JPS60217233A - Water-based acrylic resin composition - Google Patents

Abstract

PURPOSE:A novel water-based acrylic resin composition that is obtained by adding an polyepoxide to an aqueous dispersion of an acrylic resin containing a specific tertiary nitrogen, thus giving coating films of high resistances to solvents, water and corrosion. CONSTITUTION:(A) 1-15pts.wt. of a hydrophilic monomer which has 1 polymerizable vinyl group in the molecule, terminal groups of H or 1-4C alkyl and a polyoxyethylene chain of 1,500-15,000 molecular weight, 0.1-15pts.wt. of a vinyl monomer containing a tertiary nitrogen such as N,N-dimethylaminoethyl acrylate or methacrylate and other polymerizable monomers such as methyl acrylate or methacrylate, totaling to 100pts.wt., are polymerized in a water-soluble organic solvent, then dispersed. The resultant aqueous dispersion is combined with (B) a polyepoxide bearing one or more epoxy groups in the molecule in an amount of 1-50pts.wt., based on 100pts.wt. of component A on the solid basis, to give the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION 11 The present invention relates to a novel acrylic resin composition. More particularly, the present invention relates to a novel water-based acrylic resin composition that can be applied to wood, metal, plastic, and other various surfaces to provide coatings with a high degree of solvent resistance, water resistance, and corrosion resistance.

Conventionally, in order to obtain a coating film with high solvent resistance and durability, solution polymerized acrylic resin was combined with a crosslinking agent such as melamine resin, polyfunctional urethane resin, or epoxy resin.
A method of obtaining a reticulated coating film is commonly used. However, solution-type resins contain a large amount of organic solvents that are highly flammable and explosive, which not only poses a high risk of fire but also is highly harmful to the human body. There has been a strong demand for a method to obtain coatings with high solvent resistance, durability, etc. comparable to those of conventional water-based resins, but this has been difficult to achieve with conventional water-based resins. Water-based resins are generally classified into water-soluble resins and water-dispersible resins. Among these, water-soluble resins that contain acid groups such as carboxyl groups and sulfonic acid groups in the main chain and are produced by neutralizing these with ammonia or organic amino compounds require a large amount of water-soluble resins to make them water-soluble. A salt of a carboxyl group or a sulfonic acid group is required, and as a result, even if a crosslinking agent such as melamine resin is used in combination, it is difficult to obtain a reticulated coating film with high light resistance, solvent resistance, and durability. It was difficult. On the other hand, aqueous dispersions obtained by emulsion polymerization or mechanical dispersion in the presence of emulsifiers and protective colloids do not require large amounts of bases such as carboxyl groups or sulfone chain groups as do water-soluble resins. Water resistance and corrosion resistance are significantly reduced by the emulsifiers and protective colloids contained, and even when such aqueous dispersions are used in combination with crosslinking agents, the resistance is comparable to that of solution polymerized resins.

It was extremely difficult to obtain a coating film performance of the same degree.

Under these circumstances, the present inventors conducted intensive research on acrylic resin aqueous = 3-dispersions obtained by mechanically dispersing solution-polymerized acrylic resins, and found that they were able to achieve results that could not be obtained with conventional water-based resins. In addition, a water-based acrylic resin that provides a coating film with extremely excellent solvent resistance, water resistance, and corrosion resistance;
This discovery led to the present invention.

Therefore, the present invention provides a hydrophilic monomer having a polyoxyethylene chain with a molecular weight of 1500 to 15000, which has one polymerizable vinyl group in the molecule and whose terminal group is an alkyl group of H or q. Add 1 to 15 parts by weight of (A), 0.1 to 15 parts by weight of tertiary nitrogen-containing vinyl monomer (B), and other polymerizable vinyl monomers to make a total of 100 parts by weight of a polymerizable vinyl monomer in water. An aqueous acrylic resin obtained by adding a polyepoxide compound (c) having more than 1.0 epoxy groups in the molecule to an aqueous tertiary nitrogen-containing acrylic resin dispersion obtained by polymerizing in a neutral organic solvent and then dispersing it. A composition is provided.

4- The aqueous acrylic resin composition thus obtained can provide a coating film having a high degree of solvent resistance, water resistance, and corrosion resistance, and can be applied to wood, plaster, cement, various plastics,
It has been recognized that it protects metals and provides extremely useful protective coatings for various coated objects.

The tertiary nitrogen-containing acrylic resin aqueous dispersion used in the present invention does not contain large amounts of carboxyl groups or sulfonic acid group salts unlike conventional water-soluble acrylic resins, and does not contain emulsifiers or protective co-hydrogens. Unlike aqueous dispersions, it has excellent solvent resistance, water resistance, and corrosion resistance, very similar to solution-polymerized acrylic resins.

The aqueous tertiary nitrogen-containing acrylic resin dispersion used in the present invention is synthesized by the following method. That is, a hydrophilic monomer having a polyoxyethylene chain having one polymerizable vinyl group in the molecule and having a molecular weight of 1,500 to 150 and a terminal group of 1 or q to 4 alkyl groups is used. It is obtained by polymerizing 100 parts by weight of polymerizable vinyl heptamer containing 15% by weight in a water-soluble organic solvent and then dispersing it in water.

Molecular weight 1 which has a polymerizable vinyl group in the molecule used in the present invention and whose terminal group is an H-bridged C1-4 alkyl group
Examples of the hydrophilic monomer having 500 to 15,000 polyoxyethylene chains include the following compounds. For example, compounds produced by adding ethylene oxide to a vinyl heptamine containing a hydroxyl group such as β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, and β-hydroxyethyl methacrylate; A polyoxyethylene glycol whose terminal group is an alkyl group of Fic 1 to 4 and the other terminal group is a hydroxyl group is prepared, and then a vinyl group such as acrylic acid, methacrylic acid, itaconic acid, or cinnamic acid is prepared. Compounds produced by esterification reaction with calcium-containing 6-ponate; transesterified with vinyl group-containing ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, propyl acrylate, and butyl acrylate. Compound produced by reaction; molecular weight 1500 to j50
Hydroxyl group of polyoxyethylene glycol in which one end group of 00 is an H-crossed C1-4 alkyl group and one end group is a hydroxyl group, β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, Examples include compounds in which a hydroxyl group such as β-hydroxyethyl methacrylate or a carboxyl group such as acrylic acid, methacrylic acid, and itaconic acid are reacted with an organic diisocyanate compound.

Having one vinyl group in the molecule obtained in this way,
The terminal group is H or a C1-4 alkyl group. Molecular weight 1
Molecular weight of the polyoxyethylene part of the hydrophilic monomer having a polyoxyethylene chain of 5007 to 15000
The molecular weight of the polyoxyethylene moiety must be in the range of 15,000 to 15,000.If the molecular weight of the polyoxyethylene moiety is less than 1,500, a sufficient effect on water dispersion of the acrylic resin copolymer solution obtained by copolymerization will not be observed, which is not preferable. Also, when the molecular weight of the polyoxyethylene moiety is i 5000 or more, the number of copolymerized vinyl groups per unit molecular weight of the monomer is extremely small, and in this case as well, the water dispersion effect of the acrylic resin solution obtained by copolymerization is It is not preferable because it decreases significantly. The molecular weight of the polyoxyethylene portion of the hydrophilic monomer is preferably from 2,000 to 10,000, more preferably from Vis o o o to 8,000. The hydrophilic monomer is used in an amount of 1 to 15 parts by weight based on 100 parts of all the polymerizable monomers to be copolymerized. If the amount of the hydrophilic monomer used is less than 1 part by weight, the resulting acrylic resin copolymer solution will not have a sufficient water dispersion effect, making it difficult to obtain a stable aqueous dispersion. do not have. In addition, if the amount of the wood-philic monomer used exceeds 15 parts by weight per 100 parts by weight of the polymerizable monomer to be copolymerized, the water dispersing power of the acrylic copolymer resin solution will no longer be obtained even if it is used in excess. This is not preferable because it does not increase much and is not only uneconomical, but also reduces the water resistance etc. of the resulting polymer. The particularly preferable amount of the wood-philic monomer used is 10% of all the polymerizable monomers to be copolymerized
The range is from 2 to 10 parts by weight per 0 parts by weight.

Examples of the tertiary nitrogen-containing vinyl monomer used in the present invention include the following compounds. For example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-
Examples include dimethylamine propyl (meth)acrylate.

9- These can be used alone or in combination. The amount of the tertiary nitrogen-containing vinyl monomer used is in the range of 11 to 15 parts by weight per 100 parts by weight of the total polymerizable vinyl monomer.

If this amount is less than 0.1 part by weight, even if a polyepoxide compound is used in combination with the resulting aqueous acrylic resin dispersion, a reticulating composition having sufficient performance cannot be obtained, which is not preferable. Furthermore, if the amount of the tertiary nitrogen-containing vinyl monomer used is more than 15 parts by weight, even if a polyepoxide compound is added to the resulting aqueous acrylic resin dispersion, the performance improvement commensurate with the amount added will no longer be observed and it will be uneconomical. Undesirable. The preferred amount of the tertiary nitrogen-containing vinyl monomer is usually 0.00 parts per 100 parts by weight of the total polymerizable vinyl monomer.
The amount is in the range of 5 to 1.0 parts by weight, and the more preferred amount is 1 to 7 parts by weight.

Other polymerizable vinyl monomers 10 to be copolymerized with the hydrophilic heptamer and tertiary nitrogen-containing vinyl monomer used in the present invention include ethylenically unsaturated monomers, such as methyl (meth)acrylate, (meth)ethyl acrylate, (meth)
m-butyl acrylate, lauryl (meth)acrylate,
(Meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxy5-700propyl (meth)acrylate; maleic acid, fumaric acid, croton acids, such as itaconic acid, acrylic acid, methacrylic acid,
β-Monoethylenically unoriented saturated acid; α such as acrylamide tacrylamide, N-methylacrylamide, N-methylol acrylamide, etc.

Examples include unsaturated nitriles such as chloride, methacrylonitrile, and the like. Vinyl halides such as vinyl chloride and vinylidene chloride; styrene derivatives such as styrene, α-methylstyrene and vinyltoluene; vinyl esters such as vinyl acetate and vinyl propionate; conjugated dienes such as butadiene; maleic acid esters α-olefins such as ethylene can also be used. In addition, one type or two or more types of other polymerizable vinyl monomers may be used.

The aqueous dispersion of tertiary nitrogen-containing acrylic resin used in the present invention is usually produced by first reacting the hydrophilic monomer, the tertiary nitrogen-containing vinyl monomer, and other polymerizable vinyl monomers in a water-soluble organic solvent solution. Then, the above-mentioned hydrophilic monomer is added for further reaction, and water is added to the obtained tertiary nitrogen-containing acrylic copolymer resin solution by sifting for dispersion. Examples of organic solvents that can be used include alcohols such as isopropyl alcohol, m-floboxypropanol, diacetone alcohol, isobutyl alcohol, and m-butyl alcohol, propylene glycol monomethyl ether, methylcello 4-norp, ethylcero-V-lup, and ethylene glycol monomethyl. Examples include ether alcohols and ethers such as isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and dioxane, and one or more of these may be used.

The amount of the above-mentioned water-soluble organic solvent used is not particularly limited, but usually the total polymerizable vinyl monomer to be polymerized is 10
It is used in a range of 10 to 100 parts by weight per 0 parts by weight. When obtaining an acrylic copolymer resin solution, benzoyl peroxide, lauroyl peroxide,
Organic peroxides such as art-butyl peroxide, tart-butyl perbenzoate, tart-butyl peroctoate or acetyl oxide, or 2'-azobisinbutyronitrile, 2.2
It is possible to use so-called radical initiators such as quinitrile-based initiators such as '-azobisonitrile. The method for preparing the acrylic copolymer resin solution is not particularly limited. For example, while heating and stirring a water-soluble organic solvent solution containing a hydrophilic monomer whose polyoxyethylene moiety has a molecular weight of 1,500 to 15,000, a tertiary copolymer resin solution is prepared. A polymerizable vinyl monomer including a nitrogen-containing vinyl monomer and a radical initiator may be added dropwise, or a water-soluble organic solvent, a radical initiator, and a polyoxyethylene moiety with a molecular weight of 15
A hydrophilic monomer having a molecular weight of 00 to 15,000 and a polymerizable vinyl monomer containing a tertiary nitrogen-containing vinyl monomer may be simultaneously added dropwise, or a polymerizable vinyl monomer containing a tertiary nitrogen-containing vinyl monomer may be added simultaneously in a water-soluble organic solvent. It is also possible to add a hydrophilic monomer whose polyoxyethylene moiety has a molecular weight of 1,500 to 5,000 in the latter half of the polymerization of the vinyl monomer with a radical initiator for cooking.

The copolymer resin solution can be dispersed in water by gradually dropping the copolymer resin solution while stirring the water, or conversely, by gradually adding water to the copolymer resin solution. Any method of phase inversion emulsification is possible. In general, a stable dispersion with a fine particle size is easily obtained by heating a copolymer resin solution to about 50 to 100°C, gradually adding water dropwise while stirring well, and carrying out phase inversion emulsification. This is the preferred method. Incidentally, the aqueous acrylic resin dispersion of the present invention can also be formed into a salt with an organic acid or an inorganic acid, if necessary. Such acid may be added during or after the production of the aqueous dispersion.

The polyepoxide compound used in the present invention has more than 1.0 epoxy groups in the molecule. That is, any polyepoxide compound or mixture may be used as long as the average number of epoxy groups in the molecule is greater than 1,
Preferably, the average number of epoxy groups per molecule is 2 or more.

The average number of epoxy groups in the polyepoxide compound need not be an integer and is generally less than about 4, but can be as high as 6 or more.

Examples of vine polyepoxide compounds for use in the present invention include polyglycidyl ethers of polyphenols such as bisphenols. These are produced, for example, by etherifying polyphenols with epichlorohydrin or dichlorohydrin in the presence of an alkali. Phenolic compounds include bis-(4-hydroxyphene-2,2-7'ropane, 4,4'-dihydroxybenzopheno-, bis(4-hydroxy)-1,1
-isobutane, bis(4-hydroxy 5-butylphenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene and the like. Novolac resins or similar polyphenol resins can also be used as polyphenols.

Aliphatic polyglycidyl ethers of polyhydric alcohols are also applicable as polyepoxide compounds. These are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-globylene glycol, 1,4-butylene glycol, 1,5-bentanediol, 1,2
．． S-hexanetriol, glycerol, bis(4-
Human, roxycyclohexyl)-2,2-propane, etc.! Derived from polyhydric alcohols.

Polyglycidyl esters of polyhydric carboxylic acids can also be used as polyepoxide compounds. These include epichlorohydrin or similar compounds and aliphatic or aromatic polycarbohydrates.
Acids, e.g. evaxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthylenedicarboxylic acid, trimerized phosphoric acid and class 17 - prepared by reaction with offerings be done. Examples include diglycidyl adipate and diglycidyl phthalate.

Also used as polyepoxide compounds are polyepoxide compounds derived by epoxidation of olefinically unsaturated aliphatic compounds. Also used as such polyepoxy compounds are epoxide mixtures comprising dievoxides, tri- or higher epoxides and partially one or more monoepoxides. These polyepoxides are generally non-phenolic, and when aliphatic olefins are oxidized using, for example, perbenzoic acid, acetaldehyde monoperacetate or peracetic acid using oxygen and a selected catalyst, K. Manufactured.

Preferred types of polyepoxide compounds include those containing oxyalkylene groups in the epoxy molecule.

Such oxyalkylene groups typically have the following general formula, preferably lower alkyl (e.g., having 1 to 6 carbon atoms, η
In the case of 1 to 4, m is 1 to 4 and n is 2 to 50. ] is a group represented by Such groups can be attached to the main chain of the polyepoxide, or can themselves become part of the main chain.

The proportion of oxyalkylene groups in the polyepoxide compound depends on many factors, including the chain length of the oxyalkylene groups, the nature of the epoxy, and the degree of water solubility desired. Desirably, such polyepoxy compounds contain at least about 1%, preferably 5% or more, of oxyalkylene groups.

Some preferred polyepoxide compounds containing oxyalkylene groups are prepared, for example, by reacting some of the epoxy groups of polyepoxides containing no oxyalkylene groups with some alcohols containing oxyalkylene groups. Ru. Such -hydric alcohols are conveniently prepared by oxyalkylation of alcohols, such as methanol, ethanol or other alkanols, with alkylene oxides. Particularly useful alkylene oxides are ethylene oxide, 1,2-propylene oxide, and 1,2-butylene oxide. Examples of other alcohols include industrially used monoalkyl ethers of polyalkylene glycols known as cellosolve and calpitol.

The reaction between the -hydric alcohol and the polyepoxide is generally carried out in the presence of a catalyst. For this purpose, chain acids, dimethylethanolamine, diethylethanolamine, N,
N-dimethylbenzylamine and optionally stannous chloride are used. Similar polyepoxides containing oxyalkylene groups are prepared by oxyalkylation of epoxy resins by other means, such as direct reaction with alkylene oxides. The polyepoxide used to produce the oxyalkylene-containing polyepoxide compound has a sufficient content so that the average number of residual epoxy groups per molecule remaining in the reaction product after oxyalkylation is 1.0 or more. must contain a certain number of epoxy groups. A polyepoxide as described above is added to an aqueous tertiary nitrogen-containing acrylic resin dispersion.

In the aqueous acrylic resin composition of the present invention, the ratio of the tertiary nitrogen-containing acrylic resin aqueous dispersion to the polyepoxide compound can be varied. The optimum ratio varies depending on the type, physical properties, etc., but is usually 1 to 50 parts of the polyepoxide compound per 100 parts of the solid content of the tertiary nitrogen-containing aqueous acrylic resin dispersion, preferably 5 to 3 parts.
It is 0 parts by weight. The resulting water-based acrylic resin composition can be applied to wood, paper, fibers, plastics, ceramics, and inorganic cement by any method such as dipping, brushing, spraying, or roll coating. It is applied to the surface of substrates, iron, nonferrous metals, etc., and used as a cold-curing coating forming agent. It can also be used as a bake-dry coating forming agent, and can provide excellent solvent resistance, water resistance, and corrosion resistance that cannot be obtained with conventional water-based resins. The aqueous acrylic resin composition obtained in the present invention has excellent film-forming properties, and has coating workability and finish gloss comparable to those of solvent-based resins.

Although the aqueous acrylic resin composition obtained in the present invention can be used alone, it is of course possible to add various pigments, plasticizers, solvents, colorants, etc.

The acrylic resin composition of the present invention can be directly kneaded with various coloring pigments, extender pigments, etc., and has excellent dispersion stability and mechanical stability of the compounded liquid, and does not have problems such as foaming. It has the characteristic of being extremely rare.

22- Next, examples are listed to concretely illustrate the present invention, but the present invention should not be limited only to these practical examples.

Note that all parts or parts appearing in the examples are based on weight.

Materials: 1゜In a 2p flask equipped with a stirrer, a thermometer, a flow condenser, a dropping funnel, and an inert gas inlet, 300 parts of ethyl cellulose as a solvent, a polyoxygenate compound whose terminal group is a methoxy group, 35 parts of methacrylic acid methyl ester derivative whose ethylene moiety has a molecular weight of 6000 was charged, and the temperature was raised to 130° C. in a nitrogen gas stream. Separately, vinyl monomers include 476 parts of methyl methacrylate, 210 parts of butyl acrylate, and 14 parts of dimethylaminoethyl methacrylate.
Mix the parts in advance on a scale, and also mix the tertiary parts.
14 parts of butyl hydroperoxide were weighed out and injected from separate dropping funnels to uniformly drop-polymerize over 3 hours. After the dropwise addition was completed, the temperature was further maintained at 130° C. for 6 hours to complete the polymerization.

Thereafter, the resulting solution was cooled to 80°C, and 615 parts of water was added dropwise at the same temperature over about 2 hours. Then 25℃
When cooled to a uniform temperature, a slightly bluish homogeneous acrylic resin aqueous dispersion was obtained. The obtained aqueous dispersion had a nonvolatile content of 45.2, a viscosity of 1060 eps, a pH of 9.2, and an average particle diameter of α2 μm or less. To 100 parts of the obtained acrylic resin aqueous dispersion, 15 parts of an epoxy resin (average of 2 epoxy groups in the molecule) with an epoxy weight of 314 obtained by the reaction of bisphenol A and epichlorohydrin was added, and the mixture was thoroughly stirred and dispersed. It was created. As a result of extracting the above composition with acetone for 4 hours using a steel plate with a pressure-dried film thickness of 20, 79% of the coating film remained.

Further, the coating film had extremely excellent water resistance (no abnormalities were observed even after immersion in boiling water VC for 1 hour).

Without the addition of epoxy resin, the coating was easily dissolved in acetone.゛Example Z In a device similar to Example 1, 300 parts of butyl cellosolve was added, and an acrylate with a terminal -H group and a polyoxyethylene moiety having a molecular weight of 8,000 [Cpeng-p-c-o+c giftCpengO÷■,
However, add 21 parts of Mvaooo) of C ear CHg0),
A as a polymerization initiator while heating to 130°C in a nitrogen stream
A mixed solution of 6m IBN, 330 parts of styrene, 300 parts of butyl acrylate, 14 parts of methacrylic acid, and 56 parts of diethylamine ethyl methacrylate was added dropwise from another dropping port over a period of about 3 hours. After the dripping is finished,
The polymerization was completed by holding at the same temperature for 10 hours, and then the resulting solution was cooled to 70°C, and at the same temperature, 580 parts of water was added to about 2
It took some time to drip. When cooled to 25° C., a uniform aqueous acrylic resin dispersion with a slight bluish tinge was obtained. The obtained acrylic resin aqueous dispersion had a nonvolatile content of 44.6%, PHa3, and a viscosity of 980CpII.
The average particle diameter was 0.2 μm or less. To 100 parts of the obtained acrylic resin aqueous dispersion, 30 parts of an epoxidized novolak resin (average of 2 epoxy groups in the molecule) of Epoxy Equivalent Heavy Machinery 355 was added to prepare a well-stirred and dispersed composition.

The above composition was coated on a stainless steel plate to a dry film thickness of 15 μm and dried at room temperature for 6 days. The coating film was extracted with acetone for 4 hours using a Soxhlet extractor.
4% remained. This coating film had extremely excellent adhesion, water resistance, and salt water resistance. When no epoxy resin was added, the coating was easily dissolved in acetone.

Example 6 300 parts of butyl cellosolve was added to the same apparatus as in Example 1, and while heating to 130°C in a nitrogen stream, t@rt-butylperoxy 2-ethylhexanoate 6 was added as a polymerization initiator. A mixed solution consisting of 160 parts of styrene, 240 parts of methyl methacrylate, 265 parts of 2-ethylhexyl acrylate, and 35 parts of dimethylaminoethyl methacrylate was added dropwise from a separate dropping port over a period of 3 hours. . Meanwhile, 70 parts of methacrylate having a terminal group of n-butoxy group and having a molecular weight of 3 o o o of polyoxyethylene was divided into three parts and added every hour. After the dropwise addition was completed, the same temperature was maintained for 8 hours to complete the polymerization. Next, the obtained solution was cooled to 60°C, and 640°C of water was added at the same temperature.
The solution was added dropwise over a period of approximately 2 hours.

After the dropwise addition was completed, the solution was cooled to 25° C., and a uniform bluish acrylic resin aqueous dispersion was obtained. The obtained acrylic resin aqueous dispersion had a non-volatile content of 45.1% and a PHEL of 5.
The viscosity was 3100 epl, and the average particle size was 2μ or less. To 100 parts of this acrylic resin aqueous dispersion, polypropylene glycol with an epoxy equivalent weight of 425 and Kpon 854 (a polyepoxy compound consisting of bisphenol A and epichlorohydrin, 225 to 290
epoxy equivalent weight, average number of epoxy groups in the molecule: 2)
5 parts of the reaction product was added and thoroughly stirred and dispersed to prepare a composition. The above composition was applied to an ABS board to a dry film thickness of 10 μm, and dried with hot air at 60° C. for 50 minutes. The coating film was extracted with acetone for 4 hours using a Soxhlet extractor, and as a result, 87% of the coating film remained. This coating film had extremely excellent adhesion and gasoline resistance. Without the addition of epoxy resin, the coating was easily dissolved in acetone.

Actual example 4゜300 parts of butylcerone lube was added to the same apparatus as in Example 1, and while heating to 120°C in a nitrogen stream, 65 parts of methacrylate having a molecular weight of 8000 in the polyoxyethylene moiety with the terminal -H group was added, and then Tart-butylperoxy 4 was added as a polymerization initiator while heating to 120°C in a nitrogen stream.
A mixed solution of 5 parts of 2-ethylhexanoate, 350 parts of styrene as monomer components, 30 parts of lauryl methacrylate, 310 parts of butyl acrylate, 7 parts of dimethylaminoethyl methacrylate, and 5 parts of acrylic acid was added through a separate dropping port for about 3 hours. It took a while to drip. After finishing dropping, at the same temperature
The polymerization was completed by holding for a period of time. The resulting solution was heated to 60°C.
600 parts of water was added dropwise at the same temperature over a period of about 2 hours. After the dropwise addition was completed, the solution was cooled to 25° C., and a uniform bluish acrylic resin aqueous dispersion was obtained. Triethylamine was added to this acrylic resin aqueous dispersion to pH
The nonvolatile content was 46.3 tX, the pH was 92, the viscosity of the dispersion was 950 cps, and the average particle diameter was α2 μm or less. To 100 parts of this acrylic resin aqueous dispersion, 10 parts of a reaction product of polypropylene glycol with an Evo 29-oxy equivalent weight of 225 and glycerin/diglycidyl ether (average number of epoxy groups in the molecule: 2) was added, and the mixture was thoroughly stirred to form a composition. created something. The above composition was applied to a wood board with a dry film thickness of 20
It was coated to a thickness of μm and dried for 3 days at room temperature. The resulting coating film has extremely good adhesion and water resistance (1.
There was no abnormality even after being immersed for a long time. Without the addition of epoxy resin, the coating was easily dissolved in acetone.

Comparative Example 1゜In order to compare the performance with acrylic emulsion polymers, an emulsion polymer with the following composition was tested using a normal emulsion polymerization method.

Made.

30- The resulting emulsion has a non-volatile fraction of 40.2% and a viscosity of 2
It had properties of 40 eps and PHa 8.

To 100 parts of the obtained acrylic resin emulsion was added 15 parts of an epoxy resin (average number of epoxy groups in the molecule: 2) with an epoxy equivalent weight of 314 obtained by the reaction of bisphenol A and epichlorohydrin, and a well-stirred and dispersed composition was prepared. . The above composition was applied on a steel plate to a dry film thickness of 2
It was coated to a thickness of 0 μm and dried at 100° C. for 20 minutes to form a coating film. When such a coating film was immersed in boiling water, it quickly turned white and significant blistering occurred over the entire surface.

Comparative Example 2゜In order to compare the performance with acrylic water-soluble resins, the following composition was polymerized in a solvent by a conventional method, and then neutralized and diluted with water.

Methyl methacrylate 350 parts Butyl acrylate 280 Dimethylaminoethyl methacrylate 70 Butyl Cero V
Lube 490 tert-butyl peroxybenzoate 780%
Formic acid 10 1,717 The properties of the resulting water-soluble resin were as follows: non-volatile content: 41.2%, viscosity: 26.000 cps, pH: 9.4. Epoxy equivalent weight 31 obtained by reacting bisphenol A and epichlorohydrin to 100 parts of the obtained water-soluble resin
4 epoxy resin (average number of epoxy groups in molecule: 2) 1
A composition was prepared by adding 5 parts of the mixture and stirring and dispersing it well. The above composition was applied on a steel plate to a dry film thickness of 20 μm, and dried at 100° C. for 20 minutes to form a coating film. When this coating film was immersed in boiling water, significant blistering occurred over the entire surface of the coating film in a relatively short period of time.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] It has one polymerizable vinyl group in the molecule, and the terminal group is H.
Or a Cl-4 alkyl group with a molecular weight of 1500 to 1
Add 1 to 15 parts by weight of a hydrophilic monomer (A) having 5,000 phosphoryoxyethylene chains, 1 to 15 parts by weight of a tertiary nitrogen-containing vinyl monomer (B), and other polymerizable vinyl monomers, and add the whole mixture. A polyepoxide compound having more than 1.0 epoxy groups in the molecule in an aqueous tertiary nitrogen-containing acrylic resin dispersion obtained by polymerizing 100 parts by weight of a polymerizable vinyl monomer in a water-soluble organic solvent and then dispersing it. An aqueous acrylic resin composition comprising adding (c).