JPS61261366A - Paint composition - Google Patents

Abstract

PURPOSE:To provide a paint compsn. having excellent resistance to staining and weather, good pigment dispersion and coatability and no fear of yellowing, consisting of a chlorinated polyolefin and a star polymer. CONSTITUTION:A polyfunctional epoxy compd. of formula I (wherein R is a residue of an (n+m)-valent aliph., alycyclic, arom. or heterocyclic hydrocarbon; n' is 3-6), an acrylic prepolymer contg. a carbonxyl group of formula II (wherein X is an acrylic prepolymer chain) and an alkyd resin prepolymer contg. a carboxyl group of formula III (wherein Y is an alkyd residue) are reacted together to obtain a star polymer (A) having a weight-average MW of 1,000-2,000,000 (measured by gel permeation chromatography in terms of polystyrene) and a glass transition temp. of -20-100 deg.C, represented by formula IV. 25-230pts.wt. component A is blended with 100pts.wt. chlorinated polyolefin resin having a chlorine content of 45-60wt% and a number-average MW of 3,000-20,000.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a novel coating composition, and more particularly, to a coating composition comprising a resin vehicle comprising a novel combination of a chlorinated polyolefin and a star-structured polymer, which exhibits weatherability, stain resistance, and paint composition. The present invention relates to a coating composition that can provide a coating film with excellent flexibility and corrosion resistance, and has excellent coating workability, pigment dispersibility, and color separation resistance.

BACKGROUND OF THE INVENTION Chlorinated rubber paints made from chlorinated polyolefin resins obtained by chlorinating polyolefins such as polyethylene, polypropylene, and polyisoprene have been proposed. However, the chlorine content of the chlorinated polyolefin resins used in these paints is usually 60% by weight or more, and liquid plasticizers such as phthalate esters and chlorinated paraffins are included as essential ingredients, making the paint film waterproof. Although they have excellent properties such as corrosion resistance, adhesion, and chemical resistance, it has been pointed out that such anticorrosive coatings have problems with long-term stability and have poor stain resistance.

This is because polyolefin resin with a high chlorine content has poor internal flexibility, so it is difficult to form a coating without adding a liquid plasticizer, and the liquid plasticizer separates from the coating over time, causing the coating to become brittle. This is because the liquid plasticizer tends to extremely lower the softening point and glass transition point of the coating, making it easy to stain.

In Japanese Patent Publication No. 58-20990, an attempt was made to improve weather resistance and plasticizing ability by using a chlorinated polymer and a chlorinated vinyl acetate copolymer, and in another study, alkyd, acrylic Attempts have been made to reduce the amount of chlorinated polyolefin and liquid plasticizer by using polymer compounds such as It is also recognized that the advantages of rubber are reduced.

On the other hand, the reality is that there are no commercially available polyolefins with a chlorination rate of 45 to 60%, and their properties have not been elucidated.

The present inventors discovered that chlorinated polyolefin with a number average molecular weight of 6,000 to 20,000 and a chlorine content of 45 to 60% by weight has internal plasticity, eliminates the need to add a plasticizer, and has excellent stain resistance and weather resistance for use in steel structures, etc. Knowing that it is useful as an anti-corrosion paint, he filed Japanese Patent Application No. 184219-1983
A patent application was filed on September 3, 1999.

This chlorinated polyolefin has relatively good compatibility with other resins, so it is suitable for use with alkyds, epoxy-modified alkyds, alkyd-modified acrylics, acrylics, and ketones.

Various resins such as phenol, xylene, coumaron, indene, modified phenol, and petroleum resin can be blended.
Although extremely useful as a resin vehicle for paints, chlorinated polyolefins themselves tend to yellow as a result of exposure to hydrochloric acid from light or heat, and tend to have poor coating workability and pigment dispersibility.

Problems to be Solved by the Invention Therefore, the present invention is an anti-corrosion paint for steel structures, etc., which does not require the addition of plasticizers, has excellent stain resistance and weather resistance, and also has good pigment dispersibility and painting workability, and does not cause yellowing. It is an object of the present invention to obtain a coating composition that is free from such risks.

Means for Solving the Problems The above object of the present invention is to combine 100 parts by weight of a chlorinated polyolefin resin with a chlorine content of 45 to 60% by weight and a number average molecular weight of 3,000 to 20,000; , alicyclic, aromatic or heterocyclic hydrocarbon residue; X is an acrylic prepolymer chain;
Y is alkyd resin residue; n+m is a real number from 3 to 6) Weight average molecular weight (gel permeation)
Chromatography measurement, polystyrene equivalent) 1000~
This is achieved by a coating composition characterized in that it contains a resin vehicle consisting of 25 to 230 parts by weight of a star-structured polymer with a glass transition temperature of -20 to 100°C.

The first component used as a resin vehicle in the coating composition of the present invention is 1.
4219, the chlorine content is 45-60% by weight and the number average molecular weight is 45-60% by weight.

3,000 to 20,000 chlorinated polyolefin resin.

Such resins can be easily made by dissolving polyolefin in a suitable solvent such as carbon tetrachloride and chlorinating it, but conventionally, for purposes such as anticorrosion paints, the chlorine content was 60%.
Although chlorinated polyolefins have been used as described above, the above-mentioned chlorinated polyolefins having a relatively low chlorine content are not commercially available, and their properties have not been fully elucidated. The present inventors synthesized various chlorinated polyolefins with different chlorine contents and studied their properties. As a result, we found that even high chlorinated polyolefins with a chlorine content of more than 60% by weight, such as non-polyethylene, have anti-corrosion effects. However, if the chlorine content exceeds 60% by weight, the internal flexibility deteriorates and a liquid plasticizer is required, and if the chlorine content is less than 45%, the softening point is too low and the stain resistance is poor. It was found that the resin could not be used due to poor compatibility with other resins. Furthermore, the molecular weight of the chlorinated polyolefin is also important; low-molecular-weight ones with a number average molecular weight of less than 3,000 will not cure the paint sufficiently, and will not be suitable for practical use in terms of water resistance, weather resistance, and flexibility of the paint film. It has also been found that, on the contrary, when it exceeds 20,000, the coating workability and compatibility with other resins are extremely poor.

As already mentioned, when the above-mentioned chlorinated polyolefin is used, an anticorrosive paint can be prepared without the need for a liquid plasticizer, and an anticorrosive coating film with excellent water resistance, weather resistance, and stain resistance can be provided. The characteristics of chlorinated polyolefins include poor pigment dispersibility, and painting workability is also not very satisfactory.

Therefore, in the present invention, as the second resin vehicle component.

Formula (wherein R is an n+m aliphatic, alicyclic, aromatic or heterocyclic hydrocarbon residue; X is an acrylic prepolymer chain;
Y is an alkyd resin residue; n+m is a real number from 3 to 6) Weight average molecular weight (measured by gel permeation chromatography, converted to polystyrene) 1000 to 20
0,000 and a star-shaped structure polymer having a glass transition temperature of -20 to 100°C is selectively used.

This star-shaped polymer is a resin newly synthesized by the present inventors, and is a polyfunctional epoxy compound represented by, for example, An acrylic prepolymer having a carboxyl group represented by the formula X-COOH (X is an acrylic prepolymer chain) is reacted with an alkyd resin prepolymer having a carboxyl group represented by Y-COOH (Y is an alkyd residue) A branched resin of OH OH is synthesized by increasing the amount of resin, and by introducing alkyd resin Y, which is different from acrylic resin, the compatibility with various resins that are incompatible with X but compatible with Y is improved. .

The carboxyl group-containing acrylic prepolymer represented by
Alternatively, it can be obtained by copolymerizing monomers other than acid monomers using an initiator having a carboxyl group.

In the case of (1) above, the heptamer used is obtained by copolymerizing: (1) an acid monomer (2) a neutral heptamer (2) a heptamer having active hydrogen and/or an active alkoxy group.

Typical acid salts include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid.

Neutral monomers include ethylene, propylene, butadiene, isoprene, chloroprene, vinyl bromide, vinyl fluoride, acrylic esters (e.g. methyl, ethyl, butyl esters, etc.), methacrylic esters (e.g. methyl, ethyl, butyl esters, etc.) , nitrile derivatives (eg, acrylonitrile, methacrylonitrile, etc.), styrene derivatives (eg, α-methylstyrene), and the like.

On the other hand, as the functional group-containing monomer of i above, 1, for example, glycidyl acrylate as a glycidyl group-containing monomer,
Glycidyl methacrylate and the like, vinyl isocyanate and the like as the isocyanate group-containing monomer, and vinyl chloride, vinylidene chloride and the like as the chlorine-containing monomer can be selected. As the active hydrogen group-containing monomer (2) above, acrylamide, methacrylamide, etc. can be used as an amide group-containing monomer, and N-butoxymethylolacrylamide etc. can be used as an active alkoxy group-containing monomer. Alternatively, as the functional group-containing monomer (2) or the active hydrogen group-containing monomer (2'), a hydroxyl-containing monomer such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, or 2-hydroxypropyl methacrylate may be used. 1 or N-methylol acrylamide, etc. can also be used.

In such a carboxyl group-containing acrylic prepolymer, the amount of carboxyl groups contained is on average 0.1 mol to 1.5 mol per molecule, preferably 0.2 mol to 1.2 mol, calculated based on the number average molecular weight. It is. When the amount of carboxyl group exceeds 1.5 mol, the viscosity of the branched resin increases, and when the amount of carboxyl group exceeds 1.5 mol, the viscosity of the branched resin increases.
If it is less than 1 mole, a sufficient branched structure cannot be obtained, and the object of the present invention cannot be achieved.

-4 In the case of (2) above, the monomers other than the acid monomers include (1) a neutral monomer, (2) a monomer having a functional group that reacts with active hydrogen and/or an active alkoxy group, or (2) an active hydrogen and/or an active alkoxy group. In the polymerization of acrylic resins, monomers having 2.
2'-azo, -bis-isobutyronitrile, 1,1'
-Azo-bis-1-cyclobutanenitrile, 2,2'-
Azo compounds such as azo-bis-2methylbutyronitrile, 2,3-cyasobicyclo(2,2゜1]heptene, 2,2.2'-azo-bis-propane, 1,1'-
Polymerization is initiated using azo-bis-1-phenylethane, etc., and peroxide compounds such as t-butyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. ) Compound 1 containing a carboxyl group as a chain transfer agent, such as mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 0-
A carboxyl group can be introduced at the end of the acrylic prepolymer by using mercaptobenzoic acid or the like.

On the other hand, monomers other than carboxyl group-containing monomers,
When polymerizing the acrylic resin, (2) using a carboxyl group-containing initiator, such as 4,4'-azo-bis(4-cyanopentanoic acid), peroxide diglutaric acid, etc.
Carboxyl groups can also be introduced at the ends of the acrylic prepolymer by initiating polymerization. Furthermore, by using a compound containing a carboxyl group as the chain transfer agent (α) and the same compound as the carboxyl group-containing initiator (β), it is also possible to introduce a carboxyl group at the end of the acrylic prepolymer. can.

In the polymerization of the carboxyl group-containing acrylic prepolymer obtained by the methods (1) and (2) above, polymerization methods such as bulk polymerization, solution polymerization, and if necessary suspension polymerization are used, and the entire amount is charged. , by the initiator dropping method or the monomer dropping method, at a temperature higher than the decomposition temperature of the initiator, usually 70 to 170°C.
A prepolymer can be synthesized by reacting at a reaction temperature of 1 to 8 hours. When synthesizing such a prepolymer, the amount of the carboxyl group-containing chain transfer agent used in method (α) used to introduce carboxyl groups at the terminals of the acrylic prepolymer obtained by method (2) depends on the solidity of the prepolymer. The mold weight ratio is in the range of 0.2 to 8% by weight, preferably 0.3 to 5% by weight. on the other hand,
When using a carboxyl group-containing initiator in method (β), the amount used is 0.3 based on the solid content weight ratio of the prepolymer.
-12% by weight, preferably 0.4-8% by weight. If the amount of the carboxyl group-containing chain transfer agent used in method (1) exceeds the above 8% by weight, and the amount of the carboxyl group-containing initiator used in method (2) exceeds the above 12% by weight, the prepolymer Therefore, the molecular weight of the acrylic resin, which is the object of the present invention, becomes small and cannot exhibit sufficient effects in terms of durability performance such as weather resistance and chemical resistance. On the other hand, if the amount of the carboxyl group-containing chain transfer agent used is less than 0.2% by weight, or if the amount of the carboxyl group-containing initiator used is less than 0.3% by weight, the molecular weight of the prepolymer increases significantly and Reactivity with glycidyl groups of functional epoxy compounds is reduced.

Therefore, it takes a long time to synthesize the acrylic resin, which is the object of the present invention, and the molecular weight of the acrylic resin, which is the object of the present invention, becomes too large, increasing the viscosity and making it difficult to use it as a paint resin. Problems arise, such as not being able to get the required amount.

The acrylic prepolymer having a carboxyl group synthesized under the above polymerization conditions does not impair the durability such as weather resistance and chemical resistance, solvent resistance, mechanical strength, etc. of the acrylic resin, which is the object of the present invention. In order to maintain low viscosity, the weight average molecular weight of the acrylic prepolymer (measured by gel permeation chromatography, polystyrene equivalent)
1ooo=100000, and glass transition temperature -20 to 1
The temperature is preferably 00°C.

On the other hand, the compound represented by Y-COOH includes long oil or short oil alkyd resins. The amount of carboxyl groups contained in the Y-COOH resin is calculated based on the number average molecular weight and is on average 0.1 mol to 1.5 mol per molecule, preferably 0.2 mol to 1.2 mol. Carboxyl group weight is 1
．． When 5 mol is added, the viscosity of the branched resin increases, and when 0.1
If it is less than molar, the object of the present invention cannot be achieved, such as not being able to obtain a sufficient branched structure.

Acrylic prepolymers containing carboxyl groups, X-C0OH, and other resins containing carboxyl groups synthesized under such conditions, y-c.

By causing an addition reaction of OH with the glycidyl group of a polyfunctional epoxy compound having two or more glycidyl groups, a branched resin with good compatibility, which is the object of the present invention, can be synthesized.

The polyfunctional epoxy compound is a substance having two or more glycidyl groups, and these compounds may be saturated or unsaturated aliphatic, alicyclic, aromatic or heterocyclic compounds, and chlorine, These compounds, which may be substituted with substituents such as hydroxyl groups and ether groups, may be monomers or polymers.

The polyfunctional epoxy compound of the present invention includes epoxidized esters of unsaturated alcohols and polyvalent aliphatic acids,
For example, di(2,3-epoxyhexyl adipate),
Di(2,3-epoxybutyl) oxuate, di(2,3-epoxybutyl) succinate
2,3-epoxyhexyl), di(2,3-epoxybutyl) phthalate, and other glycidyl group-containing nitrogen compounds, such as diglycidylaniline and di- and triglycidylamine.

Particularly preferred polyfunctional epoxy compounds for use in the production of the novel acrylic resins of the present invention are glycidyl ethers, especially glycidyl ethers of polyhydric phenols and polyhydric alcohols. Glycidyl ethers of polyhydric phenols and polyhydric alcohols can be obtained by reacting shrimprochlorohydrin with desired polyhydric phenols or polyhydric alcohols in the presence of an alkali. For example, diglycidyl ether of bisphenol A, diglycidyl ether of resorcinol, triglycidyl ether of phloroglucinol, triglycidyl ether of trihydroxydibiphenyl, polyglycidyl ether of phenol formaldehyde novolak, polyglycidyl ether of 0-cresol formaldehyde novolak. Glycidyl ether etc. and diglycidyl ether of butanediol, diglycidyl ether of polypropylene glycol, diglycidyl ether of neopentyl glycol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane,
Tetraglycidyl ether of pentaerythritol, polyglycidyl ether of sorbitol, etc., and other polyfunctional epoxy compounds, and epoxy compounds derived from aromatic dicarboxylic acids include diglycidyl isophthalate, diglycidyl phthalate, linol dimer acid, etc. Also included are diglycidyl esters and triglycidyl isocyanurate, tetraphenylolethane epoxy, and the like.

The reaction between the polyfunctional epoxy compound having two or more glycidyl groups and the carboxyl group-containing acrylic prepolymer is based on the number of moles of glycidyl groups in the polyfunctional epoxy compound and the number of moles of carboxyl groups in the carboxyl group-containing acrylic prepolymer. The ratio of carboxyl group-containing acrylic prepolymer to other carboxyl group-containing resin is The blending ratio is 99-10 of the former
vt%, a solvent that does not react with glycidyl groups or carboxyl groups is added as necessary at 1 to 90 wt% of the latter, and the reaction temperature is 80 to 180°C, preferably 100 to 160°C.
At 0°C, the reaction rate is 80% as measured by the acid value of unreacted carboxyl groups in the carboxyl-terminated acrylic prepolymer.
Do the above.

For the reaction between the glycidyl group and the carboxyl group, for example, a base catalyst can be used as a reaction catalyst, if necessary. Examples of the base catalyst include pyridine, isoquinoline, quinoline, and N.

N-dimethylcyclohexylamine, α-picoline tri-n-butylamine, trimethylamine, N-ditylmorpholine, N,N-dimethylaniline.

N-(β-hydroxyethyl)amine, N-ethyl-3
, 5-dimethylaniline and coconut oil. Organic amines such as dimethyl coconut amine or inorganic alkalis such as caustic soda and caustic potash can be used.

The branched resin obtained by this method has improved compatibility with various resins, and the resin itself has a low viscosity.
You can replace it with a high-nonvolatile paint that has better coating workability and film performance.

However, since pigments used in paints do not have uniform surface properties, the branched resins described above may not always exhibit good dispersion performance depending on the pigment.

Based on the fact that pigment surface characteristics are classified according to the concepts of acids and bases, the present inventors used the branched resin described above. The dispersion performance of various pigments, especially the dispersion rate 1, the viscosity of the dispersion paste compared to when ordinary acrylic resin is modified, taking into account low viscosity characteristics and compatibility.

It has excellent properties such as yield value, stability over time, color mixing and stability in the paint state, non-volatile content during painting, workability, and color tone, gloss, and sharpness as a paint film. I discovered that.

Among the branched resins for pigment dispersion having such excellent dispersion, paint, painting, and coating performance, (1) the branched resin having an electron-accepting group is an acid anhydride and/or a branched resin that retains active hydrogen. Alternatively, free electron-accepting groups can be supported within the molecule by reacting with a sultone compound.

On the other hand, (2) the branched resin having an electron-donating group is
It can be obtained by copolymerizing a polymerizable basic compound heptamer and synthesizing a branched resin using a prepolymer that retains the base. Furthermore, b) the active hydrogen contained in the branched resin and the optionally introduced active alkoxy group are reacted with a basic low molecular weight compound and/or basic resin having an active alkoxy group and/or active hydrogen. Obtained by forcing.

Furthermore, (3) the amphoteric branched resin having an electron-donating group and an electron-accepting group can be used in (1) and (2) a) or (
2) Can be easily obtained by combining with b').

Note that the term "active hydrogen" used in this specification refers to primary, secondary, and tertiary hydroxyl groups.

It refers to a highly reactive hydrogen atom bonded to oxygen, sulfur, nitrogen, etc. contained in an amide bond, urethane bond, carboxyl group, etc., and the term "active alkoxy group" refers to a highly reactive hydrogen atom bonded to oxygen, sulfur, nitrogen, etc. contained in an amide bond, urethane bond, carboxyl group, etc. The term ``reactive large groups such as substituted groups'' refers to primary, secondary and tertiary groups.
The term "functional group that reacts with active alkoxy" refers to groups that easily react with active hydrogen, such as primary, secondary, and tertiary hydroxyl groups, isocyanate groups, and glycidyl groups. The term "electron-accepting group" refers to a group that reacts easily, and the term "electron-accepting group" refers to a carboxyl group,
The term "electron-donating group" refers to groups such as sulfone groups and nitro groups that tend to withdraw electrons from others when hydrogen is used as the standard.Halogen The term "basic resin" refers to groups that tend to donate electrons to others when hydrogen is the standard in the molecule, such as alkyl. The term "basic low molecular weight compound" refers to resins having basic groups, and the term "basic low molecular weight compounds" refers to hydroxylamine compounds (e.g. monoethanolamine, jetanolamine, aminopentanol, aminobenzyl alcohol) used as prepolymers or monomers of basic resins. , 2-dimethylaminoethanol, etc.)
.

It means amino acids (eg, 3-dimethylaminobenzoic acid, 2-amino-isobutyric acid, 4-amino-n-butyric acid, etc.).

A detailed explanation of the manufacturing method of (A) a branched resin having an electron accepting group, (B) a branched resin having an electron donating group, and (C) an amphoteric branched resin having an electron accepting group and an electron donating group in this application. do.

(A) In the synthesis of a branched resin having an electron-accepting group, in the synthesis of the above-mentioned acrylic prepolymer having a carboxyl group and alkyd resin having a carboxyl group, an active hydrogen group-containing compound is used to synthesize the acrylic prepolymer. Active hydrogen groups may be retained in the alkyd resin, or acrylic prepolymers and alkyd resins that do not retain active hydrogen groups may be used.

These branched resins obtained by reacting an acrylic prepolymer having a carboxyl group or an alkyd resin having a carboxyl group with a polyfunctional epoxy compound are represented by H 〇H and have a secondary hydroxyl group in the molecule. , can be utilized as an active hydrogen group.

In order to support electron-accepting groups on the branched resin that retains active hydrogen groups obtained by this method, any chemical substance that reacts with active hydrogen groups to generate free acidic groups can be used. However, typically, for example, compounds that react with active hydrogen groups to produce carboxyl groups, acid anhydrides such as acetic anhydride, succinic anhydride, phthalic anhydride,
Maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, etc.

Further, compounds that react with active hydrogen groups to produce sulfonic acid groups, fatty acid sultones, such as 1,3-propanesultone, 1,3-butanesultone, 2°4-butanesultone, and 1,4-butanesultone.

It is also possible to use 1,3-octane sultone, 2,3-decane sultone, etc., or anhydrous inorganic acids such as metaphosphoric acid.

In such an addition reaction of a sultone compound, a sultone-modified branched resin can be synthesized by reacting a solution consisting of a branched resin and a fatty acid sultone at a reaction temperature of 60 to 150° C. for 2 to 10 hours. When synthesizing such a sultone-modified branched resin, the amount of sultone used when adding sultone is in the range of 0.01 to 6% by weight, preferably 0.02 to 4% by weight based on the solid content of the branched resin. be. If the amount used exceeds 6% by weight, the melt viscosity of the polymer increases, making it difficult to manufacture the polymer.

On the other hand, in the synthesis of (B) a branched resin having an electron-donating group, a monopolymerizable basic compound such as dimethylaminoethyl acrylate is used in the synthesis of an acrylic prepolymer having a carboxyl group.

Dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, butylaminoethyl methacrylate, butylaminoethyl acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-methyl 5-vinylpyridine, 2-ethyl 5-vinylpyridine, dimethyl Allylamine, diallylamine vinylpyrroline, vinylisoquinoline, NN-
Dimethylaminoethyl vinyl ether, 2 (NN dimethylamino) 4 vinylpyrimidine, trans 1°2 dipyridylethylene, 3 cinnamoylpyridine.

By copolymerizing 2-methyl-5-cinnamoylpyridine, 4,6-diamino-2-vinyl-5-triazine, etc., and synthesizing a branched resin using such a prepolymer, an electron-donating group is supported within the molecule. I can do it.

Alternatively, when synthesizing an acrylic prepolymer having a carboxyl group and an alkyd resin having a carboxyl group, an active alkoxy group-containing compound and/or an active hydrogen group-containing compound as required are copolymerized, and such prepolymer and alkyd resin are used. The branched resin synthesized by this method is made to support active hydrogen and an active alkoxy group introduced as necessary, and the branched resin obtained by this method is reacted with a low molecular weight basic compound and/or a basic resin. By this method, a branched resin having an electron-donating group can be synthesized.

In addition, a polyvalent isocyanate compound or a glycidyl compound is blended and reacted with a branched resin carrying an active hydrogen group so that free isocyanate groups or glycidyl groups remain, and a basic resin and/or a basic low molecular weight It can also be a branched resin that can react with active hydrogen in the compound.

As the above-mentioned basic resin, urea resin, melamine resin, polyamide resin, polyurethane resin, etc. which are commonly used in the paint field are used.

Urea resins and melamine resins are obtained by condensing formaldehyde with urea or melamine, and alcohols (e.g. methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, etc.) are used as part of the raw materials for resin production, if necessary. , alkylated methylol urea resins or alkylated methylol melamine resins.

Polyamide resins are obtained by the condensation reaction of an aliphatic diamine and a dibasic acid, or the urea condensation reaction of a cyclic lactam. Examples of aliphatic diamines include 1.2 ethanediamine, N,N'-dimethyl-1°2-ethane, etc. Diamine, 1
, 6-hexanediamine, etc., and dibasic acids such as succinic acid, adipic acid, and sebacic acid are appropriately selected.

Examples of the cyclic lactam that can be used include α-pyrrolidone, δ-caprolactam, and ω-capryllactam.

In the above manufacturing process, active hydrogen or active alkoxy groups are introduced into such basic resins along with electron donating groups (
It can be subjected to an addition or condensation reaction with the functional group in the acidic resin of A).

The above (A) branched resin having an electron accepting group and (B)
(C) A branched resin having an electron accepting group and an electron donating group can be synthesized by combining techniques used in the synthesis of a branched resin having an electron donating group.

The branched resins (A), (B), and (C) obtained in this way have a viscosity of It has the characteristic that it becomes low. In addition, by appropriately using branched resins (A), (B), and (C) according to the pigment surface characteristics, we have achieved superior dispersion, paint, painting, and coating performance compared to when ordinary resins are modified. be effective.

The star-shaped structure polymer mentioned above has low polymer activity, so it has good weather resistance,
Contributes to improved painting workability, and contains low viscosity alkyd, which improves pigment dispersibility and flexibility.

In the present invention, the chlorinated polyolefin and the star-structured polymer are used in a weight ratio of 100 parts to 25 to 230 parts. This means that for every 100 copies of the former, 25 copies of the latter
Pigment dispersibility is less than 100%.

The purpose of the present invention cannot be achieved because improvements in painting workability and weather resistance cannot be obtained, and if the latter exceeds 230 parts, the properties of chlorinated rubber such as water resistance, chemical resistance, and adhesion cannot be fully expected. It is from.

All of the resin vehicles used in the present invention have extremely good compatibility with other resins, especially star-structured polymers, and optionally include alkyds, acrylics, alkyd-modified acrylics, xylene resins, ketone resins, plastic It can be optionally mixed with resins such as agents. It also has excellent pigment dispersibility and color separation resistance, extremely good painting workability, and weather resistance.

Further improvement in contamination resistance is expected, and it is expected to be used in steel structures, ships,
It is extremely useful as an anticorrosive paint for plants, bridges, etc.

The present invention will be explained below with reference to Examples. Parts and percentages are by weight unless otherwise specified.

Production Example 1 Production of chlorinated polyethylene varnish (1) Molecular weight: 3000
of polyethylene was chlorinated in a CCl4 solution and the amount of chlorine was 5
3%, converted it to Kijiroru solvent, and reduced the non-volatile content to 5%.
A varnish with a viscosity of 0% and a viscosity of 15.0 poise/25°C was obtained.

Production Example 2 Synthesis of Star Structure Polymer 33 parts of xylene is charged into a reaction vessel equipped with a dropping funnel, a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring blade, and the temperature is raised to 105°C. 3 parts of 2-hydroxyethyl methacrylate, 22 parts of methyl methacrylate, 4 parts of n-butyl acrylate, 8 parts of styrene, 0.4 parts of 1-dodecanethiol, 0.03 parts of acrylic acid, 0 parts of azobisisobutyronitrile
．． Pour 8 parts of the solution into a dropping funnel, and add 8 parts of the solution to a dropping funnel for 10 minutes under a nitrogen atmosphere.
The contents of the dropping funnel are added dropwise at a constant rate over 4 hours at 5°C.

After dropping, the temperature was maintained at 105°C for 30 minutes.

Then, t-butylperoxy 2-ethylhexanate 0
．． A solution of 1 part xylene and 4 parts xylene is charged into dropping row 1-.

This was added dropwise at a uniform rate over 30 minutes. 1 hour after completion of dripping
Hold at 05°C. Next, 1.3 parts of Bunacol EX-411 (manufactured by Nagase Kasei Kogyo Co., Ltd.), 0.2 parts of Firmin DMC,
Alkyd solution (non-volatile content: 60%, solvent: Quijirol,
Acid value: 5, oil length: 9%, modified oil: coconut oil, viscosity: T/2
A solution of 15.7 parts (5°C) and 6.6 parts of Kijirole was charged and maintained at 130°C for 6 hours to complete the addition reaction and obtain a star-shaped structured polymer.

Examples 1 to 3 Using the chlorinated polyethylene and star-structure polymer obtained in Production Examples 1 and 2, coating compositions were made according to the following formulations.

Comparative examples 1 to 3 For comparison purposes, a coating composition with the following formulation was prepared.

Comparative example 1 Chlorinated polyethylene 15 (degree of chlorination 53%) Acrylic resin 1) 15 Titanium oxide 257 Decacizer 0-130P 1 Kijiroll
44 Comparative example 2 Chlorinated polyethylene 28 (degree of chlorination 53%) Alkyd resin 2) 7 Titanium oxide 25 Adekacizer〇-130P1 Kijiroru 39 Comparative example 3 Chlorinated polyethylene 20 (degree of chlorination 68%) Titanium oxide 25 Toyoparax 150 6 (Manufactured by Toyo Soda Co., Ltd.) Alkyd resin 2) 7 Adekacizer 0-130P1 Note 1) Acrylic resin 2-hydroxyethyl methacrylate/methyl methacrylate/n-butyl acrylate/styrene/1-dodecanethiol/azoisobutyronitrile = 3/ 22/4/810.410.8 Number average molecular weight 18000 Note 2) Alkyd resin Coconut oil modified alkyd Oil length 9% The following performance tests were conducted on each of the above coating compositions.

Contaminated carbon method Each sample was applied once with a brush to a tin plate, and the dry film thickness was 30 μm.
After leaving this coating film at 60℃ for 7 days, carbon pigment was applied to the coating surface in a 20℃ atmosphere, and the coating was heated to a specified temperature (20℃, 60℃).
℃) for 30 minutes, and then washed with water to check the degree of carbon removal.

×...Significant carbon adhesion O...Each sample was applied twice with a brush to a natural Bacro sandblasted steel plate that can be completely removed, resulting in a dry film thickness of 60μ, and a Bacro test ( 6 months) to measure the L value for one color difference. When the L value is less than 90, stains are recognized, and when the L value is around 80, there is significant staining.

Weather resistance Sunshine type 1000 hours Flexibility JIS-54006,16 Dry film thickness 30μ Color resistance Evaluation by brush painting Paint workability Evaluation by brush painting 40℃ salt water immersion test Each sample was applied twice to sandblasted steel plate Apply with a brush to a dry film thickness of 80μ. After immersion in 40℃ salt water, JIS-
Check the adhesion in 54006, item 15.

The test results were as follows.

Claims (2)

[Claims] (1) Chlorine content 45-60% by weight, number average molecular weight 30
100 parts by weight of chlorinated polyolefin resin of 00 to 20,000 and the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is an n+m valent aliphatic, alicyclic, aromatic or heterocyclic hydrocarbon residue; X is an acrylic prepolymer chain;
Y is alkyd resin residue; n+m is a real number from 3 to 6) Weight average molecular weight (measured by gel permeation chromatography, converted to polystyrene) 1000 to 20
0000, glass transition temperature -20 parts. (2) Acrylic prepolymer has a weight average molecular weight of 1000
100,000C and a glass transition temperature of -20 to 100C.