JPS6157352B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition for electrodeposition paint suitable for electrodeposition coating. Conventionally, butadiene polymers have been used in electrodeposition paints by anodic electrodeposition, which is used as industrial paints for automobiles and the like. Many of these methods are known, such as Japanese Patent Publication No. 51-24532, No. 51-150597, No. 52-102347, and No. 47-3436. On the other hand, in recent years, a manufacturing method for cathodic electrodeposition paint resin has been established, and it has been adopted industrially because it can produce coatings with excellent corrosion resistance, and the cathodic electrodeposition method has spread extremely rapidly. It seems to be going.
The main components of the resin used in these cathode electrodepositions are:
Cathodic electrodeposition coating resin compositions consisting of an adduct of an epoxy resin and an amine compound and a blocked organic polyisocyanate are mainly used.
86735, Japanese Patent Application Laid-Open No. 52-121640, etc. However, the cost of these epoxy resins is high, and by using a cheaper butadiene polymer in combination, the cost can be reduced without reducing corrosion resistance, and the mechanical properties such as impact resistance of the cured coating film can be improved. It is an object of the present invention to achieve this. On the other hand, regarding the method of using butadiene polymer as a resin for cathodic electrodeposition coating,
16048, JP-A-53-8629, JP-A-51-119727, JP-A-52-147638, JP-A-53-63439, etc. However, these methods have insufficient adhesion to the iron plate, which is particularly noticeable in the cellophane tape peeling test after the salt spray test. Conventionally, the rust width from the cross cut part was 2 mm on one side during the salt spray test as a criterion for corrosion resistance.
There is a method of expressing the time when Therefore, it is necessary to maintain adhesion between the paint film and the steel plate.
Therefore, an extremely important measurement item is to peel off the tape one hour after the salt spray test and test the adhesion. Normally, the corrosion resistance time due to tape peeling is usually shorter than the time required for corrosion resistance due to the growth of the rust width of the cross cut portion. As a result of various studies aimed at improving the drawbacks of butadiene polymers, we discovered a resin composition that can form a coating film with excellent corrosion resistance and good mechanical properties in a tape peel test, and we have already filed a patent application for this resin composition. Patent applications were filed under No. 143842 (1982) and Japanese Patent Application No. 2525 (1982). Japanese Patent Application No. 53-143842 describes, for example, an addition reaction of phenol to a maleic anhydride adduct of a butadiene polymer using an acid catalyst, and then a relatively large amount of remaining unreacted phenol is removed by washing with water or alcohol. . Next, a diamine such as N/N-dimethylaminopropylamine is reacted with the succinic anhydride group to form an imidide, and this resin component is combined with a blocked organic polyisocyanate or an amine-modified epoxy resin. This is a resin composition for electrodeposition coatings consisting of coexisting components. This system has greatly improved the disadvantages of butadiene polymers through the reaction of phenols and the introduction of maleated imide groups, resulting in excellent adhesion to iron plates, surface hardness, and other physical properties of the coating. However, this system requires a step to remove a relatively large amount of unreacted phenol after phenolization of the butadiene polymer. When the removal method is, for example, hot water washing, it involves industrially complicated steps such as oil-water separation, dehydration and drying after washing, and recovery of phenol from the washing liquid. The present inventors have arrived at the present invention as a result of pursuing the elimination of these industrially disadvantageous factors and the creation of resins with even higher performance corrosion resistance. That is, the present invention relates to at least one phenol adduct obtained by adding phenols to a butadiene polymer or copolymer (hereinafter sometimes referred to as butadiene polymer) or a modified product thereof in the presence of a catalyst, and an epoxy A basic resin for electrodeposition paints whose main component is an adduct obtained by addition-reacting a compound [F] obtained by reacting a compound and an epoxy modifier with a partially blocked organic polyisocyanate. This is a resin composition for electrodeposition paint, which is a basic resin whose main components are a resin composition and a compound [F] and a completely blocked organic polyisocyanate. One of the features of the method of the present invention is that phenols are added to a butadiene polymer or a modified product thereof in the presence of a catalyst, and then the mixture is reacted with an epoxy compound in the presence of unreacted phenols. In this case, when the butadiene polymer is used as an adduct of α/β-unsaturated dicarboxylic acid or its anhydride (hereinafter referred to as maleic anhydride), the epoxy compound reacts with the carboxyl group derived from this. By doing so, the butadiene polymer component and the epoxy compound component are reactively bonded. In parallel with this reaction, unreacted phenols coexisting in the system also react with the epoxy compound, so that the amount of free phenols in the system becomes almost "0".
The components derived from the epoxy compound reacted with the phenols have a positive effect on film forming properties, hardness, water resistance, etc. during subsequent coating film formation. Furthermore, as a feature of the present invention, the performance can be greatly improved by reacting the butadiene polymer component, which is essentially incompatible with the epoxy compound, and further, by reacting and introducing phenols into the butadiene polymer, the resin It has been found that the homogeneity and compatibility of the material can be greatly improved, a very clear and dense coating film can be obtained, and the corrosion resistance can be further improved. In the present invention, the reaction sequence when phenols are subjected to an addition reaction and subjected to a reaction with an epoxy compound is as follows. For example, (1) addition of maleic anhydride to a butadiene polymer, addition of phenols, and reaction with an epoxy compound; (2) addition of maleic anhydride to a butadiene polymer, ring-opening of the acid anhydride group, addition of phenols, and reaction with an epoxy compound; Order of reaction with compounds, (3)
Addition of maleic anhydride to a butadiene polymer, addition of phenols, ring opening of the acid anhydride group, and reaction with an epoxy compound (4) Addition of phenols to a butadiene polymer and reaction with an epoxy compound (5) ) Addition of phenols to a butadiene polymer, addition of maleic anhydride, ring opening of an acid anhydride group, reaction with an epoxy compound, etc. For example, for butadiene polymers that already have functional groups such as carboxyl groups. The method (4) is preferable. The butadiene polymer used in the present invention has a number average molecular weight of 150 to 30,000, preferably 300 to 5,000,
More preferably, it is a homopolymer or copolymer of butadiene having a molecular weight of 500 to 3,000. The microstructure of double bonds is not a particular problem. 1.4 type structure, 1.
The content of type 2 structure is not a problem. In addition, depending on the type of polymerization initiation or termination of butadiene, OH group, COOH group, Br group, or
Also included are butadiene polymers or copolymers having a functional group such as _NR2 group (R represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms). It also includes butadiene polymers or copolymers chain-transferred with toluene, α-olefin, and the like. Butadiene copolymers are broadly classified according to the type of copolymerizable monomer, but include vinyl monomers, aromatic substituted monomers, α-olefins, conjugated diene monomers, acetylenes, dicyclopentadiene, norbornene derivatives, etc. It can be mentioned as a coalescing monomer. Examples of vinyl monomers include acrylic acid,
Methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic residual octyl,
Hexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, hexyl methacrylate, octyl methacrylate, dodecyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, vinyl acetate, vinyl propionate, butyric acid Vinyl, vinyl chloride, vinyl fluoride, vinylidene chloride,
vinylidene fluoride, maleic acid, maleic anhydride,
Maleic acid esters, maleic diesters,
They include acrylonitrile, methacrylonitrile, acrylamide, vinylpyridine, vinylcyclohexene, and N-vinylpyrrolidone. Examples of aromatic substituted vinyl monomers include styrene, α-methylstyrene, vinyltoluene, chlorostyrene,
These include α.p-dimethylstyrene and isopropenyltoluene. α-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1,
Examples include heptene-1, octene-1, nonene-1, decene-1, dodecene-1, and the like. Conjugated diene monomers include isoprene,
Examples include 1,3-pentadiene, chloroprene, cyclopentadiene, cyclooctadiene-1,3, cyclohexadiene-1,3, 2,3-dimethylbutadiene, and 2-phenylbutadiene. Examples of acetylenes include acetylene, methylacetylene, phenylacetylene, propargyl bromide, and propargyl chloride. Norbornene derivatives include norbornene,
Examples include 5-vinylnorbornene, 5-ethylidenenorbornene, 5-chloronorbornene, and 5-phenylnorbornene. These copolymerizable monomers may be one or two types.
It is also possible to copolymerize a mixture of more than one species, and such multicomponent copolymers are also included. If the copolymerization ratio of butadiene in the copolymer is 50 mol% or more, all butadiene is included. Examples of the α/β-unsaturated dicarboxylic acid or its anhydride include maleic acid, fumaric acid, itaconic acid, citraconic acid, and the anhydride thereof. The phenols [C] also include phenols bonded with saturated alkyl groups, unsaturated alkyl groups, aromatic groups, and halogen groups. For example, phenol, o-cresol, m-cresol, p-
Cresol, ethylphenol, isopropylphenol, butylphenol, hexylphenol, octylphenol, nonylphenol, decylphenol, dodecylphenol, xylenol, resorcinol, catechol, hydroquinone, chlorphenol, bromophenol, vinylphenol, isopropenylphenol, butenylphenol , hexenylphenol, heptenylphenol, octenylphenol, cardanol, oak oil, urushiol, etc. The catalyst required for the addition reaction between a butadiene polymer and a phenol, or for the production of an adduct between a butadiene polymer and an α/β-unsaturated dicarboxylic acid or its anhydride and a phenol, is a radical. There are catalysts, thermal reaction catalysts, anion catalysts, and acid catalysts, and among these, acid catalysts are preferred.
Examples of acid catalysts include mineral acids such as sulfuric acid, hydrochloric acid, chlorosulfonic acid, florsulfonic acid, and perchloric acid; organic acids such as benzenesulfonic acid, p-toluenesulfonic acid, trichloroacetic acid, and trifluoroacetic acid; aluminum chloride; These include Lewis acids such as ferric chloride and boron trifluoride, or phenol complexes, tetrahydrofuran complexes, alcohol complexes, organic acid complexes, and ether complexes of these Lewis acids. Ring-opening agents for the maleic anhydride adduct include hydroxyl group-containing compounds, epoxy group-containing compounds, secondary amines, and water. Examples of hydroxyl group-containing compounds include _C1 to _C18 aliphatic saturated and unsaturated primary alcohols, secondary and tertiary alcohols, _C1 to _C20 aromatic alcohols, and acrylic esters having alcoholic hydroxyl groups. , methacrylic acid ester, and amino alcohols having a tertiary amino group, and compounds having a phenolic hydroxyl group include phenol,
C _1-4 alkylphenols and the like. As an epoxy group-containing compound, 1 per molecule
A compound containing epoxy groups, including aliphatic, aromatic, acrylates, and methacrylates. Examples of secondary amines include _C1 to _C18 aliphatic monoamines, secondary amines having a tertiary amino group in the molecule, aromatic secondary monoamines, and alicyclic secondary monoamines. However, these compounds may contain substituents that do not inhibit the subsequent reaction, such as halogen,
There is no particular problem even if a cyano group or a lower alkyl group is bonded. As the epoxy compound [D], 1 per molecule
Polyepoxides having more than 1 epoxy group are preferred, such as phenyl glycidyl ether, epichlorohydrin, propylene oxide, ethylene oxide, styrene oxide, isobutylene oxide, allyl glycidyl ether, glycidyl acrylate, glycidyl acrylate, glycidyl methacrylate, etc. Epoxides containing 2 epoxy groups are also applicable to the method of the invention. Examples of polyepoxides containing two or more epoxy groups in one molecule include epoxy resins obtained from bisphenol A and epichlorohydrin, epoxy resins obtained from hydrogenated bisphenol A and epichlorohydrin, or bisphenol A and β-methylepichlorohydrin. , polyglycidyl ethers of novolac resins, polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin or trimethylolpropane, polyglycidyl esters of polycarboxylic acids such as adipic acid, phthalic acid or dimer acids, Epoxidized product of cyclic olefin or polybutadiene,
These include epoxidized natural drying oils or semi-drying oils. The epoxy modifier [E] has one active hydrogen atom in its molecule that can react with the epoxy group.
These are carboxylic acids, amines, and phenols having ~2. The carboxylic acids include _C1-18 saturated and unsaturated monocarboxylic acids and dicarboxylic acids. Examples of aliphatic monocarboxylic acids include formic acid,
Acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, cyanoacetic acid, mono-, di- and trichloroacetic acid, etc. Saturated fatty acids, acrylic acid, crotonic acid, vinyl acetic acid, methacrylic acid, allyl acetic acid, oleic acid, erucic acid, sorbic acid,
Unsaturated acids such as linoleic acid, eleostearic acid, linolenic acid and acetylenecarboxylic acid. Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
These include suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, itaconic acid, acetylenecarboxylic acid and allylmalonic acid. Examples of aromatic monocarboxylic acids include benzoic acid and its nuclear substituted products with halogen atoms, CN groups, or OH groups, phenyl acetic acid, cinnamic acid, and examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. , hexahydrophthalic acid, tetrahydrophthalic acid, or anhydrides thereof. Note that these halogen atoms, CN groups and OH
One or two H atoms are substituted with a group.
In addition, as phenols, phenol, o-,
Examples include m- and p-cresol, xylenol, vinylphenol, catechol, resorcinol, hydroquinone, bisphenol A and bisphenol S. In addition, as primary amines, methylamine,
Ethylamine, n-propylamine, isopropylamine, butylamine, isobutylamine,
Sec-butylamine, tert-butylamine, pentylamine, isopentylamine, tert-pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, vinylamine, allylamine, and alcoholic OH of these amines.
Substituents include aliphatic amines such as monoethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol and 2-amino-2-methyl-1,3-propanediol. . Examples of aromatic and alicyclic amines include aniline, toluidine, ethylaniline, p-isopropylaniline, p-tert-butylaniline, xylidine, vinylaniline, chloroaniline, α
-naphthylamine, β-naphthylamine, benzylamine, α-methylbenzylamine, phenethylamine and cyclohexylamine. Specific examples of secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diethanolamine, and dipropanolamine. These epoxy modifiers can be used alone or in combination. The synthesis of the adduct of a conjugated diene polymer or its phenol adduct and an α/β-unsaturated dicarboxylic acid or its anhydride is carried out by a known method. That is, a conjugated diene polymer or its phenol adduct and an α/β-unsaturated dicarboxylic acid or its anhydride are mixed and heated at 50 to 300°C for 1 to
It can be synthesized by reacting for 10 hours, preferably at 150 to 210°C for 2 to 7 hours. When an anti-gelling agent is required, it is added in the reaction system in an amount of 0.01 to 10% by weight, preferably 0.01 to 2% by weight. The amount of α/β-unsaturated dicarboxylic acid or its anhydride to be used is such that the content in the adduct is 3 to 30% by weight, preferably 5 to 20% by weight. In general, it is preferable that the reaction site with the epoxy compound is a carboxyl group derived from α/β-unsaturated dicarboxylic acid or its anhydride, but the OH group and epoxy group of the phenol added to the diene polymer by nuclear substitution are preferable. There is no particular problem even if there is a reactive bond with. If the content of α/β-unsaturated dicarboxylic acid or its anhydride in the adduct exceeds 30% by weight, it is not preferable because the uniform reactivity with the epoxy compound decreases. On the other hand, if it is less than 3%, its contribution as a reaction site with the above-mentioned epoxy compound decreases, which is not preferable. To ring-open the acid anhydride group of the maleic anhydride adduct or its phenol adduct, add 0.2 to 1.5 mol, preferably 0.7 to 1.1 mol, of a ring-opening agent to 1 mol of the acid anhydride group, and add 30 to 30 mol of ring-opening agent. 180℃, preferably
React at 70-150°C for 30 minutes to 5 hours. At this time, an inert solvent can be used if necessary. In addition, when the ring-opening agent is a compound having an alcoholic OH group or a phenolic OH group or a compound having an epoxy group, triethylamine or other amines are used as a catalyst to react 1 to 10 times the acid anhydride group.
Mol% can be used. Butadiene polymer or its modified product [B]
The addition reaction between and phenols is carried out in the presence of a catalyst. Usually 20~300℃, preferably 50~180℃
is within the range of The amount of catalyst in the total reaction composition is 0.01~
10% by weight, preferably 0.1-3% by weight. The amount of phenols used per 100 parts by weight of the butadiene polymer [A] or its modified product [B] is in the range of 5 to 500 parts by weight, preferably 20 to 300 parts by weight. Normally, after phenolization, the unreacted phenol is reacted with an epoxy compound without removing it, but especially when it is intended to introduce a large amount of phenol into a butadiene polymer, the unreacted phenol is phenolated in a large excess of phenol. Some or most of the reacted phenol may be removed by distillation or washing. However, it is not necessary to completely remove it. An inert solvent can be used during the addition reaction if necessary. Quantitatively analyze unreacted phenols by gas chromatography and calculate the reaction rate. The reaction time is usually 30 minutes to 10 hours, preferably 1 to 4 hours. The reaction of the phenol adduct of the butadiene polymer [A] or its modified product [B], the epoxy compound [D], and the epoxy modifier [E] starts from 20 to
The reaction is carried out at 200°C, preferably from 50 to 150°C, for 10 minutes to 10 hours, preferably for 1 to 5 hours. In this case, it is usually diluted with an inert hydrophilic organic solvent containing no free OH or COOH groups, such as ethylene glycol monoethyl ether monoacetate. Further, when the epoxy modifier [E] is other than amines, a commonly used basic catalyst such as triethylamine is used. The epoxy compound [D] may be reacted with the above-mentioned phenol adduct after a part or all of the epoxy modifier [E] is reacted in advance with a part or the whole of the epoxy modifier [E]. The adduct and the epoxy modifier [E] may be reacted simultaneously, or the phenol adduct and the epoxy compound [D] may be reacted first and then the epoxy modifier may be reacted. Usually, the epoxy group of the epoxy compound [D] is set in an amount corresponding to the sum of the carboxyl group equivalent of the phenol addition component of the butadiene polymer, the unreacted phenol equivalent, and the equivalent of the epoxy modifier, or is set to be several percent larger. . The blocked organic polyisocyanate is a blocked polyisocyanate, and the blocking agent is a volatile low-molecular active hydrogen compound. Examples of organic polyisocyanates include m- or p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, m- or p-xylylene diisocyanate, hexamethylene diisocyanate. , dimer acid diisocyanate, isophorone diisocyanate, and adducts of one or more of these diisocyanates with polyols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol. , and polyisocyanates such as trimers of the above-mentioned diisocyanates. Examples of blocking agents for organic polyisocyanates include methanol, ethanol, propanol, butanol, hexanol, heptanol,
Octanol, nonyl alcohol, decanol,
Aliphatic or aromatic monoalcohols such as dodecanol, hexadecanol, cyclohexanol, benzyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, oximes such as acetoxime, methyl ethyl ketone oxime, acetylacetone, ethyl acetoacetate and malones. These include active hydrogen compounds such as acid diethyl ester. Furthermore, acrylic ester having a hydroxyl group,
Methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc., and alkanolamines such as N.
N-dimethylaminoethanol, N・N-diethylaminoethanol, N・N-dipropylaminoethanol, N・N-dibutylaminoethanol, N・N-dimethylaminopropanol, N・
N-diethylaminopropanol, N.N-dipropylaminopropanol, N.N-dibutylaminopropanol and the like can also be used as blocking agents. Furthermore, two or more of these blocking agents can be used in combination. Blocked organic polyisocyanates can be synthesized by reacting 0.5 to 1 equivalent of a blocking agent with 1 equivalent of isocyanate groups in the organic polyisocyanate. The reaction temperature is 0 to 200°C, preferably 10 to 140°C, and if necessary, an inert solvent can be used, and if necessary, a radical inhibitor such as hydroquinones or phenothiazine can be used. The partially blocked organic polyisocyanate is reacted at a ratio of 0.1 to 1.5 equivalents, preferably 0.2 to 1.0 equivalents of free isocyanate groups per equivalent of free hydroxyl groups in compound [F]. Reaction temperature is 20℃~140℃
℃, 10 minutes to 10 hours. In addition, the completely blocked organic polyisocyanate was added in an amount of 5 parts by weight per 100 parts by weight of the compound [F].
~200 parts by weight are used, preferably 10-100 parts by weight. In the resin composition of the present invention, the amine value of the solid content of the final product (expressed as the number of KOH mg equivalent to hydrochloric acid required to neutralize 1 g of resin) is 10.
The usage ratio of each reaction component is set to be 150 to 150, preferably 25 to 100. To make the final product water-soluble or water-dispersible, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, hexylic acid, 2-ethylhexylic acid, lactic acid, hydroxyacetic acid, oxalic acid, or phosphoric acid, hydrochloric acid, Neutralize with inorganic acids such as sulfuric acid and carbonic acid. The amount of acid required for neutralization is preferably 1 equivalent or less per 1 equivalent of amine, and it is preferable to add the minimum amount of acid that can be water-dispersible or water-soluble. The resin composition thus obtained usually has a pH of 2 to 9, preferably 5 to 7, more preferably 6.
It will be adjusted to be above. In addition to the resin composition of the present invention, a pigment composition or various additives such as surfactants or wetting agents can be dispersed to prepare an aqueous electrocoating dispersion. Pigment compositions include, for example, iron oxide, lead silicate, lead oxide, strontium chromate, carbon black, titanium white, talc, kaolin, clay,
These include barium sulfate, cadmium yellow, cadmium red, and chromium yellow. The content of pigment in an electrodeposition paint is usually expressed as the ratio of the amount of pigment to the amount of resin. Normally in the practice of this invention
A pigment to resin ratio of 0.01 to 5:1 is used. Further, other additives are mixed and used in an amount of 0.01 to 4% by weight of the resin solid content. When the electrodeposition paint containing the electrodeposition resin composition of the present invention as a resin component is electrodeposited, it is deposited to form a film on an iron plate connected to a cathode. After washing this with normal water
Bake hardening at 150-250°C, preferably 170-200°C. During curing, the blocking agent in the blocked organic polyisocyanate in the resin dissociates, evaporates or polymerizes, and the generated isocyanate groups chemically bond to the OH groups in the resin composition of the present invention and simultaneously cure. Since curing occurs simultaneously due to the crosslinking reaction between double bonds, it provides even better properties. Electrodeposition paints using the resin composition of the present invention as a resin include:
It also shows excellent corrosion resistance on untreated steel sheets,
Particularly in the tape peeling test for corrosion resistance, it has excellent resistance, that is, adhesion. Examples are shown below, but the present invention is not limited thereto. Reference Example 1 Production example of maleated liquid polybutadiene The number average molecular weight
1700, the microstructure of the double bond is cis 1/4 structure75
%, trans 1/4 structure 24% and vinyl structure 1
540 g of liquid polybutadiene with a viscosity of 630 centipoise at 20°C and an iodine value (Wiss method) of 420, 60 g of maleic anhydride, and iron naphthenate (5% Fe).
2.4 g was charged and reacted at 190° C. for 4 hours under a nitrogen gas atmosphere to obtain a maleic anhydride adduct with a total acid value of 109. Reference Example 2 Example of producing a ring-opening reaction product of maleated liquid polybutadiene Reference Example 1 was placed in a 1-4 neck flask equipped with a stirrer, thermometer, cooling tube, and inert gas introduction pot.
A ring-opening reaction product was obtained by reacting 400 g of the maleated liquid polybutadiene obtained in step 1 with 73.2 g of ethylene glycol monoethyl ether acetate (abbreviated as EGA), 14.4 g of methanol, and 1.4 g of triethylamine at 60 to 80 °C for 2 hours. Ta. The acid value of this reaction solution was 45.0. Reference Example 3 Example of Modification of Epoxy Resin In a 2-4 neck flask equipped with the same equipment as in Reference Example 1, an epoxy resin obtained from bisphenol A and epichlorohydrin (hereinafter abbreviated as epibis type epoxy resin. Epoxy equivalent: 188 )570
By reacting 126.5 g of terephthalic acid, 298.5 g of EGA, and 1.0 g of triethylamine at 120°C for 4 hours, a transparent resin liquid having a viscosity of 1540 centipoise at 25°C was obtained. This thing has an acid value of 1 or less,
The epoxy content was 1.61×10 ⁻³ eq/g. Reference Example 4 Example of manufacturing masterbatch for paint In a 2- to 4-necked flask equipped with the same equipment as Reference Example 1, add epoxy equivalent using Epibis type epoxy resin.
375g of 474, 125 of the same epoxy equivalent 188
g, EGA 219.2 g, acrylic acid 104.8 g, hydroquinone 2.6 g and triethylamine 2.4 ml in 110 g.
The acid value was reduced to 3 or less by reacting at ℃ for 10 hours. Next, 965 g of N·N-diethylaminoethanol semi-blocked TDI-EGA solution prepared in the same manner as shown in Example 1 was added dropwise at 65°C, and then 70°C
After reacting for 3 hours, 40 g of ethylene glycol monoethyl ether was further added and stirred at 70° C. for 1 hour to obtain a transparent viscous resin. This product had a viscosity of 34,000 centipoise at an amine value of 67.25°C. 100 parts of this resin (solid), aluminum silicate
230 parts, carbon black 10 parts, lead chromate 18 parts
parts, ethylene glycol monoethyl ether 160
A paint masterbatch was obtained by shaking and mixing 3.3 g of 85% formic acid and 3 mm diameter glass beads in a quick mill for 90 minutes. Example 1 Reference Example 1 was placed in a 500ml 4-necked flask equipped with a stirrer, thermometer, cooling tube, and inert gas inlet.
Maleated liquid polybutadiene 100 obtained in
g, phenol 50g, toluene 30.1g and
_BF3・phenol complex 0.36g and 140g at 80~90℃
Allowed to react for minutes. When unreacted phenol was quantified by gas chromatography, the reaction rate of phenol was 20.5%. After deactivating the catalyst with triethylamine,
33.9 g of EGA was added to dilute 70 wt%. 92.4 g of this phenolization reaction solution and the same epoxy resin used in Reference Example 3 (epoxy equivalent
188) 130g, diethylamine 6.4g and
When 58.2 g of EGA was reacted at 120° C. for 3 hours, the acid value of this system was 0, and the amount of unreacted phenol was not detected by gas chromatography. Then 21.9g of acrylic acid and hydroquinone
The acid value was reduced to 2 or less by further reacting at 100°C for 5 hours. Separately synthesized N・N-diethylaminoethanol semi-blocked TDI-EGA solution was added to this reaction solution.
After adding 113.9g dropwise at 65°C or below and stirring while keeping it warm at 70°C for 2 hours, 10g of ethylene glycol monoethyl ether (abbreviated as ethyl cellosorg) was added and the reaction was further carried out at 70°C for 1 hour to increase the amine value (resin solid content). Same hereafter) 67.0, resin concentration (NV
) 70wt% and viscosity at 25℃ (η25
) A clear resin liquid of 47,000 centipoise was obtained. The semi-blocked TDI-EGA solution used above was synthesized as follows. 2.4 in a 500ml 4-necked flask equipped with a stirrer, thermometer, dropping funnel and nitrogen gas inlet.
−/2・6=80/20 (%) 47.6 g of toluene diisocyanate (hereinafter abbreviated as TDI) and
After charging 34.1 g of EGA, 32.1 g of N-N-diethylaminoethanol was added dropwise in an _N2 gas atmosphere while cooling and stirring in an ice-cooled bath to keep the internal temperature below 30°C, resulting in a semi-blocked TDI-
An EGA solution was prepared. An electrodeposition bath having a solid content of 15 wt % was prepared from 380 parts of the above resin solution, 167 parts of the paint masterbatch of Reference Example 4, 12.0 parts of 85% formic acid, and deionized water, and electrodeposition coating was performed. The electrodeposition characteristics and physical properties of the coating film are shown in Table 1. Example 2 150 g of maleated liquid polybutadiene produced in Reference Example 1, 37.5 g of phenol, and 33.1 g of EGA were placed in a 500 ml four-necked flask with the same equipment as in Example 1.
and 0.66 g of para-toluenesulfonic acid and reacted at 120 to 150°C for 4 hours to reach a phenol addition rate of 24.4%. Next, the temperature was lowered to 80℃, and 1.5g of triethylamine was added.
and 2.5g of methanol, and heated to 45℃ at 80~85℃.
After a minute reaction, 2.4 g of methanol was added and the reaction was continued at the same temperature for 1 hour. It was confirmed by infrared absorption spectrum that the acid anhydride group was ring-opened. Next, 65.4 g of this reaction solution, 2.27 g of the modified epoxy resin of Reference Example 3, 6.42 g of diethylamine, 9.4 g of sorbic acid, and 10 g of EGA were reacted at 120°C for 3.5 hours to reduce the acid value and free phenol in the system. It became almost “0”. Next, 114 g of the N/N-diethylaminoethanol semi-blocked TDI-EGA solution prepared by the method of Example 1 was added dropwise and reacted for 2 hours at 65-70°C. 1
Allowed time to react. Product has amine value 65.5, NV70
% and η ₂₅ 32000 centipoise. An electrodeposition solution having a solid content of 15 wt % was prepared from 380 parts of this resin, 167 parts of the paint master batch of Reference Example 4, 11.8 g of 85% formic acid, and deionized water, and electrodeposition coating was performed. The electrodeposition characteristics and physical properties of the coating film are shown in Table 1. Example 3 40 g of maleated liquid polybutadiene produced in Reference Example 1, 80 g of phenol, 21 g of toluene, and 0.5 g of p-toluenesulfonic acid were charged into a 200 ml four-necked flask with the same equipment as in Example 1, and the flask was heated to 120 ~
By reacting at 150°C for 4 hours, the phenol addition rate was 15%. After neutralizing the catalyst by adding 0.4 g of triethylamine, the solvent and unreacted phenol were distilled under reduced pressure to concentrate the content to 63 g. Transfer the concentrate to a 1- to 4-necked flask, and add to it an epoxy equivalent of 188 with Epibis type epoxy resin.
120g of epoxy equivalent, 15g of epoxy equivalent 475, 3.0g of diethylamine, 31g of acrylic acid and EGA89
By reacting with g at 120°C for 5 hours, the acid value and free phenol disappeared. Next, 210 g of the same N·N-diethylaminoethanol semi-blocked TDI-EGA solution prepared in Example 1 was added dropwise at 65°C, and the mixture was reacted at 65-70°C for 2 hours. Subsequently, 156 g of a separately synthesized semi-blocked TDI-EGA solution of 2-hydroxyethyl methacrylate was added dropwise and reacted at 90°C for 2 hours. Next, 10 g of ethyl cellosolve was added and the mixture was further reacted at 70°C for 30 minutes. The product has an amine number of 62.7, NV of 70% and η ₂₅ =
It was a clear resin liquid of 65,000 centipoise. An electrodeposition solution having a solid content of 15 wt % was prepared from 400 parts of this resin, 158 parts of the paint master batch of Reference Example 4, 11.9 parts of 85% formic acid, and deionized water, and electrodeposition was performed. The electrodeposition characteristics and physical properties of the coating film are shown in Table 1. The above semi-blocked TDI-EGA solution was prepared as follows. 174 g of TDI and 130 g of EGA were charged, and 130 g of 2-hydroxyethyl methacrylate (phenothiazine
0.13 g (dissolved)) was added dropwise over 1 hour. The temperature was raised to 60°C in 30 minutes after the dropwise addition, and the mixture was stirred while keeping it warm for 1.5 hours. NCO at this time was 9.6% (di-n-butylamine-HCl
titration method) and confirmed the formation of semi-blocked isocyanate. Comparative example: In a 1-4 neck flask, 120 g of Epibis type epoxy resin (epoxy equivalent: 475), the same epoxy equivalent
30g of 188, 28.2g of acrylic acid, 0.5g of hydroquinone, 66.5g of EGA and triethylamine
By charging 0.25 g and reacting at 120°C for 4 hours, the acid value was reduced to 1 or less. Next, 189 g of N/N-diethylaminoethanol semi-blocked TDI-EGA solution prepared in the same manner as in Example 1 was added dropwise to the solution at 65-70°C.
2 hours prepared in Example 3.
- Hydroxyethyl methacrylate semi-blocked
132 g of TDI-EGA solution was added dropwise and reacted at 90°C for 2 hours. Finally, add 10g of ethyl cellosolve and heat at 70℃.
Stirred for 30 minutes. This resin has an amine value of 63, NV=
70% and η ₂₅ 30,000 centipoise. An electrodeposition solution having a solid content of 15% was prepared from 400 parts of this resin, 158 parts of the paint master batch of Reference Example 4, 11.9 parts of 85% formic acid, and deionized water, and electrodeposition was performed. They are shown in Table 1 together with the paints of Examples. Example 4 In a 500 ml four-necked flask with the same equipment as in Example 1, 42 g of the maleated liquid polybutadiene ring-opening reaction product of Reference Example 2, 20 g of phenol, and 0.19 g of p-toluenesulfonic acid were heated at 120 to 150°C for 3 hours. Made it react. The phenol addition rate was 25%. To this, 20 g of Epibis type epoxy resin with an epoxy equivalent of 188, 143 g of the epoxy modified product of Reference Example 2, 10.3 g of diethylamine, and 20.5 g of EGA were added at 120°C.
The acid value and free phenol disappeared by reacting for hours. Next, N·N-diethylaminoethanol semi-blocked TDI-
Add 85.7g of EGA solution dropwise, 65-70℃ x 2 hours,
Subsequently, 2-hydroxyethyl methacrylate semi-blocked TDI prepared in the same manner as in Example 3
-Add 70g of EGA solution dropwise and react at 90℃ for 2 hours,
Furthermore, 10 g of ethyl cellosorg was added and stirred at 70°C for 30 minutes. This resin was clear with an amine value of 66.0, NV of 70 wt%, and η ₂₅ =43,000 centipoise. From 400 parts of this resin, 158 parts of the paint masterbatch of Reference Example 4, 12.5 parts of 85% formic acid, and deionized water, an electrodeposition solution with a solid content of 15 wt% was obtained. The electrodeposition characteristics and physical properties of the coating film are shown in Table 1. 【table】

Claims (1)

[Claims] 1 (a) Butadiene polymer or copolymer [A]
Alternatively, at least one phenol adduct obtained by adding phenols [C] to the modified product [B] in the presence of a catalyst is reacted with an epoxy compound [D] and an epoxy modifier [E]. A resin composition for electrodeposition paint, characterized in that the main component is an adduct [G] obtained by subjecting the resulting compound [F] to (b) an addition reaction with a partially blocked organic polyisocyanate. 2. The resin composition for electrodeposition paint according to claim 1, wherein the adduct [G] is neutralized with an organic carboxylic acid or an inorganic acid. 3 (a) Butadiene polymer or copolymer [A]
Alternatively, at least one phenol adduct obtained by adding phenols [C] to the modified product [B] in the presence of a catalyst is reacted with an epoxy compound [D] and an epoxy modifier [E]. A resin composition for electrodeposition paint, characterized in that the obtained compound [F] and (b) a completely blocked organic polyisocyanate are the main components. 4. The resin composition for electrodeposition coatings according to claim 3, wherein the composition containing the compound [F] and a completely blocked organic polyisocyanate as main components is neutralized with an organic carboxylic acid or an inorganic acid. thing.