JPS62164779A - Adhesive resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition which provides excellent adhesion between a vinyl chloride resin and a base material, and has excellent flame retardancy, by mixing a vinyl chloride-unsaturated polybasic carboxylate copolymer and a plasticizer. CONSTITUTION:A vinyl chloride-unsaturated polybasic carboxylate copolymer (A) is obtained by the suspension polymerization, in an aqueous medium, of 98-60wt% vinyl chloride and 2-40wt% unsaturated polybasic carboxylate obtained by reacting 1mol of an unsaturated polybasic carboxylic acid or its anhydride (e.g., maleic anhydride) with 1-2mol of a 5-15C alcohol (e.g., n- amylalcohol) at 50-150 deg.C. Then, 100pts.wt. component A is mixed with 10-100 pts.wt. plasticizer (B) (e.g., dibutyl phthalate) and, if necessary, a pigment, a heat stabilizer, a light stabilizer, a polymer modifier, etc.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to an adhesive resin composition.

[Conventional technology]

PVC resin has many excellent properties such as toughness and transparency, and by using plasticizers such as phthalate esters, it has a wide range of properties from highly rigid hard products to flexible soft products. Therefore, it is used in an extremely wide range of applications such as films, sheets, and molded products.

However, while vinyl chloride resin has excellent time running properties as described above, it is not compatible with other base materials.

For example, it has the disadvantage of extremely poor adhesion to synthetic resins, metals, wood, etc. Various attempts have been made to improve this adhesiveness. for example.

■ For acrylic adhesives, a known adhesive such as epoxy adhesive is applied. ■ For ethylene-vinyl acetate copolymer, polyethylene is modified by graft polymerization with unsaturated carboxylic acid or its anhydride. A method of using things as adhesives.

etc. have been proposed.

[Problem that the invention seeks to solve]

However, method (2) above requires complicated steps such as coating and drying, is complicated to operate, and has the problem of deteriorating the working environment due to the use of organic solvents. In addition, both methods (1) and (2) above use flammable adhesives, and there are problems in using them for flame retardant purposes.

[Means for solving problems]

In view of the above-mentioned prior art, the present inventors conducted intensive studies to develop a flame-retardant adhesive that can sufficiently bond a vinyl chloride resin and a base material. The present invention was completed by discovering that an adhesive having excellent adhesive properties can be obtained by blending a plasticizer in a proportional amount with a copolymer with a vinyl chloride monomer.

That is, the gist of the present invention is that 100 parts by weight of a vinyl chloride-unsaturated polycarboxylic acid ester copolymer containing 2 i% or more of an unsaturated polycarboxylic acid ester and 70 to 10 parts by weight of a plasticizer.
0 parts by weight of the adhesive resin composition.

The present invention will be explained in detail below.

The vinyl chloride-unsaturated polycarboxylic acid ester copolymer used in the present invention is a copolymer of vinyl chloride monomer and unsaturated polycarboxylic acid ester. Heavy J! It is a vinyl chloride-unsaturated polycarboxylic acid ester copolymer containing i% or more.

The unsaturated polycarboxylic acid ester, which is a copolymerization component, is an ester of an unsaturated polycarboxylic acid and an alcohol. The unsaturated polycarboxylic acid is a compound having at least two carboxyl groups and at least one olefinic double bond, and examples thereof include maleic acid, fumaric acid, citraconic acid, and itaconic acid. The above-mentioned alcohol usually has one or more carbon atoms, preferably one or more carbon atoms! ~
/! Examples include n-amyl alcohol, inamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, innonyl alcohol, lauryl alcohol, tridecyl alcohol, and the like.

The above-mentioned unsaturated polycarboxylic acid ester usually contains 1, for example, the above-mentioned unsaturated polycarboxylic acid or its anhydride and the above-mentioned alcohol! θ℃ or higher, preferably! It is manufactured by carrying out an esterification reaction at a temperature range of 0 to iro°C. For example, when using maleic anhydride as the unsaturated polyhydric carboxylic acid, i.
, added in the range of -2 mol, ! ON/! Monoesters and diesters of maleic acid are obtained by reacting in a temperature range of 0°C.

The vinyl chloride-unsaturated polycarboxylic acid ester copolymer used in the present invention has a weight ratio of 1 or more, for example, unsaturated polycarboxylic ester to vinyl chloride monomer of 2 or more.
It is produced by copolymerizing by suspension polymerization in an aqueous medium in the presence of a general amount of M-Z to Daθ, preferably Gluta, in an amount of 2% by weight. For the polymerization, a commonly known polymerization recipe can be employed.

Dispersants and emulsifiers used 1) Polymerization initiators, etc. do not need to be special, and can be used as general-purpose dispersants.

Emulsifier 1 Polymerization initiator can be used. For example, as dispersants and emulsifiers, partially saponified polyvinyl acetate,
Protective colloidal agents or natural polymer compounds such as acrylic acid copolymers, maleic anhydride copolymers, cellulose derivatives, gelatin, starch, etc.; esters of higher fatty acids and polyhydric alcohols, polyoxyethylene derivatives, etc. nonionic surfactants; anionic surfactants such as metal salts of higher fatty acids and alkali salts of higher alcohol sulfates;

As the t+ polymerization initiator, organic peroxides such as benzoyl peroxide, lauroyl peroxide, dioctyl peroxycarbonate, acetylcyclohexylsulfonyl peroxide; azobis(imbutyronitrile)
, azo compounds such as azobis(dimethylvaleronitrile); persulfates such as persulfate, ammonium persulfate, etc. are used.

In the present invention, the content of the unsaturated polycarboxylic acid ester in the vinyl chloride-unsaturated polycarboxylic acid ester copolymer is λ weight or more.

Usually 2 to 4% by weight, preferably Dal 2! A weight range is used. If the content of the unsaturated polyhydric carboxylic acid ester is less than 2 parts by weight, the adhesiveness of the resulting resin composition will be insufficient.

The adhesive resin composition of the present invention is obtained by blending a plasticizer in a proportional amount with the vinyl chloride-unsaturated polycarboxylic acid ester copolymer. The plasticizer is not particularly limited, and may be any of the various plasticizers commonly used as plasticizers for vinyl chloride resins. For example, phthalate ester plasticizers such as diptyl phthalate, dioctyl hepthalate, bis(2-ethylhexyl) phthalate, diinnonyl phthalate, diindecyl phthalate, butyl lauryl phthalate, ditridecyl phthalate, butyl benzyl phthalate; Phosphate ester plasticizers such as tricresyl phosphate and trioctyl phosphate; fatty acid ester plasticizers such as dioctyl adipate, dioctyl azelaate, dioctyl sebacate, and methyl acetyl ricinoleate; alkyl epoxy stearate, epoxy soybean oil, etc. Examples include epoxy plasticizers. Among the above, phthalate ester plasticizers and fatty acid ester plasticizers are more preferred. Moreover, these plasticizers alone have 17'
h can be used in a mixture of 2 Wt or more.

l9. The resin composition of the present invention may contain additives that are commonly added during the molding process of vinyl chloride resins, such as pigments, heat stabilizers, light stabilizers, fillers, and polymer modifiers, as necessary. Can be blended.

The blending ratio of each component in the resin composition of the present invention is as follows:
The amount of plasticizer is in the range of 10 to 100 parts by weight, preferably 30 to 70 parts by weight based on θO parts by weight. The amount of plasticizer is I
If the amount of OX is small, the adhesive performance will not improve;
If the amount is more than 0.00 parts by weight, the mechanical strength of the resulting resin composition itself will decrease significantly, which is not preferable.

The method for preparing the resin composition of the present invention is to mix the hinyl chloride-unsaturated polycarboxylic acid ester [i combination and the plasticizer with a Henschel mixer, ribbon blender, etc.
A method of pelletizing by using an extruder or the like, or by putting the vinyl chloride-unsaturated polycarboxylic acid ester copolymer and a plasticizer in a Banbury mixer (1 twin-screw roll mixer) and kneading it, then forming it into a sheet and pelletizing it. Examples include methods of converting

As described above, the resin composition of the present invention can be used as an adhesive surface coating agent for substrates or as an interlayer adhesive between substrates. For example, one method is to use an extruder to melt-extrude the composition of the present invention into a film or sheet and laminate it to a base material, or to use it by sandwiching it between two base materials and then thermocompression bonding. I can do it. Examples of the base material include synthetic resins such as vinyl chloride resin, polyethylene, polystyrene, and polyamide resin; metals such as iron and aluminum; and cellulose-based natural materials such as wood, cotton, and hemp.゛The resin composition of the present invention is particularly suitable for bonding steel pipes and vinyl chloride resin pipes, bonding steel plates and vinyl chloride resin plates, bonding aluminum plates and vinyl chloride resin plates, bonding 1gA plates and steel plates, etc. Can be used for

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited by the following examples unless it exceeds the gist thereof.

In addition, the T-type peel strength in the examples is JIB Ktrjgt.
The shear peel strength was measured in accordance with J.
IBKt? ! Please note that the measurements were made in accordance with 0.

Examples/(1) Preparation of unsaturated polyhydric carboxylic acid ester: Prepared at a ratio of 1 mole of maleic anhydride to 1 mole of coetherhexyl alcohol.

The mixture was mixed at 0° C. for a period of time to carry out an esterification reaction to produce mono(λ-ethylhexyl) maleate.

(2) Stainless steel with an internal volume of 20 tons made of vinyl chloride-unsaturated polycarboxylic acid ester copolymer! In a JlIt container, add deionized water/2kl and vinyl chloride monomer (see below).

It is abbreviated as VOM. ) 4t, 27kg and mono(2-ethylhexyl) maleate (hereinafter referred to as M
It is abbreviated as OM. ), add a dispersant and a polymerization initiator,
At a given reaction temperature under stirring, the conversion rate! Q~? Continue the reaction until j% is reached. After purging unreacted VOM when it became clear that the conversion rate was different from the predetermined conversion rate due to a drop in the internal pressure of the tank, the resulting hole-shaped combined slurry was taken out, dehydrated and dried to form vinyl chloride-maleic acid mono(2). -ethylhexyl) copolymer was produced. The physical properties of the obtained copolymer are shown in Table/.

(3) Production of laminate: Vinyl hexachloride-maleic acid mono(2) obtained in (2) above
-ethylhexyl>copolymer io.

Bis(2-ethylhexyl) phthalate in weight part! Add 0 parts by weight and 6 parts by weight of a lead-based stabilizer, and blend it in a blender to 1 part by weight.
Blend for 10 minutes at 00°C. Mix this blend with a meal at <to℃! After kneading for a minute, it was formed into a /■ thick sheet, and three of these sheets were stacked on top of each other.

Heat-compression bonding was carried out at 170°C for 3 minutes, and the sheets were laminated to a Jwr thickness.

Thickness 1■) and overlap at 200'C:%λ0 G! Heat and press for a minute to form a composite. The T-layer peel strength and shear peel strength of this composite were measured. The results are shown in Table 2.

EXAMPLES In Example 1, the same procedure as in Example 1 was carried out except that the base material shown in Table 1 was used instead of the aluminum plate.

The shear peel strength of the nine composites obtained was measured and the results are shown in Table 1.

In Comparative Example/Example/, vinyl chloride-maleic acid mono(2-
The procedure was repeated in the same manner except that the amount of mono(2-ethylhexyl) maleate to be charged in the production of the (ethylhexyl) copolymer was changed as shown in Table 1. The results are shown in Table 2.

Comparative Example/Example/The same procedure was followed except that bis(2-ethylhexyl) phthalate was not blended into the resin composition at all. The results are shown in Table 2/ *1: Weight % based on raw material VOM *2: Upper 2: 2-ethylhexyl)peroxydicarbonate *3: Nippon Gosei Kagaku Kogyo ■, Partial Ken polyvinyl acetate [Effect of the invention] The resin of the present invention obtained by blending a specific amount of a plasticizer with a vinyl chloride-unsaturated polycarboxylic acid ester copolymer containing a specific amount of an unsaturated polycarboxylic acid ester The composition has excellent adhesion to the substrate and is flame retardant. Therefore, the resin composition of the present invention can be widely used as a surface coating for substrates and as an interlayer adhesive between substrates. Furthermore, the resin composition of the present invention can be particularly suitably used as an adhesive for flame retardant applications.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent attorney required - Others/names

Claims (1)

[Claims] (1) Adhesive resin made by blending 100 parts by weight of vinyl chloride-unsaturated polycarboxylic acid ester copolymer containing 2% by weight or more of unsaturated polycarboxylic acid ester and 10 to 100 parts by weight of a plasticizer. Composition.