JPS61203101A - Emulsion resin composition - Google Patents

Abstract

PURPOSE:The titled resin composition for use in paints, excellent in film properties and storage stability, obtained by emulsion-polymerizing an alpha,beta-ethylenically unsaturated monomer in the presence of a specified polyester resin, etc. CONSTITUTION:An alpha-beta-ethylenically unsaturated monomer is emulsion- polymerized in the presence of 5-50wt% polyester resin or alkyd resin compris ing 5-50wt% OH group-containing amino sulfonic acid amphoteric compound of the formula [wherein R1 is a 1-20C alkyl which may contain at least one OH, -O- or -COO-, R2-3 may be the same or different from each other and are each H, a 1-20C alkyl or an alkyl or cyclic group having at least one OH and/or at least one SO3H, and A is a 1-6C linear or branched alkylene or a (substituted) phenylene], 20-95wt% tris(2-hydroxyethyl and/or hydro xymethyl)isocyanurate and 0-75wt% other alcohol components.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to emulsion resin compositions, and more particularly to emulsion resin compositions in the presence of a novel polyester resin or alkyd resin incorporating an aminosulfonic acid type zwitterionic compound and an isocyanurate. niα.

The present invention relates to an acrylic emulsion resin composition for paints, which is obtained by emulsion polymerization of a β-ethylenically unsaturated monomer and has excellent film performance and storage stability.

Conventional acrylic emulsion resin compositions using polyester resin as a protective colloid have poor emulsion stability, and because a large amount of polyester resin protective colloid must be used, there are problems with corrosion resistance, drying properties, water resistance, storage stability, etc. be.

In order to improve this emulsion stability, the present inventors proposed a polyester resin having an aminosulfonic acid type zwitterion (Japanese Patent Application Laid-Open No. 55-97190). An emulsion resin composition using this resin as a protective colloid has excellent storage stability and functions even when the amount of the resin used is small.

However, since the polyester resin itself originally has poor drying properties and poor corrosion resistance, emulsions still have problems in these respects.

On the other hand, using conventionally known surfactants and protective colloids, (semi-)drying oil fatty acid residues and radically polymerizable double bonds can be simultaneously synthesized as α,β-ethylenically unsaturated heptadons to be polymerized. Attempts have also been made to obtain acid-value polymerized emulsion resins using monomers containing surfactants,
Decrease in water resistance and drying properties due to protective colloids cannot be avoided.

Problems to be Solved by the Invention In view of the above, an object of the present invention is to obtain an acrylic emulsion resin composition that has excellent storage stability and excellent film properties such as drying properties, corrosion resistance, and water resistance. .

Solve the problem! In this invention, in order to achieve the above object of the invention, we have developed a general formula
RI R2N'-A-8030 In formula 1, R1 has at least one hydroxyl group,
A C1-C20 alkyl group which may contain a -〇- or -C00- bond in the chain, Rt and R3 are mutually the same or different hydrogen atoms, a C1-C20 alkyl group, or at least one Hydroxyl group and/or
Mao also has a sulfonic acid group? Alkyl group or cyclic group・A
is a hydroxyl group-containing aminosulfonic acid type zwitterionic compound (I
) and tris(2-hydroxyethyl)isocyanurate and/or tris(hydroxymethyl)isocyanurate (1) as an alcohol component. The body is emulsion polymerized.

Function The polyester resin or alkyd resin of the present invention has a zwitterionic moiety derived from an aminosulfonic acid type zwitterionic compound and an isocyanurate acid derived from tris(2-hydroxyethyl)isocyanurate or tris(hydroxymethyl)isocyanurate. The excellent emulsion stabilization function of the former and the excellent drying and corrosion resistance functions of the latter combine to make it possible to reduce
When used as a protective colloid, it is possible to provide an emulsion resin composition with excellent film properties such as drying properties, corrosion resistance, and water resistance, as well as emulsion stability and storage stability. ,.

That is, in the emulsion resin composition of the present invention,
An emulsion resin composition is provided in which there is no adverse effect of conventional emulsifiers and surfactants, the surfaces of emulsion particles are easily fused, and the performance of the entire system is significantly improved.

The main feature of the present invention is the use of a special polyester resin or alkyd resin, which is produced by the reaction of a polyhydric alcohol, a polybasic acid, and an optionally present oil or fatty acid. In particular, it can be advantageously produced by using the hydroxyl group-containing aminosulfonic acid type zwitterionic compound and tris(2-hydroxyethyl)isocyanurate or tris(hydroxymetal)isocyanurate as at least a part of the polyhydric alcohol component. It will be done.

The present inventors discovered that in the alcohol component, the general formula (I>Rz-
Aminosulfonic acid type zwitterionic compound (I) represented by Ne-A-8030 (wherein R1, R2, R3, and A are each as described above)
It has been found that it is particularly suitable for the purposes of the present invention that the amount of carbon dioxide is from 5 to 50% by weight, preferably from 10 to 40% by weight. This is because if the amount of the zwitterionic compound is less than 5% by weight of the total alcohol component, the emulsion stabilizing function derived from the zwitterionic group will not be fully exhibited, and if it exceeds 50% by weight, the corrosion resistance will tend to worsen. It is from.

Further, tris(2-hydroxyethyl)isocyanurate and/or tris(hydroxymethyl)isocyanurate present as a component of the polyhydric alcohol is selected in an amount of 20 to 95% by weight, preferably 30 to 60% by weight. It is preferable. This is because if it is less than 20% by weight, corrosion resistance tends to be poor.

The polyester resin or alkyd resin of the present invention may contain 0 to 75% by weight of other alcohol as an alcohol component, if desired, and polybasic acids, oils, fatty acids, etc. are usually added to the polyester resin or alkyd resin. Any used can be used.

The above polyester resin or alkyd resin contains α, β-ethylenically inert saturated monomers to be polymerized and has a concentration of 5 to 50%.
It is used in a proportion by weight, preferably 10/30% by weight. This is because if it is less than 5% by weight, the emulsifying function will be insufficient and good emulsion polymerization cannot be expected, and if it exceeds 50% by weight, the amount of protective colloid will be too large and will have an adverse effect on water resistance etc.

In the present invention, an acrylic emulsion is produced using such a special polyester resin or alkyd resin as an emulsifier, and a paint vehicle with excellent film performance such as storage stability, corrosion resistance, and water resistance is provided. It is something. Therefore, in the present invention, at least 4% by weight of the α,β-ethylenically inert saturated monomers to be emulsion polymerized are (semi-)drying, oil fatty acid residues and radically polymerizable monomers. Compounds with bonds. For example, (semi-)drying oil fatty acids such as linseed oil fatty acids, tall oil fatty acids, soybean oil fatty acids, safflower oil fatty acids, dehydrated castor oil fatty acids, and sunflower oil fatty acids, and oxirane compounds having radically polymerizable groups such as glycidyl methacrylate. It has also been found that the corrosion resistance of scales can be further improved by using addition reaction products of .

The emulsion resin composition according to the present invention is extremely useful as a resin vehicle for a wide range of emulsion paints, from air-drying paints for steel plates to baking-type paints containing melamine and the like.

Example The present invention will be explained below with reference to Examples.

Reference Example 1 Dehydrated castor oil (375.5 kg) was placed in a 2e kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter.
0 parts, tris(2-hydroxyethyl)isocyanurate 221.5 parts, dihydroxyethyl taurine 68.0 parts
149.8 parts of neopentyl glycol and 2.4 parts of dibutyltin oxide, and heated to 200°C for 30 Nm.
After carrying out the transesterification reaction for ~60 minutes, it is cooled to 150°C or lower.

Furthermore, 448.3 parts of isophthalic acid, 2 parts of xylene for reflux
4.1 parts were charged, heated to 210°C, dehydrated for about 2 to 3 hours, and became almost transparent, then further heated to 220°C.
The reaction was continued while maintaining the temperature at °C until the resin acid value reached 40. After the reaction was completed, the mixture was cooled to 130° C., and 181.0 parts of ethylene glycol mobutyl ether was added to obtain a dissolved varnish. In addition, this material has a non-volatile content of 85.5% and a number average molecular weight of I
It was I700.

Reference Example 2 13.2 parts of 1.6 hexanediol, 403.7 parts of tris(2-hydroxyethyl)isocyanurate, and dihydroxyethyl were added to a 2e colben equipped with a stirrer, nitrogen inlet tube, temperature controller, condenser, and decanter. 123.6 parts of taurine, 536 parts of phthalic anhydride, and 36 parts of xylene for reflux were charged, and the temperature was raised to 210°C to carry out an esterification reaction. The reaction was terminated when the resin acid value reached 48, and the mixture was cooled. This resin had a nonvolatile content of 97% and a number average molecular weight of 1,980.

Production Example 1 In a 1e colben equipped with a stirrer, nitrogen inlet tube, temperature control device, and condenser, 237 parts of linseed oil fatty acid, 119 parts of glycidyl methacrylate, 0.4 part of hydroquinone,
0.2 part of tetraethylammonium bromide was charged and the reaction was carried out at 170 to 180°C with stirring. The amount of epoxy groups and carboxyl groups was monitored while being measured. It took about 3 hours until the reaction was completed to obtain a compound having a drying oil fatty acid residue and a radically polymerizable double bond.

Example 1 200 parts of the dissolved varnish obtained in Reference Example 1, 14 parts of 28% ammonia water, and 8 parts of deionized water were placed in a 2e Kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, dropping tube, and condenser.
After charging 53 parts and uniformly dispersing the mixture while raising the temperature to 80°C, the temperature was maintained at 80°C. Separately, an aqueous solution of 3.4 parts of ammonia persulfate dissolved in 34 parts of water was added, and the mixture was stirred for approximately 10 minutes to dissolve 104 parts of methyl methacrylate, 40 parts of styrene, 468 parts of n-butyl acrylate, and 2-hydroxy-acrylate.
After 0 drops of a mixed solution of 72 parts of ethyl was added at 3 o'clock,
After stirring at this temperature for 60 minutes, the non-volatile content was 48%.
, E) H8.3, viscosity 4001) An emulsion of S was obtained.

Example 2 Resin 1 obtained in Reference Example 2 was placed in a 2e Kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, dropping funnel, and condenser.
10 parts of dimethylaminoethanol and 900 parts of deionized water were added, and the mixture was uniformly dissolved while raising the temperature to 80°C. An aqueous initiator solution prepared by dissolving 3.8 parts of ammonia persulfate in 60 parts of deionized water, prepared separately, was added and held at 80°C for about 10 minutes, followed by 180 parts of methyl methacrylate.
Add a mixture of 150 parts of styrene, 90 parts of n-butyl acrylate, and 220 parts of 2-ethylhexyl acrylate to 2:1
It was instilled for about 30 minutes. After the dropwise addition was completed, stirring was continued for 1 hour at the same temperature and the mixture was cooled. Non-volatile content 43%, EIH8,
1. An emulsion with a viscosity rR of 70 cps was obtained.

Example 3 Dissolved varnish 260I obtained in Reference Example 1 in a 2e Kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and dripper. 1 and 18 parts of dimethylaminoethanol,
850 parts of deionized water was charged and the mixture was heated to 80° C. to uniformly dissolve the mixture. Separately prepared azobiscyanovaleric acid7.
3 parts dimethylaminoethanol 5 parts deionized water 75 parts
Initiator aqueous solution and methyl methacrylate dissolved in 210 parts
120 parts of styrene, 170 parts of ethyl acrylate, and 70 parts of the compound obtained in Production Example 1 were simultaneously added dropwise at 80° C. over 1 hour and 30 minutes. After the dropwise addition was completed, stirring was continued for 1 hour at the same temperature, and then cooled to give a non-volatile content of 39%.
An emulsion with a DH of 8.4 and a viscosity of 900DS was obtained.

Example 4 Stirrer, nitrogen inlet tube, I! 64 parts of the resin obtained in Reference Example 2 were added to a 2E Kolben equipped with a temperature control device, a dropping funnel, and a condenser, and 6 parts of dimethylaminoethanol and 1 part of deionized water.
100 parts were charged and uniformly dissolved while raising the temperature to 80°C. Separately, an aqueous initiator solution prepared by dissolving 9 parts of azobiscyanovaleric acid in 6.5 parts of dimethylaminoethanol and 90 parts of deionized water, 81 parts of methyl methacrylate, 180 parts of styrene, 240 parts of ln-butyl acrylic, 12 parts of methacrylic A mixed solution of 54 parts of -hydroxyethyl and 45 parts of the compound synthesized in Production Example 1 was simultaneously added dropwise at 80°C over 2 hours. After the dropwise addition, stirring was continued for 1 hour at the same temperature and then cooled to obtain a solution with a non-volatile content of 34.8% and a pH of 8.
2. An emulsion with a viscosity of 40 C1)S was obtained.

Comparative Example 1 a. (Alkyd resin synthesis) An alkyd resin was synthesized in exactly the same manner as in Reference Example 1, except that trimethylolpropane was used instead of "tris(2-human Ogyethyl) isocyanurate" in Reference Example 1. The nonvolatile content of this resin was 85.3%, and the number average molecular weight was 1,600.

b. (Synthesis of emulsion) An emulsion was synthesized in exactly the same manner as in Example 1, except that the alkyd resin of Comparative Example 1-a was used in place of the "dissolved varnish obtained in Reference Example 1" of Example 1. This product had a nonvolatile content of 47.8%, an EIH of 8.4, and a viscosity of aocps.

Comparative Example 2 a. (Synthesis of alkyd resin) An alkyd resin was synthesized in exactly the same manner as in Reference Example 1, except that ethylene glycol was used in place of "dihydroxyethyl taurine" in Reference Example 1.

The nonvolatile content of this resin was 85.5%, and the number average molecular weight was 1300.

b. (Synthesis of emulsion) An attempt was made to synthesize an emulsion in exactly the same manner as in Example 1, except that the alkyd resin of Comparative Example 2-a was used instead of the ``dissolved varnish obtained in Reference Example 1'' of Example 1. However, it agglomerated.

Adjustment of paint A pigment paste was prepared using the following formulation (solid content weight), and to 26.2 parts of the pigment paste, 30 parts solid content of the emulsions of Examples and Comparative Examples and 3 parts pure water were added to prepare the paint. did. Furthermore, when using the emulsions of Examples 3 and 4, Dicknate 3111 (
Cobalt naphthenate (Dainippon Ink Chemical) was further added to 0.
Added 3 parts.

pigment paste pure
3.0 Hydroxyethyl cellulose 0.05
(QP-5200H: Union Carbide Co.) 25% ammonia water 0.05 α-olefin maleate 2.0 (Demol EP: Kao Soap Co.) Titanium white (R-930: 6 Hara Sangyo) 20.0 Ethylene glycol 1. 1 silicone oil
0.1 (SH-193: Toray Silicon Co., Ltd.) Formation of Coating Film The paint prepared above was applied to a degreased 0.31 m tin plate using a 40 mil doctor blade.

(Note 1) After leaving the coated plate in water at 20°C for 48 hours, it was pulled out and dried at room temperature for 10 minutes, and evaluated for blistering and whitening: O No abnormality O Blister 8F (ASTM) or slight whitening × Whitening with blisters 6 or less Note 2) Rust and blisters on the paint film after 148 hours of salt water spray were evaluated. Rust and Fukure 6D Patent Application Agent

Claims (4)

[Claims] (1) General formulas ▲ Numerical formulas, chemical formulas, tables, etc. Alkyl groups, R_2 and R_
3 are the same or different hydrogen atoms, C_1~
C_2_0 alkyl group, or an alkyl group or cyclic group having at least one hydroxyl group and/or sulfonic acid group, A is C_1 to C_6 linear or branched alkylene group, phenylene group or substituted phenylene group) In the presence of a polyester resin or alkyd resin containing a hydroxyl group-containing aminosulfonic acid type zwitterionic compound (I) and tris(2-hydroxyethyl)isocyanurate and/or tris(hydroxymethyl)isocyanurate (II) as alcohol components. , an emulsion resin composition obtained by emulsion polymerization of α,β-ethylenically unsaturated monomers. (2) The alcohol component of the polyester resin or alkyd resin is a hydroxyl group-containing aminosulfonic acid type zwitterionic compound (I) 5 to 50% by weight, tris(2-hydroxyethyl)isocyanurate and/or tris(hydroxymethyl)isocyanurate (II) 20～
The emulsion resin composition according to claim 1, comprising 95% by weight and 0 to 75% by weight of other alcohol components. (3) The polyester resin or alkyd resin is α,
The emulsion resin composition according to any one of claims 1 to 2, which is used in a proportion of 5 to 50% by weight based on the β-ethylenically unsaturated monomer. (4) at least 4 α,β-ethylenically unsaturated monomers;
Claims 1 to 3 in which the weight percent is a compound having a (semi-)drying oil fatty acid residue and a radically polymerizable double bond.
The emulsion resin composition according to any one of the above.