JPH04136023A - Plastisol composition - Google Patents

Abstract

PURPOSE:To prepare a plastisol free from discoloration during heating and having an excellent adhesion to glass, metal, etc., and little change in viscosity with time by compounding a paste PVC resin contg. epoxy groups, an epoxy resin, and polyethyleneimine. CONSTITUTION:An adhesive plastisol is prepd. by compounding 100 pts.wt. paste PVC resin contg. epoxy groups (having an epoxy group content of 0.1-10wt.% and a degree of polymn. of 600-3000), 1-40 pts.wt. epoxy resin (pref. a liq. epoxy resin having a viscosity at 25 deg.C of 20000 P or lower, pref. 5000 P or lower), and polyethyleneimine (having an average mol.wt. of 200-50000).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a plastisol that has excellent adhesiveness to metals and/or glass.

[Conventional technology]

Conventionally, plastisol has been used to form rust-preventive coatings on metals, and to bond and seal glass, metals, and other materials, and various efforts have been made to provide adhesive properties. For example, for vinyl chloride steel sheets, a method is used in which the surface of the steel sheet is treated with an acrylic primer in advance, then plastisol is applied and heat-formed, and the pre-coated metal is used as a building material or as an exterior material for electrical products. The grips of tools and metal hangers are similarly treated with primer to activate the metal surface, and then coated with plastisol to ensure a perfect bond with the metal.

As an example of bonding metal and other materials, plastisol is used to bond a paper filter to the metal case of an oil filter. In this case plastisol mixed with an adhesion promoter is used. For example, plastisol (or gel) mainly made of polyvinyl chloride is used in automobile sealants and floor coating materials.

In this case, an adhesion promoter such as a polyamide resin or blocked isocyanate is added to the plastisol to impart adhesive properties. As an example of adhesion to glass, gaskets such as polyvinyl chloride are attached to the periphery of automobile window glass or architectural window glass for decoration or sealing purposes, but in this case, the glass surface is The gasket is melt-bonded after being treated with a silane coupling agent or urethane.

In this way, the common methods for adhering metals, glass, etc. and polyvinyl chloride compositions are to apply a primer treatment to the surface of the base material or to add an adhesion promoter to plastisol to impart adhesion. It is being

However, the primer treatment method requires a process of applying the primer to the surface of the adherend in advance and heating it to vaporize or activate the solvent, which requires special equipment and processes such as a heating furnace, which increases costs. It becomes a factor. In the method of mixing an tackifier into plastisol, since the tackifier is usually a reactive substance, a reaction occurs during storage of the plastisol, resulting in a rapid increase in viscosity or solidification. Also,
When plastisol is heated and molded, there are problems such as discoloration and decomposition.

[Problem to be solved by the invention]

The purpose of the present invention is to have high adhesive strength to glass, metal, etc.
To provide a plastisol that does not discolor when heated and has good viscosity stability over time.

[Means for Solving the Problems] Thus, according to the present invention, the epoxy group content is 0.1 to
Vinyl chloride resin for paste processing, epoxy resin in the range of 10% by weight and average molecular weight of 200 to 50,000
An adhesive plastisol is provided, characterized in that it contains polyethyleneimine.

The epoxy group-containing vinyl chloride resin used in the present invention includes 1) a copolymer mainly consisting of a vinyl chloride unit, a monomer unit having an epoxy group, and an optional monomer unit copolymerizable with these; and 2) a polymer mainly composed of vinyl chloride units to which epoxy groups are added can be used.

As these epoxy group-containing vinyl chloride resins, resins consisting of vinyl chloride units alone or copolymers whose main constituent units are vinyl chloride units and monomers copolymerizable with vinyl chloride are used. be able to.

The epoxy group-containing vinyl chloride resin used in the present invention may optionally contain fatty acid vinyls such as vinyl acetate and vinyl propionate, olefins such as ethylene and propylene, vinylidene chloride, vinylidene fluoride, etc. Monomer units such as vinylidene halides, vinyl ethers such as isobutyl vinyl ether, methyl vinyl ether, and ethyl vinyl ether, and allyl compounds such as allyl chloride and methyl allyl ether can be used.

The monomer units of these desired components can be added to the reaction system in an amount of 10% by weight or less in the epoxy-containing vinyl chloride resin.

1) of the epoxy group-containing vinyl chloride resin used in the present invention
Examples of monomers having an epoxy group used in the vinyl chloride resin include glycidyl ethers of unsaturated alcohols such as acryl glycidyl ether and methallyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, glycidyl-p-vinyl benzoate,
Glycidyl esters of unsaturated acids such as methylglycidyl itaconate, glycidyl ethyl maleate, glycidyl vinyl sulfonate, glycidyl (meth)allylsulfonate, butadiene monoxide, vinylcyclohexene monooxide, 2-methyl-5,6-epoxyhexene Epoxide olefins such as, etc. can be used.

Next, 2) of the epoxy group-containing vinyl chloride resin of the present invention
Examples of the method for adding an epoxy group include a method in which vinyl chloride resin is dehydrochlorinated by heat treatment or contact with an alkali compound, and then epoxidized with an organic peracid or the like.

It is desirable that the epoxy group-containing vinyl chloride resin used in the present invention be produced by emulsion polymerization or microsuspension polymerization, which is suitable for producing vinyl chloride resins for paste processing, since this increases the fluidity of plastisol.

The degree of polymerization of the epoxy group-containing vinyl chloride resin used in the present invention is preferably 600 to 3,000.

If the degree of polymerization is less than 600, the mechanical strength will decrease, and if it is greater than 3000, there will be a drawback that a large amount of heat will be required in the molding process.

Further, the epoxy group content of the epoxy group-containing vinyl chloride resin used in the present invention can be from 0.05 to 5% by weight.

On the other hand, the epoxy resin used in the present invention has a viscosity of 20.0OOps at 25°C from the viewpoint of miscibility with plastisol.
The following liquid epoxy resins are preferred, and further
000 ps or less is more preferable.

- For boat fishing, bisphenol A type liquid epoxy resin, novolac type liquid epoxy resin, polyglycol type liquid epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin,
Tetrafunctional epoxy resins having a tertiary amino nitrogen atom, urethane-modified epoxy resins, nitrile rubber-modified epoxy resins, and the like can be suitably used. Furthermore, aliphatic epoxy resins can also be used.

The epoxy resin used in the present invention can be used in an amount of 1 to 40 parts by weight per 100 parts by weight of the epoxy group-containing vinyl chloride resin.

If the amount of epoxy resin used is less than 1 part by weight, the adhesive strength will be reduced, and if it exceeds 40 parts by weight, the mechanical strength will be reduced.

Further, the epoxy group content in the plastisol at this time is preferably about 0.1 to 10% by weight.

The polyethyleneimine used in the present invention has an average molecular weight of 2
00 to 50,000 is used. If the molecular weight deviates from this range, excellent effects cannot be obtained due to changes in reactivity, compatibility, etc.

The polyethyleneimine is preferably a polymer of ethyleneimine, but may partially contain any homologous polyalkyleneimine consisting of an alkylene unit having 4 or less carbon atoms. Further, the polyethyleneimine may be partially modified by saponifying N-acylalkyleneimine or the like.

Polyethyleneimine is affected by the presence or absence of branching, degree, and molecular weight distribution, but the average molecular weight has a large effect.

Depending on the formulation of the plastisol, plasticizers, stabilizers, ultraviolet absorbers, antioxidants, lubricants, fillers, colorants, etc. may be mixed with the epoxy group-containing vinyl chloride resin used in the present invention. can.

Furthermore, resins compatible with vinyl chloride, such as vinyl chloride resins and acrylic resins, can be blended.

As the plasticizer to be added to the plastisol used in the present invention, those generally referred to as plasticizers for polyvinyl chloride can be widely used. For example, fatty acid ester plasticizers such as dioctyl adipate, butyl diglycol adivate, dioctyl azelate, dibutyl sebacate, diisodecyl adipate, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, butyl benzyl phthalate, dilauryl phthalate, dioctyl phthalate, etc. Phthalate plasticizers, phosphoric acid plasticizers such as tricylenyl phosphate, tricresyl phosphate, talesyl diphenyl phosphate, trischloroethyl phosphate, tributyl phosphate, trischloroethyl phosphite, epoxidized soybean oil, epoxy fatty acids Epoxy derivatives such as monoesters as well as polyester plasticizers can be used.

The blending amount of plasticizer is 1:1 for epoxy group-containing vinyl chloride resin
00 parts by weight, 20 to 80 parts by weight is suitable. Too much plasticizer will reduce the adhesive strength of the film to the glass surface, while too little will make it too hard.

The thermal stabilizer optionally used in the present invention may be any commonly used stabilizer, including Ba-Zn
system, Ca-Zn system, Ca-Ba-Zn system, Cd-Ba-
In addition to metal soaps such as Zn-based and PB-based, alkylated tin compounds of fatty acids such as butyltin laurate, butyltin maleate, and octyltin maleate, and bis(isooctylthioglycolic acid ester) salts of di-normal octyltin. Alkyltin-containing sulfur compounds can be suitably used. A stabilizing agent such as a chelator or epoxidized soybean oil can also be used in combination with these.

Also, nitrilotripropionic acid tributylamide, 2
, 3-dichloroaniline, and epoxy stabilizers can also be used in combination.

As the ultraviolet absorber optionally used in the present invention, hensitriazoles are excellent, such as 2(2'-hydroxy-5'-methylphenyl)hensitriazole, 2
(2'-hydroxy-37-tert-butyl-5'
-methylphenyl)5-chlorohencitriazole, 2
(2'-hydroxy-3', 5'-tertiary-
butylphenyl)-5-chloro-benzotriazole,
2(2'-1=droxy-4'-octoxyphenyl)benzotriazole, hindered amine light stabilizers, and the like can be suitably used.

As the antioxidant optionally used in the present invention, phenolic antioxidants are excellent, such as 2,6-ditertiary-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tertiary-butylphenol) )
, 4.4'-butylidenebis(3-methyl-6-tert-butylphenol), 4.4'-thiobis(3
-methyl-6-tert-butylphenol), etc. can be used.

Furthermore, if necessary, crosslinking agents, thickeners, diluents, colorants,
Fillers such as calcium carbonate, clay, and talc, coupling agents such as titanate, and the like can be optionally blended.

The plastisol used in the present invention can be prepared by mixing and defoaming resins, plasticizers, various compounded materials, etc. in accordance with conventional methods.

In this preparation, since plastisol is in liquid form, dust and foreign matter can be removed using filters, and storage and transportation can be handled in closed systems such as tanks and pipelines, making quality control easy and automated. Also suitable for

(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in Examples, Comparative Examples, and Reference Side are based on weight unless otherwise specified.

The raw materials shown in Table 1 were placed in a vacuum high speed defoaming machine, mixed and defoamed to obtain plastisol. 15 On+m of this plastisol
x 50mm, thickness 31 glass plate and 150mm x 50
a+m, coating thickness 3mm each on 0.2mm thick steel plate
The coating was applied so that the coating width was 15 nuw, and heated for 10 minutes at the temperature shown in Table 1 using a hot air circulation open system.

One end of each of these samples was peeled off for about 15 seconds+m, held in a chuck, and peeled off at a 90'' angle at a speed of 50 mm/min to measure the adhesive strength.

(2) Adhesiveness is displayed in three levels: (adhesive), △ (3 to less than IO), and × (10 or more).

The evaluation results are shown in Table 1. From Table 1, according to the present invention, a plastisol with high adhesive strength can be proposed.

Furthermore, compared to conventional methods, there is no significant thermal discoloration and the viscosity stability of the plastisol is also good.

■ Heating discoloration Visually observe the sample after heating to determine the degree of coloration.
Evaluate in two stages: (little) and × (many).

■ Viscosity stability

Claims (1)

[Claims] An adhesive plastisol comprising a vinyl chloride resin for paste processing, an epoxy resin, and a polyethyleneimine having an average molecular weight of 200 to 50,000, with an epoxy group content in the range of 0.1 to 10% by weight.