JPS5843424B2 - Suiyouseitriyousoseibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble coating composition that has excellent physical properties such as corrosion resistance, adhesion, and impact resistance.

Traditionally, natural oils have been used as resin raw materials for water-soluble paints, but recently there have been concerns about the stable supply of natural oils, countermeasures against odor and smoke pollution, and concerns about the physical properties of paint films compared to natural oil paints.
Butadiene low polymers have high expectations because of their excellent chemical resistance, solvent resistance, water resistance, corrosion resistance, and surface smoothness.

In general, carboxyl groups, hydroxyl groups, ether groups, or
It is necessary to introduce an amino group.

Iteha, α and β, for the method of introducing carboxyl groups when using butadiene low polymers and low copolymers as raw materials.
- It is known that an adduct can be formed by heat treatment with an ethylenically unsaturated dicarboxylic acid compound.

Thus, butadiene low polymers and low copolymers,
The addition reaction with the α-β-ethylenically unsaturated dicarboxylic acid compound can be carried out by either a radical reaction or a thermal reaction, but in both cases, a cross-linking reaction occurs between the molecules of the raw material polymer at the same time as the addition reaction. That is, gelation also occurs, which is a major hindrance in the production of adducts.

On the other hand, it is known that an adduct can be obtained by coexisting hydroquinone, 2,6-di-tert-butyl-4-methylphenol, a urethane compound, and a metal salt in the thermal reaction system in order to improve these defects. However, with these methods, the amount of α/β-ethylenically unsaturated dicarboxylic acid compound added is extremely small, the coloration is noticeable, and the viscosity of the adduct is so high that it is difficult to handle. However, there are drawbacks such as the molecular weight of the starting material polymer being limited to a very small one, and it does not have sufficient physical properties as a water-soluble paint film-forming substance.

In view of these circumstances, the present inventors have discovered that various undesirable side reactions, including gelation, occur during the addition reaction of butadiene low polymers and low copolymers with α/β-ethylenically unsaturated dicarboxylic acid compounds. As a result of examining various compounds for the purpose of preventing this, we discovered that several types of compounds showed extremely excellent effects, and we filed a patent application (Japanese Patent Application No. 47).
-126461, 48-57676).

According to these inventions of the present inventors, butadiene low polymers, low copolymers, oil components and α/β-ethylenic-
In the addition reaction of unsaturated dicarboxylic acid compounds, undesirable side reactions such as gelation can be completely suppressed, and it has become possible to obtain adducts with a high addition amount even if the raw material polymer has a high molecular weight.

Furthermore, the present inventors investigated the evaluation of these adducts as water-soluble coating compositions, and found that these adducts had better corrosion resistance than adducts using conventional compounds called anti-gelling agents. The inventors discovered the surprising fact that this is a water-soluble coating composition with extremely excellent properties, adhesion, and impact resistance, leading to the completion of the present invention.

To explain the present invention in more detail, the present invention comprises (1
) A butadiene low polymer or low copolymer and an α/β-ethylenically unsaturated dicarboxylic acid compound selected from para-phenylenediamine derivatives, catechol derivatives, pyrogallol derivatives, nitrosamines, quinoline derivatives, and naphthol derivatives. or an α/β-ethylenically unsaturated dicarboxylic acid compound adduct of a butadiene low polymer or low copolymer obtained by reacting in the presence of two or more compounds, (2) a hydrophilic solvent and (3) The present invention is characterized by providing a water-soluble coating composition containing a Japanese additive.

To explain the present invention in more detail, the present invention provides a case where an adduct of a butadiene low polymer or a low copolymer and an α/β-ethylenically unsaturated dicarboxylic acid compound is used as the main component of a water-soluble paint. , para-phenylenediamine derivatives, catechol derivatives, pyrogallol derivatives, quinoline derivatives, nitrosamines, and naphthol derivatives, by coexisting one or more compounds selected from
The obtained adduct is characterized in that it is optimal.

According to the present invention, the conventional drawbacks such as insufficient corrosion resistance, impact resistance, and adhesion of butadiene low polymer system and oil thread water-soluble paint coating film properties can be improved all at once. I can do it.

The butadiene low polymer and low copolymer used in the present invention include 1.
2-Butadiene polymer containing many double bonds, 1.4-
Butadiene polymers containing many double bonds and 1,2-
Polymers containing both double bonds and 1/4 double bonds can be used.

That is, a typical example is a polymer obtained by polymerizing butadiene alone or butadiene and other monomers using an alkali metal or an organic alkali metal compound as a catalyst.

In this case, a living polymerization method in a tetrahydrofuran solvent is used to control the molecular weight, reduce gel content, and obtain a light-colored low polymer, or add ethers such as dioxane and alcohols such as isopropyl alcohol. , chain transfer polymerization using aromatic hydrocarbons such as toluene and xylene as chain transfer agents or solvents are typical. In the present invention, the double bond of the butadiene unit obtained by these methods is 1.2 - Bond-rich oligomers can be used.

In addition, in the present invention, the double bond of butadiene units is obtained by polymerizing butadiene or copolymerizing it with other monomers using a catalyst consisting of a Group Ⅰ metal compound and an alkyl aluminum halide. Low polymers rich in 4-bonds are also available.

In addition, the low copolymer referred to in the present invention refers to butadiene,
Copolymerized using conjugated diolefins other than butadiene such as isoprene, 2,3-dimethylbutadiene, and piperylene or vinyl-substituted aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, and divinylbenzene as monomers. means a low copolymer.

In this case, a copolymer containing 50% or less of comonomer units is preferably used.

Furthermore, in the present invention, the butadiene low polymer and low copolymer are partially oxidized by blowing air into them while heating in the coexistence of a drying agent of a carboxylic acid metal salt such as cobalt naphthenate or manganese octenoate. Alternatively, modified products of butadiene low polymers and low copolymers, such as those thermally polymerized in the presence of an organic peroxide, can also be used.

The butadiene low polymer and low copolymer of the present invention are liquid or semisolid at room temperature and have a number average molecular weight of 200 to 1000.
0.

α/β-ethylenically unsaturated radical in the present invention Claim 1 (1) Butadiene low polymer or low copolymer and α/β
- ethylenically unsaturated dicarboxylic acid compound and N-phenyl-N'-isopropyl-para-phenylenediamine,
N-N'-diphenyl-para-phenylenediamine, N
-N'-di-5ee-butyl-para-phenylenediamine, para-tert-butylcatechol, hyrogallol, N-nitroso-diethylamine, N-nitroso-diphenylamine, l,2-dihydro-2,2,4-trimethyl-6- Nitoxyquinoline, 1,5-dihydroxynaphthalene, 3-nitro-1-naphthol, 4-amino-
α/β-ethylenically unsaturated dicarboxylic acid compound adduct of a butadiene low polymer or copolymer obtained by reaction in the presence of one or more compounds selected from 1-naphthol, (2) A water-soluble paint ff1ff product containing a hydrophilic solvent and (3) a neutralizing agent.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble coating composition that has excellent physical properties such as corrosion resistance, adhesion, and impact resistance.

Traditionally, natural oils have been used as resin raw materials for water-soluble paints, but recently there have been concerns about the stable supply of natural oils, countermeasures against odor and smoke pollution, and concerns about the physical properties of paint films compared to natural oil paints.
Butadiene low polymers have high expectations because of their excellent chemical resistance, solvent resistance, water resistance, corrosion resistance, and surface smoothness.

In general, carboxyl groups, hydroxyl groups, ether groups, or
It is necessary to introduce an amino group.

In the method of introducing carboxyl groups when using butadiene low polymers and low copolymers as raw materials, α and β
- It is known that an adduct can be formed by heat treatment with an ethylenically unsaturated dicarboxylic acid compound.

Thus, butadiene low polymers and low copolymers,
The addition reaction with the α/β-ethylenically unsaturated dicarboxylic acid compound can be carried out by either a radical reaction or a thermal reaction, but in both cases, a cross-linking reaction occurs between the molecules of the raw material polymer at the same time as the addition reaction. That is, gelation also occurs, which is a major hindrance in the production of adducts.

On the other hand, it is known that an adduct can be obtained by coexisting hydroquinone, 2,6-di-tert-butyl-4-methylphenol, a urethane compound, and a metal salt in the thermal reaction system in order to improve these defects. However, with these methods, the amount of α/β-ethylenically unsaturated dicarboxylic acid compound added is extremely small, the coloration is noticeable, and the viscosity of the adduct is so high that it is difficult to handle. However, there are drawbacks such as the molecular weight of the starting material polymer being limited to a very small one, and it does not have sufficient physical properties as a water-soluble paint film-forming substance.

In view of these circumstances, the present inventors proposed that butadiene low polymers and low copolymers and α/β-ethylene, p-propylcatechol, p-isofurovircatechol, p-n-
7” tylcatechol, p-5ec-butylcatechol,
para-tert-butylcatechol, para-tert
t-amylcatechol, ■・2-dihydroxy-3-t
Alkyl-substituted catechols such as ert-butyl-5-methylbenzene, or p-phenylcatechol,
Aromatic substituted catechols such as I)-(p-methylphenyl)catechol can be mentioned, among which para-tert-butylcatechol is a preferred compound.

- The pyrogallol derivative as used in the invention is defined by the general formula (wherein R2 represents a saturated hydrocarbon residue or aromatic hydrocarbon residue having 1 to 10 carbon atoms, and m is 0.1.2 or 3. ), such as pyrogallol, 1.2
-3-Helihydroxy-5-methylbenzene can be mentioned, among which pyrogallol is a preferred compound.

Furthermore, the nitrosamines referred to in the present invention are of the general formula (wherein R1 and R2 are the same or different carbon numbers 1 to 2).
N-nitroso-
Dimethylamine, N-nitrone-diethylamine, N-
Nitroso-di-n-furobylamine, N-nitroso-'
)-n-butylamine, N-nitroso-n-pentylamine, N-nitroso-di-n-hexylamine, N-nitrone-dicyclohexylamine, N-nitrone-diphenylamine, N-nitrosodicumenylamine, N −
Nitroso-ditolylamine, N-nitrosodixylylamine, N-nitroso-methylphenylamine, N-nitroso-ethylphenylamine, and N-nitroso-
Examples include N-nitronamines such as dinaphthylamine, among which N-nitroso-
Diethylamine and N-nitroso-diphenyl-amine are preferred compounds.

Furthermore, the quinoline derivative referred to in the present invention has the general formula (in the formula R
1 represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, and R2, R3, and R4 represent the same or different alkyl groups having 1 to 5 carbon atoms, and 1,2-
Dihydro-2,2,4-trimethylquinoline, 1,2-
Dihydro-2,2,4-triethylquinoline, 1,2-
Dihydro-2・2・4-)! J -n-7''ropylquinoline, 1,2-dihydro-2,2,4-tri-n-butylquinoline, 1,2-dihydro-2,2-dimethyl-
4-ethyl-quinoliy11,2-dihydro-2,2,4
-trimethyl-6-medoxyquinoline, ■2-dihydro-2,2,4-trimethyl-6-nitoxyquinoline,
1,2-dihydro-2,2,4-trimethyl-6-glocoxyquinoline, 1,2-dihydro-2,2,4-
Quinoline derivatives such as trimethyl-6-n-butoxyquinoline can be mentioned, and among them, 1,2-dihydro-2,2,4-trimethyl-6-nitoxyquinoline is a preferred compound.

Furthermore, the naphthol derivative as used in the present invention is defined by the general formula (where R1 and R2 represent a hydrogen atom, an alkyl group, a nitro group, a hydroxyl group, or an amino group, and n is 1.2 or 3
, m is 1.2.3 or 4, and (R□)n and (
R2) One or more of m is a nitro group,
hydroxyl group or amino group),
■・2-dihydroxynaphthalene, ■・3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, ■・
5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, ■Amino-2- naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol,
5-amino-1-naphthol, 6-amino-1-naphthol, 7-amino-1-naphthol, 7-amino-2-
Naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-nitro-2-naphthol, 2-
Examples include nitro-naphthols represented by nitro-1-naphthol, 3-nitro-1-naphthol, and 4-nitro-1-naphthol, among which 1,5-dihydroxynaphthalene, 4-amino -1-
Naphthol, 3-nitro-1-naphthol is a preferred compound.

Para-phenylenediamine derivatives, catechol derivatives, pyrogallol derivatives used as additives in the production of adducts of α / β-ethylenically unsaturated dicarboxylic acid compounds and butadiene low polymers, low copolymers and oil components,
The amount of one or more compounds selected from nitrosamines, quinoline derivatives, and naphthol derivatives is not particularly limited, but O, OO 5 weight percent 5 weight percent per butadiene low polymer and low copolymer. %, preferably from 0.1 to 2.0 weight percent.

If the amount of the anti-gelling agent is too small, the viscosity of the adduct increases significantly and sometimes gelation is reached or the water solubilization process becomes extremely difficult.

On the other hand, it is unwise to use too much, and it may also impede the addition reaction and may have an unfavorable effect on the physical properties of the water-soluble paint.

Further, the effects of the above additives do not decrease even if additives having other functions such as hydroquinone and 2,6-di-tert-7'thyl-4-methyl-phenol, which usually have little anti-gelling effect, coexist.

The temperature range for the production of adducts of α/β-ethylenically unsaturated dicarboxylic acid compounds with butadiene oligomers and copolymers and oil components in the presence of the additive according to the invention is:
The temperature is 120°C to 250°C, preferably 150°C to 220°C. If the reaction temperature is low, it will take a long time to complete the reaction, and if it is high, the reaction will be completed in a short time, but there is a risk of gelation. There is.

In the present invention, the following oil component can be present during the reaction between the butadiene-based low polymer and the α/β-unsaturated dicarboxylic acid anhydride.

In other words, the 5 oil components here mean (1) an iodine value of 100;
(2) Linoleic acid, Riluic acid, Oleic acid, α-eriostearic acid Unsaturated fatty acids such as (3X
Boiled oil and stand oil obtained by heating the animal and vegetable oils shown in 1), fatty acid dimers (dimer acids) shown in (2), copolymerization of the animal and vegetable oils shown in (1) and styrene. Examples include styrenated oil.

These oil components can be used by mixing them with butadiene low polymers or low copolymers in any ratio, and the mixture can also be mixed with carbohydrates such as copper naphthenate, manganese octenoate, etc., which are common drying agents for paints. 6 in the presence of acid metal salts
Heating to 0' to 200°C and blowing air for partial oxidation modification, or heating to 50 to 280°C in the presence or absence of organic peroxide such as dicumyl peroxide or benzoyl peroxide for thermal polymerization. Modified ones can also be used.

In the present invention, when the viscosity of the butadiene polymer is high, a diluent can be used for the purpose of lowering the viscosity and facilitating the addition reaction.

Such diluents have a boiling point equal to or lower than the addition reaction temperature, and include butadiene-based polymers, α
- A diluent that is inert to β-ethylenically unsaturated dicarboxylic acid compounds, para-phelenediamine derivatives, catechol derivatives, pyrogallol derivatives, nitrosamines, quinoline derivatives and naphthol derivatives is used,
Petroleum fractions such as toluene, xylene, kerosene, and the like are preferred.

para-phenylenediamine derivatives, catechol derivatives, pyrogallol derivatives, nitrosamines according to the present invention,
Adducts of α/β-ethylenically unsaturated dicarboxylic acid compounds and butadiene low polymers or low copolymers produced in the presence of quinoline derivatives and/or naphthol derivatives are usually colorless to light brown in color. It is liquid or semi-solid at room temperature and has a number average molecular weight of 200 to 10,000, and its molecular weight increases compared to the raw material butadiene polymer by the addition of an α/β-ethylenically unsaturated dicarboxylic acid compound.
Furthermore, the viscosity increases slightly, while the iodine number decreases slightly.

The water-soluble coating composition of the present invention is a butadiene low polymer or low copolymer produced in the coexistence of the above additives and α.
The adduct with a β-ethylenically unsaturated dicarboxylic acid compound can be made into a water-soluble paint by neutralizing it with a neutralizing agent in the presence of a hydrophilic solvent, or by adding a hydrophilic solvent after adding the neutralizing agent. can.

If necessary, the composition of the present invention can be diluted with water depending on the purpose after adding a desiccant, a pigment, and other auxiliary agents to uniformly dissolve or disperse the composition.

The term "water-soluble paint" as referred to in the present invention includes not only cases in which the paint components are completely dissolved in water or a hydrophilic solvent, but also cases in which the paint components are dispersed in the form of small particles.

Typical water-soluble paints of the present invention include so-called water-soluble paints, electrodeposition paints, etc., which are usually diluted with any proportion of water and applied.

The hydrophilic solvent referred to here is an oxygen-containing compound that has a substantial affinity with water, such as alcohols such as methanol, ethanol, and butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. These include cellosolves, cyclic ethers such as tetrahydrofuran and dioxane, keto alcohols such as diacetone alcohol, keto ethers such as diacetone alcohol methyl ether, ketones such as acetone and methyl ethyl ketone, and esters such as methyl acetate. , can be added in an amount usually not more than 100 parts by weight, preferably in the range of 5 to 50 parts by weight, per 100 parts by weight of the Bukudiene yarn low polymer.

Adding more than 100 parts by weight is not only uneconomical, but also reduces its advantages as a water-soluble coating.

Furthermore, the neutralizing agent referred to in the present invention is a basic compound,
Alkali metal hydroxides such as caustic soda, caustic potash, aqueous ammonia, diethylamine, triethylamine, alkylamines such as N-morpholine, polyamines such as ethylenediamine, diethylenetriamine, monoethanolamine, jetanolamine, and triethanolamine. alkanolamines, such as
Organic amines such as alkyl alkanolamines such as dimethylaminoethanol and alicyclic amines such as cyclohexylamines are included.

These neutralizing agents may be used alone or in combination in an amount of 0.2 to 2.0 equivalents relative to the amount of the added α/β-ethylenically unsaturated dicarboxylic acid compound.

Usually, it can be used until the pH is in the range of 6.0 to 9.0.

Using more than 2.0 equivalents is not only uneconomical, but also results in poor water resistance.

The drying agent that may be added to the insoluble paint of the present invention is for promoting drying and hardening of butadiene low polymers, low copolymers, and adducts of oil components and α/β-ethylenically unsaturated dicarboxylic acid compounds. It is a general-purpose desiccant, such as one or two metal salts of carboxylic acids, such as cobalt, manganese, lead, iron, zinc, zirconium, and calcium salts of octenoic acid, naphthenic acid, rosin acid, and tall oil fatty acids.
A mixture of more than one species is used, and the amount added is 1.0% by weight or less as a metal content with respect to the above adduct. suitable.

Furthermore, the pigments that can be added to the water-soluble paint of the present invention include general-purpose paints such as titanium white, zinc white, lead white,
These include inorganic pigments such as chromium oxide, ultramarine, red iron, and carbon black, and organic pigments such as nitron thread, nitro-based, azo thread pigments, lake-based pigments, and phthalocyanine thread. Preferably, it is stable in phase.

The water-soluble coating composition obtained by the present invention is thus neutralized with a neutralizing agent, diluted with a solvent, blended with a pigment and a drying agent, and diluted with water to a solid content concentration depending on the purpose. It is used for electrodeposition coatings and water-soluble coatings for dip coating, but it is usually cured under baking conditions of 100 to 250°C for 2 to 90 minutes to form a tough coating film.

The water-soluble coating composition obtained by the present invention has good stability in water, and has excellent corrosion resistance and throwing power even when coated by electrodeposition or dip coating on either untreated steel plate or chemically treated steel plate. Excellent hardness, impact resistance, adhesion, smoothness, and hardening properties.

The present invention will be specifically explained by giving examples below of typical additives based on the present invention.

Example 1 1000 parts by weight of a butadiene low polymer with a number average molecular weight of 1000 and a viscosity of 42 poise (25°C), 333 parts by weight of xylene, 163 parts by weight of maleic anhydride, N-phenyl-N'
- 2 parts by weight of isopropyl para-phenylenediamine,
After filling an electromagnetically stirred stainless steel autoclave with an internal volume of 21 cm and thoroughly replacing the air in the system with dry nitrogen gas, it was heated at 190°C for 8 hours with stirring to perform an addition reaction, and then the contents were brought to room temperature. After cooling until
xylene as a solvent and a trace amount of unreacted maleic anhydride in 1
The acid value was 80.
A maleic anhydride adduct with an O1 viscosity of 9500 poise (25°C) was obtained.

500 parts by weight of this adduct was charged into a reflux condenser and then into 11 separable flasks, and the contents were adjusted to 70°C.
After adding 40 parts by weight of water and 10 parts by weight of triethylamine and ring-opening the acid anhydride group at 80°C for 2 hours, 80 parts by weight of ethylene glycol monoethyl ether was added and cooled to room temperature. Using a deionized aqueous solution of triethylamine, the solution was neutralized to a pH of 8.2 in an aqueous solution with a solid content concentration of 10% by weight, and further diluted with deionized water so that the solid content concentration was 10% by weight. , a clear electrodeposition solution was prepared.

Using the clear electrodeposition solution prepared in this way, the electrode gap was 10 crn and the anode surface area (0.8 mm x 70 mm x 1
50mm) zinc phosphate treated plate, bath temperature 25℃, energization time 3 minutes, voltage 80.100.1 with stirring.
After applying electricity at 20.150, 200.250 and 300 volts, the electrodeposited test piece was taken out.
After spraying a strong stream of water onto the coated film surface to wash off the adhering electrodeposition liquid, it is air-dried for 2 hours in a room at 25° C. and 75% relative humidity.

After air drying, the coating film was cured by placing it in a hot air circulation oven at 160° C. for 30 minutes.

When the thickness of the obtained coating film was measured, it was found to have the following relationship with the voltage (voltage/film thickness).

80V/10μ, 100V/12μ, 120V/13μ
, 150V/15μ, 200V/20μ, 250V/2
3μ, 300V/25μ.

The coated surface was in good condition at all film thicknesses, and no cissing, dents, etc. were observed.

Furthermore, the physical properties of the coating film with a thickness of 20 μm were measured, and the results showed that the pencil hardness was 4H1, the corrosion resistance was 240 hours or more, the Erichsen 6.5, the DuPont impact value was 40 CrrL, and the adhesion (substrate test) was 100/100.

Comparative Example 1 Using the same butadiene polymer as in Example 1, using the same conditions and operations, and using 2.6 as an antigelation agent instead of N-phenyl-N'-isopropylpara-phenylenediamine.
-di-tert-butyl-4-methyl-phenol 3
．． 0 parts by weight was added to obtain a maleic anhydride adduct having an acid value of 76 and a viscosity of 45,000 poise (25° C.), and then an electrodeposition solution was prepared.

Using this, electrodeposition coating was performed in the same manner as in Example 1, and a coating film was obtained by curing.

The relationship between the thickness of this coating film and the voltage during electrolysis was as follows.

Voltage/film thickness: 80V/8μ, 100V/10μ, 120
v/12μ, 150V/15μ, 200V/18μ, 2
50V/20μ, 300V/21μ.

The surface condition of the paint film is that there are repellents and the gloss is poor.
There was no smoothness.

Furthermore, physical properties of the coating film with a thickness of 20μ were measured and found that the pencil hardness was 2B, the corrosion resistance was 50 hours, and the Erichsen 2.
0, DuPont Impact 30CrfL and adhesion (baseline test) 65/100.

As described above, when compared with Example 1, due to the difference in the type of antigelation agent, the obtained butadiene low polymer and α/β
- When an adduct of an ethylenically unsaturated dicarboxylic acid compound is used as a water-soluble paint, the differences in the physical properties of the coating film become clear, and the above-mentioned adduct of the present invention is excellent as a water-soluble paint composition. It became clear that

Examples 2 to 12, Comparative Examples 2 to 7 1000 parts by weight of a butadiene low polymer with a number average molecular weight of 2000 and a viscosity of 150 poise (25°C), 333 parts by weight of xylene, 163 parts by weight of maleic anhydride, various materials used in the present invention 2.0 parts by weight of the additive and 4.0 parts by weight of the conventional anti-gelling agent were charged into a stainless steel electromagnetic stirring autoclave with an internal volume of 21 cm, and the air in the system was replaced with dry nitrogen gas. After sufficient substitution with
An adduct was obtained in the same manner as in Example 1.

500 parts by weight of these adducts were added with 150 parts by weight of water and 20 parts by weight of triethylamine, stirred and mixed at 30°C for 30 minutes, and then all 100 parts by weight of ethylene glycol monobutyl ether were added and dissolved, and the pH was adjusted to 8.
Add triethylamine until the resin solids content is 60.
A water-dispersible varnish of % by weight was obtained.

These varnishes were mixed with pigments in the following proportions, and the pigments were dispersed in a ball mill. Each sample obtained was diluted with deionized water so that the solid content was 10% by weight, and the same as in Example 1 was prepared. The coating was electrodeposited under the following conditions, and the coating was cured in a hot air circulation oven at 170°C for 30 minutes.The physical properties of the coating were measured.The results are shown in Table 1.

Approximately 60% varnish 100 parts by weight (as solid content) Rutile titanium white 30 p-pump rack 0.5 strontium chrome) 1.0 Example 13, Comparative Example 7 Number average molecular weight 3500, viscosity 1100 poise (25°C )
500 parts by weight of butadiene low polymer, 500 parts by weight of linseed oil, and 333 parts by weight of xylene were charged into an autoclave with an internal volume of 21, and after the system was sufficiently purged with dry nitrogen gas, heat treatment was performed at 26oC for 3 hours with stirring. After that, the autoclave was allowed to cool to room temperature, the lid of the autoclave was opened, 192 parts by weight of maleic anhydride and 2 parts by weight of N-phenyl-N'-isopropylpara-phenylenediamine were added, and the system was replaced with nitrogen gas again. The mixture was heated at 190°C for 10 hours with stirring to complete the addition reaction.

The adduct was recovered according to Example 1. The adduct has an acid value of 90
, and the viscosity was 6000 poise (25°C).

Further, according to Example 2, a varnish with a solid content of 60% by weight was obtained, and a pigment was mixed therein and electrodeposited as an electrodeposition liquid.The physical properties of the coating film were measured.The results are shown in Table 2.

For comparison, an adduct produced using the same recipe as above using 3.0 parts by weight of para-tert-butyl-hydroquinone had an acid value of 89 and a viscosity of 35,000 poise (25°C
), and in the same manner as above, it was made into a paint, electrocoated, and the coating film was evaluated. The results are also shown in Table 2.

Claims (1)

[Claims] 1 (1) Butadiene low polymer or low copolymer and α/β
- ethylenically unsaturated dicarboxylic acid compound and N phenyl-N/-isopropyl-para-phenylene diamine, N
-N'-diphenyl-hala-phenylenediamine, N-
N'-di5ee-butyl-para-phenylenediamine, para-tert-butylcatechol, pyrogallol, N-nitroso-diethylamine, N-nitroso-diphenylamine, 1,2-dihydro-2,2,4-trimethyl-6- Nitoxyquinoline, 1,5-dihydroxynaphthalene, 3-nitro-1-naphthol, 4-amino-
α/β-ethylenically unsaturated dicarboxylic acid compound adduct of a butadiene low polymer or copolymer obtained by reaction in the presence of one or more compounds selected from 1-naphthol, (2) A water-soluble coating composition containing a hydrophilic solvent and (3) a neutralizing agent.