JPH04136002A - Cationically electrodepositable gelled particulate polymer and preparation thereof - Google Patents

Abstract

PURPOSE:To prepare the title polymer with an excellent polymn. stability by emulsion copolymerizing a specific monomer mixture in the presence of a water- base cationic resin using a water-sol. azoamide compd. as a polymn. initiator. CONSTITUTION:A process for the emulsion copolymn. of a polymerizable vinylsilane monomer having a vinylic double bond and a hydrolyzable alkoxysilane group, a polymerizable monomer having at two radical polymerizable unsatd. groups in the molecule, a polymerizable unsatd. monomer having a vinylic double bond and a hydroxyl group in the molecule, and other polymerizable unsatd. monomers in the presence of a water-base cationic resin, wherein a water-sol. azoamide compd. is used as a polymn. initiator to give the title polymer. The polymer, when added to a cationic electrodeposition coating material, is electrodeposited together with the coating material, acts as a flow controller during thermal curing of an electrodeposition coating film, and is excellent in cissing prevention and edge covering effects.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a cationic electrodepositable gelatinized fine particle polymer and a method for producing the same, and more specifically relates to emulsion polymerization using a cationic aqueous resin as a dispersion stabilizer. A cationically electrodepositable gelling fine particle polymer containing an internally crosslinked hydrolyzable alkoxysilane group and a hydroxyl group, and a stable polymerization comprising using a water-soluble azoamide compound as a polymerization initiator during emulsion polymerization. The present invention relates to a method for producing a cationic electrodepositable gelling fine particle polymer with good properties.

(Prior Art) Microparticle polymers gelled by intraparticle crosslinking reaction and methods for producing the same have been widely known. For example, a crosslinking monomer containing at least two ethylenic double bonds is A method of emulsion polymerizing the monomer mixture contained in an aqueous system (British Patent No. 967051, JP-A-63-63
Publication No. 761) - A method in which a monomer mixture containing grindyl (meth)acrylate, (meth)acrylic acid, etc. is dispersed and polymerized in a non-aqueous system using a dispersion stabilizer, and at the same time, these functional groups are reacted. (Tokuko Showa 5
7-34846). In particular, as a method for producing a gelled microparticle polymer using an alkoxysilane monomer in an aqueous medium, a method is to emulsion polymerize a mixture of an alkoxysilane monomer and other monomers in an aqueous medium using a non-reactive surfactant. (JP 60-181173),
A method of copolymerizing alcoquine 7-run monomer, (meth)acrylic acid, and other monomers and then dispersing them in water to obtain a matte electrodeposited coating film for aluminum building materials (Japanese Patent Application Laid-Open No. 59-6
No. 7396), an aqueous solution composition combining an acrylic polymer containing an alkoxysilane group and a carboxyl group and colloidal phosphoric acid (Japanese Patent Publication No. 47178/1983), containing an alkoxysilane group and a cationic group A method of dispersing an acrylic copolymer in water and crosslinking it particulately (Japanese Patent Application No. 6254141) has been proposed.

(Problem to be Solved by the Invention) Gelled particulate polymers obtained by conventional methods are added to coating compositions to influence the rheological and physical properties, resulting in poor coating spray efficiency and coating film. Contributes to improvements such as prevention of dripping and slam control of metallic pigments.

On the other hand, cationic electrodeposition paints, which are widely used mainly in the automobile industry, have excellent anti-corrosion properties, but have the disadvantage that the coating film does not thicken at the edges of the object to be coated, resulting in poor edge coverage. There is a need for improvement. Therefore, in order to solve the above problems, the present inventors have investigated the application of the above-mentioned gelled fine particle polymers to cationic electrodeposition paints. Even if it is an aqueous dispersion, it is an anionic or nonionic dispersion obtained by emulsion polymerization using a non-reactive surfactant, and it is usually difficult to use it for cationic electrodeposition coatings. It is. Even if this product could be applied to cationic electrodeposition paint,
It impairs the stability of the electrodeposition bath, the electrodeposition properties, the water resistance and anticorrosion properties of the coating film, and cannot be put to practical use in this field.

On the other hand, the present inventors have previously proposed an internally crosslinked gelling fine particle polymer having an alkoxysilane group, a hydroxyl group, and a cationic group, and a method for producing the same (Japanese Patent Laid-Open No. 2-47107). This internally crosslinked gelatinized fine particle polymer has cationic electrodeposition properties, and even when added to cationic electrodeposition paints, it maintains bath stability and
Although the electrodeposition properties are not impaired and the baked coating film is particularly excellent in edge coverage, it still has the drawback of being somewhat inferior in wet corrosion protection, making it unsatisfactory in practical terms.

(Means for Solving the Problems) The present inventors have conducted extensive research to develop a cationic electrodepositable gelling fine particle polymer useful as a rheology control agent for cationic electrolyte M paints, and as a result, the alkoxysilane group It has been found that an internally crosslinked gelling fine particle polymer having a hydroxyl group and a cationic group, and in which an Evoquin compound is localized on the particle surface, is extremely effective in solving the above problems.

In addition, this product has cationic electrodeposition properties, and even when added to cationic electrodeposition paints, it does not impair the bath stability or electrodeposition properties, and during baking, it is produced by the decomposition of water from the alphoxydisilane group. The silanol groups are condensed with each other and with the hydroxyl group, resulting in interparticle crosslinking and crosslinking with the base resin, creating a cationic electrodeposition coating without impairing the water resistance, corrosion resistance, or coating surface smoothness of the coating. The present inventors have discovered that this is extremely effective in preventing repellency and improving edge coverage, adhesion, and chipping resistance, leading to the completion of the present invention.

Thus, according to the present invention, (a) a polymerizable unsaturated vinylsilane monomer containing a vinylic double bond and a hydrolyzable alkoxysilane group, (b) at least two radically polymerizable unsaturated groups in the molecule; (c) Polymerizable unsaturated monomer 1 containing a vinyl double bond and a hydroxyl group and (d) Other polymerizable unsaturated monomers are emulsion polymerized in the presence of a cationic aqueous resin. A cationically electrodepositable gelling microparticle polymer is provided.

Further, according to the present invention, (a) a polymerizable unsaturated vinyl silane monomer containing a vinylic double bond and a hydrolyzable alkoxysilane group; ω) at least two radically polymerizable unsaturated groups in the molecule; (c) a polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group; and (d) other polymerizable unsaturated monomers in the presence of a cationic aqueous resin. There is also provided a method for producing a cationically electrodepositable gelatinized fine particle polymer with good polymerization stability, which is characterized by using a water-soluble azoamide compound as a polymerization initiator.

According to the present invention, the monomers constituting the cationically electrodepositable gelatinized fine particle polymer are (,) a polymerizable unsaturated vinylsilane monomer containing a vinylic double bond and a hydrolyzable alkoxysilane group, (b ) a polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule; (C) a polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group; and (d) a polymerizable unsaturated monomer other than the above. It is over saturated.

The vinyl silane monomer in (,) above includes compounds represented by the following general formula %. In the above formula, X represents a polymerizable unsaturated group such as γ-methacryloxypropyl group or vinyl group, and R represents an acetoxy group or an alkoxy group having 1 to 8 carbon atoms. Examples of the above alkoxy groups include methoxy/, ethoxy/, propoquine, butoxy, imbutoxy, bentoquine, hexaoquine, as well as methoxyethoxy, ethoxymethoxy,
Examples include alcoquine allyloxy and ethoxyphenoxy. Preferred R is methquin or ethoxy group. The silane monomers are known per se or are prepared analogously to those known per se.

Specific examples of such silane monomers include vinyltrimethoxysilane, vinyltrinidoxinlan, vinyltris(2-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, etc. Among these, γ-methacryloxypropyltrimethoxysilane is particularly preferred.

The polymerizable hexamer containing at least two radically polymerizable unsaturated groups in the molecule of (b) includes polymerizable unsaturated monocarboxylic acid esters of polyhydric alcohols and polymerizable unsaturated monocarboxylic acid esters of polybasic acids. Saturated alcohol esters and aromatic compounds substituted with two or more vinyl groups are included, and specific examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. , 1.3-butylene glycoldimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1.
4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate Erythritol tetramethacrylate, glycerol dimethacrylate, glycerol diacrylate, glycerol aryloxy dimethacrylate-1-,1,
1,1-1-trishydroxymethylethane diacrylate, 1,1.1-trishydroxy, methylethane triacrylate, l.

1.1-trishydroki/methylethane dimethacrylate
1-11,1,1-trishydroquine methylethane trimethacrylate, 1.1-1 trishydroquine methylpropane diacrylate, 1,1.1 trishydroquine methylpropane triacrylate, 1,1. 1-trishydroxy/methylpronochloride dimethacrylate, 1,
1.1-1 Lishydroquine methylpropane trimethacrylate, triallyl cyanurate, triallylysone anurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, divinylbenzene, etc.

The polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group (C) is a heptamer component that introduces a hydroxyl group into the gelled fine particle polymer, and the hydroxyl group is used to produce the gelled fine particle polymer. It acts as a hydrophilic group or a functional group for a crosslinking reaction between dispersed particles. Examples of the unsaturated monomer include 2-hydroquinethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

The other polymerizable unsaturated monomers (d) are the remaining components constituting the kelized fine particle polymer, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. Alkyl CC+ of (meth)acrylic acids such as meth)acrylate, butyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)acrylate, lauryl(meth)acrylate, and cyclohexyl acrylate
~C+a) ester; styrene, a-methylstyrene,
Vinyl aromatic monomer of vinyl toluenate; (meth)
An amide compound of acrylic acid: (meth)acrylonitrile can be used as a known compound used in the synthesis of ordinary acrylic resins. These (d
) are appropriately selected depending on the desired properties, and may be used alone or in combination of two or more.

The blending ratio of the seven polymers (a) to (d) constituting the gelled fine particle polymer in the present invention is not strictly limited, and depends on the desired physical properties of the gelled fine particle polymer to be produced. E(a) Monomer: 1 to 3, which can be varied as follows, generally within the ranges set out below:
0% by weight, preferably 3-20% by weight (b) Monomer 21-30% by weight, preferably 3-20% by weight
Weight% (e) Monomer 21-30% by weight, preferably 3-20
Weight% (d) Monomer: 10-97% by weight, preferably 40-97% by weight
91% by weight.

The cationic aqueous resin in the present invention can be used as a film-forming resin used in the production of cationic electrodeposition paints for boat fishing. They have cationic functional groups that give the resin a positive charge and hydrophilicity, and can be neutralized with acid to form an aqueous bath that can be electrodeposited on the cathode. Various types of resins are known as such resins, and any of them can be used in the present invention.A preferred typical water-based resin with excellent corrosion resistance is a resin based on the epoxy group of a polyepoxide compound. It is a reaction product obtained by reacting a cationizing agent.

The polyepoxide compound is suitably an epoxy group compound, generally having a number average molecular weight of at least 200, preferably within the range of 4 to 2,000. As such polyepoxide compounds, those known per se can be used, and include, for example, polyglycidyl ethers of polyphenols that can be produced by reacting polyphenols with epichlorohydrin in the presence of an alkali. Examples of polyphenols that can be used here include bis(4-hydroxyphenyl)-
2,2-propane, 4,4'-dihydroquine benzophenone, bis(4-hydroquine phenyl)-1,1-ethane, his-(4-hydroxyphenyl)-1,1-isobutane, his(4-hydroquine- tert-butyl-phenyl)-2゜2-70pan, his(2-naphthyl)methane, 1,5-dihydroquinnaphthalene, his(2,4-dihydroquinphenyl)methane, tetra(4
-hydroxyphenyl)-1,1,2,2-ethane, 4
．． 4'-dihydroxydiphenyl ether, 4+4'-
Examples include dihydroquine diphenyl sulfone, phenol novolac, and talesol novolac.

Among the polyepoxide compounds described above, those particularly suitable for the production of cationic aqueous resins have a number average molecular weight of at least about 380, preferably about 800 to 2,000, and an epoxy equivalent weight of 190 to 2,000. Preferably 400-1,
It is a polygrindyl ether of a polyphenol having a range of 0.000 to 0.000, especially one represented by the general formula % below. The polyepoxide compound may be partially reacted with polyols, polyether polyols, polyester polyols, polyamide amines, polycarboxylic acids, polyisocyanates, etc., and may also be graft-polymerized with δ-caprolactone, acrylic monomers, etc. .

On the other hand, as the cationizing agent to be reacted with the polyepoxide compound, aliphatic, alicyclic or aromatic-aliphatic primary
and secondary amines, tertiary amine salts, secondary sulfide salts, and tertiary phosphine salts. These react with the evoquino group to form a cationic group. Furthermore, a tertiary amino monoisomer obtained by the reaction of a tertiary amino alcohol and an iso/anate can be reacted with an epoxy equivalent of a hydroxyl group to form a cationic group.

Examples of the amino compound in the cationizing agent include:
Examples can include the following:

(1) Methylamine, ethylamine, n- or 1s
O-propylamine, monoethanolamine, n or 1
Primary amines such as so-propanolamine: (2) diethylamine, jetanolamine, di-n-
or secondary amines such as 1so-propertoolamine, N-methylethanolamine, N-ethylethanolamine; (3) ethylenediamine, diethylenetriamine, hydroquinoethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, dimethylamino Polyamines such as ethylamine and dimethylaminopropylamine.

Among cholera, alkanolamines having a hydroxyl group are preferred. The primary amine group may be blocked by reacting with a ketone in advance, and then reacted with the epochine group using the remaining active hydrogen.

Furthermore, in addition to the above-mentioned amine compounds, basic compounds such as ammonia, hydroquinolamine, hydrazine, hydroxyethylhydrazine, and N-hydroquinoethylimidacyline compounds can also be used. The basic group formed using these compounds can be protonated to a cationic group with an acid, particularly preferably a water-soluble organic carboxylic acid such as formic acid, acetic acid, or lactic acid.

The content of cationic groups in the cationic aqueous resin used in the present invention is desirably a small amount that allows the cationic aqueous resin to be stably dispersed in water (KOHCml/2 solid content).
The converted number is generally in the range of 3-100, particularly preferably in the range of 10-80. However, even if the content of cationic groups is 3 or less, it is possible to use aqueous dispersion using a surfactant, but in this case, the aqueous dispersion composition It is desirable to adjust the cationic group so that the pH is 4-9, preferably 6-7.

The amount of the cationic aqueous resin used is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the solid content of the kelized fine particle polymer.

Polymerization initiators that can be used in the polymerization of the monomers (,) to (b) include the following general formula % (wherein, X represents a linear or branched alkylene group having 2 to 12 carbon atoms). Particularly suitable are water-soluble azoamide compounds represented by the following general formula % (in which at least one of xl, X2 and X3 represents a hydroxyl group and the rest represent hydrogen). These products are known per se (JP-A-61-218618, JP-A-61-63643) and are commercially available as VA/Lease (trade name, manufactured by Wako Pure Chemical Industries, Ltd.). The polymerization initiator can be used in amounts commonly used in the art, or - for boat fishing, from 0.1 to 1.5 parts by weight per 100 parts by weight of gelled particulate polymer solids. is within the range of .

The copolymerization of the unsaturated monomers (a) to (d) can be carried out by emulsion polymerization, which is a known method for producing acrylic copolymers. For example, the monomer mixture of (a) to (d) above is mixed in an aqueous medium in the presence of a cationic aqueous resin and a water-soluble azoamide compound polymerization initiator at a reaction temperature of usually about 50 to about 100°C. This can be carried out by continuing the reaction for 1 to about 20 hours.

The resulting cationically electrodepositable gelling particulate polymer can typically have a resin solids content of about 10-40% by weight, based on the total weight of the aqueous dispersion.

Gelled particulate polymers generally have a particle size of 500n+u or less, preferably 10 to 300 nm, more preferably 50 to 1
It can have an average particle size within the range of 00r+m.

The particle size can be adjusted by adjusting the amount of cationic aqueous resin, and it can be easily obtained within the desired range.

(Functions and Effects) When the cationic electrodepositable gelling fine particle polymer of the present invention is added to a normal cationic electrodeposition paint, it can be co-electrodeposited without causing problems such as agglomeration, direct electrodeposition, or sedimentation. The kelized fine particle polymer acts as a flow regulator during heat curing of the electrodeposited coating, and exhibits excellent repellency prevention effects and edge covering effects. Furthermore, the coating film forms a micro-separated structure, resulting in a significant improvement in the physical properties of the coating film.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Parts and % indicate parts by weight and % by weight, respectively.

Production Example I Bisphenol A type epoxy resin with an epoxy equivalent of 950. Trade name: "Epicote 1004." manufactured by Neru Kagaku Co., Ltd.
1,900 parts of butyl cellosolve was dissolved in 993 parts of butyl cellosolve, 210 parts of jetanolamine was added dropwise at 80 to +00°C, and the mixture was kept at 100°C for 2 hours to form an Epoquin resin with an amine value of 68% and an amine value of 53 with a solid content of 68%. I got something. After neutralizing 100 parts of this resin by adding 3.7 parts of acetic acid, 123 parts of deionized water was added to obtain an aqueous dispersion of a cationic aqueous resin having a solid content of 30%.

Production Example 2 39 parts of monoethanolamine was kept at 60°C in a reaction vessel, 100 parts of N,N-dimethylaminopropylacrylamide was added dropwise, and the mixture was reacted at 60°C for 5 hours.
A monoethanolamine adduct of dimethylaminopropylacrylamide was obtained.

Separately, 950 parts of bisphenol A diglycidyl ether with an epoxy equivalent of 190, about 340 parts of propylene glycol diglycidyl ether with an epoxy equivalent of about 340, 456 parts of bisphenol A, and 21 parts of jetanolamine were charged, the temperature was raised to 120°C, and the epoxy/valent After reacting until the concentration was 1.02 mmol/2, diluting with 479 parts of ethylene glycol monobutyl ether and cooling, the temperature was maintained at 100°C and 158 parts of jetanolamine was added.
1 part and 43 parts of the monoethanolamine adduct of the above N,N-dimethylaminopropylacrylamide were added, and the reaction was allowed to proceed until the viscosity increase stopped to obtain a resin with a resin solid content of 80%. After neutralizing 100 parts of this resin by adding 4.3 parts of acetic acid, 162.4 parts of deionized water was added to obtain an aqueous dispersion of a cationic aqueous resin having a solid content of 30%.

Example 1 L equipped with stirrer, thermometer, cooling tube and heating mantle
2920-5 parts of deionized water and 667 parts of the aqueous dispersion of the cationic aqueous resin with a solid content of 30% obtained in Production Example 1 were placed in a flask, and the temperature was raised to 90°C while stirring.

The polymerization initiator VA, -086(2,2'-azobis[2-methyl N-(2-hydroxyethyl)
-Pionamide: manufactured by Wako Pure Chemical Industries, Ltd.) 12.
2 of an aqueous mixture of 5 parts dissolved in 500 parts of deionized water.
Added 0%. After 15 minutes, 5% of the above mixture was added.

Styrene 430 parts n-butyl acrylate 440 parts 1,6-hexanediol diacrylate 40 parts 2-hydroquine ethyl acrylate 40 parts KBM-503'
50 parts* γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Next, after further stirring for 30 minutes, dropwise addition of the remaining monomer mixture and aqueous polymerization initiator solution was started. The seven-mer mixture was fed for 3 hours, the aqueous polymerization initiator solution was fed for 3.5 hours, and the polymerization temperature was maintained at 90°C. After the dropwise addition of the aqueous polymerization initiator solution was completed, the mixture was heated for 30 minutes and maintained at 90°C, then cooled to room temperature, filtered using a filter cloth, and taken out. Thus, the solids content was 23.5%, the pH was 4.6, and the viscosity was 25 cps (B
M-type rotational viscometer, No. 2 spindle), average particle size 6
A gelled fine particle polymer of 1 nm (measured with Coulter Nanosizer N-4) was obtained.

Example 2 The polymerization initiator was VA-080 (2,2'-azohis(2-
Methyl-N-N,! '-His(hydroxymethyl)-2
Emulsion polymerization was carried out in the same manner as in Example 1 except for changing to hydroxyethyl propionamide) (manufactured by Wako Pure Chemical Industries, Ltd.), and the solid content was 23.6% and the pH was
Gelled fine particle polymers with viscosities of 4, 7, and 30 cps and an average particle size of 65 nm were obtained.

Example 3 Emulsion polymerization was carried out in the same manner as in Example 1 except that the aqueous dispersion of the cationic aqueous resin was changed to that obtained in Production Example 2. A gelled fine particle polymer having a viscosity and an average particle diameter of 70 nm was obtained.

Comparative Example 1 I equipped with a stirrer, thermometer, cooling tube and heating mantle
In a J flask, add 3507.5 parts of deionized water and -180 (quaternary ammonium salt-based allyl group-containing cationic reactive emulsifier, manufactured by Kao Corporation, 25% aqueous solution) 8
0 part was added, and the temperature was raised to 90°C while stirring. To this was added 20 percent of an aqueous mixture of 12.5 parts of VA-086, a polymerization initiator, dissolved in 500 parts of deionized water. After 15 minutes, 5 percent of the above mixture was added.

Styrene 430 parts N-butyl acrylate 440 parts 1,6-hexanediol diacrylate 40 parts 2-hydroxyethyl acrylate 40 parts Dripping was started. The seven-mer mixture was fed for 3 hours, the aqueous polymerization initiator solution was fed for 3.5 hours, and the polymerization temperature was maintained at 90°C. After the dropwise addition of the aqueous polymerization initiator solution was completed, the mixture was heated for 30 minutes and maintained at 90°C, then cooled to room temperature, filtered using a filter cloth, and taken out. In this way, a gelled fine particle polymer having a solid content of 20%, a pH of 3.7, a viscosity of 90 cps, and an average particle size of 71 nm was obtained.

Comparative Example 2 Emulsion polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization initiator was changed to VA-080, and the solid content was 19.9%.
, pH 3, 7, 25 cps viscosity, average particle size 72 nm
A gelled fine particle polymer was obtained.

Application Example 1 75 parts of the gelled fine particle polymer obtained in Example 1 was added to 572 parts of a cationic electrodepositing clear emulsion (trade name, Nileclone 9450, manufactured by Kansai Paint Co., Ltd.) with a solid content of 35% consisting of a polyamide-modified epoxy resin and a completely blocked diisocyanate. Pigment paste 1 below with a solid content of 43%
Add 39.4 parts while stirring, add 588.5 parts of deionized water.
A cationic electrodeposition paint was obtained by diluting the solution in 100%.

Application Examples 2 to 5 In Application Example 1, Example 2 was used as the gelling fine particle polymer.
Cationic electrodeposition paints were obtained in the same manner except that 75 parts of each of the dispersions obtained in Example 3 and Comparative Examples 1 and 2 were used.

In the cationic electrodeposition paint obtained in Application Examples 1 to 5, cold-rolled dull steel sheets (end faces and flat areas) of 0.8 x 300 x 90 mm were chemically treated with Palbond #3030 (manufactured by Nippon Bar Riki Rising Co., Ltd., zinc phosphate type). 45 degree angle),
Using this as a cathode, TTR painting was performed. Electrodeposition coating conditions were: electrodeposition paint bath temperature 30°C, pH 6.5, voltage 300.
An electrodeposition coating film having a film thickness of 20 μm (based on the dry film thickness) was formed, and after electrodeposition, the coating film was washed with water and baked at 185° C. for 20 minutes. The performance test results of this painted board are shown in Table 1 below.
Shown below. Table 1 also shows the measurement results of coating film melt viscosity.
Shown below.

Further, the cationic electrodeposition paints obtained in Application Examples 1 to 5 were stored for one month at 30 DEG C. with closed stirring, and the above electrodeposition tests were also conducted on them. The results are also shown in the table below.
Shown in 1.

[Performance test method] (*l) Coating film melt viscosity The melt viscosity of the electrodeposited film during baking was measured using the rolling ball viscosity measurement method (J I
5-Z-0237) was evaluated based on the thermal fluid appearance of the scratch marks. The value is the lowest viscosity (
centipoise).

(*2) @ Surface coverage The cured film thickness of the flat part is 20. um, electrodeposition is applied to a steel plate with an edge angle of 45", and the test plate is prepared by curing it under the specified baking conditions. Set the test plate in a Tsuruto slaying device so that the edge of the test plate is vertical. , J l
5-Z-2371 Salt water spray test evaluates the corrosion resistance of the edge after 168 hours.

◎: No sahi occurred at all ○: Slight occurrence of sahi ×: Significant occurrence of sahi (*3) Smoothness of painted surface Visually evaluate the finish of the electrodeposited surface.

○: Good ■: Fairly good △: Slightly poor (*4) Impact resistance Tested in accordance with JIS-5400-19796, 13, 3B method in an atmosphere at 20°C. Weight 500
g, indicates the maximum height without causing paint film damage under the condition of center of impact tip diameter % inches (cm). The maximum value was 50 cm.

(*5) Chipping resistance Baked electrodeposition coated board is coated with a rough thermosetting intermediate coating 1i and top coating, and the following tests are conducted on the heated and cured product.

■ Test equipment: Q-G-R gravelometer (product of Q Panel Company) ■ Stone to be sprayed: Crushed stone with a diameter of 15 to 20 mm ■ Capacity of stone to be sprayed: Approximately 500 - ■ Sprayed with air pressure crab approximately 4 kg / cm ”■Temperature during test:
The test piece was mounted on a test piece holder at about 20°C, and crushed stones of about 500 kg were sprayed onto the test piece using air pressure of about 4 kg/cm 2 , and the condition of the coated surface was evaluated.

The condition of the painted surface is visually observed and evaluated using the following criteria.

(Evaluation) ◎ (Good) Only a few scratches due to impact were observed on a part of the second top coat, and no peeling of the electrodeposited coating was observed at all.

■ (Slightly poor): Kisses due to impact are observed in the top coat and intermediate coat, and slight peeling of the electrodeposited film is observed.

△ (Poor): Many scratches due to impact were observed in the top coat and intermediate coat, and also considerable peeling of the electrodeposited coating was observed.

(*6) Water immersion 2-fire adhesion After 20 days of immersion in water at 40°C, JIS-540
0-1979 6.15, make gongs on the coating film, apply adhesive cellophane tape to the surface, and after abruptly peeling off, evaluate the coated surface.

◎: Good with no abnormalities △: Slight peeling at the edges of the goblin ×: Part of the goblin is peeling (*7) Cross-cut scratches were made on the coating film with a knife to reach the anti-corrosion base. 840 according to JIS 22371
A time salt spray test was conducted and evaluation was made based on rust and blistering from knife scratches.

○: The maximum width of rust or 7 creases is less than 1 mm from the cut part (one side).

■ = The maximum width of rust or blisters is 1 mm or more and less than 2 mm from the cut part (one side).

△: The maximum width of rust or blisters is 2 mm or more and less than 3 mm from the cut part (on one side), and there is a lot of firister on the flat part! Tip.

×: The maximum width of rust or blisters is 3 mm or more from the cut part, and blisters are observed on the entire painted surface.

(*8) Cross-cut scratches are made on the electrodeposited coating with a knife to reach the wet anti-corrosion substrate, and this is placed in 5% saline solution kept at 50°C.
After being immersed for 0 hours, evaluation was made based on the rust from the knife scratches and the width of the blisters.

○: The maximum width of rust or blisters is less than 1 mm from the cut part (one side).

■: The maximum width of rust or blisters is 1 mm or more and less than 2 mm from the cut part (one side).

△: The maximum width of rust or blisters is 2 mm or more and less than 3 mm from the cut part (on one side, and there is no blister or force on the flat part)
Look! Huge.

×: The maximum width of rust or blisters is 3 mm or more from the cut portion, and blisters are observed on the entire painted surface.

Table-1

Claims (1)

[Claims] 1. (a) a polymerizable unsaturated vinyl silane monomer containing a vinyl double bond and a hydrolyzable alkoxysilane group; (b) at least two radically polymerizable unsaturated groups in the molecule; (c) a polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group, and (d) other polymerizable unsaturated monomers are emulsion polymerized in the presence of a cationic aqueous resin. A cationically electrodepositable gelling fine particle polymer. 2. (a) Polymerizable unsaturated vinyl silane monomer containing a vinyl double bond and a hydrolyzable alkoxysilane group, (b) Polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule , (c) When emulsion polymerizing a polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group, and (d) other polymerizable unsaturated monomers in the presence of a cationic aqueous resin,
1. A method for producing a cationically electrodepositable gelling fine particle polymer, the method comprising using a water-soluble azoamide compound as a polymerization initiator.