JPH05179178A - Production of anionic electrodeposition coating resin - Google Patents

Abstract

PURPOSE:To obtain the title resin excellent in weather resistance and mattedness by polymerizing a polymerizable unsaturated acid monomer and a polymerizable unsaturated monomer in the presence of a specified polysiloxane compound and subjecting the obtained polymer to specified treatments. CONSTITUTION:40-98wt.% monomer mixture comprising a polymerizable unsaturated acid monomer (e.g. methacrylic acid) and a polymerizable unsaturated monomer copolymerizable therewith (e.g. butyl acrylate) is radical-polymerized in a hydrophilic solvent (e.g. ethylene glycol monomethyl ether) in the presence of 2-60wt.% azoic polysiloxane compound comprising repeating units of the formula [wherein R2 is lower alkyl; R1 is R2 or CN; R3 is (halogen-substituted) alkyl or phenyl; l is 0-6; m is 0-200; A is -O- or -NH- ; and D is (CH2)n (wherein n is 1) or -(CH2)3 -O-(CH2)2- ], having at least one azo group in the molecule and a number-average molecular weight of 1500-100000. The obtained polymer is neutralized with NH3 and/or an amine (e.g. triethylamine) and then converted into a water-base resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an anion electrodeposition coating resin having high weather resistance.

[0002]

2. Description of the Related Art Conventionally, for painting aluminum materials,
A paint in which an amino resin such as melamine resin is mixed as a curing agent with an acrylic water-based resin is used, and this paint is put to practical use by applying anion electrodeposition coating to building materials such as aluminum sashes or curtain walls of ordinary houses and high-rise buildings. However, in recent years, due to the demands of the times,
Furthermore, a coating with good weather resistance is regarded as important. As a matter of course, acryl / silicone blend resins or acryl-silicone graft copolymer resins, and further fluorine resins have been developed in response to this.

However, since the acrylic / silicone type resin is a blend of both resins, it lacks the silicone resin in the long term and is superior to the acrylic type resin, but
Does not show long-term weather resistance. In addition, in the acrylic-silicone graft copolymer resin, in many cases, the copolymerization reaction between the acrylic monomer and the unsaturated silicone (macromonomer) is not effectively performed in the course of the reaction, and in general, Although superior to blended systems, it still leaves a problem with weather resistance. And although the fluororesin is sufficient in performance, it is economically disadvantageous and poor in versatility. In addition, as a recent user need, a matte paint surface that can create a calm atmosphere rather than the metallic luster of the paint surface has been demanded abundantly. Electrodeposition paints for single-coating finish that give this matte coating surface are also being actively developed, but at present, development is being carried out of those that have high weather resistance and matte properties, and are inexpensive, such as fluororesins. It is not.

[0004]

DISCLOSURE OF THE INVENTION The present invention overcomes the above-mentioned drawbacks of conventional resins for electrodeposition coatings, and efficiently and robustly introduces a copolymer unit derived from a mixed monomer and an azo group-containing unit. An object of the present invention is to provide a method for producing a resin for an anionic electrodeposition coating composition in which a silicone unit derived from a polysiloxane compound is bonded and which has improved weather resistance and matting properties.

[0005]

According to the present invention, there is provided a method for producing a resin for anionic electrodeposition coating composition which can achieve the above objects.

That is, the present invention has the general formula [I]

[Chemical 2] [Wherein R ₁ is the same or different and represents a lower alkyl group or a nitrile group, R ₂ is the same or different and represents a lower alkyl group, and R ₃ is the same or different and is a halogen atom-substituted or unsubstituted alkyl group. Represents a group or a phenyl group. l is the same or different and represents 0 or an integer of 1 to 6, m represents an integer of 0 or 1 to 200, A represents —O— or —NH—, and D represents (CH ₂ ) _n (however,
n are the same or different 0 or an integer from 1 to 6) or _{- (CH 2) 3 -O- (} CH 2) 2 - has a repeating unit represented by the indicating], at least one in one molecule Number average molecular weight having azo bond is 1,500 to 100,00
2 to 60% by weight of 0 azo group-containing polysiloxane compound
In the presence of a polymerizable unsaturated acid monomer (a) and a polymerizable unsaturated monomer (b) copolymerizable therewith mixed monomer 40 to
The present invention relates to a method for producing a resin for anion electrodeposition coating, which comprises radical polymerization of 98% by weight in a hydrophilic solvent, neutralization with ammonia and / or amines, and then hydration.

The present invention will be described in more detail below. The present invention comprises a copolymer unit (A) derived from a mixed monomer of a polymerizable unsaturated acid monomer (a) and a polymerizable unsaturated monomer (b) copolymerizable therewith, and an azo Block copolymer in which each unit with a polysiloxane unit (B) derived from a group-containing polysiloxane compound is mainly bonded to AB, ABAA and / or-(AB) _n- The present invention relates to a method for producing a resin for anion electrodeposition coating containing as a main component.

First, the polymerizable unsaturated acid monomer (a) used in the production of the resin for anion electrodeposition coating is necessary in the step of making the resulting block copolymer aqueous or the anion electrodeposition coating process. Needless to say. Specific examples of the polymerizable unsaturated acid monomer that can be used include (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid, and these can be used alone or in combination.

Other polymerizable unsaturated acid monomers (a) that can be used include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, and acid phosphooxypolyoxyethylene glycol mono. Unsaturated organic phosphoric acid such as (meth) acrylate, acid phosphooxypolyoxypropylene glycol mono (meth) acrylate; vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, P-styrene sulfonic acid Examples thereof include saturated organic sulfonic acid. Among these polymerizable unsaturated acid monomers (a), (meth) acrylic acid is particularly preferable.

The amount of the polymerizable unsaturated acid monomer (a) to be used varies depending on the properties of the monomer (b) to be a copolymerization partner or the reaction conditions, but usually, the acid value is 15 to 150, It should preferably be prepared in the range of 20 to 100.

Specific examples of the polymerizable unsaturated monomer (b) used for producing the resin for anionic electrodeposition coating composition include (meth) acrylic acid esters having 1 to 22 carbon atoms, for example, (meth) acrylic. Methyl acid, ethyl, isopropyl, n
-Butyl, isobutyl, 2-ethylhexyl, lauryl, stearyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl; vinyl esters of alkane monocarboxylic acids having 1 to 12 carbon atoms, For example vinyl acetate, vinyl propionate, vinyl-n-butyrate, vinyl versatate; unsaturated amides or imides, such as (meth) acrylamide, N-methyl (meth) acrylamide, N,
N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, alkoxymethyl (meth) acrylamide such as N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic acid imide, maleic acid diamide; vinyl aromatic monoamine Examples include polymers such as styrene and P-methylstyrene.

Generally, any monomer can be used as the monomer of the present invention as long as it has a radically polymerizable monomer, and a halogen-containing vinyl compound such as vinyl chloride, vinylidene chloride or vinylidene fluoride; ethylene. , 1,3
-Mono- or di-olefins such as butadiene; α, β
-Olefinically unsaturated acids such as esters of maleic acid and fumaric acid; and (meth) acrylonitrile. These monomers can be used alone or in combination.

The amount of the mixed monomer containing the polymerizable unsaturated acid monomer (a) and the polymerizable unsaturated monomer (b) is 40 to 98.
%, Preferably 70 to 95% by weight. When the amount of the mixed monomer used is less than 40% by weight, the molecular weight of the block copolymer is lowered, which is not preferable. When the amount of the mixed monomer used is more than 98% by weight, the block copolymer may be synthesized. It's extremely difficult.

The azo group-containing polysiloxane compound used in the production of the resin for anionic electrodeposition coating is represented by the general formula [I]

[Chemical 3] [Wherein R ₁ is the same or different and represents a lower alkyl group or a nitrile group, R ₂ is the same or different and represents a lower alkyl group, and R ₃ is the same or different and is a halogen atom-substituted or unsubstituted alkyl group. Represents a group or a phenyl group. l is the same or different and represents 0 or an integer of 1 to 6, m represents an integer of 0 or 1 to 200, A represents —O— or —NH—, and D represents (CH ₂ ) _n (however,
n is the same or different and represents 0 or an integer of 1 to 6. ) Or _{- (CH 2) 3 O (} CH 2) 2 - shows a. ] And has a number average molecular weight of 1,500 to 1 having at least one azo bond in one molecule.
The amount thereof is 0,000, and the amount used is 2 to 60% by weight, preferably 5 to 30% by weight.

In the above general formula [I], examples of the lower alkyl group include methyl, ethyl, propyl,
Examples thereof include linear or branched alkyl groups having 1 to 6 carbon atoms such as isopropyl, butyl, t-butyl, pentyl and hexyl groups. Further, as the alkyl group,
In addition to the above lower alkyl group, it has 7 carbon atoms such as heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups.
There may be mentioned straight-chain or branched alkyl groups of ˜12. Further, the halogen atom-substituted alkyl group is a halogenated version of the above alkyl group, for example, chloromethyl, bromomethyl, trifluoromethyl, 2-
Chloroethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 1,1,2,
A 2-tetrahydroperfluorooctyl group may be mentioned. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The azo group-containing polysiloxane compound having a repeating unit represented by the general formula [I] is represented by the general formula [II]

[0017]

[Chemical 4] [In the formula, R ₁ and l are the same as defined above. ]

Constituent components represented by the general formula [III]

[0019]

[Chemical 5] [Wherein R ₂ , R ₃ , A, D and m are the same as defined above. ]

It goes without saying that the constituent components represented by the formula (II) are alternately bonded and a part of the constituent components represented by the general formula (II) is represented by the general formula (IV).

[0021]

[Image Omitted] —CO—Y—CO— [IV] [In the formula, Y represents a dibasic acid residue. ]

It also includes those in which the constituent components represented by are replaced. The amount that can be replaced with the constituent component represented by the general formula [IV] is limited to the amount at which the radical polymerization activity of the azo group-containing polysiloxane compound does not disappear.

Examples of dibasic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid,
Examples thereof include azelaic acid, sebacic acid, fumaric acid, itaconic acid, terephthalic acid, isophthalic acid and phthalic acid.

The azo group-containing polysiloxane compound represented by the general formula [I] is, for example, the general formula [V]

[0025]

[Chemical 7] [In the formula, D is (CH ₂ ) ₁ or-(CH ₂ ) ₃ OCH ₂ CH ₂
-, E represents NH ₂ or OH, and R ₂ , R ₃ , l and m are the same as above. ]

A diamine or dihydroxy compound containing a polysiloxane (including disiloxane) segment represented by the following general formula [VI]

[0027]

[Chemical 8] [In the formula, R ₁ and l are the same as defined above. X represents a halogen atom. ]

It can be produced in high yield by reacting with a dibasic acid dihalide containing an azo group represented by In the case of producing an azo group-containing polysiloxane compound having a constituent represented by the general formula [IV], a part of the dibasic acid dihalide containing the azo group of the general formula [VI] is used. A mixture in which is replaced by the corresponding dibasic acid dihalide may be used.

The azo group-containing polysiloxane compound is preferably produced in the presence of a base catalyst. Examples of the base catalyst include triethylamine, tributylamine, N, N-dimethylaniline, piperidine, pyridine, 1,5-diazabicyclo [4,3,0] nonene-
5,1,8-diazabicyclo [5,4,0] undecene-7, tri-n-butylamine, sodium hydride, n-butyllithium and the like can be mentioned, and they can be appropriately selected from these.

The azo group-containing polysiloxane compound is usually produced in a solvent. Examples of the solvent include ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane and dioxane, halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and trichlene, hydrocarbons such as n-hexane, benzene and xylene, Acetonitrile, N, N-dimethylformamide and the like can be mentioned, and one or more of these are used.

The use ratio of the diamine or dihydroxy compound represented by the general formula [V] and the dibasic acid dihalide containing an azo group represented by the general formula [VI] is not particularly limited and may be appropriately determined. In order to obtain one having a molecular weight, it is preferable to make the both ratios approximately equimolar.
When a base catalyst is used, the amount used is the starting compound [V
It is preferably used in an amount of about 0.5 to 1.5 times the molar amount of I].

The reaction temperature is not particularly limited, but in order to prevent decomposition of the azo group and increase the molecular weight of the product,
10-80 degreeC is preferable. The reaction time is not particularly limited, but is preferably 0.5 to 24 hours. The reaction temperature may be gradually raised from low temperature to room temperature.

The target substance is collected by using the used raw material, base catalyst,
This is appropriately performed depending on the type of solvent and the like. For example, the reaction is carried out by diluting the viscous reaction solution with a solvent, washing the by-produced quaternary ammonium salt with water to remove, drying and removing the solvent.

The azo group-containing polysiloxane compound thus obtained is composed of the constituent components [II] and [II] as described above.
I] or an oligomer or polymer composed of constituents [II], [III] and [IV]. Although its properties vary depending on the molecular weight and the content of the polysiloxane segment, it is usually a colorless or simple yellowish powdery, viscous oily or rubber-like substance. The solubility in a solvent also varies depending on the molecular weight and the content of the polysiloxane segment as described above, but ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane; carbon tetrachloride, chloroform, methylene chloride, trichlene, etc. Aromatic hydrocarbons such as toluene, benzene, xylene, etc .; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; Methyl acetate, ethyl acetate, propyl acetate, acetic acid-n- Butyl,
It is soluble in acetic acid esters such as amyl acetate.

When the amount of the azo group-containing polysiloxane compound represented by the general formula [I] is less than 2% by weight, block copolymerization is extremely difficult, and when it exceeds 60% by weight, the molecular weight of the block copolymer decreases. Not only is it economically unfavorable.

The number average molecular weight of the azo group-containing polysiloxane compound represented by the general formula [I] is 1,500 to 10
It is 50,000, preferably 2,000 to 60,000. When the number average molecular weight is less than 1,500, a large number of molecules that do not substantially have an azo bond exist, so that the efficiency of block copolymerization with a polymerizable monomer decreases and the original function is not achieved. No longer show. On the other hand, if it exceeds 100,000, the solubility in the hydrophilic solvent used for the block copolymerization is lowered and the solution viscosity is increased, so that the block copolymerization must be carried out at a low concentration. Since the polymerization rate of the polymerizable monomer used for the copolymerization is lowered, the reaction for a long time is forced.

Specific examples of the hydrophilic solvent used for producing the resin for anionic electrodeposition coating include monoalcohols having 1 to 4 carbon atoms, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol and isobutyl. Alcohol and t-butyl alcohol; ethylene glycol and its derivatives such as ethylene glycol monomethyl ether, monomethyl ether acetate, monoethyl ether, diethyl ether,
Monoethyl ether acetate, monoisopropyl ether, monobutyl ether, diethyl ether, monoethyl ether acetate, monoisopropyl ether,
Monobutyl ether acetate; diethylene glycol and its derivatives such as diethylene glycol monomethyl ether, monoethyl ether, monoethyl ether acetate, mono-n-butyl ether, mono-t-
Butyl ether, dimethyl ether, methyl ethyl ether, diethyl ether monoacetate; triethylene glycol and its derivatives, such as triethylene glycol monomethyl ether, monoethyl ether; propylene glycol and its derivatives, such as propylene glycol monomethyl ether, monoethyl ether,
Mono-n-butyl ether, mono-t-butyl ether, methyl ether acetate; dipropylene glycol and its derivatives, such as dipropylene glycol monomethyl ether, monoethyl ether; tripropylene glycol and its derivatives, such as tripropylene glycol monomethyl ether; Glycerin and its derivatives, such as glycerin monoacetate; trimethylene glycol and its derivatives, such as 1-butoxy-ethoxypropanol, 3,3-dimethyl-3-methoxypropanol, 3-methoxybutylacetate; butanediol and its derivatives, such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutylacetate, 3-methyl-1,3
-Butanediol; acetylene glycol derivatives such as 2,4,7,9-tetramethyl-5-decyne-4,7
-Diols and their ethylene oxide adducts, 2,6
-Dimethyl-4-octyne-3,6-diol; Others include dioxane, 1,5-pentanediol, hexylene glycol, trimethylolpropane, 1,2,6-hexanetriol and low molecular weight polyethylene glycol. Generally, it is preferable to use a monoalkyl ether of ethylene glycol or propylene glycol and a monoalcohol having 5 or less carbon atoms in combination. In addition,
These solvents can be used alone or in combination.

The neutralizing agent used in the production of the resin for anion electrodeposition coating is ammonia and / or amines, and specific amines that can be used are diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropyl. Examples thereof include alkylamines such as amines, monobutylamine, dibutylamine and tributylamine; alkanolamines such as diethanolamine and triethanolamine; alkylalkanolamines such as dimethylaminoethanol. The amount used varies depending on the concentration (acid value) of the polymerizable unsaturated acid monomer used, but is usually 50 to 95 mol% with respect to the acid group.

The method for producing the resin for the present anion electrodeposition coating composition is as follows:
Unlike the method used for a general resin for anion electrodeposition coating, since the above-mentioned azo group-containing polysiloxane compound is used, a commonly used low molecular weight polymerization initiator is not required. That is, the azo group-containing polysiloxane compound is dissolved in the hydrophilic solvent, the polymerizable unsaturated acid monomer (a) and the polymerizable unsaturated monomer (b) copolymerizable therewith, and then the temperature is raised. As a result, the azo group contained in the azo group-containing polysiloxane compound is decomposed, and the resulting carbon radical serves as a field for initiating polymerization. Therefore, the polymerization reaction of the unsaturated monomer occurs from both ends of the extended molecule of the polysiloxane unit.

The raw materials may be charged all at once or separately. The reaction temperature is usually 60 to 140 ° C. and the reaction time is about 4 to 20 hours.

When the concentration of the azo group-containing polysiloxane compound is low, or when the concentration of the azo group contained in the same molecule is decreased because the molecular weight of the polysiloxane unit in the azo group-containing polysiloxane compound is high, or When it is feared that the polymerization rate will decrease due to a decrease in catalyst efficiency, a peroxide-type and / or azo-type polymerization initiator can be added particularly in the latter half of the reaction to improve the polymerization rate.

The polymerization initiator used may be a general peroxide type or azo type initiator. Specific examples of the peroxide type polymerization initiator include methyl ethyl ketone peroxide, lauroyl peroxide, benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide and the like. Also,
Specific examples of the azo-based polymerization initiator include 2,2'-azobisisobutyronitrile and 1,1'-azobis (cyclohexane-1-carbonitrile).

If necessary, various chain transfer agents such as octyl mercaptan, lauryl mercaptan, β-mercaptopropionic acid and octyl thioglycolate can be used for controlling the molecular weight.

The resin solution containing the block copolymer thus polymerized as a main component is neutralized with ammonia and / or amines, and then deionized water is added thereto to obtain a stable aqueous fine particle dispersion (anion electrodeposition). Resin for paint).
Incidentally, the stable hydrated fine particle dispersion, in addition to the block copolymer of the main component, for example, chain transfer due to the solvent during the reaction, or when using a chain transfer agent undergoes chain transfer due to it, Does not become a block copolymer (a),
(b) A copolymer derived from only a mixed monomer of monomers is produced. In addition, even when an ordinary peroxide-based or azo-based initiator is used in combination with an azo group-containing polysiloxane compound, it is possible to obtain a compound from only a mixed monomer of (a) and (b) that does not become a block copolymer. The resulting copolymer is formed. Strictly speaking, the azo group-containing polysiloxane compound in which the azo group is deactivated during the block copolymerization reaction and the polydimethylsiloxane represented by the general formula [V] having an unreacted hydroxyl group or amino are also included.

The solid content of the hydrated and stable fine particle dispersion can be produced usually in the range of 20 to 40%, and the anionic electrodeposition coating composition including the curing agent component is usually prepared to a concentration of about 10%. To be done. The hardener added and mixed after the production of the block copolymer may be either before or after the addition of deionized water to make it aqueous.

[0046]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, "parts" in the production examples, examples, comparative examples and applied reference examples are "parts by weight" unless otherwise specified.

Production Example 1 In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a calcium chloride tube, a polydimethylsiloxane having a molecular weight of 4,600 and having amino groups at both ends of the molecule (general formula [V ], R ₂ and R ₃ are methyl groups, and E is —NH
_2, D is _{- (CH 2) 3 -,} m is the average 60 manufactured by Shin-product X-22-161C) 100 parts was charged with 4.38 parts of triethylamine and chloroform 86.8 parts, thoroughly stirred did. Then, under ice cooling, 4,4'-azobis
A solution consisting of 6.89 parts of (-4-cyanopentanoic acid chloride) and 86.8 parts of chloroform was added dropwise over 40 minutes. After completion of dropping, the mixture was reacted at room temperature for 2 hours, and then 50 parts of chloroform was additionally diluted to remove water-soluble components such as triethylamine hydrochloride by washing with water and then dried under reduced pressure.

The number average molecular weight of the obtained azo group-containing polydimethylsiloxane amide was found to be 29.00 by GPC analysis.
It was 0. The decomposition temperature of the azo group determined by DSC (Differential Scanning Calorimeter) was 93.6 ° C, and the decomposition enthalpy was -39.3 mJ / mg, but the heat balance after heat treatment at 140 ° C for 5 hours was Didn't show up.

Production Example 2 Instead of the polydimethylsiloxane having amino groups at both ends used in Production Example 1, a polydimethylsiloxane having a molecular weight of 3,200 and having hydroxyl groups at both ends (in the general formula [V], R ₂ and R ₃ are methyl groups, E is —OH,
D is _{- (CH 2) 3 -O- (} CH 2) 2 -, Shin-Etsu Chemical m is the average 40 Co. Product KF-6002) except for using 69.55 parts in the same manner as described in Example 1 I did.

The number average molecular weight of the obtained azo group-containing polydimethylsiloxane ester was determined by GPC analysis to be 16,
It was 000. The decomposition temperature of the azo group determined by DSC was 92.3 ° C, and the decomposition enthalpy was -44.1 mJ.
However, the heat balance after heat treatment at 140 ° C. for 5 hours did not appear.

Examples 1 to 4 A 1000 ml four-necked flask equipped with a stirrer, a heat exchanger and a thermometer was placed in accordance with the formulation shown in Table 1 and Production Example 1 was performed.
To the azo group-containing polydimethylsiloxane compound obtained in 1 to 2, the polymerizable unsaturated acid monomer and the polymerizable unsaturated monomer are collectively charged, and solution polymerization is carried out at a temperature of about 100 ° C. for 7 hours with stirring. Then the diluent solvent was added. Then, the temperature of the reaction solution was adjusted to about 60 ° C., neutralized with a neutralizing agent solution, and deionized water was gradually added to make the solution water-soluble to obtain a stable fine particle dispersion (resin for anionic electrodeposition coating). .. The properties of the resulting fine particle dispersion are shown in Table 1.

Comparative Examples 1 to 2 Same as Examples 1 to 4 except that 2,2'-azobisisobutyronitrile was used instead of the azo group-containing polydimethylsiloxane compound obtained in Production Examples 1 and 2. To obtain a polymer.

[0053]

[Table 1]

Application Reference Examples 1 to 4 and Application (Comparative) Reference Examples 1 to 2 Anion electrodeposition coating compositions containing the block copolymer having the polydimethylsiloxane unit obtained in Examples 1 to 4 in the main chain as a main component. Cymel 303 (water-soluble melamine resin manufactured by Mitsui Toatsu Chemicals, Inc.) as a curing agent component was added to the resins for resins and Comparative Examples 1 and 2 according to the prescription of Table 2, and anion electrodeposition coating was performed. The results shown in Table 2 were obtained.

The objects to be coated, the conditions for electrodeposition coating, and the method of evaluating the coating film performance used were as follows.

A) Aluminum plate: JIS H400 (A1050P) 1.5 × 35 × 70
mm B) Anodization: ・ Immersion in 10% NaOH aqueous solution for 2 minutes / 60 ° C, deionized water cleaning ・ 15% HNO ₃ aqueous solution for 30 seconds / 25 ° C immersion, deionized water cleaning ・ 15% H ₂ SO ₄ 30 minutes at 1 A / dm ² current for aqueous solution
After energizing at 30 ° C, wash with deionized water c) Electrodeposition coating: voltage 150 V, 2 minutes / 25 ° C, distance between electrodes 150 mm d) Film thickness: using a film thickness meter (Isoscope MP2, Helmto Fisher product) Measurement E) Smoothness of coating film: Visually observe the appearance of the coating film after coating,
The appearance, unevenness, and pinholes were examined. F) Adhesiveness: 1 mm spacing on the coated surface (10 x 10)
, And then peeled off after applying cellophane tape, and evaluated by the number of remaining coatings. Gloss: Glossmeter [Digital variable angle glossmeter UGV-5D,
Suga Test Machine Co., Ltd.] is used to measure 60-degree specular gloss. H) Weather resistance: Gloss retention (%) after 1000 hours of sunshine weatherometer) Pencil hardness: "Mitsubishi Uni" (Mitsubishi Pencil ( (Product) is used to evaluate the hardness until the coating film is scratched. N) Alkali resistance: The coating film is applied to a 5% Na ₂ CO ₃ aqueous solution for 24 hours.
Observing the state after immersion for 20 hours at 20 ° C) Acid resistance: Coating film in 5% H ₂ SO ₄ aqueous solution for 24 hours / 2
Observe the condition after soaking at 0 ℃

[0057]

[Table 2]

[0058]

INDUSTRIAL APPLICABILITY The aqueous product of the block copolymer of the polysiloxane unit and the vinyl component of the present invention is useful as an anion electrodeposition coating resin having high weather resistance and excellent matting properties.

Claims (1)

[Claims] 1. A compound represented by the general formula [I]: [Wherein R ₁ is the same or different and represents a lower alkyl group or a nitrile group, R ₂ is the same or different and represents a lower alkyl group, and R ₃ is the same or different and is a halogen atom-substituted or unsubstituted alkyl group. Represents a group or a phenyl group. l is the same or different and represents 0 or an integer of 1 to 6, m represents an integer of 0 or 1 to 200, A represents —O— or —NH—, and D represents (CH ₂ ) _n (however,
n are the same or different 0 or an integer from 1 to 6) or _{- (CH 2) 3 -O- (} CH 2) 2 - has a repeating unit represented by the indicating], at least one in one molecule Number average molecular weight having azo bond is 1,500 to 100,00
2 to 60% by weight of 0 azo group-containing polysiloxane compound
In the presence of a polymerizable unsaturated acid monomer (a) and a polymerizable unsaturated monomer (b) copolymerizable therewith mixed monomer 40 to
A method for producing a resin for anionic electrodeposition coating, which comprises radically polymerizing 98% by weight in a hydrophilic solvent, neutralizing with ammonia and / or amines, and then making the resin aqueous.