JPH0273842A - Vinyl chloride plastisol composition - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride plastisol composition having excellent adhesiveness to metallic face, storage stability, etc., comprising a vinyl chloride (co)polymer, unsaturated double bond OH-containing modified epoxy resin and block isocyanate compound. CONSTITUTION:A plastisol composition containing (A) a vinyl chloride (co) polymerhaving 1,000-1,700 degree of polymerization, (B) a plasticizer, preferably phthalic ester, especially dioctyl phthalate (C) a modified epoxy resin prepared by reacting C1: an epoxy resin containing one or more adjoining epoxy groups in the molecule, preferably epoxy resin containing one or more glycidyl ether group shown by formula I (Z is H, methyl or ethyl), glycidyl ester group shown by formula II, etc., with C2: unsaturated fatty acid, preferably >=6C unsaturated fatty acid, especially >=14C unsaturated fatty acid, (D) a block isocyanate compound and optionally (E) a latent curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to vinyl chloride plastisol compositions. More specifically, it adheres strongly to various metal surfaces or various undercoated metal surfaces by short-term heat treatment at 120 to 200°C, does not fade after heat treatment at high temperatures, has excellent flexibility, and has excellent storage stability. The present invention relates to a plastisol composition of a vinyl chloride polymer or copolymer that has excellent adhesive properties even after storage.

[Prior Art and Problems to be Solved by the Invention] Various studies have been made to improve the adhesion of chlorinated chemical plastisol compositions to various metal surfaces (particularly bare metal) and various undercoated metal surfaces.

Examples include (i) acrylic monomer, [2] liquid epoxy resin and curing agent, (3) polyamide and blocked urethane prepolymer (Japanese Patent Publication No. 59-52901), (
4) A method of blending polyamide and/or polyamine with carboxylic acid (Japanese Unexamined Patent Publication No. 59-120651) is known, but it has insufficient adhesion at relatively low temperatures and resistance to heat treatment of vinyl chloride plastisol at high temperatures. Discoloration,
There were problems with flexibility, storage stability, etc., and it was not possible to satisfy all of the above demands.

[Means to solve the problem]

The inventors of the present invention have conducted intensive studies to improve these drawbacks, and have found that vinyl chloride plastisol containing a specific adhesion promoter can be applied to various metal surfaces or various undercoated surfaces of metal.
Bonds very strongly with short heat treatment at 20-200℃,
It does not fade even when heat treated at high temperatures, and has excellent flexibility.In other words, heat treatment from relatively low to high temperatures (i20 to 200℃) improves adhesion, foaming properties, discoloration, and flexibility. They found that it also has good stability and completed the present invention.

That is, the vinyl chloride plastisol composition of the present invention contains (i) a vinyl chloride polymer and/or copolymer, and (i1) as essential components.
plasticizer, (iii) an unsaturated double bond hydroxyl group obtained by reacting an epoxy resin (iii-1) having an average of more than one adjacent epoxy group in the molecule with an unsaturated fatty acid (iii-2); It is characterized by containing a modified epoxy resin and (iv) a blocked isocyanate compound.

Furthermore, the vinyl chloride plastisol composition of the present invention comprises (i) a vinyl chloride polymer and/or copolymer, (i1)
Plasticizer, (iii) unsaturated double bond hydroxyl group obtained by reacting an epoxy resin (iii-1) having an average of more than one adjacent evoquine group in the molecule with an unsaturated fatty acid (iii-2) It is characterized by containing a modified epoxy resin, (iv) a blocked isocyanate compound, and (v) a latent curing agent for epoxy resin.

As the vinyl chloride polymer and/or copolymer (i) used in the present invention, commonly used vinyl chloride polymers and/or copolymers (i) can be used. Examples of the vinyl chloride copolymer include copolymers of vinyl chloride and other vinyl monomers that can be copolymerized with vinyl chloride, such as vinyl acetate, maleic anhydride or hamaerate, and vinyl ether.

The degree of polymerization of vinyl chloride polymer or copolymer is usually 100.
It is 0-1700. Commercially available vinyl chloride polymers or copolymers include Zeon 121, Zeon 135J, and Zeon 103ZX (manufactured by Nippon Zeon), Tenka Vinyl PA-100, Tenka Vinyl M-180 (manufactured by Denki Kagaku Kogyo), and Kanevinyl. Examples include PSL-10, Kanevinyl PSH-10, Kanevinyl PSM-30, and Kanevinyl PCH-12 (all manufactured by Hitomi-Sai Kagaku Kogyo).

These can also be used in combination of two or more types.

As the plasticizer (i1) in the present invention, those commonly used for vinyl chloride plastisol can be used. for example,
Phthalate esters such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, distearyl phthalate, adipic esters such as dioctyl adipate, sepatic esters such as dioctyl sebacate, phosphoric esters such as tricresyl phosphate, etc. Examples include ester plasticizers and mixtures of two or more thereof. Preferred among these are phthalate esters, especially dioctyl phthalate.

Here, as an epoxy resin (iii-1) having an average of more than one adjacent epoxy group in the molecule in order to obtain a modified epoxy resin (iii) containing an unsaturated double bond hydroxyl group, which is an essential component of the present invention. Preferred examples include epoxy resins (I-1> , an epoxy resin (i-2) having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule represented by the formula (where Z is a hydrogen atom, methyl group, or ethyl group), (where Z is Epoxy resins (■-
3) etc. are included. Further, particularly preferred epoxy resin (iii-1) is an epoxy resin having an epoxy equivalent of 180 to 500.

The epoxy resin (Ii) having more than one substituted or unsubstituted glycidyl ether group in the molecule is an epoxy resin in which a phenolic hydroxyl group is converted into a glycidyl ether, and an epoxy resin in which an alcoholic hydroxyl group is converted into a glycidyl ether. Preferred examples of such epoxy resins (I-1) include polyglycidyl ethers of polyhydric phenols (I-1-1) having one or more aromatic nuclei and one or more aromatic nuclei. Polyglycidyl ether of an alcoholic polyhydroxyl compound (
I-1-2) and the like.

However, polyglycidyl ether (I-1-1) is
For example, hydroxylating a polyhydric phenol (A) containing at least one aromatic nucleus and an epihalohydrin (b))
Epoxy resins containing polyglycidyl ether as the main reaction product, such as those obtained by reaction in the presence of a basic catalyst or a reactive amount of a basic compound such as IJum, by a conventional method; phenol (
A) and epihalohydrin (b) are reacted with a polyhalohydrin ether obtained by a conventional method in the presence of an amount of an acidic catalyst such as boron trifluoride; Polyhydric phenol (A) having at least one aromatic nucleus and epihalohydrin (b) are reacted by a conventional method in the presence of a catalytic amount of a basic catalyst such as triethylamine. It is an epoxy resin obtained by reacting a halohydrin ether with a basic compound such as sodium hydroxide.

Similarly, polyglycidyl ether (I-1-2) is a polyhydroxyl compound ( A polyhalohydrin ether obtained by reacting B) and epihalohydrin (b) in the presence of a catalytic amount of an acidic catalyst such as boron trifluoride in a conventional manner with a basic compound such as sodium hydroxide. It is an epoxy resin containing a polyglycidyl ether as a main reaction product.

Here, the polyhydric phenol (A) having at least one aromatic nucleus includes a mononuclear polyhydric phenol (Δ-1) having one aromatic nucleus and a polyhydric phenol having two or more aromatic nuclei. phenol (A-2).

Examples of such mononuclear polyhydric phenols (A-1>) include resorcinol, hydroquinone, pyrocatechonopefloroglucinol, 1,S-cyhydroquinaphculene, 2,7-dihydroxynaphthalene, 2,6- Examples include dihydroxynaphthalene.

Moreover, as an example of polynuclear polyhydric phenol (A-2), -
Substitution: [In the formula, ^r is an aromatic divalent hydrocarbon group such as a naphthylene group or a phenylene group, with a phenylene group being preferred for the purposes of the present invention. Y' and Yl may be the same or different,
Alkyl groups, preferably with up to 4 carbon atoms, such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl, or halogen atoms, i.e. chlorine, bromine, Iodine or fluorine atoms, or alkoxy groups, preferably with up to 4 carbon atoms, such as methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy.

When a substituent other than a hydroxyl group is present on either or both of the above-mentioned aromatic divalent hydrocarbon groups, these substituents may be the same or different. m and Z are 0 corresponding to the number of hydrogen atoms in the aromatic ring (Ar) that can be substituted by a substituent.
An integer with a value from (zero) to a maximum value, which can be the same or different values. R1 is, for example, -C-, -O-
, -S-.

SO-, -8O2-, or an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group,
Pentamethylene group, hexamethylene group, 2-ethylhexamethylene group, octamethylene group, nonamethylene group, decamethylene group, or alkylidene group such as ethylidene group, propylidene group, isopropylidene group, isobutylidene group, amylidene group, isobutylidene group, 1- Phenylethylidene group or cycloaliphatic group, such as flies. 4-cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene group, halogenated alkylene group, halogenated alkylidene group, halogenated cycloaliphatic group, or alkoxy- and aryloxy- Substituted alkylidene groups or alkoxy- and aryloxy-substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups such as methoxymethylene, ethoxymethylene, ethoxyethylene, 2-ethoxytrimethylene,
3-ethoxypentamethylene group, 1.4-(2-methoxycyclohexane) group, phenoxyethylene group, 2-phenoxytrimethylene group, 1.3-(2=phenoxycyclohexane) group, or arylalkylene group Basic engineering I
f phenylethylene group, 2-phenyltrimethylene group,
1-phenylpentamethylene group, 2-phenyldecamethylene group, or aromatic group such as phenylene group, naphthylene group, or halogenated aromatic group such as 1,4-
(2-chlorophenylene) group, 1.4-(2-bromphenylene) group, 1.4-(2-fluorophenylene) group, or alkoxy- and aryloxy-substituted aromatic groups such as 1.4-2 -methoxyphenylene) group, 1
．． 4-(2=ethoxyphenylene) group, 1.4-(2-
n propoxyphenylene) group, 1.4-(2-phenoxyphenylene) group, or an alkyl-substituted aromatic group such as 1.4-(2-methylphenylene) L 1
, 4-(2-ethylphenylene) group, 1.4-(2-
divalent groups such as divalent hydrocarbon groups such as n-propylphenylene) group, 1゜4-(2-n-butylphenylene) group, and 1.4-(2-n-dodecylphenylene) group; , or R1 can be a ring fused to the Ar group, as is the case in the compound of the formula, or R1 can be a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group. , a polyalkoxy group such as a polyphenylethoxy group, or R1 may be a group containing a silicon atom such as a polydimethylsiloxy group, a polydiphenylsiloxy group, a polymethylphenylsiloxy group, etc. or R1 can be an aromatic ring, a tertiary amino group, an ether bond, a carbonyl group, or two or more alkylene or alkylidene groups separated by a sulfur or sulfur-containing bond, such as a sulfoxide.] There is a polynuclear dihydric phenol represented by

Among these polynuclear dihydric phenols, particularly preferred are those having the general formula (wherein Y' and Yl have the same meanings as above, m and 2
is a polynuclear dihydric phenol, preferably an alkylene or alkylidene group having 1 to 3 carbon atoms or a saturated group of the formula.

Examples of such dihydric phenols include 2,2-his-(p-hydroxyphenyl)-propane, commonly referred to by the trade name bisphenol A, 2,4'-dihydroxydiphenylmethane, bis-(2-hydroxyphenyl)-methane. ,
Bis-(4-hydroxyphenyl)-methane, bis-(
4-Hydroxy-2,6-dimethyl-3-methoxyphenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 1.2-bis-(4-hydroxyphenyl)-ethane, 1.1 -bis-(4-1=)'waxy2-10ulfenyl)-ethane, 1,1-bis-(3
,5-dimethyl-4-hydroxyphenyl)-ethane,
1.3-bis-15=(3-methyl-4-hydroxyphenyl)-propane,
2,2-bis-(3,5-dichloro-4hydroxyphenyl)-propane, 2,2-bis-(3-phenyl-4
-hydroxyphenyl)propane, 2,2-bis-(3
-isopropyl 4-t: )'roxyphenyl)-furopane, 2.2-bis-(2-isopropyl-4-hydroxyphenyl)-propane, 2.2-bis-(4-hydroxynaphthyl)-propane, 2. 2-bis(4-hydroxyphenyl)-pentane, 313=bis-(4-hydroxyphenyl)-pentane, 2.2-bis-(4-
hydroxyphenyl)-hebutane, bis-(4-hydroxyphenyl)-methane, bis-(4-hydroxyphenyl)-cyclohexylmethane, 1,2-bis-(4-hydroxyphenyl)-1,2-bis-( phenyl)-propane, 2,2-bis-(4-hydroxyphenyl)-
Nabis-(hydroxyphenyl) alkanes such as 1-phenylpropane or dihydroxybiphenyl or bis(4 -hydroxyphenyl)-sulfone, 2,4°dihydroxydiphenylsulfone, chlor2,4-dihydroxydiphenylsulfone, 5-chloro-4,4″-dihydroxydiphenylsulfone, 3″-chloro-4,4°-dihydroxydiphenylsulfone Di (hydroxyphenyl) like
Sulfone or bis-(4-hydroxyphenyl)-ethenope 4,3''-(or 4,2''- or 2゜21-dihydroxy-diphenyl) ether, 4゜4゛-dihydroxy-2,6-cyphthyldiphenyl ether, bis-
(4-hydroxy-3-imbutylphenyl)-ether, bis-(4-hydroxy-3-isopropylphenyl)-ether, bis-(4-hydroxy-3-chlorophenyl)-ether, bis-(4-hydroxy -3-
fluorophenyl)-ether, bis(4-hydroxy-3-bromphenyl)-ether, bis-(4-hydroxynaphthyl)-ether, bis-(4-hydroxy-3-chlornaphthyl)-ether, bis- (2-Hydroxybiphenyl)-ether, 44'-dihydroxy-2,6-shifted xydiphenyl ether, 4.4°
-di(hydroxyphenyl)-ethers such as -dihydroxy-25-jethoxydiphenyl ether, and also 1,1-bis-(4hydroxyphenyl)-2-
Phenylethane, 1.3.3-)limethyl-1-(4-
2. hydroxyphenyl)-6-hydroxyindan;
4-His-(p-hydroxyphenyl)-4-methylpentane is also suitable.

Furthermore, another preferred group of polynuclear dihydric phenols has the general formula (where Ro is a methyl or ethyl group, and R2 has 1 to 1 carbon atoms).
9 alkylidene groups or other alkylene groups, p is 0 to 4), such as 1,4-bis-(4-hydroxybenzyl)-benzene, 14-bis-(4-hydroxybenzyl)- Tetramethylbenzene, lI4-bis-(4-hydroxybenzyl)-tetraethylbenzene, 1,4-bis-(p-hydroxycumyl)-benzene, 1,3-bis-(p-hydroxycumyl)-benzene, etc. can be mentioned.

Other polynuclear polyhydric phenols (A-2) include, for example, initial condensates of phenols and carbonyl compounds (e.g., initial condensates of phenol resins, condensation reaction products of phenol and acrolein, phenol and glyoxal condensation reaction product, phenol and pentanediallyl condensation reaction product, resolunol and acetone condensation reaction product, xylene-phenol-formalin initial condensation product), condensation product of phenols and polychloromethylated aromatic compounds (Example: condensation product of phenol and bischloromethylxylene), etc.

Here, the polyhydroxyl compound (B) refers to a catalyst that promotes the reaction between the above polyhydric phenol (A>) having at least one aromatic nucleus and an alkylene oxide with a DH group and an epoxy group. -(R
O), H (here, R is an alkylene group derived from alkylene oxide, and one polyoxyalkylene group may contain different alkylene groups, and the number is an integer of 2 or more indicating the number of polymerized oxyalkylene groups) ) is a compound having the following atomic group.

In this case, the ratio of the polyhydric phenol (A>& alkylene oxide) is 1:1 (mol: mol) or more, but preferably the ratio of alkylene oxide to the leaf group of the polyhydric phenol (A) is 1:1 (mol: mol) or more. :1 to 10, preferably 1:1 to 3 (two equivalents).

Here, alkylene oxides include, for example, ethylene oxide, propylene oxide, butylene oxide, etc., but those that produce side chains when they react with the polyhydric phenol (A) to form an ether bond are particularly preferred. Preferred examples include propylene oxide, 1.2-butylene oxide, 2.3-
Butylene oxide is preferred, especially propylene oxide.

A particularly preferred group of such polyhydroxyl compounds is - hydroxyl (wherein Y' + Yl+ m+ Z and R1 are the above-mentioned (i
-1), where R is an alkylene group having 2 to 4 carbon atoms, and nl and n2 have values of 1 to 3).

Furthermore, another preferable group of such polyhydroxyl compounds has the general formula (wherein R,,R,,p are the same as those in formula (i-2) above, and R is a carbon number of 2 to 4
alkylene groups, n and n2 have values of 1 to 3).

In addition, epihalohydrin (b) is represented by the following formula: (where Z is a hydrogen atom, methyl group, or ethyl group, and X' is a halogen atom).
) Examples include epichlorohydrin, epibromohydrin, 1,2-epoxy-2-methyl-3-chloropropane, 12-epoxy-2-ethyl-3-chloropropane, and the like.

The above epihalohydrin (b) and polyhydric phenol (A
) or as acidic catalysts that promote the reaction with the polyhydroxyl compound (B), boron trifluoride, tin chloride,
Lewis acids such as zinc chloride and ferric chloride, derivatives exhibiting these activities (eg, boron trifluoride-ether complex compounds), or mixtures thereof can be used.

Similarly, as basic catalysts that promote the reaction between epihalohydrin (b) and polyhydric phenol (A), alkali metal hydroxides (e.g., sodium hydroxide), alkali metal alcoholides (e.g., sodium ethylate), ),
Tertiary amine compounds (e.g., triethylamine, triethanolamine), quaternary ammonium compounds (e.g., tetramethylammonium bromide), or mixtures thereof can be used, thus producing glycidyl ether simultaneously with such reactions. Alternatively, alkaline metal hydroxides (e.g.
sodium hydroxide), alkali metal aluminates (e.g.
Sodium aluminate) etc. are conveniently used.

Of course, these catalysts and basic compounds can be used as they are or as a solution in an appropriate inorganic or organic solvent.

In addition, the epoxy resin (I-2) having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule,
Examples include polygrindyl esters of aliphatic polycarboxylic acids or aromatic polycarboxylic acids.
Also included are epoxy resins obtained by polymerizing glycidyl methacrylate synthesized from epihalohydrin (b) shown in ) and methacrylic acid.

In addition, epoxy resins having an average of more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule (
Examples of I-3) include epoxy resins obtained from aromatic amines (e.g. aniline or aniline having an alkyl substituent in the nucleus) and epihalohydrin (b) represented by the above-mentioned formula <2); Examples include epoxy resins obtained from epihalohydrin (b) and initial condensates with aldehydes (for example, aniline-formaldehyde initial condensates, aniline-phenol-formaldehyde initial condensates), hydantoin diglycidyl ether, triglycidyl isocyanurate, and the like.

In addition, linear aliphatic epoxy resins such as epoxidized polybutadiene, epoxidized vegetable oils such as epoxidized linseed oil, epoxidized soybean oil, 3,4-epoxy-6-methylcyclohexylmethyl, 3,4-epoxy-6- Alicyclic epoxy resins such as methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, vinylcyclohexene dieboxide, bis(2゜3-ehoquininclobentyl)ether, etc. These can be used alone or in combination of two or more.

In addition, conventionally known epoxy resins containing adjacent epoxy groups, such as various epoxy resins described in "Production and Application of Epoxy Resins" (edited by Hiroshi Kakiuchi), may be used.

In addition, unsaturated fatty acids (ii
i-2) is a fatty acid having at least one unsaturated double bond in the molecule such as oleic acid, preferably an unsaturated fatty acid having 6 or more carbon atoms, and particularly preferably an unsaturated fatty acid having 14 or more carbon atoms. . Representative examples include unsaturated fatty acids obtained from drying or semi-drying oils.

Preferred unsaturated fatty acids (iii-2) are unsaturated fatty acids isolated from dehydrated castor oil, linseed oil, soybean oil, tall oil, safflower oil, etc., synthetic drying oil fatty acids (for example, , trade name Hydien) and the like, and examples thereof include one type or a mixture of two or more types thereof.

Unsaturated double bond hydroxyl group-containing modified epoxy resin of the present invention (
The reaction to obtain iii) is carried out by the usual reaction method of an Epoquine group and a carboxyl group, and the reaction temperature is 70-1
The temperature is 50°C, preferably 90-130°C.

In order to accelerate the reaction, it is advantageous to use known polymerization catalysts, tertiary amines, quaternary ammonium salts, Lewis acid salts, and the like.

Epoxy resin (i11-1) and unsaturated fatty acid (ii12)
) is usually 0.1 to 0.69 molar ratio of unsaturated fatty acid (iii-2) to 1 mol of epoxy resin (iii1).
mol, preferably 0.3 to 0.6 mol.

Blocked isocyanate compound (i
The incyanates used in step v) include aromatic polyisocyanate compounds, polymers of aromatic polyisocyanate compounds, and mixtures thereof, as well as aromatic polyisocyanate compounds and polymers of aromatic polyisocyanate compounds. Examples include urethane prepolymer compounds and mixtures of one or more thereof.

Here, as aromatic polyisocyanate compounds, -
(Here, ○ is a benzene ring or naphthalene ring, NCO is a nuclear-substituted isocyanate group, Z is a nuclear-substituted halogen atom, or an alkyl or alkoxy group having 3 or less carbon atoms, n
is 0. Diisocyanate represented by 1 or 2) (e.g. 2.1-) ylene diisocyanate, 2.6-)
Louis diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1
゜3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-isopropylbenzo-2
, 4-diisocyanate> Ni-satsu (here ○ is a benzene ring or naphthalene ring, (C) 1
2), NCO is a nuclear-substituted alkylene isocyanene = 28 monogroup, Z is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, m is l or 2, and n is 1
or 2) diisocyanate (e.g. ω, ω′-
Diisocyanate 1゜2-dimethylpenzole, ω1
ω1-diisocyanate)-1,3-dimethylpenzole); -killing% formula% (where A is an alkylene group having 3 or less carbon atoms such as -CH2- or CL-C-CH3, ○ is a benzene ring or naphthalene ring) , Z is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, n is 0.1 or 2)
Diisocyanates represented by (e.g. 4.4°-diphenylmethane diisocyanate, 2.2"-dimethyldiphenylmethane 44'-diisocyanate, diphenyldimethylmethane-44'-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-44'- diisocyanate), general formula (where Z is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, m is 0 or 1, and n is 0
．． Diisocyanate represented by 1 or 2) (e.g. biphenyl-2,4'-diisocyanate, biphenyl-4
, 4'-diisocyanate), 3,3'-dimethylbiphenyl-4,4''-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate), diphenylsulfone-4,4'-diisocyanate, etc. It will be done.

In addition, as the polymer of the aromatic polyisocyanate compound, the above-mentioned polyisocyanate monomer, preferably tolylene diisocyanate, diphenylmethane diisocyanate, for example, an inert compound such as methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxane, etc. In solvent or diethyl phthalate, dibutyl phthalate,
Phthalic acid esters such as di-2-ethylhexyl phthalate, mixed alkyl phthalates whose alkyl group has 7 to 11 carbon atoms (hereinafter referred to as C7 to C11), butylbenzyl phthalate, hexanolbenzyl phthalate, triscredyl phosphate, tris In a plasticizer such as a phosphoric acid ester such as phenyl phosphate, an adipic acid ester such as di-2-ethylhequinyl adipate, or a trimellitic acid ester such as C7-C,I mixed alkyl trimellitate, well-known catalysts, For example, it can be obtained by polymerization using a known method using a tertiary amine, a Mannich base, an alkali metal of a fatty acid, an alcoholade, or the like. It is desirable that the polymerization reaction carried out in a highly volatile solvent is finally subjected to a solvent substitution treatment with a suitable high boiling point solvent, such as a plasticizer.

The polyisocyanate polymer is preferably polymerized in a phthalate plasticizer, particularly dialkyl phthalate or alkyl benzyl phthalate having C7 or more.

=31 The urethane prepolymer compound used in the present invention is a polyhydroxyl compound such as a polyether polyol, a polyester polyol, or a mixture thereof, and an excess of the above-mentioned aromatic polyisocyanate compound or a polymer of the polyisocyanate compound, or a mixture thereof. The normal NC
It is obtained by reacting in the same manner as the method for producing O-containing urethane prepolymers.

Preferred examples of the above polyether polyols include, for example, - (% formula %)) (where R is a polyhydric alcohol residue; (OR+) is a polyether polyol consisting of an oxyalkylene group having an alkylene group having 2 to 4 carbon atoms; Oxyalkylene chain; n is a number indicating the degree of polymerization of the oxyalkylene group, and the molecular weight is 100 to 4.500
p is preferably a number corresponding to 2 to 4).

Preferred examples of polyhydric alcohol residues corresponding to the above-described OR include, for example, aliphatic dihydric alcohols (e.g., ethylene glycol, propylene glycol, 1,4-phthylene gelicol, neopentane glycol), trihydric alcohols (Example: glycerin, trioquine isobutane, 1
2.3-butanetriol, 1.2.3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2, 3-butanetriol, 2.3,4-pentanetriol, 2.3.4-hexanetriol,
4-propyl-3,4,5-hexanetriol, 2,
4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1.2.4-
butanetriol, 1,2,4-pentanetriol, trimethylolpropane, etc.), tetrahydric alcohols (e.g.
Erythritol, pentaerythritol, 1,2.3.4-
Pentanetetrol, 2,3.4.5-Hexanetetrol, 1,2.3.5-Pentanetetrol 1.3.
Examples include residues of polyhydric alcohols such as 4,5-hexanetetrol, etc.), trihydric alcohols (eg, adonitol, arabitol, xylitol, etc.), and hexahydric alcohols (eg, sorbitol, mannitol, idiolite, etc.).

Also, preferred residues of the polyhydric alcohol are 2-
It is a tetrahydric alcohol residue, and residues such as propylene glycol and glycerin are particularly preferable.

In addition, the polyether polyol shown in the above-mentioned
It can be produced by adding an alkylene oxide having 2 to 4 carbon atoms to such a polyhydric alcohol by a conventional method so as to have a desired molecular weight.

In addition, as alkylene oxide having 2 to 4 carbon atoms,
Examples include ethylene oxide, propylene oxide, and butylene oxide, and it is particularly preferable to use propylene oxide.

Examples of the polyester polyols include conventionally known polyesters produced from polycarboxylic acids and polyhydric alcohols, and polyesters obtained from lactams.

Examples of such polycarboxylic acids include benzenetricarboxylic acid, adipic acid, succinic acid, superric acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, and thiodipic acid. Any suitable carboxylic acid such as propionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or the like can be used.

In addition, examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol,
1,3-butanediol, 1.5bentanediol, 1
．． 6-hexanediol, bis(humanized oxymethylchlorohexane), diethylene glycol, 2,2-dimethylpropylene glycol, 1,3,6-hexandrionopetrimethylolpropane, pentaerythritol, sorbitol, glycerin or any similar Any suitable polyhydric alcohol can be used.

In addition, polytetramethylene glycol, polycaprolactone glycol, etc. can also be used as the polyhydroxyl compound.

The urethane prepolymer compound used in the present invention is a polyhydroxyl compound such as the above-mentioned polyether polyol, polyester polyol, or a mixture thereof, or a mixture of these and an OH group-containing glyceride such as castor oil; It can be obtained by reacting with an isocyanate compound, a polymer of a polyisocyanate compound, or a mixture thereof.

When obtaining a urethane prepolymer compound, the molar ratio of the aromatic polyisocyanate compound, the polymer of the aromatic polyisocyanate compound, or a mixture thereof and the polyhydroxyl compound is usually set to ( polymer or mixture thereof)/polyhydroxyl compound = 1.5~
3.5/L is preferably 2.0 to 3.0/1 = 36= Also, the NC0% of the prepolymer is usually 1 to 20%, preferably 2 to 15%.

Urethane prepolymers can be obtained by conventional methods. When carrying out the urethane prepolymer production reaction, the reaction temperature is usually 40 to 110°C, preferably 50 to 100°C.
It is. When performing the urethane prepolymer production reaction,
Known catalysts for urethane polymerization, such as dibutyltin dilaurate, stannous octoate,
Stanus octoate, lead octylate, lead naphthenate,
It is also possible to use organometallic compounds such as zinc octylate, and tertiary amine compounds such as triethylenediamine and triethylamine.

In addition, blocking agents used in the blocked isocyanate compound (iv) include phenols, such as phenol, cresol (metacresol, orthocresol, para-cresol, and mixtures thereof), xylenol, octylphenol, nonylphenol, dinonylphenol, and tert. -butylphenol, 5e
Examples include alkylphenols such as c-butylphenol, styrenated phenols, and oxybenzoic acid esters.

Examples of oxybenzoic acid esters include 0-oxybenzoic acid ester, m-oxybenzoic acid ester, and p-oxybenzoic acid ester, among which p-substituted ones are particularly preferred.

One group constituting the oxybenzoic acid ester is, for example, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, in the case of m- and p-substituted products.
Long-chain alkyl groups such as dodecyl groups, alkoxyalkyl groups bonded to long-chain polyoxyethylene groups or polyoxypropylene groups, or alkoxyalkyl groups bonded to oxyethylene groups or oxypropylene groups to long-chain alkyl groups, etc. preferable. In addition, in the case of a 0-substituted group, a methyl group, an ethyl group, an isopropyl group, an isoamyl group, an n-butyl group,
Isobutyl group, 5ec-butyl group, n-heptyl group, n
Examples thereof include alkyl groups such as octyl group, 2-ethylhexyl group, nonyl group, and dodecyl group, alkoxyalkyl groups bonded to (poly)oxyethylene or (poly)oxypropylene groups, and aryl groups such as phenyl group and hensyl group.

The blocking reaction to obtain the blocked isocyanate compound (IV) is carried out by a known reaction method. The amount of the blocking agent added is usually 1 equivalent or more and 2 equivalents or less, preferably 1.05 to 1.5 equivalents, based on the free incyanate group.
It is equivalent.

Usually, in the blocking reaction of an aromatic polyisocyanate compound or a polymer of an aromatic polyisocyanate compound, a blocking agent is added in the final reaction.

In addition, when a urethane prepolymer compound is subjected to a blocking reaction, a blocking agent is added at any stage and reacted,
A blocked urethane prepolymer can be obtained.

The blocking agent can be added at the predetermined end of polymerization, or at the beginning of polymerization, or partially added at the beginning of polymerization and the remainder added at the end of polymerization. Preferably, it is added at the end of polymerization. In this case, as a guideline for the completion of a predetermined polymerization, incyanate% (for example, "Polyurethane" Maki Shoten,
(can be measured by the method described on page 21, published in 1960) may be used as a standard. The reaction temperature when adding a blocking agent is usually 50 to 150°C, preferably 60 to 150°C.
The temperature is 0 to 120°C. The reaction time is about 1 to 7 hours. During the reaction, it is also possible to accelerate the reaction by adding the above-mentioned known catalyst for urethane polymerization. Further, any amount of the plasticizer of the present invention may be added.

In addition, as the blocked isocyanate compound (IV),
One or a mixture of two or more of the aforementioned blocked aromatic polyisocyanate compounds, polymers of blocked aromatic polyisocyanate compounds, and blocked urethane prepolymer compounds may be used.

The latent curing agent (v) for epoxy resin of the present invention includes:
Dicyandiamide (DICY), melamine, diallylmelamine, benzoguanamine, acetoguanamine, imidazoles such as Curazole 2M2 2BZ, 28
4MZ, 212. C,,Z, C,,Z.

2PZ 2P4MZ, IB2MZ, 2MZ-CN
, 2B4MZ-CN, 21Z-CN.

C,,Z-CN, 2P2-CN, 2MZ-CNS,
2E4MZ-CNS, C,, ZCNS 2PZ-
CNS, 2MZ-AZINB, 284MZ-AZI
NB (manufactured by Shikoku Kasei Kogyo ■), and metal salt complexes of the above imidazole, such as CUREZOL 2M.
A-OK (manufactured by Shikoku Kasei Kogyo ■), biguanides such as benzimidazole, pentutriazole, 1-ortho-tolyl biguanide, amide imides consisting of phthalic acid or phthalic anhydride and diethylenetriamine, ethylenediamine, hexamethylenediamine, diethylamino Amine salt compounds of propylamine, dimethylamine, propylamine, etc. and bisphenol A1 bisphenol F1 phenol resins or tetrabromobisphenol A, or tertiary amine-containing modified compounds, 3
-(p-chlorophenyl)-1,1-dimethylurea,
Alkyl ureas such as 3-(3,4-dichlorophenyl)-1,1-dimethyl urea, dimethyl urea, tetramethyl urea, and tetramethylthiourea; trifluorols such as BF3-monoethylamine, BF3-aniline, and BF3-dimethylaniline; Boron amine salts, imidacillins, such as 2-methylimidacillin, 2-ethylimidacillin, 2-n-butylimidacillin, 2-(4'-sulfamidobenzyl)imidacilline, 2-dodecylimidacillin Phosphorus, 2-tetradecylimidacillin, 2-benzylimidacillin, 2-(3'-phenylpropyl)imidacilline, 2-(3''-cyclohexylpropyl)imidacilline, 2-(4'-aminobenzyl) imidacillin, 2-
Sulfamidomethylimidacilline, 2,2''-bisimidacilline, 2,2'-ethylenediimidacillin, 1,3
-bis(2'-imidazolinyl)propane, 1,4-bis(2'-imidazolinyl)butane, 1,5-bis(2
1.
8-bis(2″-imidazolinyl)octane, 1.11
-bis(2'-imidazolinyl)undecane, 2-phenylimidacilline, 2-(4'-chlorphenyl)imitasoline, 2-(p-phenyl)imidacilline, 2-
(3″,4°-dimethoxyphenyl)imidacillin,
2-(2'-nitrophenyl)imitasoline, 2-(4
'-sulfophenyl) imidacilline, 2-(4'-sulfonamidophenyl) imidacilline, 2-(4''-methylsulfonylphenyl) imidacilline, 2-α-naphthylimidacillin, 2-β-naphthylimidacillin, 2 −
(i)--methylphenyl)imidacilline, 1,3-bis(2"-imidazolinyl)benzene, 1,4-bis(
2″-imidazolinyl)benzene, 4,4′-bis(2
゛-imidazolinyl)diphenyl, 4.4″-bis(2
″-imidazolinyl)stilbene, 2-phenyl-4-
Methylimidasol 7.1.4-His[4-methylimidazolinyl(2)]benzene, 2-α-pyridylimidacilline, 2-β-pyridylimidacilline, etc., and salts thereof can be used.

Further, carboxylic acid dihydrazide compounds can also be used, and specific examples include adipic acid dihydrazide, sepatic acid dihydrazide, isophthalic acid dihydrazide, 1.
3-bis-(hydrazinocarboethyl)-5-isopropylhydantoin eicosanniic acid dihydrazide HzNHNC-(CHz)1a CNHNH2hydroquinone diglycolic acid dihydrazide, resorcinol diglycolic acid dihydrazide, 4.4゛-ethylidene bisphenol diglycol, etc. be able to.

Furthermore, the present invention also includes the use of one or more of these in combination.

Unsaturated double bond hydroxyl group-containing modified epoxy resin (ii
i) and the blocked isocyanate compound (IV) is usually the unsaturated double bond hydroxyl group-containing modified epoxy resin (iii)/blocked isocyanate compound (iv).
)=5-95/95-5 (wt%), preferably 10
~90/90~10 (wt%).

The composition of the present invention includes the above (i), (ii), and (iii).
), (iv), and (v), various additives such as fillers or stabilizers can also be blended.

Examples of fillers include inorganic fillers (calcium carbonate, talc, diatomaceous earth, kaolin, etc.) and organic fillers (cellulose powder, powdered rubber, recycled rubber, etc.). In addition, stabilizers6 include metal soaps (calcium stearate, aluminum stearate, etc.), inorganic acid salts (dibasic phosphites, dibasic sulfates, etc.), and organic metal compounds (dibutyltin dilaurate, etc.). , dibutyltin malate, etc.)
can be mentioned.

Further, coloring agents such as pigments can also be optionally added.

Although the ratio of each component in the vinyl chloride plastisol composition of the present invention is not particularly limited, the following combination may be used, for example.

Usual range Preferred range (i) 10-50% by weight (20-40% by weight (ii) 10-50% by weight (20-4
0% by weight (iii) + (iv) 0.1-30% by weight (0.5-15% by weight Filler 0-70% by weight (i0-60% by weight Stabilizer 0-3% by weight
(0.1 to 2% by weight Also, when adding the latent curing agent (v) for epoxy resin, usually (iii) + (i
v) / (v) 10010, 3 to 50 (parts by weight),
Preferably it is 10010.5 to 30 parts by weight).

In the composition of the invention, adhesion promoter (iii+iv)
If it is less than 0.1% by weight, no effect will be obtained, and if it exceeds 30% by weight, the plastisol will become hard after curing, which is not preferred. The latent curing agent (v) for epoxy resin is not effective if it is less than 0.3 parts by weight based on 100 parts by weight of (unsaturated double bond hydroxyl group-containing modified epoxy resin (iii) + blocked isocyanate compound (iv)). If the amount exceeds 50 parts by weight, thickening of plastisol will occur, which is not preferable.

The vinyl chloride plastisol composition of the present invention can be produced by kneading the above-mentioned components in a conventional manner.

The composition of the present invention can be applied to various metal surfaces and various undercoated and painted surfaces of metals, but is also useful on cationic electrodeposition coated surfaces. As a cationic electrodeposition coating, an adduct of an epoxy resin and a primary or secondary amine is made water-soluble by neutralizing it with an acid, and is applied to the metal surface of the cathode together with a blocked isocyanate. An example is a method of painting using direct current.

The amount of the vinyl chloride plastisol composition of the present invention applied to the painted surface is usually 1000 to 5000 g/unit, and the film thickness is 0.3 to 2 mm. After application, 120-20
It is heated and cured at 0°C for 20 to 40 minutes. The application method may be any conventional method, for example, a method in which the material is supplied from a pressure pump and then discharged and applied using a flow gun, airless spray, or the like.

〔Effect of the invention〕

As described above, the vinyl chloride plastisol composition comprising the essential components of the present invention has significantly improved adhesion to metal surfaces compared to conventional vinyl chloride plastisol/epoxy resin systems or vinyl chloride plastisol/acrylic resin systems. ,
Furthermore, compared to vinyl chloride plastisol/epoxy resin/blocked isocyanurate systems, the adhesiveness, flexibility, and discoloration resistance during high-temperature heat treatment are improved, and compared to vinyl chloride plastisol/polyamide resins and blocked isocyanate combination systems. , storage stability, and discoloration resistance during high-temperature heat treatment were significantly improved.Furthermore, compared to conventional adhesion promoter systems, adhesion to oil-surface steel plates during relatively low-temperature heat treatment was also significantly improved.

Therefore, as detailed above, the vinyl chloride plastisol composition of the present invention can be baked on various metal surfaces, various undercoated metal surfaces, cationic electrodeposition painted surfaces, etc. at a temperature of 120 to 200°C for 30 minutes or less. It adheres strongly under various conditions, does not foam, and has excellent adhesion after immersion in hot water and heat treatment.It also does not discolor or fade even after high temperature heat treatment, and has good storage stability for vinyl chloride plastisol compositions. It is excellent and useful as a body sealer or undercoat paint for automobile bodies.

〔Example〕

Hereinafter, the effects of the present invention will be specifically shown in Examples and Comparative Examples, but these are not intended to limit the present invention.

Unsaturated double bond hydroxyl group-containing modified epoxy resin (iii
) Production Reference Example 1 Adeka Resin EP4100'' 380
Prepare 284g of "Guki Hygiene", mix and heat,
Add 0.5 g of diethylamine hydrochloride at 0°C, raise the temperature and react at 110°C for 5 hours, acid value = 0, epoxy equivalent =
664 unsaturated double bond hydroxyl group-containing modified epoxy resin■
I got it.

Resistance Adekal Resin EP-4100, Hisphenol A type epoxy resin manufactured by Asahi Denka Kogyo ■ (epoxy equivalent = 190) Zero 2 Hydiene; Highly conjugated linoleic acid manufactured by Soken Chemical ■ (neutralization value = 198, iodine value = 167, conjugated diene ( %)
-51) Reference Example 2 Using a four-bottle flask equipped with a stirrer, thermometer, cooling tube, and nitrogen introduction tube, 190 g of BP-4100, 145 g of tall oil fatty acid, and 0.4 g of reethanolamine were mixed, and the mixture was mixed with 0.4 g of ethanolamine. A modified epoxy resin (2) containing an unsaturated double bond hydroxyl group and having an epoxy equivalent of -670 was obtained by the same reaction as in 1.

Reference Example 3 Using a 4-bottle flask equipped with a stirrer, thermometer, cooling tube, and nitrogen introduction tube, Epikote [01” 450M
Parts by weight Diethylamine hydrochloride 0.1 parts by weight Hydiene 142 parts by weight Dioctyl phthalate 450 parts by weight In the same reaction as in Reference Example 1, epoxy equivalent -2080
A modified epoxy resin (2) containing unsaturated double bond hydroxyl groups was obtained.

Water oil shell (bisphenol A type epoxy resin manufactured by II (epoxy equivalent: -450) Reference example 4 for the production of blocked isocyanate compound (iv) Using a four-bottle flask equipped with a stirrer, thermometer and nitrogen inlet tube, toluylene didiison 74 parts by weight of dioctyl fucrate (674 parts by weight) 0.01 parts by weight of dibutyl tin dilaure) were charged, and the mixture was reacted at 80°C for 5 hours under nitrogen blowing.
A blocked isocyanate compound (2) in which O groups were completely blocked was obtained.

Zero 2,4-) 80% lye diisocyanate and 2
．． 6-) Mixture with 20% lylene diisocyanate Reference example 5 Using a four-bottle flask equipped with a stirrer, thermometer and nitrogen inlet tube, Coronate 20309 100 parts by weight Dioctyl phthalate 200 parts by weight Nonylphenol 50 parts by weight Dibutyltin dilaurate 0 .05 parts by weight was prepared, Reference Example 4
The butyl acetate solvent of Coronae) 2030 was removed under reduced pressure to obtain a blocked isocyanate compound (2).

Incyanurate compound of toluylene diisocyanate manufactured by Nippon Polyurethane ■, solid content: 50%, solvent: butyl acetate Reference Example 6 Using a 4-bottle flask equipped with a stirrer, thermometer and nitrogen inlet tube, Abcany Ace was prepared. P1212-5” 500
Part by weight (diphenylmethane diisocyanate) 500f
filN dioctyl phthalate 1495
Parts by weight were charged and reacted at 60°C for 3 hours.Next, 495 parts by weight of nonylphenol was added and reacted at 80°C for 5 hours to obtain a blocked isocyanate compound (2) in which the NGO groups were completely blocked.

Kyoadeka New Ace F1212-5; Polyester diol manufactured by Asahi Denka Kogyo ■ (molecule 1 = 500) Example 1
~7 Polyvinyl chloride powder (a) (Zeon 121 manufactured by Nippon Zeon)
) 60 parts (by weight, the same applies hereinafter), polyvinyl chloride powder (
b) (Zeon 1032X manufactured by Nippon Zeon) 20 parts, dioctyl phthalate (DOP) 100 parts, calcium carbonate (a) (Shiroishi Calcium Shiroenka CC) 80 parts, Calciramura carbonate) (Shiraishi Calcium manufactured Whiten S8)
20 parts, titanium oxide (Titan Kogyo KR-380) 3 parts, anti-aging agent 1.5 parts, fluidity regulator 0.5 parts, Table 1
Unsaturated double bond hydroxyl group-containing modified epoxy resin (iii) and blocked isocyanate compound (i) as shown in
(2) were adjusted and added, kneaded, and defoamed under vacuum to produce various vinyl chloride plastisol compositions.

This composition has good adhesion to mild steel plates after gelation.
Flexibility, burn resistance, and stability after storage at 40°C were evaluated. The results are shown in Table-1.

Comparative Examples 1 to 3 In the same vinyl chloride plastisol compositions as in Examples 1 to 7, a substance other than the product of the present invention was added instead of the adhesion promoter. The test results are shown in Table-1.

Test method in Table-1 (i) Adherent: Mild steel plate (2) Application method: Apply to a thickness of 2 mm with a spacer (3
) Baking method: 180°C x 20 minutes (4) Adhesive strength evaluation method; Nail peeling (5) Flexibility evaluation method: 180° bending 180° bending (6) Baking evaluation method: No cracks...○ Cracks appear...x (7) Adhesion after storage at 40°C for 3 days; After storing vinyl chloride plastisol at 40°C for 3 days, the adhesive strength to a mild steel plate was examined.

Compared to Examples 1 to 7, Comparative Examples 1 to 3 were all inferior in terms of adhesion and scorching, and the vinyl chloride plastisol composition of the present invention had poor adhesive strength, flexibility, and discoloration due to scorching.
A significant improvement in stability after storage at °C was observed.

Examples 8 to 14 Polyvinyl chloride copolymer powder (C) (Zeon 135J manufactured by Nippon Zeon) 80 parts, DOP 100 parts, carbonic acid (a) 50 parts, calcium carbonate (b) 50 parts, titanium oxide 3 parts, aging Latent curing for epoxy resin with 1.5 parts of inhibitor, 0.5 parts of fluidity regulator, unsaturated double bond hydroxyl group-containing modified epoxy resin (iii) and blocked incyanate compound (iv) as shown in Table 2 A vinyl chloride plastisol composition is prepared by adjusting and adding agent (v), kneading, and defoaming under vacuum. The adhesion was evaluated. The results are shown in Table-2.

Comparative Example 4 A test was carried out using the same formulation as above but with 2 parts of ACR Hardener H-270 (polymerized fatty acid polyamide, amine value -300) instead of the adhesion promoter. The results are shown in Table-2.

Table-: Test of 2-7l method (i) 1 piece to be covered (i,'! Kaji: Cow: Dentani board ■' 7) lh surface steel plate (2)・Painting j-5 method, sub-base →S1, T-ba-ding:)
11fl] applied to the 7th part (:l) with bladder', J Xa
'? =: (Cadion electrodeposition (reverse) 1', 3 l',)
"To ri ゛:) 0 minutes (4) Attachment crab ÷"
filI] -,,'J 7: l!mir1 (Peeling lPe OF Busu: 3 vine cohesive failure ・(D complete, hepatic adhesive surface failure Xi Ap゛C
rPa・Partial ν collection and adhesive surface destruction...／＼(5) Possible+
1.3 in standing 1 1111 Chin, +80' bend l) Bending No cracks) 0181]' Folding)) Bending Crack in place White surface 0 1' White surface - 4y Lito color ○・Surface brown... \(7) Oil 1f11 net temporary -\,
1.180℃ x 2 for mild steel plate immersed in adhesive mason oil
Baked in 0 minutes, tested for adhesion, Example 8-
Compared to Comparative Example □1, No. 14 has a relatively low temperature baking (even when twisted, the adhesion is strong), and the flexibility and
A remarkable improvement was observed in the storage stability of i) 4 colors and +10τ due to burn resistance.1. )is.

Example 15.16 The vinyl chloride plastisol composition according to the present invention was tested for use as a body sealer and undercoat for automobile bodies.The results are not shown in the table.

The vinyl chloride plastisol composition was prepared in accordance with Example 1. Comparative Example 5 The vinyl chloride plastisol composition of Example 15 except for the adhesion promoter was tested in the same manner. The results are not shown in Table 3.1゜Table: (6Σ *1. Adeka Argus) Flu-based stabilizer *2:
PVC on two electric @' boards! - Rubrasti y month composition 1
15mm [)! Apply it to the sand inch (,.

Bake at 130℃ for 20 minutes.
Also.

PVC plastic assembly of the present invention t? , U has been found to have excellent adhesion to cationic electrodeposited plates, and

Claims (1)

[Claims] 1. As essential constituents: (i) vinyl chloride polymer and/or copolymer, (ii) plasticizer, (iii) epoxy having on average more than one adjacent epoxy group in the molecule. A chlorinated epoxy resin containing an unsaturated double bond hydroxyl group-containing modified epoxy resin obtained by reacting a resin (iii-1) with an unsaturated fatty acid (iii-2), and (iv) a blocked isocyanate compound. Vinyl plastisol composition. 2 As essential constituents: (i) vinyl chloride polymer and/or copolymer, (ii) plasticizer, (iii) epoxy resin (iii-1) having an average of more than one adjacent epoxy group in the molecule. and an unsaturated fatty acid (iii-2), containing an unsaturated double bond hydroxyl group-containing modified epoxy resin, (iv) a blocked isocyanate compound, and (v) a latent curing agent for epoxy resin. A vinyl chloride plastisol composition characterized by: