JPH0586345A - Adhesive plastisol composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive plastisol composition which prevents reduction of the water-resistant bond strength of moldings surrounded by moisture in the air or immersed in hot water, and hence can be used, for example, as a sealant between metal plates or coating material for metal plate surfaces in the fabrication of automobiles or a solvent-free adhesive material suitable for glass fiber by using an oxazoline polymer as a water-resistant bond strength modifier. CONSTITUTION:The objective adhesive plastisol composition comprises 100 pts.wt. vinyl chloride resin, 30-200 pts.wt. plasticizer, 0-200 pts.wt. filler, 0.5-6 pts.wt. tackifier and 0.2-5 pts.wt. oxazoline polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel adhesive plastisol composition, and more particularly, to prevent a decrease in water-resistant adhesive strength of a molded article immersed in water in the air or hot water, for example, in automobile manufacturing. The present invention relates to a sealant between metal plates, a paint for the surface of metal plates, and a solvent-free adhesive plastisol suitable for glass fibers and the like.

[0002]

2. Description of the Related Art Vinyl chloride resin plastisol is a plasticizer containing fine vinyl chloride resin powder having a primary particle diameter of 0.2 to 3 μm together with a heat stabilizer, a filler, a pigment and other compounding agents. A resin composition that is mixed and dispersed, and is molded into a final molded product by a molding method such as cast molding, slush molding, rotational molding, spread coat molding such as knife coating or roll coating, or screen coating molding. Plastisols that have been processed, especially with adhesive properties,
For example, it is used as a sealant between metal plates at the time of manufacturing automobiles or as a paint on the surface of metal plates. As the performance required for such an adhesive vinyl chloride resin plastisol, for example, viscosity stability over time is good,
It is possible to perform gelling adhesion at low temperature and to have high adhesive strength. The plastisol includes, as a vinyl chloride resin, usually polyvinyl chloride or vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer and the like. Although a vinyl chloride copolymer is used, a method of adding an adhesion improver such as a polyamide or an isocyanate compound to the vinyl chloride resin has been often used in order to impart adhesive strength. However, a method of adding a polyamide or an isocyanate compound or a method of increasing the content of the carboxyl group in the vinyl chloride copolymer to improve the adhesiveness is the production of the adhesive plastisol or the molding using the adhesive plastisol. When a product is exposed to a place with high humidity or hot water, it easily absorbs or adsorbs moisture, which causes problems such as poor adhesion and severe foaming during molding. As a countermeasure against this, a method of adding an inorganic water-absorbing agent such as calcium oxide is generally used. However, since the physical properties are deteriorated in proportion to the addition amount, a sufficient addition amount cannot be used.

[0003]

Under these circumstances, the present invention has been made with the object of providing an adhesive plastisol composition having excellent water resistance and high adhesive strength.

[0004]

Means for Solving the Problems As a result of intensive studies to develop an adhesive plastisol composition having the above-mentioned preferable properties, the present inventors have found that a specific additive (compounding agent),
It was found that the object can be achieved by a composition containing a vinyl chloride resin, a plasticizer, a filler, and an adhesion imparting agent, and the present invention has been completed based on this finding.
That is, the present invention comprises 100 parts by weight of vinyl chloride resin, 30 to 200 parts by weight of a plasticizer, 0 to 200 parts by weight of a filler, 0.5 to 6 parts by weight of an adhesive imparting agent, and 0.5 part of an oxazoline polymer.
An adhesive plastisol composition comprising 2 to 5 parts by weight is provided. The vinyl chloride resin used in the composition of the present invention is, for example, a vinyl chloride homopolymer or a copolymer mainly containing vinyl chloride units. Examples of the monomer that is copolymerized with vinyl chloride of the copolymerized vinyl chloride resin that can be used in the composition of the present invention include acrylic acid, methacrylic acid,
Unsaturated monocarboxylic acids such as ethacrylic acid, maleic acid, cinnamic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride, unsaturated dicarboxylic acids and their acid anhydrides, fumaric acid monoalkyl esters, itaconic acid mono Unsaturated dicarboxylic acid monoalkyl ester such as alkyl ester, methyl (meth) acrylic acid, ethyl,
Unsaturated monocarboxylic acid esters such as propyl, butyl, octyl, cyclohexyl and benzyl esters, unsaturated dicarboxylic diesters such as dimethyl, diethyl, dipropyl, dibutyl, dioctyl, dicyclohexyl and dibenzyl esters of maleic acid and fumaric acid, methyl Vinyl ethers such as vinyl ether, ethyl vinyl ether and propyl vinyl ether; olefins such as ethylene, propylene, butene-1 and pentene-1; aromatic monovinyl compounds such as styrene and α-methylstyrene; and cyanation such as acrylonitrile and methacrylonitrile. Examples thereof include vinyl compounds, vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl caproate, and vinyl caprylate, and vinylidene chloride. These copolymerizable monomers may be used alone or in combination of two or more.

The vinyl chloride resin used in the composition of the present invention is
There is no particular limitation, and a method conventionally used for producing a vinyl chloride copolymer conventionally used in plastisols, for example, one produced by a fine suspension polymerization method or a seed emulsion polymerization method can be used. In particular, in the fine suspension polymerization method, an oil-soluble catalyst is used as a catalyst, and the particle diameter of the monomer oil droplets is preliminarily adjusted by a homogenization treatment before the initiation of polymerization, and a method of homogeneous dispersion polymerization is used for the present invention. It is suitable for the production of vinyl resins. In such a fine suspension polymerization method,
An oil-soluble radical initiator is used as a catalyst, and examples of the oil-soluble radical initiator include dibenzoyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide and other diacyl peroxides, diisopropyl peroxide. Peroxydicarbonate, di-sec-butyl peroxydicarbonate,
Peroxydicarbonates such as di-2-ethylhexyl peroxydicarbonate, peroxyesters such as t-butylperoxypivalate and t-butylperoxyneodecanoate, or organic peroxides such as acetylcyclohexylsulfonyl peroxide and disuccinic acid peroxide. Oxides, and even 2,2'-
Azobisisobutyronitrile, 2,2'-azobis-2-
Examples thereof include azo compounds such as methylbutyronitrile and 2,2′-azobisdimethylvaleronitrile. These catalysts may be used alone or in combination of two or more, and the use amount thereof is appropriately selected depending on the type, amount and charging system of the monomer, but usually used monomer 1
It is selected in the range of 0.001 to 5.0 parts by weight per 100 parts by weight.

Further, in the fine suspension polymerization method used for producing the vinyl chloride resin for use in the present invention, a surfactant is usually used. Examples of the surfactant include alkyl sulfate ester salts such as sodium lauryl sulfate ester and sodium myristyl sulfate ester, alkylarylsulfonate salts such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, dihexylsulfosuccinate. Sulfosuccinate salts such as sodium acid salt, ammonium laurate, fatty acid salts such as potassium stearate, polyoxyethylene alkyl sulfate ester salts, anionic surfactants such as polyoxyethylene alkylaryl sulfate ester salts, sorbitan monooleate, Sorbitan esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene alkyl ethers, polio Examples include nonionic surfactants such as cyethylene alkylphenyl ethers and polyoxyethylene alkyl esters, cationic surfactants such as cetylpyridinium chloride and cetyltrimethylammonium bromide, and these may be used alone. However, two or more kinds may be used in combination,
The amount used is usually 100 parts by weight of the monomer used,
It is selected in the range of 0.05 to 5 parts by weight, preferably 0.2 to 4.0 parts by weight.

In this fine suspension polymerization method, first, in a water-based medium, the oil-soluble catalyst, the monomer, the surfactant, and a polymerization aid such as higher fatty acids and higher alcohols, which are optionally used, are added. , Other additives are added, premixed, and homogenized by a homogenizer to adjust the particle size of oil droplets. Examples of the homogenizer include a colloid mill, a vibration stirrer, a two-stage high pressure pump, a high pressure jet from a nozzle or an orifice, and ultrasonic stirring. In addition, controlling the particle size of oil droplets is affected by controlling the shearing force during homogenization, stirring conditions during polymerization, type of reactor, amount of surfactants and additives, etc. Suitable conditions can be selected by various preliminary experiments. Next, the liquid thus homogenized is sent to a polymerization vessel and heated slowly with stirring, usually at 30-
The polymerization is carried out at a temperature in the range of 80 ° C.

Thus, a latex in which fine particles of vinyl chloride copolymer having a particle diameter of about 0.2 to 3 μm are uniformly dispersed can be 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 the reaction temperature and the molecular weight modifier according to the purpose. On the other hand, the seeded emulsion polymerization method used for the vinyl chloride resin for the present invention is based on vinyl chloride resin particles prepared in advance by usual emulsion polymerization or fine suspension polymerization as an anionic surfactant or a nonionic surfactant with it. It is a method of causing a particle enlargement polymerization reaction in an aqueous medium using an agent. The diameter of the core particles used in this case is usually in the range of 0.03 to 0.7 μm on average, and the amount used is usually 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 generally used in emulsion polymerization, for example, alkyl aryl sulfonates, alkyl sulfonates, alkyl sulfate ester salts, fatty acid salts, polyoxyethylene alkyl ether sulfate ester salts, polyoxyethylene carboxylic acid ester sulfate ester salts, poly Examples thereof include oxyethylene alkylaryl ether sulfuric acid ester salts and sulfosuccinic acid ester salts. 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 ester, polyoxyethylene. A compound having a polyoxyethylene chain in the molecule, such as an alkyl ether phosphate, polyoxyethylene, etc., and having surface-active ability, and the polyoxyethylene chain of the compound is replaced with a copolymer of oxyethylene and oxypropylene. Compounds, sorbitan fatty acid ester, fatty acid glycerin ester, glycerin fatty acid ester, pentaerythritol fatty acid ester, etc.
One kind may be used, or two or more kinds may be used in combination.

Regarding the amount of these surfactants used,
The anionic surfactant is usually selected in the range of 0.1 to 5 parts by weight, and the nonionic surfactant is usually selected in the range of 0 to 5 parts by weight, per 100 parts by weight of the monomer used. In this seed emulsion polymerization, a water-soluble radical initiator such as potassium persulfate or ammonium persulfate, or a combination of a water-soluble reducing agent and an organic peroxide is used as a catalyst. The amount of the water-soluble radical initiator used is usually selected in the range of 0.005 to 1 part by weight per 100 parts by weight of the monomer used. Examples of the water-soluble reducing agent include reducing agents used as water-soluble ordinary radical redox polymerization catalyst components, such as ethylenediaminetetraacetic acid or its sodium salt or potassium salt, or iron, copper, chromium, etc. Complex compound with heavy metal, sulfinic acid or sodium salt or potassium salt thereof, l-ascorbic acid or sodium salt thereof, potassium salt, calcium salt, ferrous pyrophosphate, ferrous sulfate, ammonium ferrous sulfate, sodium sulfite , Acidic sodium sulfite, sodium formaldehyde sulfoxylate, reducing sugars, and the like, and these may be used alone or in combination of two or more. The amount of these reducing agents used is usually 0.00 per 100 parts by weight of the monomers used.
It is selected in the range of 001 to 5 parts by weight.

On the other hand, examples of the organic peroxides include cumene hydroperoxide, p-cymene hydroperoxide, t-butyl isopropylbenzene hydroperoxide, diisopropylbenzene hydroperoxide, p-.
Mentioned are hydroperoxides such as menthane hydroperoxide, decalin hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide and isopropyl hydroperoxide. These organic peroxides may be used alone or in combination of two or more kinds, and the amount thereof is usually 10
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 seeded 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 and heated. And maintain the temperature at about 30 to 80 ° C. On the other hand, an aqueous emulsion of an organic peroxide and a surfactant aqueous solution are separately prepared by using the surfactant, and these are added with the vinyl chloride resin core particles, the water-soluble reducing agent and the monomer. 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, higher fatty acids, higher alcohols, inorganic salts, water-soluble polymer compounds and the like may be used in combination in order to promote the action of the surfactant and the polymerization catalyst used. After the 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 above-mentioned fine suspension polymerization method. The molecular weight of the copolymer is appropriately adjusted by the reaction temperature, the molecular weight modifier, etc. depending on the purpose.

The adhesion promoter used in the composition of the present invention is, for example, an acrylate, an isocyanurate or a polyamide amine. As acrylate, the number of functional groups is 1 to 4
, Monoester, diester, triester, or tetraester can be used, and urethane-modified urethane acrylate can also be used. As the isocyanurate, one that is trimerized with tolylene diisocyanate and whose isocyanate group is blocked with alkylphenol or the like can be used. Further, as the polyamide amine, a polyamide having a total amine value of 90 to 760 and the polyamide amine such as alicyclic amine-modified or NBR-modified and the amidoamine-based one having an active hydrogen equivalent of 60 to 110 can also be used. The addition amount of the adhesion promoter in the composition of the present invention is 10% by weight of vinyl chloride resin.
It is 0.5 to 6 parts by weight per 0 parts by weight. If the amount is less than 0.5 parts by weight, the adhesive strength will be small, and if the amount is more than 6 parts by weight, the coloring will be strong and the appearance will be deteriorated.

The plasticizer used in the composition of the present invention 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, butylbenzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate and other phthalic acid derivatives, dimethyl isophthalate, di- ( 2-Ethylhexyl) isophthalate, isophthalic acid derivatives such as diisooctyl isophthalate, di- (2-ethylhexyl)
Tetrahydrophthalate, di-n-octyltetrahydrophthalate, tetrahydrophthalic acid derivative such as diisodecyltetrahydrophthalate, di-n-butyl adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate, adipic acid derivative such as diisononyl adipate, di- Azelaic acid derivatives such as (2-ethylhexyl) azelate, diisooctyl azelate and di-n-hexyl azelate, sebacic acid derivatives such as di-n-butyl sebacate and di- (2-ethylhexyl) sebacate, di-n- Butyl maleate, dimethyl maleate, diethyl maleate, di- (2-ethylhexyl) maleate and other maleic acid derivatives, di-n-butyl fumarate, di- (2-ethylhexyl) fumarate and other fumaric acid derivatives, -(2-Ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-hexyl trimellitate, triisononyl trimellitate, etc. Acid derivative,
Pyromellitic acid derivatives such as tetra- (2-ethylhexyl) pyromellitate and tetra-n-octylpyromellitate, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri- (2-ethylhexyl) citrate Itaconic acid derivatives such as citric acid derivatives, monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate, butyl oleate, glyceryl monooleate, diethylene glycol mono Oleate and other oleic acid derivatives, methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, diethylene glycol monoricinoleate and other ricinoleic acid derivatives , Stearic acid derivatives such as n-butyl stearate, glycerin monostearate, diethylene glycol distearate, other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester, triethyl phosphate, tributyl phosphate, tributyl phosphate. Phosphoric acid derivatives such as-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate, diethylene glycol dibenzoate, dipropylene glycol Dibenzoate, triethylene glycol dibenzoate, triethylene glycol Ruji -
(2-ethyl butyrate), triethylene glycol di- (2-ethylhexoate), glycol derivative such as dibutylmethylene bisthioglycolate, glycerol monoacetate, glycerol triacetate, glycerol derivative such as glycerol tributyrate, epoxy Soybean oil, Epoxy butyl stearate, Epoxy hexahydrophthalate di-2-ethylhexyl, Epoxy hexahydrophthalate diisodecyl, Epoxy triglyceride, Epoxidized octyl oleate, Epoxidized decyl oleate and other epoxy derivatives, Adipic acid polyester , Polyester plasticizers such as sebacic acid polyesters and phthalic acid polyesters, partially hydrogenated terphenyls, adhesive plasticizers, and the like.

One of these plasticizers may be used, or 2
One or more species may be used in combination, and the blending amount is usually selected in the range of 30 to 200 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount is less than 30 parts by weight, the elongation of the film is small but becomes brittle, and if the amount is more than 200 parts by weight, the tensile strength becomes small. Fillers optionally used in the composition of the present invention include, for example, precipitated calcium carbonate, ground calcium carbonate, calcium carbonate such as ultrafine calcium carbonate, magnesium carbonate, silica, talc, diatomaceous earth, clay,
Any of silicates such as mica and alumina can be used. Vinyl chloride resin 10 parts
It is 0 to 200 parts by weight per 0 parts by weight. If it is more than 200 parts by weight, the physical properties of the coating film, such as strength and elongation, will be significantly deteriorated. The oxazoline polymer used in the composition of the present invention has the following general structural formula:

[0016]

[Chemical 1]

What is used is as follows. As R in this formula,
A hydrogen atom or an alkyl group having 10 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group can be used. The function of the oxazoline polymer is important in the present invention. Oxazoline polymers are compatible with both vinyl chloride resin and plasticizers, and can also dissolve water, so water is dispersed and adsorbed throughout the system during film formation, separating water from the adhesive surface and adhering water. It can be presumed that the effect of causing defects or peeling is prevented. The amount of the oxazoline polymer used is 0.2 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin. 0.2
If it is less than 5 parts by weight, the water resistance of the coating film will decrease, and if it is more than 5 parts by weight, the elongation and tensile strength of the coating film will decrease. The composition of the present invention may contain other additive components conventionally used in vinyl chloride resin plastisols, within a range that does not impair the object of the present invention. It is also effective to add a highly water-absorbent resin such as a starch-acrylic acid graft copolymer or a sodium polyacrylate cross-linked polymer. The plastisol composition of the present invention thus obtained has a water resistance and an excellent adhesive strength in which the adhesion failure due to water and the foaming during molding are largely suppressed.

[0018]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 5 and Comparative Examples 1 to 4 The vinyl chloride resins used in Examples 1 to 5 and Comparative Examples 1 to 4 have a vinyl chloride unit / vinyl acetate unit weight ratio of 94/6 and a polymerization degree determined from a solution specific viscosity. 100 parts by weight of 1600 were used. Further, as a plasticizer, 100 parts by weight of diisononyl phthalate, and as a filler, precipitated calcium carbonate 15
0 parts by weight, 3 parts by weight of isocyanurate and 3 parts by weight of polyamide amine were used as adhesion promoters. The water resistant adhesion improver shown in Table 1 was blended in the compounded composition in the indicated amounts for each of Examples and Comparative Examples. This mixing operation was carried out using an Ishikawa stirrer machine No. 18 (rotation speed 37 rpm) for uniform mixing. After that, decompressing and stirring defoaming machine (rotation speed 55rp
m, decompression degree 3 to 4 mmHg) to perform defoaming treatment to prepare the adhesive plastisol composition of each Example and Comparative Example. The adhesive strength of each plastisol composition, the adhesive strength after immersion in 45 ° C. warm water, and the presence or absence of foaming during processing were observed. The results are shown in Table 1. The adhesive strength was evaluated as follows.

(1) Adhesive Strength A plastisol composition was applied onto a degreased 1 mm thick zinc iron plate, heated in a hot air circulation oven at 140 ° C. for 20 minutes, and allowed to stand at room temperature for one day. Was evaluated and evaluated according to the following criteria. ×: The tensile shear strength is less than 15kgf / cm ² △: tensile shear strength is less than 15 kgf / cm ² or more 25kgf / cm ² ○: tensile shear strength of 25 kgf / cm ² or more 35 kgf / cm less than ² ◎: Tensile shear Strength of 35kgf / cm ² or more

The zinc iron plate coated with the plastisol composition was heated in the same manner as above at 140 ° C. for 20 minutes in a hot air circulation type oven, and then immersed in water at 45 ° C. for 10 minutes.
Six hours after being taken out after being left for one day, the tensile shear adhesive strength was determined, and the water resistant adhesive strength was determined according to the following criteria. Criteria x: Tensile shear strength reduction rate 50% or more △: Tensile shear strength reduction rate 30 to 49% ○: Tensile shear strength reduction rate 10 to 29% ◎: Tensile shear strength reduction rate 9% or less Reduction rate What is

[0021]

[Equation 1]

The one obtained in.

[0023]

[Table 1]

[0024]

The adhesive plastisol composition of the present invention comprises:
By using an oxazoline polymer as a water resistant adhesion improver, it is possible to prevent a decrease in water resistant adhesive strength of molded products immersed in water in the air or warm water, for example, a sealant between metal plates or a metal plate surface during automobile manufacturing There is an advantage that it can be used as a solventless adhesive material suitable for paints and glass fibers.

Claims (1)

[Claims] 1. A vinyl chloride resin 100 parts by weight, a plasticizer 3
0-200 parts by weight, filler 0-200 parts by weight, adhesion-imparting agent 0.5-6 parts by weight and oxazolin polymer 0.2-5
An adhesive plastisol composition consisting of parts by weight.