JP3077302B2 - Adhesive plastisol composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel adhesive plastisol composition, and more particularly, it has excellent adhesiveness and water resistance to the surface of a metal plate to which a rust-preventive oil is adhered, and is suitable for a sealing agent or a paint. The present invention relates to an adhesive plastisol composition used in the above.

[0002]

2. Description of the Related Art A vinyl chloride resin plastisol is obtained by mixing and dispersing a vinyl chloride resin powder having a primary particle diameter of about 0.2 to 3 μm together with a heat stabilizer, a filler, a pigment and other compounding agents in a plasticizer. A resin composition comprising:
It is processed into final molded products by molding methods such as slush molding, rotational molding, etc., spread coat molding such as knife coat and roll coat, or screen coating molding.For example, sealants and metal plates between metal plates during automobile manufacturing Used as a paint for the surface. In particular, the performance required for the vinyl chloride resin plastisol for bonding includes, for example, good stability over time of viscosity, gelation bonding at a low temperature, and high bonding strength. The plastisol includes, as a vinyl chloride resin, usually a vinyl chloride copolymer such as a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-vinyl acetate-maleic acid copolymer, or a vinyl chloride-vinyl acetate-vinyl alcohol copolymer. Coalescence is used, but since these copolymers alone have insufficient bonding strength, conventionally,
A method of adding an adhesion improver such as a polyamidoamine or an isocyanate compound to the copolymer is often used. However, in the method of adding a polyamidoamine or an isocyanate compound, (1) the viscosity of the plastisol increases with time, (2) adhesion to an oil-adhered metal surface such as a rust-preventive oil is impossible, ( 3) 180-2
If it does not gel at a high temperature of about 20 ° C, the adhesive strength will be low,
When using plastic parts and chemical fiber products on metal around them, there is a risk of deteriorating them.
It has disadvantages such as. Further, it is known that increasing the content of the carboxyl group in the vinyl chloride copolymer improves the adhesiveness.However, when the content of the carboxyl group is increased, foaming during molding becomes severe, As a result, there is a problem that the adhesive strength tends to fluctuate. As a vinyl chloride resin plastisol capable of gelling and bonding at a low temperature, for example, a composition containing a vinyl chloride homopolymer or copolymer, a plasticizer, an epoxy resin, an acid anhydride and a filler or an imide compound as required. It has been disclosed (JP-A-2-18442). However, although this plastisol is capable of gelling and bonding at a low temperature of about 100 to 120 ° C., it is not always satisfactory with respect to viscosity stability over time and adhesive strength, and it is difficult to adhere to an oil surface. Has the disadvantage of On the other hand, as an adhesive composition using a vinyl chloride copolymer, for example, (1)
Aqueous synthetic resin emulsion obtained by emulsion polymerization of vinyl chloride and a specific monomer (Japanese Patent Application Laid-Open No. 2-91141); (2) vinyl chloride-vinyl acetate-maleic acid copolymer in an organic solvent; A solution-type adhesive obtained by dissolving a high molecular weight polymer, an alicyclic saturated hydrocarbon resin and a thermoplastic acrylic resin (JP-A-62-212483), (3) vinyl chloride units, carboxylic acid vinyl ester units and carbon A solution type adhesive containing a copolymer having an average degree of polymerization of 100 to 900 comprising a phosphate ester unit having a carbon double bond (JP-A-63-112675), and (4) containing a phosphate group Solution-type adhesive composition containing a vinyl chloride copolymer, an ethylene-vinyl acetate copolymer, an adhesive resin and an organic solvent.
No. 91141). However, the aqueous synthetic resin emulsion of the above (1) is an aqueous emulsion used as a paint for the surface or inside of a metal can, a coating agent for an aluminum skin of a retort food container, and the like. It is different from plastisol used as a sealant or a paint on the surface of a metal plate, and is also different from (2) and (3) above.
Since the adhesives of (4) and (4) are of a solution type and contain an organic solvent, they have problems such as safety for human body, air pollution, fire and explosion, and the present invention which does not use an organic solvent. Plastisol. By the way, a steel plate, a steel part, a machine part, and the like are usually coated with rust-preventive oil in the distribution process for rust prevention. When processing these materials, such as in automobile manufacturing, when bonding with an adhesive material or when painting, conventional adhesive materials and paints do not work on metal surfaces (oil surface) coated with rust-preventive oil. Since the adhesive strength and the adhesiveness are reduced, it is necessary to previously clean the surface by a degreasing treatment.

[0003]

Under such circumstances, the present invention is capable of (a) adhering to the surface of a metal plate to which rust-preventive oil has adhered. (B) about 110 to 160 ° C. A solventless sealant that has the characteristics of being capable of gelling at low temperatures, (c) having high adhesive strength, (d) having excellent water resistance, and (e) having a long-term stability of sol viscosity. The purpose of the present invention is to provide an adhesive plastisol composition which is suitably used for coatings and chipping paints.

[0004]

The present inventors have made intensive studies to develop an adhesive plastisol composition having the above-mentioned excellent characteristics, and as a result, a specific vinyl chloride copolymer,
It has been found that a composition comprising a thiol group-containing compound, a divalent metal salt and a plasticizer can achieve the object, and based on this finding, the present invention has been completed. That is, the present invention relates to (A) a vinyl chloride unit and a general formula

[0005]

Embedded image

(R ¹ in the formula is an alkyl group having 1 to 8 carbon atoms) and a maleic acid monoalkyl ester unit in a weight ratio of 60:40 to 98: 2. An adhesive plastisol composition comprising a vinyl chloride copolymer, (B) a thiol group-containing compound, (C) a divalent metal salt, and (D) a plasticizer. Hereinafter, the present invention will be described in detail.

In the composition of the present invention, the vinyl chloride copolymer used as the component (A) is obtained by copolymerizing vinyl chloride and a monoalkyl maleate ester represented by the above general formula [1]. . At this time, other copolymerizable monomers can be used in combination as long as the object of the present invention is not impaired. In the monoalkyl maleate ester represented by the general formula [1], R ¹ in the formula [1] is an alkyl group having 1 to 8 carbon atoms. Monomethyl, monoethyl, monopropyl, monobutyl, monopentyl, monohexyl, monoheptyl, monooctyl, monocyclohexyl ester and the like may be used, and these may be used alone or in combination of two or more.

[0008] Further, other copolymerizable monomers used as desired include, for example, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, cinnamic acid, maleic anhydride, fumaric acid, itaconic acid, Unsaturated monocarboxylic acids such as itaconic anhydride, unsaturated dicarboxylic acids and their anhydrides, monoalkyl esters of fumaric acid, monoalkyl esters of unsaturated dicarboxylic acids such as monoalkyl esters of itaconic acid, methyl (meth) acrylate, Unsaturated monocarboxylic esters such as ethyl, propyl, butyl, octyl, cyclohexyl, and benzyl esters; dimethyl, maleic acid and fumaric acid, diethyl, dipropyl, dibutyl, dioctyl, dicyclohexyl,
Unsaturated dicarboxylic diesters such as dibenzyl ester; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; olefins such as ethylene, propylene, butene-1 and pentene-1; and aromatics such as styrene and α-methylstyrene. Monovinyl compounds, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl caproate and vinyl caprylate, and vinylidene chloride are also included. One of these monomers used as desired may be used alone, or two or more may be used in combination.

The method for producing the vinyl chloride copolymer of the component (A) is not particularly limited, and may be a method conventionally used for producing a vinyl chloride copolymer conventionally used in plastisols, for example, a fine suspension polymer. Synthetic methods, seeded emulsion polymerization methods, and the like can be used. The fine suspension polymerization method is a method in which an oil-soluble catalyst is used as a catalyst, the particle diameter of monomer oil droplets is adjusted beforehand by a homogenization treatment, and homogenous dispersion polymerization is performed. In such a fine suspension polymerization method, an oil-soluble radical initiator is used as a catalyst. Examples of the oil-soluble radical initiator include dibenzoyl peroxide and di-3,5,5-trimethylhexanoyl peroxide. , Diacyl peroxides such as dilauroyl peroxide, diisopropyl peroxydicarbonate,
Di-sec-butyl peroxydicarbonate, di-2
Organic peroxides such as peroxydicarbonates such as -ethylhexyl peroxydicarbonate, peroxyesters such as t-butylperoxypivalate and t-butylperoxyneodecanoate, or acetylcyclohexylsulfonyl peroxide and disuccinic acid peroxide; Further, azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, and 2,2′-azobisdimethylvaleronitrile are exemplified. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is appropriately selected depending on the type and amount of the monomer and the charging method. It is selected in the range of 0.001 to 5.0 parts by weight per 100 parts by weight.

In the fine suspension polymerization method, a surfactant is usually used. Examples of the surfactant include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate; alkyl aryl sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate; sodium dioctyl sulfosuccinate; and dihexyl sulfosuccinate. Sulfosuccinate salts such as sodium silicate, ammonium laurate, fatty acid salts such as potassium stearate, polyoxyethylene alkyl sulfate salts, anionic surfactants such as polyoxyethylene alkyl aryl sulfate salts, sorbitan monooleate, Sorbitan esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene alkyl ethers, Shi alkylphenyl ethers, nonionic surfactants such as polyoxyethylene alkyl esters, cetyl pyridinium chloride, and cationic surfactants such as cetyl trimethyl ammonium bromide and the like,
These may be used alone or in combination of two or more, and the amount of use is usually 0.05 to 5 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of the monomer used.
It is selected in the range of 4.0 parts by weight.

In this fine suspension polymerization method, first, in an aqueous medium, the oil-soluble catalyst, the monomer, the surfactant and, if desired, a polymerization aid such as a higher fatty acid or a higher alcohol. , And other additives, and homogenized by a homogenizer, and premixed to adjust the particle size of the oil droplets. Examples of the homogenizer include a colloid mill, a vibration stirrer, a two-stage high-pressure pump, high-pressure ejection from a nozzle or an orifice, and ultrasonic stirring. Furthermore, the adjustment of the particle size of oil droplets is affected by the control of shear force during homogenization, the stirring conditions during polymerization, the type of reactor, the amount of surfactants and additives, etc., but these are simple. By appropriate preliminary experiments, appropriate conditions can be selected.

Next, the premix liquid thus homogenized is sent to a polymerization vessel, and the temperature is increased while stirring slowly, and polymerization is usually performed at a temperature in the range of 30 to 80 ° C. In this manner, a latex in which vinyl chloride copolymer fine particles having a particle diameter of about 0.2 to 3 μm are uniformly dispersed is obtained. This latex is usually subjected to a known treatment such as salting out or spray drying, and the polymer is taken out as a solid. The molecular weight of the polymer is appropriately adjusted by a reaction temperature or a molecular weight regulator depending on the purpose.

On the other hand, in the seed emulsion polymerization method, an anionic surfactant or a nonionic surfactant is used as a nucleus with vinyl chloride resin particles previously prepared by ordinary emulsion polymerization or milk suspension polymerization, This is a method in which the particles undergo a polymerization polymerization reaction in a medium. The diameter of the core particles used at this time is usually in the range of 0.03 to 0.7 μm on average, and the amount used is generally selected in the range of 1 to 50 parts by weight per 100 parts by weight of the monomer used. .

Further, as the anionic surfactant,
Known compounds usually used for emulsion polymerization, such as alkyl benzene sulfonate, alkyl sulfonate, alkyl sulfate, fatty acid metal salt, polyoxyalkyl ether sulfate, polyoxyethylene carboxylate sulfate, polyoxyethylene sulfate Ethylene alkyl phenyl ether sulfate, dialkyl succinate sulfonate and the like may be mentioned, and these may be used alone or in combination of two or more.

Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether glycerin borate, Polyoxyethylene alkyl ether phosphate, such as polyoxyethylene, having a polyoxyethylene chain in the molecule, a compound having surface active ability and a polyoxyethylene chain of the compound is a copolymer of oxyethylene and oxypropylene. Substituted compounds, further, sorbitan fatty acid esters, fatty acid glycerin esters, glycerin fatty acid esters, pentaerythritol fatty acid esters, and the like. Stone, may be used in combination of two or more.

Regarding the amount of these surfactants used,
The anionic surfactant is selected in the range of 0.1 to 5 parts by weight, and the nonionic surfactant is generally selected in the range of 0 to 5 parts by weight, based on 100 parts by weight of the monomer usually used. In this seeded emulsion polymerization, a combination of a water-soluble reducing agent and an organic peroxide is used as a catalyst. As the water-soluble reducing agent, for example, a reducing agent used as a normal water-soluble radical redox polymerization catalyst component, for example, ethylenediaminetetraacetic acid or its sodium or potassium salt, or iron and copper, chromium, etc. Complex compounds with heavy metals, sulfinic acid or its sodium or potassium salt, l-ascorbic acid or its sodium, potassium, calcium salt, ferrous pyrophosphate, ferrous sulfate, ferrous ammonium sulfate, sodium sulfite And sodium acid sulfite, sodium formaldehyde sulfoxylate, reducing sugars, and the like. These may be used alone or in combination of two or more. The amount of these reducing agents to be used is generally selected in the range of 0.000001 to 5 parts by weight per 100 parts by weight of the monomer used.

On the other hand, the organic peroxides include, for example, cumene hydroperoxide, p-cymene hydroperoxide, t-butylisopropylbenzene hydroperoxide, diisopropylbenzene hydroperoxide,
Hydroperoxides such as menthane hydroperoxide, decalin hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide, isopropyl hydroperoxide and the like can be mentioned. These organic peroxides may be used singly or in combination of two or more.
It is selected in the range of 0.001 to 5 parts by weight per 0 parts by weight.

Next, a preferred example of the seed emulsion polymerization method will be described. First, an aqueous emulsion of vinyl chloride resin core particles is prepared, and then the water-soluble reducing agent and the monomer are charged into the emulsion, followed by heating. To a temperature of about 30 to 80 ° C. On the other hand, an aqueous emulsion of an organic peroxide and the aqueous solution of the surfactant are separately prepared using the surfactant, and these are prepared by containing the vinyl chloride resin core particles, the water-soluble reducing agent and the monomer. Aqueous emulsion, usually 3
The polymerization reaction is carried out by continuously charging while maintaining the temperature in the range of 0 to 80 ° C. In this seeded emulsion polymerization, a higher fatty acid, a higher alcohol, an inorganic salt, a water-soluble polymer compound or the like may be used in combination in order to promote the action of a surfactant or a polymerization catalyst to be used.

After completion of the polymerization reaction, the vinyl chloride copolymer is taken out as a solid from the emulsion containing the produced vinyl chloride copolymer particles in the same manner as in the case of the fine suspension polymerization method described above. The molecular weight of the copolymer is appropriately adjusted by a reaction temperature, a molecular weight regulator and the like according to the purpose. The vinyl chloride copolymer of the component (A) thus obtained contains vinyl chloride units and monoalkyl maleate units as essential units in a weight ratio of 60:40 to 98: 2. is necessary. With a vinyl chloride copolymer having a weight ratio outside the above range, the object of the present invention cannot be sufficiently achieved.

In the composition of the present invention, a thiol group-containing compound is used as the component (B). Examples of the thiol group-containing compound include an aliphatic thiol and an aromatic thiol represented by the general formula R ² -SH (2) (wherein R ² is an organic group), and a thiol group and a hydroxyl group. Examples thereof include a compound having a thiol group and another functional group such as a thiol group and an organometallic compound.

These thiol group-containing compounds may be used singly or in combination of two or more. The compounding amount thereof is determined according to the amount of the vinyl chloride copolymer 1 (A).
The amount of thiol groups is preferably 0.0
It is chosen to be 2 to 5.0 parts by weight. In the composition of the present invention, a divalent metal salt is used as the component (C). As the divalent metal salt, for example, zinc, lead,
Examples include carbonates, acetates, sulfates, and chlorides of divalent metals such as magnesium, calcium, and barium. The object of the present invention cannot be sufficiently achieved with a monovalent or trivalent metal salt.

When these metal salts are blended, the metal adhesion of plastisol generally deteriorates in the presence of water, whereas the composition of the present invention contains a thiol group-containing compound. Even if the metal salt is blended, the metal adhesion does not decrease and the water resistance is also excellent. One kind of the divalent metal salt may be used alone, or two or more kinds thereof may be used in combination. The amount of the divalent metal salt is usually 80 to 200 parts by weight per 100 parts by weight of the vinyl chloride copolymer (A). It is selected in the range of parts by weight.

In the composition of the present invention, the plasticizer used as the component (D) is not particularly limited, and those conventionally used as plasticizers for vinyl chloride resin plastisols, such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, Di- (2-ethylhexyl)
Phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, di (heptyl, nonyl, undecyl) phthalate, benzyl phthalate, butyl benzyl phthalate, dinonyl phthalate Phthalic acid derivatives such as dicyclohexyl phthalate, isophthalic acid derivatives such as dimethyl isophthalate, di- (2-ethylhexyl) isophthalate, diisooctyl isophthalate, di- (2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydro Phthalates, tetrahydrophthalic acid derivatives such as diisodecyltetrahydrophthalate, di-n-butyl adipate, di- (2-ethylhexyl) Adipic acid derivatives such as dipate, diisodecyl adipate, diisononyl adipate, azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctyl azelate, di-n-hexyl azelate, di-n-butyl sebacate, di- ( Sebacic acid derivatives such as 2-ethylhexyl) sebacate, di-n-butylmalate, dimethylmalate,
Maleic acid derivatives such as diethyl maleate and di- (2-ethylhexyl) malate; fumaric acid derivatives such as di-n-butyl fumarate and di- (2-ethylhexyl) fumarate; tri- (2-ethylhexyl) trimellitate; Trimellitic acid derivatives such as -n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-hexyl trimellitate, triisononyl trimellitate, tetra- (2-ethylhexyl) ) Pyromellitate, tetra-n
-Pyromellitic acid derivatives such as octyl pyromellitate, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-
Citric acid derivatives such as (2-ethylhexyl) citrate, itaconic acid derivatives such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate, butyl oleate, Oleic acid derivatives such as glyceryl monooleate and diethylene glycol monooleate, ricinoleic acid derivatives such as methyl acetyl ricinolate, butyl acetyl ricinolate, glyceryl monoricinolate and diethylene glycol monoricinolate, n-butyl stearate, glycerin monostearate and diethylene glycol Stearic acid derivatives such as distearate, diethylene glycol monolaurate, diethylene glycol diperargonate, pentaerythritol Other fatty acid derivatives such as lititol fatty acid ester, triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris Phosphoric acid derivatives such as (chloroethyl) phosphate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-
(2-ethyl butyrate), glycol derivatives such as triethylene glycol di- (2-ethylhexoate), dibutyl methylene bisthioglycolate, glycerin derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate, epoxy Soybean oil, epoxybutyl stearate, epoxy-2-diethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxytriglyceride, epoxidized octyl oleate, epoxy derivatives such as epoxidized decyl oleate, adipic acid-based polyester And polyester-based plasticizers such as sebacic acid-based polyester and phthalic acid-based polyester, or partially hydrogenated terphenyl, adhesive plasticizer and the like.

One of these plasticizers may be used,
You may use more than one kind in combination, and the compounding amount is
(A) Per 100 parts by weight of the vinyl chloride copolymer of the component,
Usually, it is selected in the range of 40 to 250 parts by weight. The composition of the present invention may contain other additives conventionally used in vinyl chloride resin plastisols as long as the object of the present invention is not impaired.

The plastisol composition of the present invention thus obtained has excellent adhesion to the surface of a metal plate to which rust-preventive oil has been applied. For example, JIS K-2246
Adhesion between the metal plates is possible without degreasing the metal plate to which the fingerprint removal type rust inhibitor oil, general rust inhibitor oil, vaporizable rust inhibitor oil, etc. specified in
Further, the paint using this plastisol can form a coating film having good adhesion on the surface of the metal plate without degreasing the metal plate. Furthermore, the plastisol composition of the present invention is capable of gel bonding even at a low temperature of about 110 to 160 ° C., does not foam during processing, has high adhesive strength, and has good viscosity stability over time, Moreover, it has excellent water resistance.

[0026]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, the performance of the plastisol composition was evaluated as follows. (1) Adhesive strength Steel plate SP manufactured by Nippon Test Panel Co., Ltd. coated with rust-preventive oil
Shirring CC-SD (0.8mm thick) and 10cm
A test piece having a size of 7 cm was degreased by washing with toluene, and a rust preventive oil “Antilast P-1400” [Kerosene fraction 76, manufactured by Nippon Oil Co., Ltd.]
Wt% or more, lubricating oil 10 wt% or less, antioxidant 14 wt% or less], the plastisol composition is applied thereto, and heated at 140 ° C. for 20 minutes in a hot-air circulation oven, then 25 ° C. After standing for 24 hours in a constant temperature / humidity room at a relative humidity of 60%, a descending speed of 50 mm was measured in the same room using a universal tensile and compression tester TCM-500 manufactured by Shinko Tsushin Kogyo Co., Ltd.
/ Min was determined as the tensile shear adhesive strength, and the normal adhesive strength was evaluated according to the following criteria. Further, the plastisol composition was applied and heated in the same manner as described above, and after 24 hours under constant temperature and humidity, immersed in 40 ° C. water and left for 7 days, and then again in a room at 25 ° C. and 60% relative humidity. After 24 hours, the tensile shear bond strength was determined in the same manner as above, and the water resistant bond strength was determined according to the following criteria. Criteria ×: tensile shear strength 15 kgf / cm ² or less △: tensile shear strength 25 kgf / cm ² or less ○: tensile shear strength 35 kgf / cm ² or less ◎: tensile shear strength 35 kgf / cm ² above atmospheric (2) storage stability of the sol After storing the plastisol composition in a hot air circulation oven at 40 ° C. for 7 days, return to 25 ° C., measure the viscosity, and determine the viscosity ratio R to the initial value.

[0027]

(Equation 1)

And evaluated according to the following criteria. Criteria ×: R is 10 or more Δ: R is 3 or more and less than 10 ：: R is 1.5 or more and less than 3 ：: R is less than 1.5

Example 1 100 parts by weight of a vinyl chloride copolymer (vinyl chloride unit / monomethyl maleate unit weight ratio 90/10, solution specific viscosity 0.463 according to JIS K-6721), thioglycolate methanol 0.1 weight part Parts (as -SH group), 150 parts by weight of sedimentable calcium carbonate and 100 parts by weight of diisononyl phthalate are homogeneously mixed using an Ishikawa stirring stirrer No. 18 (rotation speed: 37 rpm), and then the mixture is decompressed under reduced pressure. Defoaming treatment was carried out with a foaming machine (rotational speed 55 rpm, degree of vacuum 3-4 mmHg) to prepare an adhesive plastisol composition.
The adhesive strength of the plastisol composition, the storage stability of the sol, and the presence or absence of discoloration during processing were determined. Table 1 shows the results.

Examples 2 to 4 In Example 1, instead of thioglycolate methanol, a thiol group-containing compound 0.1 of the type shown in Table 1 was used.
The procedure was performed in the same manner as in Example 1 except that parts by weight (as the -SH group) were used. Table 1 shows the results.

Comparative Example 1 The procedure of Example 1 was repeated, except that thioglycolate methanol was not used.
Table 1 shows the results.

[0032]

[Table 1]

Examples 5 to 6 Example 1 was repeated except that divalent metal salts of the type shown in Table 2 were used in place of the precipitated calcium carbonate.
It carried out similarly to. Table 2 shows the results.

Comparative Examples 2 to 5 The same procedures as in Example 1 were carried out except that divalent metal salts of the type shown in Table 2 were used in place of the precipitated calcium carbonate and thioglycolate methanol was not used. It carried out similarly to. Table 2 shows the results.

[0035]

[Table 2]

Comparative Example 6 As a vinyl chloride copolymer, the average degree of polymerization was 440, 88.8% by weight of vinyl chloride units, 3.2% by weight of maleic acid units,
A plastisol composition was prepared in the same manner as in Example 1 except that the vinyl acetate unit was used in an amount of 8% by weight. Regarding the adhesive strength of this plastisol composition, both the normal-state adhesive strength and the water-resistant adhesive strength were evaluated as poor for both the degreased iron plate and the rust-preventive oil-coated iron plate.

[0037]

According to the present invention, excellent adhesion to the surface of a metal plate coated with a rust-preventive oil is achieved.
Gelling adhesion is possible even at a low temperature, and the adhesive strength is high, and it also has good viscosity stability over time and water resistance, and provides an adhesive plastisol composition that is suitably used for, for example, sealing agents and paints. Can be

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI (C08K 13/02 3:26 5:37) (56) References JP-A-62-45641 (JP, A) JP-A-4-142380 ( JP, A) JP-A-60-170647 (JP, A) JP-A-1-292621 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/06 C09D 127/06 C09J 127/06 C09K 3/10 C08K 3/10-3/26 C08K 5/37

Claims (1)

(57) [Claims] (A) A vinyl chloride unit and a general formula: (Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms).
A vinyl chloride copolymer containing a weight ratio of 60:40 to 98: 2, (B) a thiol group-containing compound, (C) a divalent metal salt, and (D) a plasticizer. An adhesive plastisol composition comprising: