JPS6067571A - Paint composition - Google Patents

Abstract

PURPOSE:To provide a paint composition for spraying mastic coating, etc., composed of a specific ethylene-acrylic copolymer containing a specific amount of an alpha,beta-ethylenic unsaturated monomer, and having high flexibility and excellent blocking resistance and stain resistance. CONSTITUTION:The objective paint is produced by the emulsion polymerization of (A) 99-60(wt)% alpha,beta-ethylenic unsaturated monomer and (B) 0-10% monomer containing copolymerizable polar group, in the presence of (C) 1-40% copolymer emulsion (based on total solid content) composed of (i) an emulsion having a particle diameter of 0.01-2.0mu and a solid concentration of 20-65% and consisting of 95-70% acrylic acid ester and/ormethacrylic acid ester, 5-30% ethylene and 0-10% copolymerizable polar-group containing monomer and/or (ii) an emulsion having a particle diameter of 0.5-4.0mu and a solid concentration of 20-65% and consisting of 95-40% vinyl acetate, 5-60% ethylene and 0-10% copolymerizable monomer containing polar group, and (D) an emulsifier.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating composition that is highly flexible, exhibits little slippage, that is, has good stain resistance, and is durable.

Conventionally, acrylic ester and/or methacrylic ester copolymer emulsions have been commercially available as acrylic emulsions9, and have been used to cover plants due to their excellent properties such as weather resistance, adhesion, and alkali resistance. However, the range of use may be limited because the coatings formed in these application fields often cause blocking. Methods for improving this blocking property include (1) making the copolymer harder by increasing the copolymerization amount of a monomer that forms a hard polymer, such as methyl methacrylate; Methods include emulsifying a sticky substance and adding it to an emulsion, and (3) introducing a crosslinking group into a polymer to internally crosslink it. however,
If a copolymer like (1) is hardened, the film formed will naturally become harder and blocking will be reduced, but the minimum film-forming temperature of the emulsion will increase, resulting in a decrease in film-forming properties.
Although the strength of the film increases, it has disadvantages such as decreased elongation and loss of flexibility. Addition of a non-adhesive substance such as (2) causes disadvantages such as a significant decrease in the adhesion of the film and bleeding due to poor compatibility between the waxy substance and the copolymer.

Furthermore, although it is relatively effective to reduce blocking through internal crosslinking of copolymers as described in (3), internal crosslinking reduces the elongation of the film, and if the crosslinking density becomes excessive, the film becomes brittle. Problematic noise occurs. In addition, introducing a crosslinkable functional group into a copolymer has a limit on the amount of copolymerization due to the stability of the emulsion and the copolymerizability of the crosslinkable functional group monomer, and blocking cannot necessarily be prevented. In many cases, sufficient amounts cannot be introduced. The present inventors have conducted intensive research to obtain a copolymer emulsion paint that forms a film that is highly flexible and has little blocking.
An excellent coating composition can be obtained by emulsion polymerizing α,β-ethylenically unsaturated a-mer in the presence of a copolymer emulsion obtained by emulsion copolymerizing acrylic ester or vinyl acetate with ethylene. The present invention was based on the discovery that this can be achieved.

That is, the present invention provides the following ethylene-acrylic copolymer emulsion (N and/or the following ethylene-vinyl acetate copolymer emulsion 4B) from 1 to 40% by weight (in terms of solid content, solid content of (A) and IBI). and the following (C) and (
relative to the total amount with Di) and in the presence of an emulsifier, α,
β-ethylenically unsaturated monomer (099-60% by weight ((
A) The solid content of zn+ (relative to the total amount of CI and manure) and the polar group-containing monomer copolymerizable with this (mD)
Emulsion obtained by emulsion polymerization of 0 to 10% by weight (same as above) (Coating composition-5 containing It) = The composition of the present invention is a general acrylic ester and/or
Alternatively, it is possible to form a film that is more flexible and less blocking than methacrylic acid ester synonymous V latex, and because the minimum film forming temperature of the emulsion is low, film forming properties are improved and the film has elasticity. The addition of ethylene improves both the strength and elongation of the film, and the introduction of ethylene improves the saponification resistance of the copolymer, improving the alkali resistance of the film. The crosslinkable copolymer copolymerized in a small amount exhibits special features such as providing a film with excellent solvent resistance through crosslinking.

The composition of the present invention having such features can be obtained by graft polymerizing a vinyl monomer of arbitrary hardness to an ethylene-acrylic copolymer emulsion (A) and/or an ethylene-vinyl acetate copolymer emulsion (Bl). This can be obtained by

Ethylene-acrylic copolymer emulsion (al CH!=CRI COOR2(R+:
Acrylic acid ester or methacrylic ester represented by hydrogen or methyl group, R2: alkyl group 95~
70 wt%s (bl ethylene 5-30 wt% and lc
) Consisting of 0 to 10% by weight of a polar group-containing monomer copolymerizable with these. In addition, ethylene-vinyl acetate copolymer emulsion (Bl is (d) 95 to 40% by weight of vinyl acetate represented by CH, =CH-00CCH, (e) 5 to 60% by weight of ethylene, and (Af) these. Consisting of 0 to 10% by weight of a copolymerizable polar group-containing monomer.Both of these copolymer emulsions have a solid content concentration of 20 to 65% by weight, the former having a particle size of 0.01 to 2.0 microns, and the latter having a particle size of 0.01 to 2.0 microns. It contains a polymer with a particle size of 0.5 to 4.0 microns.These are manufactured by adding each monomer under pressure of ethylene and emulsion copolymerizing.At this time,
Is the ethylene pressure 15-150 kg/cIr? A relatively low pressure of
(2) Pressure injection after the start of polymerization of acrylic ester and/or methacrylic ester, or vinyl acetate; (3) Pressure injection in the late stage of polymerization of acrylic ester and/or Kayatake methacrylic ester, or vinyl acetate. introduced by et al.

It is a constituent component of the ethylene-acrylic copolymer (
Examples of meth)acrylic acid esters include methyl, ethyl, propyl, n-butyl, and 1so- of (meth)acrylic acid.
Examples include esters such as butyl, t-butyl, n-amyl, hexyl, octyl, nonyl, f-7''yl, octadecyl, cyclohexyl, phenyl, and benzyl, and (meth)acrylic acid alkyl esters. Preferred. In addition, examples of polar group-containing monomers that can be copolymerized with these include carboxyl groups, sulfonic acid groups, glycidyl groups,
An unsaturated monomer having a polar group such as an amide group, a methylol group, a 7A/koxy group, a silanol group, or a hydroxyl group. Unsaturated acids or salts thereof, such as can carboxylic acid, vinyl sulfonic acid, 2-sulfonethyl (meth)acrylate, and styrene sulfonic acid; glycidyl compounds such as glycidyl (meth)acrylate; (meth)acrylamide and their N- Methylol compounds and their alkoxylated compounds; silane-containing α,β-ethylenically unsaturated monomers such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane; hydroxy group-containing monomers such as β-hydro-9-xyethyl methacrylate; α
.

Examples include β-ethylenically unsaturated monomers.

As mentioned above, the ethylene content in the ethylene-acrylic copolymer is 5 to 30% by weight, preferably 10 to 6% by weight.
If the amount is 0% by weight, the effect of the present invention cannot be obtained, and if it is less than 5% by weight, the adhesiveness decreases, and the transparency of the emulsion film tends to decrease. Undesirable. As mentioned above, the ethylene content in the ethylene-vinyl acetate copolymer is 5 to 60% by weight, preferably 20 to 60%, and if it is less than 5% by weight, the effect of the present invention cannot be obtained, and if it is less than 60% by weight, Exceeding this is not preferable because it tends to lower the adhesiveness and the transparency of the emulsion film. The polar group-containing monomer that can be used to synthesize each copolymer emulsion must have an unsaturated bond, and can improve the stability of the emulsion or impart -10= crosslinkability to the copolymer or copolymerize it. It is copolymerized for the purpose of improving adhesion to polar substances (base materials), etc., but if it exceeds 10% by weight in the copolymer, the stability of the emulsion tends to decrease, The alkali resistance and water resistance are also lowered, and the polarity of the co-electrode is increased, which causes blocking noise in the film, which is undesirable. In addition, during the production of each of the above copolymer emulsions, it is also possible to copolymerize other copolymerizable monomers, such as aromatic vinyl compounds such as styrene, vinyl halides such as vinyl chloride, etc. However, aromatic vinyl compounds have poor copolymerizability with ethylene, making it impossible to obtain a copolymer with a high ethylene content, and the degree of softening of the polymer by heat is large, making it difficult to copolymerize with so-called temperature-sensitive polymers. It is undesirable because it forms a high film thickness, tends to harden at low temperatures, and exhibits severe softening at high temperatures. In addition, vinyl halides such as vinyl chloride have little influence in this respect, and have good copolymerizability with ethylene and acrylic esters and methacrylic esters.
Although it has the advantage of producing a film with little blocking, which is the objective of the present invention, it has problems in light resistance and heat resistance9, and copolymerization of the low f' results in a film that easily yellows when exposed to heat or light. , it is preferable not to use either of these, as they are inappropriate unless such points pose a serious problem.

Examples of emulsifiers used in the production of these copolymer emulsions include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, other reactive emulsifiers, and substances with surfactant properties such as acrylic oligomers. Alternatively, two or more types can be used in combination. Among these, nonionic and anionic emulsifiers are preferred because they produce less aggregates during polymerization and provide stable emulsions. As the nonionic emulsifier, any commercially available nonionic emulsifier such as polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, ethylene oxide-propylene oxide block copolymer, etc. can be used, and As the anionic emulsifier, any of commercially available anionic emulsifiers such as alkylbenzene sulfonic acid alkali salts, alkyl sulfate alkali salts, and polyoxyethylene alkylphenol sulfate alkali lJ can be used. Furthermore, it is also possible to use all water-soluble oligomers in place of or in combination with the above-mentioned anionic emulsifiers, and in particular, those consisting of polycarboxylic acids or sulfonates are commercially available and are easily available. It is also possible to obtain a so-called soap-free emulsion composition. On the other hand, the protective colloid that is often used in emulsion polymerization is the emulsion 13 of the emulsion composition of the present invention.
- It is preferable not to use it in polymerization. That is, when water-soluble polymer substances such as polyvinyl alcohol and hydroxyethyl cellulose, which are generally used as protective colloids, are added to the aqueous phase of an emulsion polymerization system, the particle size of the resulting emulsion tends to become coarse; This is because the presence of the water-soluble polymer reduces the water resistance, weather resistance, etc. of the film. Even if it is used in temporary adhesives, it should be used in an amount of 1% by weight or less based on the weight of the copolymer. However, depending on the intended use, it is possible to adjust the viscosity of the formulation by adding a small amount of a water bath solution of these water-soluble polymer substances after producing the copolymer emulsion. However, in this case as well, it is necessary to adjust the amount used to the minimum necessary based on the relationship between the required water resistance, weather resistance, and so-called viscosity. The amount of emulsifier used is not particularly limited, but
Usually 0.1 to 10% by weight of the total amount of monomers including ethylene
used in degrees.

Catalysts used in the emulsion polymerization of each of the copolymer emulsions mentioned above include radical-forming catalysts such as water-soluble inorganic peroxides, persulfates, and organic peroxides, and these together with reducing agents and/or polymers. Redox catalytic systems based on the incorporation of valence metal ions may be mentioned. In addition, the polymerization temperature is 0℃
The temperature range is preferably between 10°C and 70°C, and is particularly preferably within the range of 10°C to 60°C from the viewpoint of solubility of ethylene in the aqueous phase and control of the polymerization rate of acrylic ester and/or methacrylic ester.

Furthermore, as a method for adding the catalyst and monomers other than ethylene to the polymerization system, 10 to 50% of the catalyst is added to the aqueous phase before the start of polymerization.
After adding 00 to 50% by weight of the total amount of monomers other than ethylene and adjusting the reaction temperature, the remaining catalyst and monomers were added to
A method in which polymerization is carried out dropwise over a period of up to 24 hours is preferable; by this method, it is easy to control heat generation during polymerization, and an emulsion composition with stable quality can be obtained. The monomers other than ethylene may be used as they are or after being emulsified in advance with an emulsifier and a portion of water. Furthermore,
During emulsion polymerization, it is also possible to replace part of the water with a water-soluble organic solvent to increase the solubility of ethylene in the dispersion medium phase and thereby increase the total content of ethylene in the copolymer. , lower alcohols such as propyl alcohol are preferred, and 6th-butyl alcohol is particularly preferred. However, if a large amount of AtC is used, the stability of the emulsion decreases.

Since it acts as a chain transfer agent during polymerization and lowers the molecular weight of the copolymer produced, the lid used is 2 times the amount of water in the aqueous phase at the initial stage of the reaction.
It should be less than 5% by weight.

The ethylene-acrylic copolymer emulsion and ethylene-vinyl acetate copolymer emulsion obtained as described above have a practically and economically preferable solid content concentration of 20 to 65 weight depending on the amount of water during emulsion polymerization. %, and their particle diameters are adjusted within the ranges mentioned above by combining emulsifiers and polymerization conditions. The particle size of the polymer in the emulsion can be adjusted by (1) increasing the amount of emulsifier used, (2) increasing the HLB'i of the emulsifier used, (3) lowering the solid content concentration during emulsion polymerization, (4) It can be made smaller by increasing the initial addition of emulsifier, and it can be made larger by doing the opposite. By combining these methods, the particle size of the polymer can be easily adjusted. Generally, the smaller the particle size, the better the film-forming properties and the better the formation of a tight film, which is preferable. However, if the particle size is too small, the miscibility of the final emulsion with various substances such as pigments and fillers may deteriorate. Application of the resulting coating composition to a porous surface results in excessive penetration, which is undesirable.

The composition of the present invention comprises an ethylene-acrylic copolymer emulsion and/or an ethylene-acrylic copolymer emulsion synthesized as described above.
Vinyl acetate copolymer emulsion (B) 1 to 40% by weight
(solid content = 17-) and in the presence of an emulsifier, α, β-ethylenically unsaturated monomer (2E(C) 99 to 60% by weight and polar group-containing monomer copolymerizable therewith mD) 0 to 10% by weight was emulsion polymerized using a radical-generating catalyst at a temperature of 0 to 90°C so that the total amount was 100% by weight. The amount of the ethylene copolymer emulsion (A) and/or (B) used is determined by the solid content of (N and IBI and (C).
) and (parrot).If the amount used is less than 1% by weight, the effect of improving the flexibility, stain resistance, durability, etc. of the resulting coating film cannot be obtained. Exceeding the weight percentage is not preferable because the secondary physical properties of the resulting coating film, such as strength and elongation after water immersion, decrease.

Examples of the α,β-ethylenically unsaturated monomer used in the present invention include (meth)acrylic esters, such as methyl, ethyl, propyl, n-butyl, I-butyl, t-butyl, n18-amyl, l -amyl, hexyl, octyl, nonyl,
Esters such as decyl, dodecyl, octadecyl, cyclohexyl, phenyl, benzyl; vinyl esters, such as vinyl acetate, vinyl propionate, vinyl butylade, vinyl versatate, etc.; vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether , amyl vinyl ether, hexyl vinyl ether, etc.; vinyl cyanides, such as acrylonitrile; aromatic vinyl compounds, such as styrene, vinyl toluene, etc.; olefins, such as ethylene; dienes, such as butadiene; vinyl halides, such as vinyl chloride, vinylidene chloride, etc.; Unsaturated dibasic acid alkyl diesters include, for example, dialkyl maleate, dialkyl fumarate, dialkyl itaconate, etc., and one or more of these may be used.

In addition, the copolymerizable polar group-containing monomer used in the synthesis of the above emulsion (1) is used in the synthesis of ethylene-acrylic copolymer emulsion and ethylene-vinyl acetate copolymer emulsion. It may be the same as those that can be used.

Further, the amount of the polar group-containing monomer used is 10% by weight or less, preferably 0.5 to 8% by weight. It is preferable to use this polar group-containing monomer because it improves pigment dispersibility and coating film durability, but if the amount exceeds 10% by weight, the alkali resistance of the coating film decreases and efflorescence occurs in weather resistance. This is not desirable because it occurs. As the radical initiator used in emulsion (scent) synthesis, oil-soluble, water-soluble, or redox-based radical initiators can be used.

Emulsion (reaction temperature during polymerization is usually 0°C to 9°C)
It will be held in 09C.

In addition, emulsifiers are usually used when synthesizing emulsions (odors), and such emulsifiers include those used when synthesizing ethylene-acrylic copolymer emulsions and ethylene-vinyl acetate copolymer emulsions. There is no problem, and the amount used may be the same.

In addition, as a polymerization initiator commonly used in the synthesis of emulsions (smells), any catalyst commonly used in emulsion polymerization can be used, including ethylene-acrylic copolymers and ethylene-vinyl acetate copolymers. It may be the same as that used in the synthesis of the combined emulsion.

The amount used is about 0.1 to 2% based on the total weight of the monomers.

The various monomers described above used for synthesizing the emulsion may be added all at once, in portions, or continuously dropwise, and in the presence of the catalyst described above, Polymerization is carried out at a temperature of 0 to 90°C, practically 30 to 90°C.The emulsion thus obtained is mixed with heavy calcium carbonate, light calcium carbonate, kansui powder, goko powder, kaolin clay, and Narilay, talc, silica sand, silica lime,
Bentonite, asbestos, pulp powder, white carbon, ultrafine anhydrous silica, dolomite powder, magnesium carbonate.

Precipitated barium sulfate, lithopone, titanium oxide, zinc white,
Fillers or pigments such as iron oxide, carbon black, chromium oxide, and ultramarine; phthalate esters such as dibutyl phthalate and dioctyl hepthalate; aliphatic dibasic acid esters such as diisodecyl succinate and dioctyl adipate; Various plasticizers such as phosphoric acid esters such as cresyl phosphate, glycol esters such as diethylene glycol dibenzoate, epoxy plasticizers such as epoxidized soybean oil, chlorinated paraffins, polyoxyethylene alkyl phenyl ethers, and polybutene. ;
Various anionic and nonionic surfactants; pyrophosphoric acid, tripolyphosphoric acid,
Dispersants such as salts of condensed phosphoric acid such as hexametaphosphoric acid, polycarboxylic acid salts, and naphthalene sulfonate salts; Drying regulators such as mineral spirits and turpentine oil;
A coating composition can be obtained by appropriately blending ethylene glycol, propylene glycol, glycerin, methanol, etc., a freezing agent, a melting stabilizing agent, an antifoaming agent, a preservative, and the like. The resulting coating composition of the present invention is highly flexible and has little blocking, that is, has good stain resistance.
It is suitable as a single-layer sprayed mastic paint, a multi-layer sprayed mastic paint, a removable paint, etc. that forms a durable coating film, and can also be used as a caulking material.

Next, the present invention will be explained in more detail with reference to Examples, but the scope of the present invention is not limited thereby.

All parts and percentages shown below are based on weight.

Production Example-1 (Production of ethylene-acrylic copolymer emulsion powder) Electromagnetic stirrer, pressure-resistant dropping funnel, thermometer, gas introduction pipe,
The following raw materials were charged into a pressure-resistant reactor equipped with a system pressure equalization pipe, a safety valve, and a pressure gauge.

Water 129 parts Thiethylene nonylphenyl sulfate ammonium salt; Dai-Kogyo Seiyaku Co., Ltd. product) 200,003 parts FeCl,.6H The above raw materials were dissolved at a temperature of 50°C for 30 minutes, and then cooled to a total temperature of 25°C. . Next, after removing all the air in the pot with nitrogen gas, ethylene k 10 kg/cII?
The pressure was then reduced to 2 to 5 kg/crl.

After repeating ethylene injection and pressure reduction twice, the pressure inside the pot was maintained at 20 kvcrIL'' using ethylene.

Thereafter, 10% of a premixed monomer mixture consisting of 50 parts of ethyl acrylate, 48 parts of methyl methacrylate, and 2 parts of acrylic acid was added, and then 0% of sodium pyrosulfite was added.
．． A solution of 5 parts dissolved in 5 parts water was added to the kettle. After stirring for 5 minutes, 10 parts of a 2% aqueous solution of potassium persulfate was added to initiate polymerization, and the internal temperature was raised to 45°C while controlling heat generation, and the remaining monomer (90% of the total amount) was added. and 15 parts of a 2% aqueous potassium persulfate solution were added dropwise over 3 hours to polymerize. Immediately after starting the dropwise addition of the monomer and catalyst aqueous solutions, ethylene was further added to maintain the ethylene pressure during the reaction at v6 okp/i, and the temperature was maintained at 45°C.

After dropping the monomer and catalyst aqueous solutions, the ethylene pressure and temperature were maintained at the same level as during the dropping reaction for another 2 hours, and then 25 hours.
It was cooled to 25°C. After cooling, ethylene pressure f: 2-3 kg
/crI? The pressure was further reduced to about 50 s+tHg to remove unreacted ethylene gas, and 0.4 part of a 25% ammonia aqueous solution was added to adjust the pH to 75.

The obtained emulsion had a solid content concentration of 45.0% and a viscosity of 1.
80 eps (BM type rotational viscosity needle rotor/I62, number of revolutions 6 Orpm, temperature 25° C.), pH 7.5, p, and the average particle diameter measured with an electron microscope was 0.06 μm.

Furthermore, the copolymer in the obtained emulsion was saponified with caustic soda, and the total ethylene content was measured to be 17%.

This emulsion is called eA-1.

Production Example 2 (same as above) An aqueous solution in which the following raw materials were dissolved in advance was placed in a pressure-resistant reaction vessel.

Water 100 parts 26- Emal 0 (sodium lauryl sulfate; 1.5 parts Kao Atlas product) Sodium bicarbonate 0.4 parts Then, after adjusting the temperature to 30°C, 96 parts of butyl acrylate.

0.3 part of methyl methacrylate and 0.1 part of acrylic acid were mixed in advance and added, and the air in the pot was replaced with nitrogen gas.

Thereafter, an aqueous catalyst solution dissolved in 0.2 parts of ammonium sulfate and 5 parts of gold water pressurized to 2 parts with nitrogen gas was added, and the temperature was gradually raised. Polymerization started at 50°C, and the temperature was further raised to 60°C while controlling heat generation. At this temperature, 864 parts of butyl acrylate, 2 parts of methyl methacrylate,
．． A catalyst aqueous solution prepared by dissolving 7 parts of acrylic acid, 0.4 parts of gold and 0.6 parts of ammonium persulfate in 25 parts of water was added dropwise for polymerization over a period of 4 hours for the former and 5 hours for the latter. . During this time, 1 hour after the start of dropping the catalyst and monomer, ethylene was pressurized into the kettle and the internal pressure of the kettle was increased to 4.
The pressure was set at 0 ky/cd and maintained at this pressure during the polymerization. After dropping the catalyst solution, the same temperature and pressure were maintained for 2 hours, and then the ethylene pressure in the pot was gradually reduced to 2-3 kg/ld, and then the unreacted ethylene and monomers were removed by reducing the pressure to 50 miHg. After removing the solids, the pressure was returned to normal pressure, cooled, and taken out. Then, the pH of the emulsion was adjusted to 8.0 with 25% ammonia water.

The obtained emulsion had a solid content concentration of 44.8% and a viscosity of 1.
The average particle size of the copolymer was 0.1 micron. Also, the ethylene content in the copolymer is 6.8
%Met.

This emulsion is designated as A-2.

Production Example-3 (Production of ethylene-vinyl acetate copolymer emulsion (B)) Dodecylbenzene sulfo Δ dredge sorter 1.5 parts Water 60
Part Fe C1,.6H, 00,003 parts The above ingredients were placed in an autoclave equipped with a stirrer and heated at 50°C.
After dissolving for 0 minutes, the mixture was cooled to 25°C. Next, after removing air with nitrogen gas, ethylene was pressurized to 9/ld in 10 and then reduced to 9/ld in 2 to 3. Furthermore, after repeating the injection of ethylene and depressurization twice, the pressure inside the pot was increased to 20 kl with ethylene. /(kept at n”. Then,
Add 40 parts of vinyl acetate, and add 0.0 parts of sodium pyrosulfite.
5 parts were dissolved in 5 parts of water and added to the pot. The mixture was stirred for 5 minutes while keeping the ethylene pressure at 60.9/L at a temperature of 30.degree. C., and 10 parts of a 2% ammonium sulfate aqueous solution was added to initiate polymerization. After polymerization for 15 hours while maintaining the copolymerization temperature at 30 to 35°C, the copolymer was cooled to 25°C, and the unreacted ethylene gas was removed after reducing the pressure to 2 to 5 kg/1 m)'. 0.2 part of a 25% aqueous ammonia solution was added to the resulting emulsion to adjust the pH to 5.5.

The resulting emulsion had a solid content of 40.2%, an ethylene content of 41.2%, a viscosity of 670 cps, and a copolymer particle size of 1.0 micron. This emulsion is designated as B-1.

29-ar Example-4 (Production of ethylene-acrylic copolymer emulsion (A)) In Production Example 1, except that the emulsifier was changed to 01.5 parts of emal and the reducing agent was changed to 0.4 parts of sodium bicarbonate. Manufacturing example 1
An emulsion was obtained in exactly the same manner. The resulting emulsion had a solid content of 40.2% and an ethylene content of 35.7%.
%, viscosity 400ep8, and particle size of the copolymer 1.
It was 5 microns.

This emulsion is designated as A-3.

Examples 1 to 4 and Comparative Example 1 (a) A condenser, a thermometer, and a dropping funnel were placed in a stainless steel reaction container equipped with a stirrer, and after replacing the air in the container with nitrogen, a solution of the following composition (formulation 1) was prepared. I prepared it.

(Formulation 1) 200 parts of deionized water 5 parts of Emulgen 120 (manufactured by Kao Atlas Co., Ltd.) 250 parts of the ethylene copolymer obtained in the production example Emulsion (adjusted to a solid content concentration of 40%) 30 The temperature was adjusted to 80 parts at 2°C, and a solution with the following composition (Formulation 2) and an aqueous catalyst solution in which 1.5 parts of potassium persulfate was dissolved in 50 parts of deionized water were added dropwise over 180 minutes to perform polymerization. Ta. During this time, the temperature inside the reaction vessel was adjusted to 80 parts and 2°C. After the dropwise addition was completed, the mixture was stirred at the same temperature for 1 hour. After stirring, the contents are heated to 30°C.
The mixture was cooled to pH 7 to 9 with 28% aqueous ammonia, and filtered.

(Formulation 2) Butyl acrylate 175.5 parts Methyl methacrylate 214.5 Methacrylic acid 10.0 Deionized water 12G.0 Emulgen 120 10.0 Neogen R16.5 The obtained emulsion had a solid content concentration as shown in Table 7. It was stable.

For comparison, the above emulsion was produced in exactly the same manner as in Example 1 except that the ethylene copolymer emulsion obtained in Production Example was not used and the amount of deionized water in Formulation 1 was changed to 250 parts. An emulsion whose concentration was adjusted to 50% was obtained.

Examples 5 to 8 and Comparative Example 2 In Examples 1 to 4, the addition amount of the ethylene copolymer emulsion obtained in the production example was 500 parts, and the amount of deionized water used was 163 parts. All were reacted in the same manner to obtain an emulsion whose solid content concentration was adjusted to 50%. For comparison, the reaction was carried out in the same manner except that the amount of the ethylene copolymer emulsion obtained in the production example used was 1250 parts and the amount of deionized water was 0 parts during the production of the above emulsion, and the solid content concentration was 49%. An emulsion was obtained.

Examples 9 to 12 and Comparative Example 3 In Examples 1 to 4, except that the composition of Formulation 2 was changed to the following Formulation B, the reactions were carried out in the same manner to obtain emulsions whose solid content concentration was adjusted to 50%. For comparison, Example 9
The experiment was conducted without using the copolymer emulsion obtained in Production Example 1.

Examples 13 to 16 and Comparative Examples 4 to 5 In Examples 1 to 4, the reaction was carried out in the same manner except that the composition of Formulation 2 was changed to the above Formulation 4, and the solid content concentration was 50%.
Adjust to the following and obtain the emulsion. For comparison, in Example IK, the reaction was carried out in the same manner except that the composition of 33-Formulation 2 was changed to the following composition 5 or the following composition B, and the solid content concentration was 50.
An emulsion adjusted to % was obtained.

Each emulsion composition of Examples 1 to 16 and Comparative Examples 1 to 5 was used to obtain each coating composition according to the coating composition shown in Table 1. The coating composition has a PVC of 21.5% and a PWC of 50%.

34- Table 1 (Paint formulation) 1) Rutile-type titanium oxide: Right-hand Industry ■, 2) Surfactant: Kao Soap ■, 3) Polycarboxylic acid dispersant: Rohm and Haas Company (USA)% 4) Methyl cellulose: Shin-Etsu Chemical ■, 5) Antifoaming agent: Sannopco ■ Table 2 shows the physical properties of the obtained composition.

Test method〉 Emulsion minimum film forming temperature - Apply the emulsion using a 0.05 mg applicator on a stainless steel plate with a temperature gradient where one end is cooled to -1D°C and the other end is heated to 60°C and dried. Thereafter, the boundary temperature between the area where the emulsion formed a continuous film and the area where the continuous film was not formed was measured with a thermocouple thermometer and determined as the minimum film forming temperature.

Strength and elongation of coating film: Testing machine: Tensilon VTM, tensile speed = 200 min/min Sample (1) Film thickness: approx. 0.7 mm (23°C, 60%
RHX (dried for 14 days) Measurement conditions using a No. 2 dumbbell punched specimen: 23°C and -10°C Coating film strength and elongation after water resistance: A specimen of the above sample (1) was placed in water (2
After soaking at 3°C for 24 hours, drying in a 60°C dryer for 24 hours, and then drying for 24 hours at 23°C and 60% RH, measurements were taken.

Alkali resistance of paint film: The paint was applied to a slate board with a 6 mil applicator, dried for 5 days at 26°C and 60% RH, and then immersed in a 5% NaOH room temperature aqueous solution (23°C) for 1 day or 7 days. , changes were visually observed.

The evaluation is ◎(excellent)〉○(good)〉△(average)〉×
(Poor) Stain resistance of the paint film: The paint was applied with a roller to a slate board, and after drying at 23°C and 60% RH for 2 days, an exposure test was conducted to visually check the degree of stain resistance of the paint film. I observed it. The evaluation is expressed as: Good (O)〉37- Average (△)〉Poor (×).

Blocking resistance of the coating The coating was applied onto a glass plate using a 3 mil applicator, dried at room temperature for 1 day, and then heated at 50°C for 3 mils.
After 0 minutes of treatment, a nylon pile was sprinkled on the sample, and the sample was taken out at 50° C. for 10 minutes, and the state of adhesion of the pile was visually observed.

The evaluation is good (O)〉fair (Δ)〉poor (×) Displayed in

Stability of paint: The state of the paint composition was observed after it was placed in a container in a dryer at 50°C, sealed and left for one month.

The evaluation was expressed as ○ (good), △ (fair), and × (poor).

38-

Claims (1)

[Claims] The following ethylene-acrylic copolymer emulsion (A)
and/or the following ethylene-vinyl acetate copolymer emulsion (B) 1 to 40% by weight (in terms of solid content, the solid content of (A) and IBI and the following (based on the total amount of Cl and (DJ)) and In the presence of an emulsifier, α, β-ethylenically unsaturated monomer (099 to 60% by weight (based on the total amount of solid content of (A) and IBI and (C) and D below) and this An emulsion (coating composition) obtained by emulsion polymerization of 0 to 10% by weight (same as above) of a polar group-containing monomer (D) copolymerizable with ethylene-acrylic copolymer emulsion ( A) Contains 95 to 70% by weight of diacrylic ester and/or methacrylic ester, 5 to 30% by weight of ethylene, and 0 to 10% by weight of a polar group-containing monomer copolymerizable with these, particle size 0.01 ~2.0 microns, solids concentration 2
0-65% by weight copolymer emulsion. Ethylene-vinyl acetate copolymer emulsion (B):
Vinyl acetate 95-40% by weight, ethylene 5-60% by weight
and 0 to 10 polar group-containing monomers copolymerizable with these
% by weight, a particle size of 0.5 to 4.0 microns, and a solid content concentration of 20 to 65% by weight.