H-NMR
The peak derived from the double bond near δ 4.5 to 5 disappeared, and the generation of a proton peak derived from the epoxy group near δ 2.9 to 3.3 was confirmed. When analyzed by GPC, a monomer (H-1) having a molecular weight of 212 having one alicyclic structure, a dimer having a molecular weight of 352 having two alicyclic structures (H-2), and an alicyclic structure were obtained. 3 with a molecular weight of 492
Monomer and higher (H-3) are respectively H-1:
H-2: H-3 = 35.6: 49.5: 14.9 (GP
C area%).

Example 1 A reactor equipped with a reflux condenser and a nitrogen inlet was charged with 60 parts by weight of water and an emulsifier (Emulgen-12).
0: manufactured by Kao Corporation) was initially charged and mixed with stirring. After the temperature was raised to 70 ° C, epoxy acrylate A (EA-
B) 10 parts by weight, butyl acrylate (Bt. Ac) 1
80 parts by weight, 10 parts by weight of methacrylic acid, 125 parts by weight of water, 8 parts by weight of emulsifier (Emulgen-120: manufactured by Kao Corporation), 0. Molecular weight regulator (t-dodecyl mercaptan)
An emulsion of 05 parts by weight and 5 parts by weight of a 10% aqueous ammonium persulfate solution were added dropwise over 2 hours. At this time, the temperature in the reaction system was kept at 70 to 80 ° C. After completion of the dropwise addition, 2 parts by weight of a 10% ammonium persulfate aqueous solution was further added, and the mixture was reacted at 70 to 80 ° C. for 4 hours, and the solid content was 49.6%.
An emulsion composition was obtained. The polymerization stability and mechanical stability of the obtained emulsion were evaluated, and the results are shown in Table 1.

Examples 2 to 6 In the same manner as in Example 1 under the conditions shown in Table 1, each emulsion was synthesized and its properties were evaluated. The results are shown in Table 1.

Comparative Examples 1 and 2 Each emulsion was synthesized in the same manner as in Example 1 except that the raw materials shown in Table 1 were used. Table 1 shows the evaluation results of the properties of each emulsion.

[0041]

[Table 1]

[0042]

According to the present invention, an emulsion composition having excellent polymerization stability and mechanical stability can be obtained. The emulsion composition of the present invention is an emulsion composition having an epoxy group of a specific epoxy group-containing acrylic acid derivative as a cross-linking component, and includes an emulsion paint, an adhesive, a sealing agent, an ink binder, a fiber treatment agent, and the like. When used, an extremely safe emulsion composition free from irritating odors and irritants can be obtained.

Claims (4)

[Claims] 1. An emulsion composition comprising a homopolymer of an epoxy group-containing acrylic acid derivative represented by the formula (1) or a copolymer of a monomer copolymerizable with the derivative. Embedded image 2. The emulsion composition according to claim 1, wherein the monomer copolymerizable with the derivative is a vinyl monomer. 3. An epoxy group-containing acrylic acid derivative.
3. The emulsion composition according to claim 2, comprising a copolymer of 1 to 50.0 parts by weight and 50.0 to 99.9 parts by weight of a vinyl monomer copolymerizable with the derivative. 4. An emulsion polymerization of an epoxy group-containing acrylic acid derivative alone or an epoxy group-containing acrylic acid derivative and a monomer copolymerizable with the derivative in an aqueous medium. A method for producing the emulsion composition according to item 1.