JPS5942706B2 - Dark-curing water-based paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-based paint that cures at room temperature and has a high degree of durability and non-polluting properties.

Conventionally, oil-based or synthetic resin-based organic solvent paints have been used as highly durable room-temperature-curing paints, but these paints also have problems with pollution such as odor and air pollution caused by solvents.
The development of highly durable water-based paints that cure at room temperature has been an important issue due to social demands.

As such a water-based paint, for example, there is a water-based emulsion paint described in JP-A No. 48-73488, but this emulsion has drawbacks such as curing too quickly and poor fusion properties of emulsion particles. Therefore, when used in a wide range of environments, the coating workability is insufficient. In particular, it has drawbacks such as being extremely difficult to apply under high temperature and low humidity conditions. An object of the present invention is to provide a cold-curing water-based paint that eliminates the above-mentioned conventional drawbacks.

An object of the present invention is to provide a water-based paint that cures at room temperature and provides a coating film with high water resistance and weather resistance. An object of the present invention is to provide a water-based paint that cures at room temperature and has excellent coating workability and storage stability.

That is, the present invention provides (1) a neutralized product of 5 to 95 parts by weight (solid content) of a maleated 1,2-vinyl polybutadiene resin and a maleic acid-modified unsaturated oil and/or an unsaturated fatty acid-modified water-soluble resin; Using a mixture containing ~95 parts by weight (solid content) as an emulsifier, the Q value of the Q-e theory is about 0.1 or more and the general formula CH2-C(R_4)COOR_2 (however, R_1
is hydrogen or a methyl group; when R_ is hydrogen, R_2 is an alkyl group having 2 to 14 carbon atoms; when R is a methyl group, R2 is an alkyl group having 1 to 14 carbon atoms; Vinyl obtained by emulsion polymerization of one or more polymerizable vinyl monomers selected from methacrylate, allyl acrylate, allyl methacrylate, hydroxyethyl methacrylate, styrene, vinyltoluene, α-methylstyrene, and methacrylonitrile. Polymer emulsion and (2)
A fatty acid modified monomer obtained by reacting an unsaturated fatty acid having a non-conjugated double bond with a glycidyl ester of an α-β-ethylenically unsaturated acid, an α,β-ethylenically unsaturated acid, and the above polymerizable vinyl monomer. The invention relates to a water-soluble paint that cures at room temperature and contains a water-soluble or water-dispersed copolymer resin.

The water-based paint of the present invention has the same coating film performance as the paint using the emulsion disclosed in JP-A-8-73488, but can greatly improve painting workability, especially brushing workability.

In the present invention, a neutralized product of maleic acid-modified unsaturated oil and/or A saturated fatty acid-modified water-soluble resin (hereinafter referred to as a water-soluble substance containing an oil and fat structure) is maleated with 1,
By using the maleated 1,2-vinyl polybutadiene resin in combination with the 2-vinyl polybutadiene resin, the above-mentioned drawbacks of the maleated 1,2-vinyl polybutadiene resin as an emulsifier can be solved. It is possible to take advantage of the advantages of the resin.

When emulsion polymerization is carried out using a simple chain transfer agent as an emulsifier instead of the oil-and-fat structure-containing water-soluble substance of the present invention, many oxidative crosslinks occur because the vinyl monomer chain is cut by the chain transfer agent. This results in a polymer that is hard to cure, resulting in poor curability and may not harden over time.

On the other hand, when chain transfer is performed using the water-soluble substance containing an oil and fat structure of the present invention, a vinyl monomer is graft-polymerized to the radicals generated in the water-soluble substance by chain transfer to produce a polymer, and at least one end of this polymer is oxidized. Due to the presence of crosslinkable semi-drying oil or drying oil type unsaturated bonds, it can be completely cured.

If the resin containing the fatty acid groups of the semi-drying oil and/or drying oil is not water-soluble, it must be made water-solubilized; if used without water-solubilization, it will mix (be compatible) with the vinyl monomer and form the emulsion particles. Mixed inside, maleated 1,2-
Because it exists in a different location from vinyl-type polybutadiene resin, it cannot fully demonstrate its effectiveness as an emulsifier. The maleated 1,2-vinyl polybutadiene resin in the present invention is, for example, (1) 1,2-vinyl polybutadiene, (2) a copolymer of butadiene and another polymerizable unsaturated monomer (butadiene units are 10% by weight or more, preferably 40% by weight or more) or (3) a resin such as a modified polymer of the above polybutadiene or polybutadiene copolymer (number average molecular weight is preferably about 200 to about 20,000,
(more preferably about 500 to 10,000) is neutralized to be water-solubilized or water-dispersed. Comonomers for producing the above polybutadiene copolymer include, for example, styrene, α-methylstyrene, vinyltoluene, olefin monomer, diene monomer (excluding butadiene), acrylonitrile, methacrylonitrile, acrylic ester, methacrylate ester. Vinyl monomers commonly used in the art, such as, are used. Modification methods for obtaining the modified polymer include hydrogenation, epoxidation, hydroxylization, cyclization, etc., and the modification may be performed either before or after maleation. The maleated 1,2-vinyl polybutadiene resin before neutralization preferably has a total acid value of 20 to 35.
0, more preferably 40-250. After maleation, esterification and amidation can also be carried out. maleation l
When maleic anhydride is used, the acid anhydride group is ring-opened with water, alcohol, ammonia, amine, etc., and then neutralized with ammonia, amine, alkali metal compound, etc. to make it water-soluble. When ammonia or amine is used as a ring-opening agent, neutralization can also be carried out at the same time. When maleic acid is used for maleation, the ring-opening step can be omitted, and the above-mentioned neutralizing agents can be used for neutralization. Among the oil-and-fat structure-containing water-soluble substances in the present invention, the unsaturated fatty acid-modified water-soluble resins include:
Examples include fatty acid-modified water-soluble alkyd resins containing trimellitic acid or dimethylolpropionic acid as one component, maleated fatty acid-modified alkyd resins, maleated fatty acid-modified epoxy resins, fatty acid-modified acrylic resins, etc. Examples of neutralized products of saturated oil include neutralized products such as maleated oil, maleated stand oil, and maleated pole oil. Typical fatty acid-modified acrylic resins listed above include, for example, glycidyl (meth)acrylate, 2-hydroxyethyl methacrylate, (meth)acrylic acid, (meth)
Examples include those obtained by copolymerizing with acrylic acid ester or the like and reacting the remaining glycidyl groups and hydroxyl groups with fatty acids. The oil-and-fat structure-containing water-soluble substance of the present invention preferably has a number average molecular weight of 350 to 20,000, a total acid value of preferably 20 to 350, more preferably 40 to 250, and a fatty acid oil length of preferably 15 or more, more preferably is preferably 25 or more, and these are neutralized and made water-soluble. When the acid value is in the range of 20 to 350, the resin can be easily water-solubilized, and the resulting coating film has good water resistance and coating surface condition, which is preferable. Examples of the fats and fatty acids used in the production of the water-soluble substance containing an oil and fat structure include semi-drying oils, drying oils, and their fatty acids.Specifically, examples include safflower oil, linseed oil, soybean oil, sesame oil, Poppy oil, eno oil, hempseed oil, grape kernel oil, corn oil,
Tall oil, sunflower oil, cottonseed oil, walnut oil, sesame seed oil and their fatty acids are preferred, and tung oil, ostica oil, dehydrated castor oil and their fatty acids and high diene fatty acids can also be used. As a modification method for obtaining a water-soluble substance containing an oil and fat structure, a well-known modification method used for obtaining modified resins and modified oils can be used. In the present invention, such a water-soluble substance containing an oil and fat structure and the maleated 1, 2
A polymerizable vinyl monomer is emulsion polymerized using a mixture containing -vinyl type polybutadiene type Shinko resin as an emulsifier to obtain an emulsion.

The mixing ratio of both components in such an emulsifier is as follows:
5 to 95 parts by weight, preferably 1 to 95 parts by weight, preferably 10 to 90 parts by weight of the water-soluble substance containing an oil and fat structure
The amount is preferably 0 to 90 parts by weight. The mixing ratio is 5 above.
-95: When the ratio is in the range of 95 to 5 (parts by weight), the coating workability and curing of the coating film are excellent, and the resulting coating film does not become porous or crack, which is preferable. In addition, when both of the above-mentioned resins are maleated, both resins may be mixed before maleation and then maleated, or the maleated resins may be mixed.

Examples of polymerizable vinyl monomers used in the present invention include those having a Q value of approximately 0.1 or more as determined by the Q-e theory. It is not recommended to use it for

In the present invention, the polymerizable vinyl monomer is of the general formula CH2C(R1)COOR2 (where R1 is hydrogen or a methyl group, when R1 is hydrogen, R2 is an alkyl group having 2 to 14 carbon atoms, and when R1 is a methyl group, R2 represents an alkyl group having 1 to 14 carbon atoms), allyl acrylate, allyl methacrylate, hydroxyethyl methacrylate,
Styrene, vinyltoluene, α-methylstyrene and methacrylonitrile are used. These polymerizable vinyl monomers may be used alone or in combination of two or more, and furthermore, the vinyl monomers may contain about 10% by weight or less of acrylic acid, methacrylic acid, itaconic acid, acrylamide, methalylamide, and N-methylacrylamide. , N-
Ethyl acrylamide, dimethylaminoethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, hydroxyethyl acrylate,
Water-soluble or hydrophilic vinyl monomers such as vinylpyridine, acrylonitrile, methyl acrylate, vinylpyrrolidone and acrolein may also be used in combination. At this time, if the emulsifier of the present invention is used in the emulsion polymerization of polymerizable vinyl monomers such as vinyl acetate whose Q value determined by the Q-e theory does not reach 0.1, the activity of the radicals produced from the monomer is too strong. This reacts too much with the maleated 1,2-vinyl polybutazinine resin, inhibiting the polymerization reaction. The ratio of the emulsifier to these polymerizable vinyl monomers is such that the acid value in the total solid content of the produced emulsion before neutralization is preferably about 3 to 150, more preferably about 15.
It is desirable to set the value to 50. However, if acrylic acid or methacrylic acid is added as a monomer, the acid value of these acids shall not be taken into account. The solid content concentration of the emulsion composition is preferably about 15 to 65 (Ft). As the emulsion polymerization method, generally known methods can be used. For example, monomers are dispersed in an aqueous medium, and the emulsifier of the present invention is used in the presence or absence of an aqueous or oil-based initiator to form a system. Radical polymerization may be carried out between the freezing point and the boiling point of the emulsion under stirring until it becomes an emulsion state, and after it becomes an emulsion state, under stirring or standing still. In order to obtain a water-based paint that cures at room temperature with higher gloss using the emulsion thus obtained, in the present invention (4) glycidyl of an α,β monoethylenically unsaturated acid is added to the unsaturated fatty acid having a nonconjugated double bond. Fatty acid modified monomer obtained by reacting ester, (B) α,
Achieving the objective by jointly using a β-monythylenic unsaturated acid and a water-solubilized or water-dispersed copolymer resin made of a polymerizable vinyl monomer having a Q value of (0Q-e theory of about 0.1 or more) was completed.

In the present invention, the unsaturated fatty acids used to obtain the fatty acid-modified monomer prison include drying oil and semi-drying oil fatty acids having non-conjugated double bonds.

For example, safflower oil fatty acids, linseed oil fatty acids,
Soybean oil fatty acids, sesame oil fatty acids, poppy oil fatty acids, eno oil fatty acids, hempseed oil fatty acids, grape kernel oil fatty acids, corn oil fatty acids, tall oil fatty acids, sunflower oil fatty acids, cottonseed oil fatty acids, walnut oil fatty acids, rubber seed oil fatty acids, etc. .
The amount of these unsaturated fatty acids to be used is usually 5 to 65% by weight based on the copolymer resin in view of the relationship between drying properties and coating performance. If necessary, a conjugated fatty acid such as tung oil fatty acid, oiticica oil fatty acid, dehydrated castor oil fatty acid, or hydene fatty acid may be added together with the unsaturated fatty acid having a non-conjugated double bond, and in this case, the amount used is preferably 30% by weight or less based on the total unsaturated fatty acids. In addition, α, which is the other raw material for obtaining the fatty acid modified monomer (4),
As the glycidyl ester of β-ethylenically unsaturated acid, for example, glycidyl acrylate or glycidyl methacrylate can be used, and the amount thereof is preferably 0.8 to 12 moles per mole of unsaturated fatty acid.

Examples of the α,β monoethylenically unsaturated acid (B) used in the present invention include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc., and are usually used in copolymer resins. It is used in an amount of 5 to 20% by weight. Q used in the production of the above copolymer resin in the present invention
- A polymerizable vinyl monomer with a Q value of about 0.1 or more (
0 is a polymerizable vinyl monomer described as having a Q theory of about 0.1 or more in the Q,e theory used in the production of the vinyl polymer emulsion of the present invention.

These polymerizable vinyl monomers may be used alone or in combination of two or more. These polymerizable vinyl monomers with a Q value of about 0.1 or more (O is usually 20% in the copolymer resin)
~70% by weight is used. Polymerizable vinyl monomers (such as vinyl acetate) whose Q value does not reach 0.1 tend to gel during the copolymerization reaction, so the synthesis conditions for the fatty acid-modified monomer (4) are based on the unsaturated fatty acid used. Although it varies depending on the type, generally the reaction temperature is 60 to 220°C, preferably 120 to 170°C, and the reaction time is 0.5 to 40 hours, preferably 10 to 30 hours.

Fatty acid modified monomer (4), α, β monoethylenically unsaturated acid (B), and a polymerizable vinyl monomer with a Q value of about 0.1 or more according to the Q-e theory (the copolymerization reaction of O is an acrylic resin) It can be carried out by employing a conventionally known polymerization method to obtain the reaction temperature, generally at a reaction temperature of 0 to 200°C, preferably 40 to 170°C.
The reaction time may be 1 to 20 hours, preferably 6 to 10 hours.

The reaction is carried out when the number average molecular weight of the copolymer is usually 500 to 8000.
0, preferably 1,000 to 50,000. In addition, to prevent gelation during the copolymerization reaction,
It is desirable to use a solvent that dissolves the copolymer and is soluble in water. Particularly preferred are those that can be used as they are without being removed when obtaining an aqueous coating composition. An example of such a solvent is HO-CH2CH2-0R (R is H or C
1-C8 alkyl group) cellosolve solvents, such as ethylene glycol, butyl cellosolve, ethyl cellosolve, etc., HO-CH2CH2-0CH2CH2-0R
(R is H or a C1-C8 alkyl group) carbitol solvents, such as diethylene glycol, methyl carbitol, butyl carbitol, RlO-CH2C
H2-0R2 (R1 and R2 are C1 to C3 alkyl groups)
gram-based solvents such as ethylene glycol dimethyl ether, R2O-CH2CH2OCH2-CH2
OR2 (R and R2 are C, ~C3 alkyl groups) diglyme solvents such as diethylene glycol dimethyl ether, RO-CH2CH2OCO-CH3 (R is H or CH3 is C2H5) cellosolve acetate solvents such as ethylene glycol mono Acetate, methyl cellosolve acetate, etc., diacetone alcohol, dioxane, tetrahydrofuran, acetone, dimethylformamide, etc. can be used.

Even if it is not soluble in water, any solvent with a boiling point of 250° C. or less can be used in the same manner, as it can be removed by distillation at normal pressure or reduced pressure after the polymerization reaction is completed. For example, [/″/1]
(R is H or a C1-C4 alkyl group)
, R2 is a C, ~C4 alkyl group), such as benzene, toluene, xylene, etc., R1
-COO-R2 (R, is a C, ~C6 alkyl group, R2
is H or an acid or ester represented by a C1-C6 alkyl group or cyclohexyl group, such as ethyl formate, butyl acetate, cyclohexyl acetate, etc., RlCOR
2 (R1 and R2 are C1 to C8 alkyl groups) and 〈
Ketones represented by XO, such as methyl ethyl ketone, cyclohexanone, R1-0-R2 (R1
and R2 is a C1-C8 alkyl group), such as ethyl ether, hexyl ether, etc. can be used. The amount of these solvents used is usually 1% of the copolymer.
The content may be in the range of 5 to 90% by weight. Further, as the above-mentioned copolymerization catalyst, radical initiators that can be used for normal radical polymerization such as azo type, peroxide type, sulfide, sulfin, sulfinic acid, diazo compound, nitroso compound, redox type, and ionizing radiation are used. can. In order to make the copolymer resin thus obtained water-soluble or water-dispersible, the carboxyl groups in the copolymer resin may be neutralized using a conventionally known neutralizing agent by a conventional method.

Examples of neutralizing agents include ammonia, amines, alkali metal hydroxides, carbonates, and bicarbonates. Examples of amines include primary, secondary, and tertiary alkylamines, aliphatic amines, primary, secondary, and tertiary alkanolamines, and cyclic alkylamines. The mixing ratio of the above-mentioned resin in the cold-curing water-based paint according to the present invention is vinyl polymer emulsion/copolymer resin - 9/1 in terms of solid content ratio.
~3/7 is preferred.

A dryer may be used to further improve curing properties. A regular dryer can be used as a dryer, but cobalt naphthenate, cobalt chloride, manganese naphthenate, copper naphthenate, zinc naphthenate, and lead naphthenate are effective among them, and the amount added is the metal amount relative to the total resin solid content. It is preferably 0.005 to 1.0% by weight, preferably 0.01 to 0.5% by weight. Note that the room temperature curable water-based paint of the present invention may be a clear paint or may be made into a colored paint by adding a coloring pigment.

Furthermore, a dispersion medium, a filler, and other additives commonly used in water-based paints may be added. The room-temperature-curing water-based paint of the present invention contains ingredients such as powder, ball mill, attritor,
It can be manufactured using ordinary paint manufacturing equipment such as a roll mill.
The water-based water-based paint that cures at room temperature in the present invention can be applied to metals, mortar, concrete, slate boards, calcium silicate boards, etc. by ordinary painting methods such as air spray painting, airless spray painting, brush painting, dipping, roller painting, and electrostatic painting.
It can be applied to a wide range of materials such as wood, has excellent coating workability, and has the advantage of being able to obtain coatings with high water resistance, weather resistance, and chemical resistance.

Furthermore, the drying properties of the film are superior to those of ordinary water-based paints due to oxidative polymerization, and sufficient hardness can be obtained in 1 to 4 days at room temperature. Next, the present invention will be explained in more detail with reference to Examples.

In the examples, parts and % indicate parts by weight and % by weight, respectively. Table 1 shows the compositions of the pigment pastes used in Examples 1-7 and 9-11. The pigment paste shown in Table 1 was uniformly dispersed in a ball mill to a particle size of 10 μm or less (finess gauge). Further, the cold-curable water-based paints shown in Tables 2 and 3 were obtained by blending each raw material and then uniformly mixing the mixture in a disperser for about 30 minutes. The manufacturing method of the vehicle used in the paint is given in Reference Examples 1 to 6. Reference example for manufacturing vinyl polymer emulsion 1 Maleation 1 with number average molecular weight of about 3000 and acid value of about 100
, 2-vinyl type polybutadiene solid content 770/) Butyl cellosolve solution and stand linseed oil with Cardner viscosity M to N maleated to an acid value of 96 were mixed in a ratio of 60/40, and a small amount of butyl cellosolve was added to this. The mixture is placed in a four-hole flask containing 1609 as solid content, neutralized with an equivalent amount of ammonia water, and water-solubilized by adding approximately 7809 water.

Further, 4,149 g of n-butyl methacrylate was added, and the mixture was thoroughly stirred to form an emulsion. A solution of ammonium persulfite 19 in water 209 is added to this and heated. It generates heat at 60-65°C and exceeds 80°C, so it is cooled and kept at 80°C for 2 hours.

Approximately 780 f with the small amount of butyl cellosolve mentioned above! By finely adjusting the water content, the amount of butyl cellosolve was 3.8% and the theoretical solid content was 40(f). The emulsion thus obtained had a solid content of 39.6%, a viscosity of 5.2 centipoise, and a pH of 8.
．． It was 75. Reference example 22-(a) Oxidation 75 obtained by maleating 1,2-vinyl polybutadiene with a number average molecular weight of 3000 and opening the ring with methanol and water.
Adduct of maleated polybutadiene (4) with glycidyl methacrylate and safflower monofatty acid 4009
, a fatty acid-modified acrylic resin (self) with a peak molecular weight of 7000 to 8000 and an acid value of 74 obtained by dropwise polymerizing n-butyl methacrylate 4709 and 130 g of acrylic acid in butyl cellosolve at a solid content ratio of 1:1. After adding 56 g of butyl cellosolve to 160 g of the mixture and neutralizing the equivalent amount with ammonia, water 8009 was added to make an aqueous solution, and further n-butyl methacrylate 41
49 was added and stirred to form an emulsion, and ammonium persulfite 19 was added and heated.

When heated to 80°C, it generated heat and polymerized.

After being left at 80° C. for 2 hours, it was cooled to obtain a stable emulsion with a solid content of 40%.

2-(b) A solid was prepared in the same manner as in 2-(a) except that styrene 2009, 2-ethylhexyl acrylate 2009 and acrylonitrile 149 were used instead of n-butyl methacrylate 4149 used in 2-(a). A stable emulsion of 40% was obtained.

2-(c) Same as 2-(a) except that about 2.5% of the n-butyl methacrylate 4149 used in 2-(a), that is, 109, was replaced with allyl methacrylate, but the solid content was 40%. A stable emulsion was obtained.

Reference Example 33-(a) Maleated polybutadiene (4) in Reference Example 2,
A fatty acid-modified acrylic resin with a peak molecular weight of 7,000 to 8,000 and an acid value of 74 (O and Butyl cellosolve was added to 1609, which was mixed at a solid content ratio of 1:1, and the solid content was 8.
After making a 0% solution, it was hydrated with aqueous ammonia and purified water
After adding 79 and further adding n-butyl methacrylate 4149 containing 2,2'-azobisvaleronitrile of 129 and stirring well, adding ammonium persulfite of 29 and reacting in the same manner as in Reference Example 2, Solid content 4
A stable emulsion of 00I) was obtained.

3-(b) The n-butyl methacrylate 4149 used in 3-(a) was replaced with 264 g of n-butyl methacrylate, lauryl methacrylate 1209 and methacrylonitrile 3.
The solid content was 40 in the same manner as 3-(a) except that it was replaced with 0g.
% stable emulsion was obtained.

3-(c) In place of n-butyl methacrylate 4149 used in 3-(a), 2-ethylhexyl acrylate 2
A stable emulsion with a solid content of 40% was obtained in the same manner as in 3-(a) except that 50 g of vinyl toluene 1509 and hydroxyethyl methacrylate 149 were used.

Reference example of manufacturing water-soluble or water-dispersible copolymer resin 4 into the reaction vessel.

The reaction was carried out at a temperature of 140-150°C with stirring. The addition reaction between epoxy groups and carboxyl groups was monitored while measuring the amount of remaining carboxyl groups. The reaction took approximately 4 hours to complete. 4-(b) Put 100 parts of n-butyl cellosolve into a reaction vessel and heat to 1200C.

A mixture in the proportions shown below was then added dropwise to this solution over a period of about 2 hours. The reaction was carried out under nitrogen injection. While maintaining the reaction temperature at 120° C. and stirring the reaction solution, the above mixture is added dropwise.

One hour after the completion of the dropwise addition, 1 part of azobisisobutyronitrile was added to the reaction solution, and after another 2 hours, 1 part of azobisisobutyronitrile was added to the reaction solution, and the reaction was then maintained at 120°C for 3 hours. I did this. A polymer with a polymerization rate of 99.5% and an acid value of 91 was obtained. 4-(c) 50 parts of n-butyl cellosolve is placed in a reaction vessel and heated to 120°C.

A mixture in the proportions shown below was then added dropwise to this solution over a period of about 2 hours. The reaction was carried out under nitrogen injection. The reaction temperature was maintained at 120° C., and the above mixture was added dropwise while stirring the reaction solution.

One hour after the completion of the dropwise addition, 1 part of azobisisobutyronitrile was added to the reaction solution, and after another 2 hours, 1 part of azobisisobutyronitrile was added to the reaction solution, and then the mixture was heated for 120 hours for 3 hours.
The reaction was carried out while maintaining the temperature at °C. A polymer with a polymerization rate of 99.7% and an acid value of 75 was obtained. 4-(b) and 4-(c
) in the copolymer of 28(
Ff) After neutralization using aqueous ammonia, the solid content was adjusted to 40 (: fl) with water.

Put Reference Example 5 into a reaction container.

The reaction was carried out at a temperature of 140-150°C with stirring. The reaction was followed by the same measurement method as in 4-(a). The reaction took approximately 5 hours to complete. 5-(b) 50 parts of n-butyl cellosolve is placed in a reaction vessel and heated to 120°C.

A mixture in the proportions shown below was then added dropwise to this solution over a period of about 2 hours while stirring. The reaction was carried out under nitrogen injection. The reaction temperature was maintained at 120° C., and the above mixture was added dropwise while stirring the reaction solution. One hour after the completion of the dropwise addition, 1 part of azobisdimethylvaleronitrile was added to the reaction solution, and after another 2 hours, 1 part of azobisdimethylvaleronitrile was added to the reaction solution.
of the solution was added to the reaction solution, and then the reaction was carried out while maintaining the temperature at 120° C. for 2.5 hours. Polymerization rate 99.201), acid value 9
A copolymer of No. 1 was obtained. 5-(c) 50 parts of n-butyl cellosolve is placed in a reaction vessel, heated and maintained at 120°C.

A mixture in the proportions shown below is then added dropwise to this solution over a period of 1.5 hours. The reaction was carried out with nitrogen injection. ′
▼ l no 1 V] ◆ 1 hour after the completion of dropping P, add 1 part of azobisisobutyronitrile to the reaction solution,
After a further 2 hours, 1 part of azobisisobutyronitrile was added to the reaction solution, and the reaction was then carried out while maintaining the temperature at 120° C. for 3 hours.

A copolymer with a polymerization rate of 99.50/) and an acid value of 97 was obtained. The carboxyl groups in the copolymers of 5-(b) and 5-(c) were neutralized with approximately equivalent amount of 28% ammonia water, and the solid content was adjusted to 40% with water.

Reference example 6 6-(a) into the reaction vessel.

The reaction was carried out at a temperature of 140-150°C with stirring. The reaction was followed by the same measurement method as in 4-(a). The reaction took approximately 6 hours to complete. 6-(b) 50 parts of n-butyl carbitol is placed in a reaction vessel and heated to 120°C.

Next, a mixture having the composition shown below was added dropwise to this solution over a period of about 2 hours. The reaction was carried out under nitrogen injection. The reaction temperature was maintained at 120° C., and the above mixture was added dropwise while stirring the reaction solution.

One hour after the completion of the dropwise addition, 1 part of azobisisobutyronitrile was added to the reaction solution, and after another 2 hours, 1 part of azobisisobutyronitrile was added to the reaction solution, and the reaction was then carried out while maintaining the temperature at 120°C for 3 hours. Ta. Polymerization rate 99.3%, acid value 9
A copolymer of 0 was obtained. 6-(c) In 6-(b), 24 parts of n-butyl methacrylate, 16 parts of lauryl acrylate, 4 parts of methacrylonitrile
6- parts and 4 parts of allyl methacrylate.
A copolymer was obtained in the same manner as in (b).

The carboxyl groups in the copolymers of 6-(b) and 6-(c) were neutralized with approximately equivalent amount of 28% ammonia water, and the solid content was adjusted to 40% with water.

Examples 1 to 12 Using the pigment pastes shown in Table 1 and the blending ratios shown in Tables 2 and 3, room temperature curable water-based paints of the present invention are obtained.

Comparative Example 1 A water-based paint that dries at room temperature (resin: styrene-n-butyl acrylate-acrylic acid copolymer, pigment: titanium white, resin:pigment:water ratio: 17:25:58) was used.

Comparative Example 2 A water-based paint that dries at room temperature (resin: soybean oil fatty acid-glycerin-pentol monophthalic anhydride type alkyd, pigment: titanium white, resin: pigment: water = 19:28:53) was used.

The paints of Examples and Comparative Examples were applied to mild steel plates (150 x 75 x 0.
8mTIL) was applied with a brush to a dry film thickness of 50μ, dried at 20°C for 7 days, and then tested.

Claims (1)

[Claims] 1 (1) Neutralized product of 5 to 95 parts by weight (solid content) of maleated 1,2-vinyl polybutadiene resin and maleic acid-modified unsaturated oil and/or unsaturated fatty acid-modified water-soluble resin 5
Using a mixture containing ~95 parts by weight (solid content) as an emulsifier, the Q value of the Q-e theory is about 0.1 or more and the general formula CH
_2=C(R_1)COOR_2 (where R_1 is hydrogen or a methyl group, and when R_1 is hydrogen, R_2 has 2 to 1 carbon atoms)
acrylic ester or methacrylic ester, allyl acrylate, allyl methacrylate, hydroxyethyl methacrylate, styrene, vinyl toluene, A vinyl polymer emulsion obtained by emulsion polymerization of one or more polymerizable vinyl monomers selected from α-methylstyrene and methacrylonitrile, and (2) an unsaturated fatty acid having a non-conjugated double bond. Fatty acid modified monomer obtained by reacting glycidyl ester of α,β-ethylenically unsaturated acid, water-soluble product or water-soluble copolymer resin consisting of α,β-ethylenically unsaturated acid and the above polymerizable vinyl monomer A water-based paint that cures at room temperature and contains a dispersion.