JPH11269407A - Putty composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a putty composition having excellent adhesion to a polyolefin resin molding by using (A) a chlorinated polyolefin and/or an amorphous polyolefin, (B) a polymerizable unsaturated compound, and (C) a polymerization initiator as the essential components. SOLUTION: The total content of component A is, desirably, 3-90 pts.wt., more desirably, 5-70 pts.wt., per 100 pts.wt. putty composition, that of component B is 5-95 pts.wt., and that of component C is 0.01-30 pts.wt. As for component A, the chlorinated polyolefin is a product of chlorination of a polyolefin containing units derived from propylene and has a degree of chlorination of 10-60%, and the amorphous polyolefin contains units derived from propylene and is particularly desirably atactic polypropylene. Component C is desirably a thermal polymerization initiator. Component B additionally contains a compound having at least two polymerizable unsaturated groups in the molecule. This composition is used to repair polypropylene resin moldings such as bumpers and door mirror covers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a putty composition having good adhesiveness which does not require the use of a primer and which can be easily applied directly to a polyolefin resin molded article represented by polypropylene. More specifically, it is used for repairing polyolefin resin molded products represented by polypropylene used in bumpers, door mirror covers, moldings, spoilers, etc. The present invention relates to a putty composition which is excellent in safety, and is excellent in water resistance and solvent resistance.

[0002]

2. Description of the Related Art Recently, molded articles of polyolefin resin have been used in many applications. A typical example is a car exterior part. As automotive exterior parts, resin products other than metals and glass have been widely used. For example, bumpers, door mirror covers, malls,
In many cases, resin molded products are used for spoilers and the like. As such a molded product, from the economical aspect,
Polyolefin-based resin materials are increasingly used in greater amounts than urethane-based resins. In addition, polyolefin-based resins are excellent in chemical resistance, water resistance, moldability, and the like. However, repairing these scratches and recesses in the polyolefin resin material is subject to various restrictions as compared with repairing metal. For example, a polyolefin-based resin material has low polarity, and thus has poor adhesion of a coating film. Also,
Since the polyolefin resin material is weak to heat, it is required that the temperature be lower than, for example, 140 ° C. in heating and drying the paint. In the case of repair, usually a method of improving the adhesion of the paint to the polyolefin resin molded article, for example, on the surface of the polyolefin resin molded article,
A method of performing a pre-treatment such as a flame treatment, a corona discharge, a plasma treatment, a chromic sulfuric acid treatment and the like, and then applying a top coat cannot be performed. Therefore, generally, a method of coating a putty after applying a primer having good adhesiveness has been studied.
However, in these methods, satisfactory adhesion is not always obtained, and the number of steps is increased, which is complicated, and further, there is a problem in that the use of a dedicated and expensive primer is disadvantageous in terms of cost. Against this background,
There has been a strong demand for a putty that is excellent in handleability and safety, excellent in water resistance and solvent resistance, and excellent in adhesion to a polyolefin resin molded article.

[0003]

SUMMARY OF THE INVENTION The present invention provides a putty composition having excellent handleability and safety, excellent durability such as water resistance and solvent resistance, and excellent adhesion to a polyolefin resin molded article. The purpose is to do.

[0004]

Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that the following objects can be achieved and the present invention has been achieved. That is, 1. (1) chlorinated polyolefin and / or non-crystalline polyolefin, (2) polymerizable unsaturated compound,
(3) a putty composition containing a polymerization initiator as an essential component; 2. The putty composition according to 1 above, wherein the total amount of the chlorinated polyolefin and the non-crystalline polyolefin is 3 to 90 parts by weight, based on 100 parts by weight of the putty composition. In 100 parts by weight of the putty composition, (1) total amount of 5-70 parts by weight of chlorinated polyolefin and non-crystalline polyolefin, (2) 5-95 parts by weight of polymerizable unsaturated compound, (3)
3. the putty composition according to the above 2, which contains 0.01 to 30 parts by weight of a polymerization initiator; The chlorinated polyolefin is a chlorinated product of a polyolefin containing a propylene-derived repeating unit (hereinafter, referred to as a unit), and the amorphous polyolefin is an amorphous polyolefin containing a propylene-derived unit. 4. a putty composition as described above; 5. The putty composition according to any one of the above items 1 to 4, wherein the chlorinated polyolefin and the non-crystalline polyolefin are a chlorinated polypropylene and an atactic polypropylene, respectively. 6. The putty composition according to any one of the above 1 to 5, wherein the chlorination rate of the chlorinated polyolefin is 10 to 60% by weight; The present invention relates to the putty composition according to any one of the above 1 to 6, wherein the polymerization initiator is an initiator containing a thermal polymerization initiator as an essential component.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Incidentally, the `` putty '' of the present invention is a coating for overlay used to fill in defects such as dents, cracks and holes in the base, and to improve the flatness of the coating system.
Most are paste-like (JIS K5500). Further, the "putty composition" described herein refers to a material mixture forming the putty.

The chlorinated polyolefin used in the putty composition of the present invention is, for example, a chlorinated olefin polymer or a modified product obtained by introducing a carboxyl group, an acid anhydride group or a hydroxyl group into the polymer. It is. Examples of the olefin polymer include polyethylene, polypropylene, an ethylene-propylene copolymer, a propylene-butadiene copolymer, and a hydride thereof. Polyethylene, polypropylene, ethylene-propylene copolymer or propylene-butadiene copolymer or their (co) polymers obtained by chlorinating modified products obtained by introducing carboxyl groups, acid anhydride groups, hydroxyl groups, etc. are chlorinated. It is called polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, or chlorinated propylene-butadiene copolymer, and is preferably used.

A propylene-butadiene copolymer and a copolymer obtained by introducing a carboxyl group, an acid anhydride group, a hydroxyl group, or the like into a chlorinated hydride are chlorinated propylene-butadiene copolymers. Called monster,
It is preferably used. Further, the non-crystalline polyolefin used in the putty composition of the present invention has a non-crystalline portion in the molecule, hexane, an aliphatic hydrocarbon solvent such as heptane,
It is a polyolefin that is easily dissolved in aromatic hydrocarbon solvents such as toluene and xylene, and chlorine solvents such as carbon tetrachloride and chloroform. Carboxyl groups, acid anhydride groups, hydroxyl groups, etc. And a modified polypropylene having an introduced thereinto, for example, atactic polypropylene (amorphous low-molecular-weight polypropylene produced as a by-product during the production of polypropylene) and hydrogenated polybutadiene. In general, most recent automotive exterior parts are mainly made of polypropylene. Therefore, among the above chlorinated polyolefins and amorphous polyolefins, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, chlorinated Propylene-butadiene copolymer,
It is preferable to use a chlorinated propylene-butadiene copolymer hydride or a polyolefin having a unit derived from propylene such as atactic polypropylene or a non-crystallized polyolefin containing a unit derived from propylene, and more preferably chlorine. Or atactic polypropylene.

The total amount of the chlorinated polyolefin and the non-crystalline polyolefin used in the present invention is preferably 3 to 90 parts by weight, more preferably 5 to 70 parts by weight, per 100 parts by weight of the putty composition. When the total amount of the chlorinated polyolefin and the amorphous polyolefin is the putty composition 1
If the amount is less than 3 parts by weight, the adhesion of the putty composition to the polyolefin resin molded article will be weak, and if it is more than 90 parts by weight, the fluidity of the putty composition will be extremely poor. It is not preferable. The chlorine content of the chlorinated polyolefin used in the present invention is preferably from 10 to 60% by weight, and more preferably from 15 to 50% by weight. If it exceeds 60% by weight, the adhesion to the polyolefin-based resin molded article tends to decrease. On the other hand, when the content is less than 10% by weight, the solubility in the polymerizable unsaturated compound is extremely reduced, which is not preferable.

The weight average molecular weight of the chlorinated polyolefin and the non-crystalline polyolefin used in the present invention is generally from 1,000 to 200,000, preferably from 2,000 to 100,000.
000, and more preferably 3,000 to 60,000. If the weight average molecular weight is less than 1000, solvent resistance,
Hardness and adhesion tend to be poor. On the other hand, if it exceeds 200,000, the viscosity of the paint is too high, so that the viscosity of the putty composition will be extremely increased, or the viscosity will be kept low by using a large amount of a low viscosity polymerizable unsaturated compound. Therefore, the coating workability is poor or the shrinkage when the putty composition is cured tends to be extremely large, which is not preferable.

The polymerizable unsaturated compound used in the present invention is a polymerizable unsaturated monomer or a polymerizable unsaturated oligomer or polymer, or a mixture thereof. These polymerizable monomers, oligomers and polymers may be used alone or in combination.
Alternatively, two or more kinds can be used as a mixture. Examples of the polymerizable unsaturated compound include the following compounds. In the following, “(meth) acryl” means both “methacryl” and “acryl”.

Polymerizable unsaturated compounds having one polymerizable unsaturated group in the molecule: styrene, α-methylstyrene, p-
Methylstyrene, chlorostyrene, vinylpyridine, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert -Butyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, isodecyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate and the like having 1 to 18 carbon atoms in the alcohol residue (meth) acrylate, (meth) acryloyloxydiethylene glycol methyl ether, (Meth) acryloyloxy polyethylene glycol methyl ether,
(Meth) acryloyloxytripropylene glycol methyl ether, (meth) acryloyloxy polypropylene glycol methyl ether, tetrahydrofurfuryl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) ) Acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, tetracyclododecyl (meth)
Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryl acid,
Crotonic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, (meth) acryloyloxyethyl succinic acid, (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate,
N, N-dimethylaminoethyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
Morpholinoethyl (meth) acrylate, vinyl oxazoline, isopropenyl oxazoline, 2-[(meth)
Acryloyloxypropyl] oxazoline, 2-
[(Meth) acryloyloxypropyl] -4-dimethyloxazoline, 2-[(meth) acryloyloxypentyl] oxazoline, 2-[(meth) acryloyloxypentyl] -4-dimethyloxazoline, (meth)
Acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N,
N-dimethylaminopropyl (meth) acrylamide,
N-acryloylmorpholine, (meth) acrylonitrile, methyl vinyl ketone, methyl isopropenyl ketone, vinyl acetate, vinyl propionate, vinyl benzoate, N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N -Vinyl-ε-caprolactam, N-vinyl pyrrolidone, trifluoromethyl vinyl ether, phenoxy polyethylene glycol (meth) acrylate, phenyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) ) Acrylate, isopropylidene glyceryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-phenoxy-2-
Hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 13-hydroxytridecyl (meth) acrylate, 14-hydroxytetradecyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene Glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate and the like can be mentioned.

It is also possible to use an ethylenically unsaturated group-containing monomer having a hydroxyl group obtained by reacting a lactone with an ethylenically unsaturated group-containing monomer having a primary or secondary hydroxyl group. Lactones used include β-propiolactone, γ-butyrolactone, δ-valerolactone and ε-
And caprolactone. Specific examples of these lactone-added ethylenically unsaturated group-containing monomers include the following compounds.

[0013]

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Polymerizable unsaturated compound having two or more polymerizable unsaturated groups in the molecule: diethylene glycol di (meth)
Acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, zinc di (meth) acrylate, 1,3-butanediol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hydro Shipenta (meth) acrylate, and dimethylol tricyclodecane di (meth) acrylate. In addition, the following compounds can also be mentioned.

[0015]

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[0016]

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[0017]

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Further, epoxy (meth) acrylate,
Oligomers such as polyester (meth) acrylate, unsaturated polyester and urethane (meth) acrylate can also be used. Epoxy (meth) acrylate is also called a vinyl ester resin, and generally has a compound having an epoxy group represented by an epoxy resin,
A resin having a polymerizable unsaturated group formed by a ring-opening reaction with a carboxyl group of a carboxyl compound having a polymerizable unsaturated group such as acrylic acid, or a compound having a carboxyl group and a compound such as glycidyl (meth) acrylate A resin having a polymerizable unsaturated group generated by a ring-opening reaction of a polymerizable unsaturated compound having an epoxy group with an epoxy group, and is referred to as “Polyester Resin Handbook” (Nikkan Kogyo Shimbun 1988), “Coating Dictionary”. (Edited by The Coloring Materials Association, 1993), and the resin is produced by a known method.

The epoxy resin used as a raw material of the epoxy (meth) acrylate includes bisphenol A diglycidyl ether and its high-molecular-weight homologues, bisphenol A
Glycidyl ethers of alkylene oxide adducts, diglycidyl ethers of bisphenol F and high molecular weight homologs thereof, glycidyl ethers of bisphenol F alkylene oxide adducts, and novolak-type polyglycidyl ethers are exemplified.

Polyester (meth) acrylate refers to a polyester having a terminal carboxyl group obtained from a saturated polycarboxylic acid and / or an unsaturated polycarboxylic acid and a polyhydric alcohol, and an α, β-unsaturated carboxylic acid ester group. (Meth) acrylate obtained by reacting an epoxy compound containing a carboxylic acid, a saturated polycarboxylic acid and / or an unsaturated polycarboxylic acid and a polyester having a carboxyl group at a terminal obtained from a polyhydric alcohol with a hydroxyl group-containing acrylate. It is obtained by reacting (meth) acrylic acid with a (meth) acrylate obtained by reacting, and a polyester having a hydroxyl group at a terminal obtained from a saturated polycarboxylic acid and / or an unsaturated polycarboxylic acid and a polyhydric alcohol. (Meth) acrylate and the like. K ”(Industry Research Institute Inc. 19
1989), and its production is carried out by a known method.

The above saturated polycarboxylic acids include:
Polycarboxylic acids having no polymerizable unsaturated groups, such as phthalic acid, isophthalic acid, terephthalic acid, adipic acid,
Sebacic acid and the like. Examples of unsaturated polycarboxylic acids include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, maleic anhydride, and itaconic acid. Furthermore, as a polyhydric alcohol component,
For example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2
-Butanediol, 1,3-butanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,
Polyhydric alcohols such as cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A are exemplified.

Glycidyl methacrylate is a typical example of an epoxy compound containing an α, β-unsaturated carboxylic acid ester group. An unsaturated polyester is a condensation product obtained by an esterification reaction between a polyhydric alcohol and a polybasic acid having an unsaturated bond or an anhydride thereof (and, if necessary, a saturated polybasic acid). It is dissolved in such a polymerizable unsaturated compound, and is referred to as “Polyester Resin Handbook” (Nikkan Kogyo Shimbun, 19
1988), “Glossary of Paint Terms” (edited by the Society of Colorants, 1993)
), And its production is carried out by a known method. Specific examples of the polybasic acid having an unsaturated bond or its anhydride include fumaric acid, maleic anhydride, maleic acid, and itaconic acid. If necessary, phthalic anhydride, isophthalic acid, terephthalic acid, a saturated polybasic acid having no active unsaturated bond such as adipic acid or its anhydride, benzoic acid,
Monocarboxylic acids such as abietic acid and maleic acid half ester can be used. Also, 2 in one molecule
Specific examples of the alcohol having at least two hydroxyl groups include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,
Examples thereof include polyhydric alcohols such as 2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, and alkylene oxide adducts of bisphenol A.

The urethane (meth) acrylate is obtained by reacting an alcohol having one or more hydroxyl groups in one molecule with a compound having two or more isocyanate groups in one molecule and containing a terminal isocyanate group and a hydroxyl group ( (Meth) acrylate obtained by reacting (meth) acrylate and (meth) acrylate obtained by reacting (meth) acrylate containing isocyanate group with alcohol containing one or more hydroxyl groups in one molecule,
"Photopolymer Handbook" (Industry Research Association, 1989), "Paint Glossary" (Coloring Material Association, 19)
1993), and its production method is performed by a known method.

Specific examples of the alcohol having one or more hydroxyl groups in one molecule used as a raw material of urethane (meth) acrylate include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and , 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3
-Alkylene oxide adduct of propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, bisphenol A,
Examples thereof include a polyester having a terminal hydroxyl group obtained from a saturated dicarboxylic acid and / or an unsaturated dicarboxylic acid and a polyhydric alcohol.

The hydroxyl group-containing (meth) acrylate used as a raw material for urethane (meth) acrylate includes 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methacryloyloxyethyl-2-hydroxybutyl phthalate, and the like. The (meth) acrylate containing an isocyanate group used as a raw material of urethane (meth) acrylate includes 2
-(Meth) acryloyloxyethyl isocyanate,
(Meth) acryloyl isocyanate. Compounds having two or more isocyanate groups in one molecule used as a raw material of urethane (meth) acrylate include methylene diphenyl diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate,
Tetramethylxylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydride of xylylene diisocyanate, hexamethylene diisocyanate, norbornene diisocyanate, a polymer of methylene diphenyl diisocyanate,
Dianisidine diisocyanate, diphenyl ether diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, triisocyanate phenyl thiophosphate, lysine diisocyanate methyl ester, lysine triisocyanate, 2,2,4
-Trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, a dimer of tolylene diisocyanate, and methylcyclohexane diisocyanate.

Of the above-mentioned polymerizable unsaturated compounds, a polymerizable unsaturated compound having one polymerizable unsaturated group in a molecule is rarely used alone, and the solvent resistance of the cured product is maintained. For this purpose, a polymerizable unsaturated compound having two or more polymerizable unsaturated groups in a molecule is usually used in combination. The polymerizable unsaturated compound having two or more polymerizable unsaturated groups in the molecule is preferably used in an amount of 10% by weight or more based on the total amount of the polymerizable unsaturated compound. The amount of the polymerizable unsaturated compound used is 5 to 95% by weight of the putty composition, preferably 1 to 95% by weight.
0 to 90% by weight. If the amount of the polymerizable unsaturated compound is too large, the required physical properties of the cured product such as hardness are insufficient, and the internal stress increases due to shrinkage during polymerization, which is not preferable. On the other hand, if the amount of the polymerizable unsaturated compound is too small, the flexibility of the cured product may decrease and become brittle, or the cured product after polymerization may have poor resistance to solvents.

The polymerization initiator used in the putty composition of the present invention may be a radical polymerization initiator,
Various photoinitiators and / or thermal initiators can be mentioned. As a specific example of the photopolymerization initiator,
2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,
Thioxanthones such as 4-dichlorothioxanthone and 4
-Ethyl-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, N, N-dimethylaniline, triethanolamine, methyldiethanolamine, triisopropanolamine, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate , 4-dimethylamino (2-n-butoxy) ethyl, 4
-2-ethylhexyl dimethylaminobenzoate, 4,
Combination with amines such as 4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, N, N-dimethyl-p-toluidine, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4 ′ -Dichlorobenzophenone, 4-
Hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-
Benzophenones such as tetra (tert-butylperoxycarbonyl) benzophenone and ethyl 4-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate,
N, N-dimethylaniline, triethanolamine, methyldiethanolamine, triisopropanolamine, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, (2-n-butoxy) ethyl 4-dimethylaminobenzoate , 4-dimethylamino 2-ethylhexyl, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, a combination with amines such as N, N-dimethyl-p-toluidine, tetraarylbiimidazole and , Mercaptobenzothiazole, mercaptobenzimidazole, and other hydrogen donors, α-diketones such as camphorquinone, benzyl, 9,10-phenanthrenequinone and ethyl 4-dimethylaminobenzoate and 4-dimethylaminobenzoate Acid methyl, N, N-dimethylaniline, triethanolamine, methyldiethanolamine, triisopropanolamine, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4-dimethylaminobenzoic acid (n-butoxy) Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, 4,4′-dimethylaminobenzophenone,
Combinations with amines such as 4,4′-diethylaminobenzophenone, N, N-dimethyl-p-toluidine,
Bisacylphosphine oxide compounds described in JP-A-61-130296, acylphosphine oxide compounds described in JP-A-55-15471, diethoxyacetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; Benzyldimethyl ketal, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) Acetophenones such as propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, and benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Ethers, a photopolymerization initiator comprising a quaternary boron compound complex of a visible light absorbing dye described in JP-A-62-143044, and a photopolymerization initiator comprising a near infrared light absorbing dye and a quaternary boron compound described in JP-A-5-194609. Combination photopolymerization initiator, UV Diazonium compound which generates an acid by light, sulfonium compounds, iodonium compounds, may be mentioned combinations of quaternary boron compound represented by the latent acid generating agent and the following formula of the metal complex compound or the like (1). Two or more of these photopolymerization initiators may be used in combination. By selecting an appropriate initiator from these photopolymerization initiators, it is possible to provide a complete one-pack type putty composition.

General formula (1);

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group, an aryl group, an aralkyl group, an alkenyl group,
It represents an alkynyl group, a silyl group, a heterocyclic group or a halogen atom, and Z ⁺ represents an arbitrary cation. Here, in R ₁ , R ₂ , R ₃ and R ₄ of the general formula (1), the alkyl group, the aryl group, the aralkyl group, the alkenyl group, the alkynyl group, the silyl group and the heterocyclic group have an arbitrary substituent. You may. Specific examples of such substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-octyl, n- Dodecyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, anisyl, biphenyl, naphthyl, benzyl, phenethyl, diphenylmethyl, methoxy, ethoxy, n-propoxy, isopropoxy Group, n-butoxy group, sec-butoxy group, tert-butoxy group, methylenedioxy group,
Ethylenedioxy, phenoxy, naphthoxy, benzyloxy, methylthio, phenylthio, 2-
Examples thereof include a furyl group, a 2-thienyl group, a 2-pyridyl group, and a fluoro group, but are not limited to these examples.

Specific examples of the quaternary boron anion in the general formula (1) include n-butyltriphenylborate,
n-octyl triphenyl borate, n-dodecyl triphenyl borate, sec-butyl triphenyl borate, tert-butyl triphenyl borate, benzyl triphenyl borate, n-butyl tri (p-anisyl) borate, n-octyl tri (p-anisyl) ) Borate, n-dodecyltri (p-anisyl) borate, n
-Butyl tri (p-tolyl) borate, n-butyl tri (o-tolyl) borate, n-butyl tri (4-ter
t-butylphenyl) borate, n-butyltri (4-
(Fluoro-2-methylphenyl) borate, n-butyl tri (4-fluorophenyl) borate, n-butyl trinaphthyl borate, triphenyl silyl triphenyl borate, trimethyl silyl triphenyl borate, tetra-n-butyl borate, di-n- Butyl diphenyl borate, tetrabenzyl borate and the like,
Those in which R ₁ has an alkyl group structure and R ₂ , R ₃ and R ₄ have an aryl group structure are preferred because they have a good balance between stability and polymerizability.

In the general formula (1), Z ⁺ is an arbitrary cation. Specific examples include tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, tetraoctylammonium, N-methylquinolinium, -Ethylquinolium, N-methylpyridinium, N-ethylpyridinium, tetramethylphosphonium, tetra-n-butylphosphonium, trimethylsulfonium, triphenylsulfonium, trimethylsulfoxonium, diphenyliodonium, di (4-tert-butylphenyl) Examples include iodonium, lithium cation, and sodium cation.

Specific examples of the thermal polymerization initiator include 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,
2-bis (tert-butylperoxy) octane,
2,2-bis (tert-butylperoxy) butane,
tert-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, diisopropylbenzene hydroperoxide,
2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide , Α, α'-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, acetyl peroxide, isobutyl peroxide, octanoyl Peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, diisopropylperoxydicarbonate , Di-n-propylperoxydicarbonate, bis (4-butylcyclohexyl) peroxydicarbonate, dimyristylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate , Di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, diallylperoxydicarbonate, tert-butylperoxyacetate, tert
-Butyl peroxyisobutyrate, tert-butyl peroxy pivalate, tert-butyl peroxy neodecanoate, cumyl peroxy neodecanoate,
tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tert-butylperoxybenzoate, di-tert-butyl Peroxyisophthalate, 2,5
-Dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxymaleic acid, ter
t-butyl peroxyisopropyl carbonate, cumyl peroxy octoate, tert-hexyl peroxy pivalate, tert-butyl peroxy neohexanoate, tert-hexyl peroxy neohexanoate, acetylcyclohexylsulfonyl peroxide, tert- Organic peroxides such as butyl peroxyallyl carbonate; the above organic peroxides and ethyl 4-dimethylaminobenzoate or methyl 4-dimethylaminobenzoate; N, N-dimethylaniline; triethanolamine; methyldiethanolamine; triisopropanol Amine, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, (2-n-butoxy) ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2 Combination with an amine-based reducing agent such as ethylhexyl, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, N, N-dimethyl-p-toluidine, the organic peroxide and cobalt naphthenate, octenoic acid Combination with a metal-based reducing agent such as cobalt, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2 ′ -Azobisisobutyronitrile, 2,2'-azobis (2-
Methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1
-Bis (hydroxymethyl) -2-hydroxyethyl]
Propionamide {, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-
N- (2-hydroxyethyl) propionamide],
2,2'-azobis (2-methylpropionamide) 2
Hydrate, 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis (2-methylpropane), dimethyl-2,2′-azobis (2-methylpropionate) Azo compounds such as 2,4'-azobis (4-cyanopentanoic acid) and 2,2'-azobis [2- (hydroxymethyl) propionitrile], and self-decomposable compounds such as N-phenylglycine and dimedone Polymerization initiator,
JP-A-6-329712 describes a combination of a quaternary boron compound and an acidic compound, a latent acid generator such as a diazonium compound, a sulfonium compound, an iodonium compound, or a metal complex compound, which generates an acid by heat, and the compound represented by the general formula (1). And a quaternary boron compound represented by the general formula (1).

When the putty composition having a high concealing property containing a high concentration of a pigment among the above-mentioned polymerization initiators is cured thickly,
When only the photopolymerization initiator is used, light may not penetrate to the deep part of the putty composition and the deep part may not be cured. Therefore, since there is no restriction on the type and amount of the pigment, the thickness of the putty to be applied, and the like, the thermal polymerization initiator is used when the putty composition having a high concealing property containing a high concentration of the pigment is cured thickly. Is preferred. Further, among the thermal polymerization initiators, it is preferable to use a base neutralized product of a quaternary boron compound represented by the general formula (1) and an acid. Further, a photopolymerization initiator and a thermal polymerization initiator may be used in combination. The amount of the polymerization initiator used is preferably 0.01 to 30% by weight of the total amount of the putty composition,
More preferably, it is 0.05 to 10% by weight. 0.0
If it is less than 1% by weight, curing by polymerization may be insufficient. On the other hand, if it exceeds 30% by weight, it is economically unfavorable and may adversely affect the physical properties of the cured product.

In addition to the chlorinated polyolefin and / or the non-crystalline polyolefin, the polymerizable unsaturated compound and the polymerization initiator, which are essential components, the putty composition of the present invention may optionally contain a filler. Good. Powder as filler,
Examples include various shapes of organic substances, inorganic substances, composites and mixtures thereof such as spheres, whiskers, scales, and viscous liquids. Specific examples of the inorganic filler include, for example, calcium carbonate, talc, clay, glass powder, silica, aluminum hydroxide, barium sulfate, titanium oxide, asbestos,
Alumina, silica-alumina, carbon black, aluminum powder, aluminum paste, gold powder, silver powder, quartz, kaolin, mica, aluminum sulfate, calcium sulfate, calcium phosphate, etc. and the surface of these powders is polyfunctional (meth)
Those coated with an acrylate monomer or a silane coupling agent may be used. Examples of the composite include those obtained by mixing the above inorganic filler with an ethylenically unsaturated compound, polymerizing and curing, and then finely pulverizing the mixture. Also,
Two or more of these fillers can be used in combination.

Specific examples of the organic filler include polystyrene, coumarone-indene-styrene copolymer, polyvinyl acetate, poly α-methylstyrene, polymethyl methacrylate, polyester, chlorinated polyester, and polyvinylidene chloride microballoon. And polyacrylonitrile microballoons. Two or more of these organic fillers can be used in combination.
Further, an organic filler and an inorganic filler may be used in combination. The amount of these inorganic and / or organic fillers other than the chlorinated polyolefin and the non-crystalline polyolefin is generally less than 90% by weight of the total amount of the putty composition, preferably 85%.
Less than 80% by weight, more preferably less than 80% by weight.
If the amount of the filler is too large, the flexibility of the cured product may be reduced and become brittle, or the cured product after polymerization may have poor solvent resistance.

Curing of the putty composition of the present invention is generally performed in the following procedure. First, a composition is obtained by sufficiently kneading a chlorinated polyolefin and / or a non-crystalline polyolefin, a polymerizable unsaturated compound, a polymerization initiator, and various fillers and additives added as needed. Next, this putty composition is built up on the object to be coated to a desired thickness. The thickness is arbitrarily determined as necessary, but is generally 1 m
m to 1 cm. The method for curing the putty composition of the present invention includes:
Depending on the type of polymerization initiator used, a heat source or a light source may be required. The light source or heat source used for curing the putty composition of the present invention is typically a lamp capable of supplying both light and heat, such as a xenon lamp, a halogen lamp, an incandescent lamp, a metal halide lamp, sunlight, an infrared lamp, and an oven. A heating furnace or the like can be used, and one or more of these may be used. Also,
When a polymerization initiator such as the redox polymerization initiator that can initiate polymerization at a sufficient rate at room temperature is used, a special light source or heat source may not be required.

In the curing reaction, it is preferable to irradiate light at a low oxygen concentration in order to reduce the inhibition of polymerization of the composition surface by oxygen. For example, after the composition of the present invention is applied, the surface of the polymerizable composition and the putty composition is covered with a light-transmitting film or the like and irradiated with light, or an inert gas atmosphere such as nitrogen, argon, or carbon dioxide is used. Alternatively, it is also possible to reduce the oxygen concentration by blowing the above-mentioned inert gas into the surface of the composition in the air to accelerate the curing. The polymerizable composition of the present invention can be used as a solventless curable composition, and is expected to contribute to improving the global environment. Of course, it can also be used in the form diluted with a conventional solvent.

[0037]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to this. “Parts” in Examples and Comparative Examples represents parts by weight unless otherwise specified. (Example 1) Chlorinated isotactic polypropylene (chlorine content 41% by weight, weight average molecular weight 9000) /
40 parts of a mixture of isobornyl acrylate / methyltripropylene glycol acrylate / tripropylene glycol diacrylate (weight ratio) = 4/3/3/4, N, N-dimethyl-p-toluidine 0.07 as a reducing agent
Parts and cobalt naphthenate (Co content 6% by weight) 0.7
Parts, 0.1 part of a 10% by weight solution of α-naphthoquinone in isobornyl acrylate as a stabilizer and 60 parts of a filler (talc (average particle size: 10 μm): 60 parts), and sufficiently stirred by a high-speed dissolver for 15 minutes. Kneaded.

Example 2 Chlorinated ethylene-propylene copolymer (chlorine content: 40% by weight, ethylene unit:
Propylene unit = 70: 30 (weight ratio), weight average molecular weight 9000) / atactic polypropylene (weight average molecular weight 5000) / isobornyl acrylate / tetrahydrofurfuryl acrylate / tripropylene glycol diacrylate = 40/1/25/25 / 9
(Weight ratio) 50 parts of a mixture, 0.07 part of N, N-dimethylaniline as a reducing agent and 0.7 part of cobalt octenoate (Co content 6% by weight), 10% by weight of α-naphthoquinone as a stabilizer isobornyl 0.1 part of an acrylate solution,
And 5 parts of ethylcellulose, and the mixture was sufficiently kneaded by stirring with a high-speed dissolver for 15 minutes.

Example 3 Chlorinated isotactic polypropylene (chlorine content: 27% by weight, weight average molecular weight: 3)
0000) / dicyclopentenyloxyethyl acrylate / phenoxyethyl acrylate / dipropylene glycol diacrylate = 50 parts of a mixture (by weight), N, N-dimethyl-p-toluidine 0.07 as a reducing agent Parts and cobalt naphthenate (Co content 6
0.7% by weight of α-naphthoquinone as a stabilizer
0.1 part of a 0% by weight isobornyl acrylate solution and a filler [50 parts of talc (average particle size: 10 μm)] were added, and the mixture was sufficiently kneaded by stirring with a high-speed dissolver for 15 minutes.

Example 4 Chlorinated atactic polypropylene (chlorine content: 32% by weight, weight average molecular weight: 500)
0) / dicyclopentenyl acrylate / dimethylol tricyclodecane diacrylate = 6/2/2 (weight ratio) 50 parts of a mixture, N, N-dimethyl-p as a reducing agent
-0.07 parts of toluidine and cobalt naphthenate (Co
0.7 parts, a 10% by weight solution of α-naphthoquinone as a stabilizer in isobornyl acrylate 0.1
Part and filler [talc (average particle size: 10 μm) 50 parts]
Was added and kneaded well by stirring with a high-speed dissolver for 15 minutes.

Example 5 Chlorinated ethylene-propylene copolymer (chlorine content: 36% by weight, ethylene unit:
Propylene unit = 30: 70 (weight ratio), polymerization average molecular weight 6000) / atactic polypropylene (weight average molecular weight 3000) / styrene / dimethylol tricyclodecane diacrylate = 17/3/60/20 (weight ratio) mixture 50 Part, N, N-dimethyl- as reducing agent
0.07 parts of p-toluidine and cobalt naphthenate (C
0.7 part, a 10% by weight solution of α-naphthoquinone as a stabilizer in isobornyl acrylate 0.1
Part and filler [talc (average particle size: 10 μm) 50 parts]
Was added and kneaded well by stirring with a high-speed dissolver for 15 minutes.

Example 6 25 parts of low molecular weight polystyrene (weight average molecular weight 1000), 5 parts of dipropylene glycol diacrylate, 20 parts of tetrahydrofurfuryl acrylate, 4 parts of atactic polypropylene (weight average molecular weight 3000), chlorinated polypropylene Product name:
Hardlen CY-9122P [Toyo Kasei Co., Ltd.] 2
Parts, 15 parts of a neutralized product of p-toluenesulfonic acid / N, N-dimethylaminoethyl acrylate and 1.0 part of the following quaternary boron compound were added, and the mixture was sufficiently kneaded by stirring with a high-speed dissolver for 15 minutes. .

[0043]

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Example 7 20 parts of low molecular weight polystyrene (weight average molecular weight 1000), 10 parts of dipropylene glycol diacrylate, 20 parts of tetrahydrofurfuryl acrylate, 5 parts of atactic polypropylene (weight average molecular weight of 3000), p-toluene Sulfonic acid / N,
15 parts of a neutralized product of N-dimethylaminoethylacrylamide and 1.0 part of the following quaternary boron compound were added, and the mixture was sufficiently kneaded by stirring with a high-speed dissolver for 15 minutes.

[0045]

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(Comparative Example 1)

Embedded image 35 parts of epoxy acrylate having the above structure, 15 parts of isobornyl acrylate, 0.07 part of N, N-dimethyl-p-toluidine as a reducing agent and 0.7 part of cobalt naphthenate (Co content 6% by weight), stable Α-
0.1 part of a 10% by weight solution of naphthoquinone in isobornyl acrylate and a filler [talc (average particle size: 10 μm)
60 parts], and the mixture was sufficiently kneaded by stirring with a high-speed dissolver for 15 minutes.

(Comparative Example 2)

Embedded image Polyester of the above structure (weight average molecular weight 1500,
Acid value 33) 30 parts, 1,6-hexanediol diacrylate = 6/4 (weight ratio) 20 parts, N, N as a reducing agent
0.07 part of dimethylaniline and 0.7 part of cobalt octenoate (Co content 6% by weight), 0.1 part of a 10% by weight solution of α-naphthoquinone in isobornyl acrylate as a stabilizer, and 5 parts of ethyl cellulose and a filler [Talc (average particle size: 10 μm), 50 parts] was added, and the mixture was sufficiently kneaded by stirring with a high-speed dissolver for 15 minutes.

Comparative Example 3 The same operation as in Example 6 was performed except that no atactic polypropylene and chlorinated polypropylene were used.

Cure Experiment Each of the compositions prepared in Examples 1 to 5 and Comparative Examples 1 and 2 was treated with methyl ethyl ketone peroxide (active ingredient 5).
(5% by weight) was added, and these were used for preparing a test coated plate. The compositions produced in Examples 6 and 7 and Comparative Example 3 were used as they were in the preparation of test coated plates. (Preparation of Test Coated Plate) Examples 1 to 5 and Comparative Example 1 in which the above-mentioned methyl ethyl ketone peroxide (active ingredient 55% by weight) was added as a test coated plate using a polypropylene bumper used in 1992 Corolla II windy. The composition No. 2 was applied with a spatula so as to have a thickness of 5 mm and left at 25 ° C. for 8 minutes to be completely cured. Table 1 shows the performance test results of the obtained test coated plates. Further, the compositions prepared in Examples 6, 7 and Comparative Example 3 were applied on each of the test plates shown below with a spatula so as to have a thickness of 5 mm.
Irradiation was carried out using a kW halogen lamp at an irradiation distance of 20 cm until it was completely cured. Table 1 shows the performance test results of the obtained test coated plates.

Performance Test of Test Coated Plate (Test Method) Drying property: The surface tack and the internal curing of the test coated plate were examined by finger touch. ：: no tack on the surface and good curing inside. Δ: The inside is cured well, although the surface has a slight tack. ×: No tack on the surface but poor curing inside. XX: There is a slight tack on the surface, and the inside is poorly cured. Adhesion: The adhesion of the cured product when each test coated plate was bent at a 90 ° angle from the center was examined and evaluated as follows. A: The cured product is completely adhered. ：: The adhesion of the cured product is 75% or more and less than 95%. Δ: Adhesion of the cured product is 50% or more and less than 75%. ×: Adhesion of the cured product is less than 50%.

Surface abrasion: The outermost surface of the test coated plate was polished using water-resistant paper # 150, and water-resistant paper # 150 was used.
The difficulty of clogging was compared and evaluated as follows. ：: Water resistant paper # 150 does not cause any clogging. Δ: Water-resistant paper # 150 is slightly clogged. X: The clogging of the water-resistant paper # 150 is severe and cannot be polished. Internal abrasiveness: After removing the outermost surface of the test coated plate, the surface below the outermost surface is polished using water-resistant paper # 150,
The easiness of polishing was compared and evaluated as follows. ：: The putty coating film is often shaved even if polished lightly. Δ: The cured product coating is shaved, but the polishing feels somewhat heavy. X: The polishing is heavy and the cured product coating film is not well shaved.

Water resistance: 1992 Corolla II wind
Using the polypropylene bumper used for y as the test plate, the test coated plate produced by the above method was polished in the order of waterproof papers # 240, # 150 and # 400 to smooth the surface. A commercially available acrylic urethane paint (trade name: Hi Art: manufactured by Isamu Co., Ltd.) is spray-coated (dry film thickness: 50 μm) on the polished cured product coating film, left at room temperature (20 ° C.) for 30 minutes, and dried at 60 ° C. It was dried for 60 minutes on a machine. After cooling, a blistering box (RH 99%, temperature 50
C.) for 48 hours, and examined the state of the coating film surface (blister, foaming having a diameter of about 2 mm) and the adhesion of the cured product when bent at 90 °. The blisters were evaluated as follows, and the adhesion of the cured product was evaluated in the same manner as described above. ：: No blister was generated. Δ: Blisters occurred in 50% or more of the coating film. From the results of the examples, it is easy to apply directly to the polyolefin resin molded article by direct coating, the adhesion is good, and the performance (drying, polishing, water resistance) of the cured product is well expressed. These are only examples of the present invention.

[0053]

[Table 1]

[0054]

According to the present invention, a bumper, a door mirror cover, and a composition comprising a chlorinated polyolefin and / or an amorphous polyolefin, a polymerizable unsaturated compound and a polymerization initiator as essential components are used as a putty. Used for repairing polypropylene resin molded products used for moldings, spoilers, etc., can be easily applied directly to polyolefin resin molded products, with good adhesion, safe, and water and solvent resistant. An excellent putty composition can be provided.

Claims (7)

[Claims] 1. A putty composition comprising (1) a chlorinated polyolefin and / or an amorphous polyolefin, (2) a polymerizable unsaturated compound, and (3) a polymerization initiator as essential components. 2. The total amount of the chlorinated polyolefin and the non-crystalline polyolefin in 100 parts by weight of the putty composition is 3 to 90.
The putty composition according to claim 1, which is in parts by weight. 3. The total amount of (1) chlorinated polyolefin and amorphous polyolefin in 100 parts by weight of the putty composition is 5 to 5.
The putty composition according to claim 2, comprising 70 parts by weight, (2) 5 to 95 parts by weight of a polymerizable unsaturated compound, and (3) 0.01 to 30 parts by weight of a polymerization initiator. 4. The chlorinated polyolefin is a chlorinated product of a polyolefin containing a unit derived from propylene, and the non-crystalline polyolefin is a non-crystalline polyolefin containing a unit derived from propylene.
4. The putty composition according to any one of items 1 to 3. 5. The putty composition according to claim 1, wherein the chlorinated polyolefin and the non-crystalline polyolefin are chlorinated polypropylene and atactic polypropylene, respectively. 6. A chlorinated polyolefin having a chlorination rate of 10
The putty composition according to any one of claims 1 to 5, the amount being from 60 to 60% by weight. 7. The putty composition according to claim 1, wherein the polymerization initiator is an initiator containing a thermal polymerization initiator as an essential component.