JPH0459849A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a copolymer of a vinyl monomer having a functional group capable of chelating with a metal and a vinyl monomer having a hydrocarbon chain, excellent in stability for a long period and further adhesion, discoloration and hot water resistance of films. CONSTITUTION:The objective composition containing (A) 10-50wt.% vinyl chloride (co)polymer, (B) 10-50wt.% plasticizer (e.g. dioctyl phthalate) and (C) 1-20wt.% copolymer of (i) 2-80wt.% (based on the total copolymerization components) vinyl monomer containing preferably nitrogen atom in a functional group capable of chelating with a metal and (ii) a vinyl monomer, having a >=2C hydrocarbon chain in one molecule and soluble in the aforementioned plasticizer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new and useful vinyl chloride resin composition. More specifically, a copolymer (C ) as an essential component, it has particularly good adhesion to the substrate, and also has anticorrosive properties.
The present invention relates to a vinyl chloride resin-based plus sol composition having excellent stability and color fastness, and particularly to a plus sol composition useful as a paint.

[Conventional technology]

Although vinyl chloride resin has excellent rust prevention and weather resistance, and has excellent properties as a coating resin, it does not necessarily have good adhesion to various base materials. For this reason, attempts have been made to improve this by adding other resins. For example, (1) polyamide resin ("
Vinyl chloride paste chemical engineering (medium)” P139-P14
3. Written by Sakae Iida, published by Rubber Digest, 1973
), (2) Liquid epoxy resin and polyamide resin (“
Comprehensive survey of vinyl chloride (2) Raw materials and processing results “P2S5-
P2S5, CMC, 1968).

(3) Blocking of a urethane prepolymer having isocyanate groups from polyols and organic diisocyanates with a blocking agent A urethane prepolymer and a mono- or polyamide-based compound containing an active amino group
(4) Lactam block polyisocyanate and active amino group-containing polyamide compound (JP-A-59-131669).

(5) Organic diisocyanate polymer (isocyanurate type polyisocyanate) long chain alkylphenol block (Japanese Patent Application Laid-Open No. 62-41278) and oxybenzoic acid ester block (Japanese Patent Application Laid-Open No. 62-198)
48583) and the like are known.

However, the addition of the polyamide resin in (1) above,
Although it improves adhesion, due to the active and hydratable amino groups of polyamide resin, it reduces corrosion resistance including water resistance and solvent resistance, and also deteriorates storage stability. However, it has the disadvantage of discoloration.

When adding the epoxy resin and polyamide resin in (2) above, both have high reactivity at room temperature, and
It also has poor storage stability, which causes problems during work.

When adding a blocked urethane prepolymer made of polyols and an organic diisocyanate as described in (3) above, and an active amino group-containing polyamide-based compound, it is easy to be influenced by the properties of the polyol, which is an essential component. ,
Decrease in corrosion resistance including water resistance and effective N generated during heating
The molecular weight is large compared to the amount of CO (NC0%), and there is a problem with stability at high temperatures in summer, and there is also a disadvantage of discoloration due to the polyamide compound.

When adding the lactam block polyisocyanate described in (4) above and a polyamide compound, the properties of the diisocyanate will greatly affect the compatibility, and the compatibility will be poor due to the strong polarity and large atomic groups of the lactam. It has the drawbacks of high dissociation temperature, poor stability due to compatibility, poor performance, and discoloration due to polyamide compounds.

When the long-chain alkylphenol or p-oxybenzoic acid ester block of the diisocyanate polymer described in (5) above is added to the vinyl chloride resin as an adhesion promoter, the stability is good, but the dissociation temperature is low. Because of the phenol-based blocking agent, it is difficult to bake when heated for a short time at a low temperature of about 30 minutes at 120°C, and as a result, the adhesion becomes worse. Therefore, it has the disadvantage that its corrosion resistance, including water resistance, and solvent resistance are not good.

In recent years, coating materials using vinyl chloride sol compositions have tended to become thinner, and emphasis has been placed on corrosion resistance, solvent resistance, and discoloration resistance.It is important to balance these conflicting properties of corrosion resistance and storage stability. has become an extremely important issue, but conventional technology cannot adequately address it.

In addition, there are a wide variety of substrates to be coated, such as various treated steel plates and cationic electrodeposition coated plates, so it is not possible to adequately cover these aspects as long as conventional techniques are followed.

[Problem to be solved by the invention]

In this way, as long as the conventional technology as described above is followed, it will definitely have excellent storage stability and adhesion to the substrate.
It is extremely difficult to provide a highly practical vinyl chloride resin composition that has excellent corrosion resistance, solvent resistance, discoloration resistance, and the like.

To this end, the present inventors have begun earnest research in order to successfully solve the various unresolved problems in the prior art as described above and to provide a highly practical vinyl chloride resin composition.

Therefore, the problem to be solved by the present invention is to provide a product that not only has excellent storage stability, but also has excellent adhesion of the coating film, and
It is an object of the present invention to provide a vinyl chloride resin composition that has extremely high practical value and has excellent corrosion resistance, solvent resistance, and modification resistance of coating films.

[Means to solve the problem]

Therefore, the inventors of the present invention set their sights on the problems to be solved by the invention as described above, and as a result of intensive studies, they found that
By adding a specific vinyl copolymer as a third essential component to a vinyl chloride resin composition whose basic components are a vinyl chloride (co)polymer and a plasticizer, adhesive properties can be improved immediately. It also has excellent corrosion resistance, solvent resistance, and discoloration resistance, and surprisingly,
The present invention was completed by discovering that a vinyl chloride resin composition having excellent storage stability can be obtained.

That is, the present invention includes, as essential components, a vinyl chloride (co)polymer (A), a plasticizer (B), and a vinyl monomer having a functional group capable of forming a chelate with a metal, in one molecule. The plasticizer (B) has a hydrocarbon chain having 2 or more carbon atoms.
The object of the present invention is to provide an extremely practical vinyl chloride resin composition comprising a vinyl copolymer (C) obtained by copolymerizing a vinyl monomer soluble in

Hereinafter, the configuration of the present invention will be explained in detail.

First, each component constituting the vinyl chloride resin composition of the present invention will be explained in order.

First, the vinyl chloride (co)polymer (A) mentioned above refers to a homopolymer and/or copolymer of vinyl chloride, and any known and commonly used one can be used.

Examples of vinyl chloride copolymers include copolymers of vinyl chloride and other vinyl monomers that can be copolymerized with vinyl chloride, such as vinyl acetate, maleic anhydride or its esters, or vinyl ether, as well as chlorinated polyethylene. and vinyl chloride-vinylidene chloride copolymer. The degree of polymerization of vinyl chloride polymer, polymer or copolymer is usually 7.
00-4,000, preferably 1,000-2,0
The range is 00. Commercially available vinyl chloride (co)polymers include “Kanevinyl PSL-10, PSH-1”
0, PSM-30 or PCH-12" (Kanebuchi Chemical Industry ■ product), "Zeon 121 or 135J.

[Nippon Zeon ■ product], “Denkabinir PA-100 or ME-400JC Denki Kagaku Kogyo ■ product” or “
Monosand 70BKJ [San IE synthetic vinyl product]
etc. are representative examples. These may be used alone or in combination of two or more.

Next, as the above-mentioned plasticizer (B), any plasticizer that is generally used for this type of purpose can be used, but diethyl phthalate is given as a representative example. , dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, distearyl phthalate, diisononyl phthalate, diiso, decyl phthalate or butyl benzyl phthalate; adipic acid esters such as dioctyl adipate; xebacic acid esters such as dioctyl sebacate. Examples include various ester plasticizers such as phosphate esters such as tricresyl phosphate, and mixtures of two or more of these.

Among these, particularly preferred are phthalic acid esters, especially dioctyl phthalate or diisononyl phthalate.

In addition, the above-mentioned vinyl copolymer (C), which is a vinyl monomer having a functional group capable of forming a chelate with a metal, and a vinyl monomer having a hydrocarbon chain of 02 or more in one molecule, and the above-mentioned To explain the vinyl copolymer component obtained by copolymerizing a vinyl monomer that dissolves in a plasticizer (B), the copolymer (C) contains a metal and a functional group capable of forming a chelate, respectively. and at least one member of the group consisting of vinyl monomers that have 02 or more hydrocarbon chains in one molecule and that are soluble in the plasticizer (B). Examples include various vinyl copolymers obtained by copolymerizing these by a conventional method.

First, the vinyl monomer having a functional group capable of forming a chelate with the above-mentioned metals has at least the following types of functional groups capable of forming a chelate with various metals.
Classified into seven groups. That is, the first group includes those having a nitrogen-containing functional group, such as an amino group, an imino group, an amide group and/or an amine group,
The second group has acid groups, the third group has acetoacetate groups, the fourth group has isocyanate groups, and the fifth group has urethane bonds and The sixth group has a hydroxyl group, and the seventh group has an epoxy group. First, the vinyl monomer having a nitrogen-containing functional group in the first group may be a vinyl monomer having an amino group, an imino group, an amide group, and/or an amine group in the molecule; Particularly representative monomers include vinylamine, 3-vinylpiperidine, vinylimidazole such as N-vinylimidazole; 2-vinylpyridine, 2-methyl 5
Vinylpyridines such as vinylpyridine; vinylpyrrolidone, (meth)acrylonitrile, vinylnitriles such as 2-methyl-3-butenenitrile; (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (
meth)acrylamide, N-isopropyl(meth)acrylamide, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-(iso)propoxymethyl(meth)acrylamide, N-n-butoxymethyl(meth)acrylamide, dia-7ton acrylamide, 2-acrylamide-2-methylpropanesulfonic acid ( Derivatives or various isomers of meth)acrylamide; vinylamides such as fumaramide and maleoamide; unsaturated basic acids such as crotonic acid! Monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monomethyl itaconate, monoethyl itaconate, motuputyl itaconate, or mono 2-ethylhexyl itaconate monoalkyl esters of unsaturated dibasic acids such as maleic anhydride, fumaric acid or itaconic acid or their anhydrides; or 2-hydroxyethyl (meth)acryloyl phosphate or 2-hydroxyethyl (meth)acryloyl phosphate; ) Examples include esters of nitric acid, sulfonic acid or phosphoric acid of hydroxyl group-containing vinyl monomers such as acryloyl sulfonate.

Vinyl monomers whose functional group capable of forming a chelate with a metal of the third group is an acetoacetate group include acetoacetate of a hydroxyl group-containing vinyl monomer such as 2-hydroxyethyl (meth)acrylate or acetoacetate. Examples include esters.

Vinyl monomers having an isocyanate group as a functional group capable of forming a chelate with a metal of the fourth group include vinyl isocyanate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate 1, di(
iso)propylaminoethyl (meth)acrylate, di(iso)butylaminoethyl (meth)acrylate, N
-cyclohexylaminoethyl (meth)acrylate,
These include β-morpholine N-ethyl-(meth)acrylate, acryloylmorpholine, or various derivatives and isomers thereof, and the above-mentioned vinyl monomers do not necessarily have to be one type, but may be used as a mixture. In addition, these chelate-forming vinyl monomers are copolymerized with a vinyl monomer that has 02 or more hydrocarbon chains in one molecule and is soluble in the plasticizer (B), which is used in combination with them. Afterwards, it can be used by changing it to a nitrogen-containing functional group such as an amino group, an imino group, an amide group, and/or an amine group using methods such as hydrogenation or hydrolysis. a nitrogen-containing functional group, i.e. an amino group,
A vinyl copolymer (C) is obtained by copolymerizing a plasticizer-soluble vinyl monomer having an imino group, an amide group, and/or an amine group.

Examples of the vinyl monomer whose functional group capable of forming a chelate with the second group metal is an acid group include (meth)acrylic acid and isocyanate (meth)acrylate.

As a vinyl monomer having a urethane bond as a functional group capable of forming a chelate with a metal in the fifth group, a vinyl monomer having an isocyanate group in the fourth group was blocked with a known blocking agent to form a urethane. Things can be mentioned. These blocking agents include active methylene compounds such as diethyl malonate such as diethyl malonate, acetoacetate such as ethyl acetoacetate, or acetylacetone, and oxime compounds such as methyl ethyl ketone such as butanone oxime. Examples include ketooximes such as acetoxime, phenol compounds such as phenol, cresol or xylenol, lactam compounds such as ε-caprolactam, and imidazole compounds such as 2-methylimidazole.

Furthermore, examples of monoamide compounds include N-ethylacetamide and N-phenylamide. (Refer to JP-A No. 57-145161.) Vinyl monomers having a hydroxyl group as a functional group capable of forming a chelate with a metal of the sixth group include β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate or hydroxyalkyl acrylate or hydroxyalkyl methacrylate such as T-hydroxybutyl (meth)acrylate. Moreover, those obtained by reacting a glycidyl group-containing vinyl monomer with monoamines, alkanolamines, etc. can also be used.

Typical vinyl monomers whose functional group capable of forming a chelate with a seventh group metal is an epoxy group include glycidyl (meth)acrylate and β-methylglycidyl (meth)acrylate.

02 in one molecule used in combination with a vinyl monomer having a functional group capable of chelating with such metals.
The vinyl copolymer (C) obtained by copolymerizing a vinyl monomer that has the above hydrocarbon chain and is soluble in a plasticizer.
0 in one such molecule, which is another component constituting
Typical vinyl monomers that have two or more hydrocarbon chains and are soluble in plasticizers include ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate.
Alkyl (meth)acrylates with a hydrocarbon chain of 03 or more, such as meth)acrylate, 2 ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, or stearyl (meth)acrylate; methoxyethyl (meth)acrylate, ethoxyethyl ( Meta)
Acrylate or tetrahydrofurfuryl (meth)
Ether ester (meth)acrylates such as acrylates; dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, diethyl fumarate, dibutyl itaconate, di-2-ethylhexyl itaconate or monomethyl itaconate, as well as styrene, Examples include vinyltoluene, vinyl acetate, vinyl propionate, and cyclohexyl methacrylate.

In the vinyl copolymer, the amount of the vinyl monomer having a functional group capable of forming a chelate with a metal is 2 to 80% by weight, preferably 10 to 80% by weight based on the total copolymer component.
A range of 40% by weight is suitable. Of course, the optimal usage ratio of the functional group-containing vinyl monomer varies depending on how each 1tllll is designed depending on the use of the composition of the present invention, but in the case of approximately 2% by weight, On the other hand, if the weight exceeds 80%, although various properties such as adhesion improve, solubility in plasticizers decreases, and storage stability deteriorates. Both cases are undesirable because they result in poor performance.

The vinyl copolymer (C) is prepared in an aromatic, ketone, or ester solvent, or in dibutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, 5AS-296 (
Nippon Petrochemical ■Products] Various functional group-containing vinyl monomers doffed in a plasticizer or diluent such as a high-boiling aromatic or hydrocarbon in the presence of a known and commonly used radical polymerization catalyst, A vinyl monomer having 02 or more hydrocarbon chains in one molecule and soluble in a plasticizer may be copolymerized by a conventional method.

The vinyl monomer (C) finally obtained can be a copolymer solution in which part or all of the polymerization solvent is replaced with a plasticizer or diluent, or a copolymer solution in which part or all of the polymerization solvent is replaced with a plasticizer or diluent. Copolymer solutions that have been removed can also be used, and copolymer solutions partially containing aliphatic or naphthenic solvents can also be used.

Further, typical radical polymerization catalysts used in the copolymerization reaction include organic polymers such as benzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, and cumene hydroperoxide. These include oxides and azo compounds such as azobisisobutyronitrile.

Furthermore, a chain transfer agent such as lauryl mercaptan or thioglycolic acid ester can be used simultaneously with these various radical polymerization catalysts, if necessary.

In addition, the polymerization conditions and method are not particularly limited, but it is generally appropriate to carry out the polymerization at a temperature of 60 to 140°C under normal pressure. When preparing a polymerized component, it is appropriate to carry out the reaction under pressure.

In this way, the vinyl copolymer or its solution is obtained.

The vinyl copolymer that has a functional group capable of forming a chelate with a metal and is soluble in a plasticizer, which is obtained as described above, usually has a molecular weight of 3,000 to 30,000, preferably 5,000 to 30,000, preferably 5, 000 to 20.000. The molecular weight is 3,
If it is less than 000, it will become hard and brittle when used as a vinyl chloride sol, resulting in deterioration of physical properties. On the other hand, if it exceeds 30,000, the adhesion to the substrate will decrease.

The vinyl chloride resin composition of the present invention may contain various other additives, such as stabilizers, fillers, lubricants, R additives, and dissociation promoters, as long as the objects of the present invention are not impaired.

It may contain a diluent and the like.

Stabilizers include metal soaps (calcium stearate, zinc stearate, aluminum stearate, etc.), inorganic acid salts (dibasic phosphites, dibasic sulfates, etc.), and organometallic compounds (organotin stabilizers). Examples include dibutyl tin maleate, dioctyl tin maleate, dioctyl tin bis (such as 2-ethylhexyl maleate), epoxidized soybean oil or epoxy resin.

Fillers include inorganic fillers (hydrated silicic acid, calcium carbonate, talc, diatomaceous earth, kaolin fleur, precipitated barium sulfate, etc.) and organic fillers (cellulose, polyethylene terephthalate, acrylic, rubber, urethane). thermoplastic resins such as thermoplastic resins).

In addition to metal soaps, lubricants include paraffins, waxes, fatty acid amides, fatty acid esters, fluorohydrocarbons, and organic silicones.
Any pigment can be used as long as it suits the purpose of coloring, but for example, inorganic pigments such as titanium oxide and Bengara, and organic pigments such as carbon black and phthalocyanine blue can be used alone or in combination of two or more. Used in combination.

In addition, in order to accelerate the reaction during heating of the vinyl chloride resin composition of the present invention, and thereby reduce the practical heat treatment temperature or shorten the time, it is possible to Catalysts commonly used to promote the dissociation of bronching agents (organometallic compounds such as zinc octylate, tin octylate, dibutyltin dilaurate, dibutyltin acetate, triethylenediamine, triethylamine, 1,8-diazabicycloundecene-7) salts, etc.) can also be used in combination as a dissociation promoter. Also, as a diluent, it can be used as a diluent with a boiling point of 70 to 24
Aliphatic solvent (c.

paraffinic hydrocarbon solvents (e.g., hexane, heptane, octane, nonane, decane, etc.), naphthenic hydrocarbon solvents (cyclohexane, methylcyclohexane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, etc.); Mixed solvents and aromatic solvents (e.g. toluene, xylene, ethylbenzene, -mistyrene, "Tsurupez #100J (manufactured by Exxon, USA)"
Turpetz #150J (same as above), etc.) can also be used, and mineral spirits that are a mixture of aliphatic and aromatic solvents (for example, ``Raus'' or ``Haus'' (product of Shell, Netherlands) can also be used. ) can also be used. Furthermore, as a part of the solvent component, it is also possible to use substances with extremely high boiling points, such as rSAS-296,5AS-LHJ (product of Nippon Petrochemicals), which is a liquid high-boiling aromatic hydrocarbon compound, and dimer acid. .

In the vinyl chloride resin composition of the present invention, each of the above components (
The blending ratios of A) to (C) are as follows.

(% is weight%.) In the present invention, when a stabilizer is used as an additive, it is usually 0 to 5% (preferably 0.1 to 3%), and when a diluent is used, it is usually 0 to 5% (preferably 0.1 to 3%). ,usually,
0 to 7% (preferably 1 to 5%), and when using a dissociation promoter etc., usually 0 to 1% (preferably 0 to 0.0%).
3%) is used in combination.

The vinyl chloride resin composition of the present invention can be produced by kneading in a conventional manner.

The vinyl chloride resin composition of the present invention can be used on various metal substrates,
It can also be applied to various painted surfaces on metal (particularly steel) surfaces, but it can be particularly advantageously applied to cationic electrodeposition painted surfaces, acrylic resin painted surfaces, or metal surfaces. The above-mentioned cationic electrodeposition coating uses, for example, a polyamine resin (an epoxy resin having an amino group in its molecule and a blocked isocyanate that reacts with the amino group or hydroxyl group contained therein) as film-forming components, which is then neutralized with a lower organic acid or the like. When an aqueous solution or aqueous dispersion) is used as a paint, the film-forming component exists as a cation, and the film-forming component is applied as a cathode by direct current to the coated object (such as a plate). This is a coating method in which paint is deposited on the surface of. Further, the acrylic resin paint used for the above-mentioned acrylic resin coating may be a thermoplastic type or a thermosetting type. The thermoplastic type is acrylic (co)
It uses a polymer in combination with a cellulose derivative (nitrified cotton, cellulose acetate butyrate, etc.), a plasticizer, etc., and is mainly used for drying at room temperature.

The thermosetting type has a functional group in the acrylic (co)polymer, and forms a crosslinked coating film by heating alone or by reaction with a crosslinking agent.

The coating amount of the vinyl chloride resin composition of the present invention on the above-mentioned painted surface is usually 150 to 3000 g/m'', and the coating film thickness is usually 0.15 to 3 cm. is carried out, but the baking temperature in that case is usually
The temperature is usually 110 to 150°C and the time is usually 20 to 40 minutes.

W1! The coating method can also be applied, such as spray coating, heka-coating,
Conventional methods such as dipping, pouring, pouring, airless spraying, etc. can be used. In addition to the above-described methods, general coating methods for the vinyl chloride resin composition of the present invention include electrostatic coating and sticky coating.

As mentioned above, the vinyl chloride resin composition of the present invention can be baked on many substrates such as cationic electrodeposition coated surfaces, acrylic coated surfaces, and metal surfaces at low temperatures and short times (120°C).
It adheres firmly at temperatures of 20 to 30 minutes at 45° C., has good color fastness, and is more stable at warm temperatures than conventional products, with little increase in viscosity even under the harsh conditions of 3 weeks at 45° C.

The vinyl chloride resin composition of the present invention can be used as a baking type paint,
It can be used in various industrial applications such as adhesives, sealants, and caulking, but it is also suitable for automotive applications, especially undercoating.
It is particularly excellent as a body sealer and undercoat paint for car bodies that have been coated with various paints or have not been painted.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples, but the present invention is not limited thereto.

Reference Examples 1 to 10 [Example of Preparation of Vinyl Copolymer (C)] Dioctyl phthalate (DOP) was added according to the synthesis example in Table 1 to a glass drawer flask with a capacity of Il equipped with a thermometer, a reflux condenser, and a stirrer. ). Nitrogen gas was introduced, the temperature was raised to 80°C while stirring, and at the same temperature, each monomer was mixed according to the synthesis example in the same table, and added dropwise together with a radical polymerization catalyst over a period of 3 hours. The polymerization reaction is then continued and terminated when the nonvolatile content (NV) reaches 99% or more and the viscosity becomes constant. Both are transparent in appearance. However, the β-hydroxyethyl methacrylate mixture exhibits slight fluorescence. Thus, a vinyl monomer having a functional group capable of forming a chelate with a metal is copolymerized with a vinyl monomer having a hydrocarbon chain of 02 or more in one molecule and soluble in a plasticizer. A dioctyl phthalate solution of vinyl copolymer (C) is obtained.

Reference Examples 11 and 12 [Preparation Example of Comparative Vinyl Copolymer] As shown in Table 1, DOP was charged into the same apparatus as Reference Examples 1 to 10. Introducing nitrogen gas and stirring for 80 minutes.
The temperature was raised to °C, and at the same temperature, each monomer was added dropwise over 3 hours together with a radical polymerization catalyst as shown in the table. Minutes (
Polymerization is terminated when the NV) reaches 99% or more or when the viscosity becomes constant. In the case of the product obtained in Reference Example 12 using methyl methacrylate, the appearance is slightly cloudy.

/ Main' B, /1 Examples 1 to 10 and Comparative Examples 1 to 3 Plastisol compositions were prepared as follows. "
70 parts of Kanevinyl PSL-10J (vinyl chloride straight resin), 30 parts of Kanevinyl PCI-12J (vinyl chloride copolymer resin), 100 parts of dioctyl phthalate (DOP), rNs#loo” (manufactured by Nitto Funka Kogyo ■) A vinyl chloride paste consisting of 100 parts of dibasic lead phosphite (calcium carbonate) and 3 parts of dibasic lead phosphite (Diphos), a vinyl monomer having a functional group capable of forming a chelate with metal, and 02 or more in one molecule A vinyl copolymer (C) obtained by copolymerizing a vinyl monomer that has a hydrocarbon chain and is soluble in a plasticizer, and a vinyl monomer that has a functional group capable of forming a chelate with a metal. A control vinyl-based copolymer without using the above was uniformly kneaded using a crusher to prepare compositions as shown in Table 2.

As Comparative Example 3, a polymerized fatty acid polyamide resin (amine value 300) was prepared without using the vinyl copolymer (C).
A product was also prepared using the following as an adhesion promoter.

Using the vinyl chloride resin compositions of Examples 1-10 and Comparative Examples 1-3, the degree of viscosity change when stored at expected temperatures was tested. Next, a vinyl chloride resin composition was applied to a steel plate, a steel plate coated with acrylic paint, and a steel plate coated with cationic electrodeposition coating using pi! It was coated to a film thickness of 0.25mm, baked at 140°C for 20 minutes, and tested for adhesion to the substrate and hot water resistance. Furthermore, how firmly the vinyl chloride resin composition adhered to the cationic electric sign was measured using a universal tensile tester according to the plane tensile method (JAS, special plywood standard). The above results are shown in Table 2, and it can be seen that the samples of Examples have better stability than those of Comparative Examples, as well as excellent adhesion, hot water resistance, and color fastness.

/ [Effects of the Invention] The vinyl chloride resin composition of the present invention contains a vinyl monomer having a functional group capable of forming a chelate with a metal, and 0% in one molecule.
A vinyl copolymer (C
), it has excellent long-term storage stability and can form coatings with excellent adhesion, color fastness, and hot water resistance on various substrates. . Therefore, the vinyl chloride resin composition of the present invention is extremely useful, especially for paints.

Claims (1)

[Claims] 1. A vinyl chloride polymer or copolymer (A), a plasticizer (B), a vinyl monomer having a functional group capable of forming a chelate with a metal, and carbon in one molecule. A chlorinated vinyl copolymer (C) obtained by copolymerizing a vinyl monomer having a hydrocarbon chain of 2 or more and dissolved in the plasticizer (B). Vinyl resin composition. 2. The vinyl chloride resin composition according to claim 1, wherein the functional group capable of forming a chelate with the metal described above contains a nitrogen atom. 3. The vinyl chloride resin composition according to claim 1, wherein the functional group capable of forming a chelate with the metal described above contains an oxygen atom.