JP2533348B2 - Adhesive composition for vinyl halide resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesive composition used for vinyl halide resins such as vinyl chloride resin and vinylidene chloride resin.

(Prior art and its problems) Vinyl halide resins such as vinyl chloride resin are used for telephone cards, cash cards, IC cards, records,
It is used in various fields as hard products such as various plates and pipes, agricultural films, electric wire coatings, and soft products such as leather for furniture.

Such a vinyl chloride resin is used by being laminated or adhered with other resin, paper or the like according to the above-mentioned use, etc., but its adhering means has been a practical problem.

That is, as the adhesion means, (1) use a solution type adhesive in which a vinyl chloride / vinyl acetate copolymer resin, an acrylate ester copolymer, a cocondensation polyester resin, a thermoplastic polyurethane or the like is dissolved in a solvent. , (2) Dissolve the surface of vinyl chloride resin, which is the adherend, with a solvent, and bond it while the solvent is not completely scattered. (3) Use dope cement (vinyl chloride resin dissolved in solvent) However, since a solvent is used in each case, there is a problem that the vinyl chloride resin is liable to be whitened, brittle, and cracked.

In order to avoid the above problems, solventless epoxy resins, reactive acrylic resins, polyurethane adhesives, etc. have been proposed, but vinyl chloride resins usually contain plasticizers and various stabilizers. The fact is that satisfactory adhesive strength has not been obtained because a large amount of agents and antistatic agents have been added.

(Means for Solving the Problems) As a result of earnest studies on the solvent-free adhesive composition, the present inventors have found that it is composed of an epoxy resin and vinyl chloride / vinyl acetate / unsaturated carboxylic acid or its anhydride. An adhesive composition having excellent adhesiveness to vinyl halide resins such as vinyl chloride resin can be obtained by using a ternary copolymer resin as a main component and using a specific amine-based curing agent. Found.

That is, according to the present invention, (a) an epoxy resin, 100 parts by weight, (b) vinyl chloride / vinyl acetate / unsaturated carboxylic acid or an anhydride thereof, having an average degree of polymerization of 200 to 800, A terpolymer resin having a vinyl acetate content of 2 to 25% by weight and an unsaturated carboxylic acid or its anhydride content of 0.1 to 10% by weight, 0.5 to 40 parts by weight, (c) a curing agent component, Alicyclic polyamine or the following formula: In the formula, R ₁ , R ₂ , and R ₃ represent a hydrogen atom, a methyl group, an ethyl group, or halogen, x, y, and z are numbers from 0 to 12, and their total value (x + y + z) is 2 A solvent-free adhesive composition for vinyl halide resins, which comprises the alkylenediamine represented by a number in the range from 1 to 12, is provided.

(Operation) In the adhesive composition of the present invention, the epoxy resin of the component (a) and the terpolymer resin of the component (b) are adhesive components, and particularly the terpolymer of the component (b) is used. The resin acts as a surfactant to improve the affinity between the epoxy resin of component (a) and the surface of the vinyl halide resin as the adherend.

In addition, as shown in Examples described later, excellent adhesive strength can be obtained by adding the specific polyamine compound of the component (c) to the combination of the components (a) and (b) as a curing agent. The adhesive composition having is obtained.

For example, while the T-type peel adhesive strength of the adhesive structure constituted by using the adhesive composition of the present invention shows a value of 1.0 Kgf / cm or more, the adhesive composition of the comparative example has 0.1 to 0.3 Kgf / cm. cm
It's just a degree.

In addition, the adhesive composition of the present invention can be cured at a temperature lower than the glass transition point (Tg) of the hard vinyl chloride resin, and can adhere at a temperature that does not deform the adherend. It also has advantages.

(Preferred embodiment of the invention) (a) Epoxy resin In the present invention, the epoxy resin used as the adhesive component is a compound containing two or more epoxy groups in one molecule.

As such an epoxy resin, for example, the following ones are used.

Bisphenol A, 2,2-bis (4-hydroxyphenylbutane (bisphenol B), 1,1'-bis (4-
Hydroxyphenyl) ethane (sometimes abbreviated as bisphenol AD), bis (4-hydroxyphenyl) methane (bisphenol F), 1,1,2,2-tetrakis (4
-Hydroxyphenyl) ethane, 4-hydroxyphenyl ether, glycidyl ether epoxy resin of polyphenol compounds such as P- (4-hydroxy) phenol.

A glycidyl ether-based epoxy resin which is a nuclear hydride of the polyphenol compound.

Glycidyl ether-based epoxy resins of polyphenols such as catechol, resorcin, hydroquinone, and phloroglucin.

Glycidyl ether-based epoxy resins of polyhydric alcohols such as ethylene glycol, butanediol, glycerol, erythritol, and polyoxyalkylene glycol.

 Novolac type epoxy resin.

Alicyclic epoxy resins such as vinylcyclohexene dioxide, limonene dioxide, and dicyclopentadiene dioxide.

Polyglycidyl ester epoxy resin of ester condensate of polycarboxylic acid such as phthalic acid and cyclohexane-1,2-dicarboxylic acid.

 Polyglycidyl amine epoxy resin.

 Methylepichloro epoxy resin.

In the present invention, the above-mentioned epoxy resins are used alone or in combination, and among them, glycidyl ether-based epoxy resins of polyphenol compounds or novolac type epoxy resins are preferable, and from the viewpoint of workability, etc. Those which are liquid at room temperature are particularly preferably used.

(B) Vinyl chloride-based terpolymer resin In the present invention, in order to increase the affinity between the epoxy resin (a) and the vinyl halide resin to be adhered, vinyl chloride / vinyl acetate / A terpolymer resin consisting of an unsaturated carboxylic acid or its anhydride is used.

This terpolymer resin is prepared by mixing the epoxy resin (a) with the curing agent of the component (c) described below in advance.
It is blended by heating and dissolving.

As such a terpolymer resin, the average degree of polymerization is in the range of 200 to 800, particularly 300 to 600 from the viewpoint of compatibility with the epoxy resin (a) and affinity with the vinyl halide resin. Those having a vinyl acetate content of 2 to 25% by weight, in particular 4 to 20% by weight, and an unsaturated carboxylic acid content of 0.1 to 10% by weight, especially
Those in the range of 0.5 to 7% by weight are preferable.

As the unsaturated carboxylic acid or its anhydride as a copolymerization component, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo [2,2,1] hept-2- Unsaturated carboxylic acids such as ene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6- An unsaturated carboxylic acid anhydride such as a dicarboxylic acid anhydride may be mentioned, and maleic anhydride, acrylic acid and methacrylic acid are particularly preferably used.

In the present invention, such a terpolymer resin is (a)
It is used in an amount of 0.5 to 40 parts by weight, particularly 1.0 to 35.0 parts by weight, per 100 parts by weight of the component epoxy resin.

If this amount is less than the above range, the adhesive strength tends to decrease, and if it is more than the above range,
The viscosity of the obtained adhesive composition is very high, and the workability tends to decrease.

(C) Hardener component In the present invention, an alicyclic polyamine or alkylenediamine is used as a hardener.

As the alicyclic polyamine, those having the number of rings in the range of 1 to 3 are preferably used, and the ring structure may be monocyclic, bicyclic or spiro ring, and other than carbon atom. It may be heterocyclic, containing atoms such as nitrogen, oxygen, sulfur and the like.

Further, the amino group contained in this compound is required to be a primary or secondary amino group, and particularly a compound containing only a primary amino group or a compound containing a primary amino group and a secondary amino group is preferable. Those containing only a tertiary amino group are not suitable.

Specifically, the following can be used.

Isophoronediamine, mensendiamine, (In the formula, n is a number from 0 to 6, and R represents H, CH ₃ , C ₂ H _5, or Cl.) N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2 , 4,8,10-Tetraoxaspiro [5,5] -undecane, Diamine having tricyclodecane skeleton such as dimer acid (fatty acid obtained by Diels-Alder reaction of unsaturated fatty acid whose main component is linoleic acid or oleic acid, the main component containing cyclohexene ring has 36 carbon atoms (Unsaturated carboxylic acid) of polyamidoamine obtained by dehydration-condensation with diethyletriamine or triethylenetetramine.

Among the above-mentioned alicyclic polyamines, some of them having a plurality of primary amino groups are solid at room temperature. ) A glycidyl ether compound, acrylonitrile, phenol / formalin or the like modified to liquefy or adjust reactivity can be used.

Further, as the alkylenediamine, in particular, the following formula, In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a methyl group, an ethyl group or a halogen, x, y and z are numbers from 0 to 12, and the total value (x + y + z) of these is 2 The number represented by the formula, for example, ethylenediamine, propylenediamine, and 1,6-diamino-2,2,4-trimethylhexane are used.

Generally speaking, these polyamines are blended so that the primary and secondary amino groups are stoichiometrically approximately equal to the glycidyl groups in the epoxy resin of component (a).
Usually, it is blended in a ratio that satisfies the following formula.

Other Compounding Agents In the present invention, various compounding agents known per se can be compounded as necessary in addition to the components (a) to (c) described above.

For example, stabilizers for vinyl chloride resins such as organic acid metal salts, sulfates, and organic tin salts; antistatic agents such as surfactants, conductive carbon, and boron-based antistatic agents; aerosil, bentonites, bisamide-based agents, waxes A fluidity adjusting agent such as a system, an organic acid salt type thixotropic agent, etc .; a silicone type, a titanium type coupling agent;

Further, known fillers or reinforcing agents can be added.

For example, silica, calcium carbonate, talc, alumina, aluminum hydroxide, magnesium hydroxide, iron oxide, magnesium oxide, magnesium silicate, aluminum silicate, mica, barium sulfate, carbon black, graphite, inorganic fillers such as asbestos and , Metal powder such as aluminum, copper, silver, nickel, chrome, stainless steel, flakes, glass fiber, ceramic fiber such as alumina and zirconia, carbon fiber, aramid fiber,
Metal fibers and the like can be blended.

Preparation of Adhesive Composition The adhesive composition of the present invention is prepared by dissolving the vinyl chloride terpolymer resin (b) in the epoxy resin (a) at a temperature of usually 80 to 150 ° C. It is obtained by adding the curing agent of the component (c) after cooling it to room temperature.

In this case, when the vinyl chloride copolymer resin as the component (b) is heated and dissolved in the epoxy resin as the component (a), the viscosity of the mixture may remarkably increase, which may lead to a decrease in workability.

In such a case, for example, the viscosity at 25 ° C is 1000 cp
The epoxy diluent of s or less is usually added in a proportion of 5 to 100 parts by weight per 100 parts by weight of the epoxy resin.

The following can be illustrated as such a diluent.

Polyethylene glycol diglycidyl ether Polypropylene glycol diglycidyl ether Polytetramethylene glycol diglycidyl ether Neopentyl grille diglycidyl ether 1,6-hexanediol diglycidyl ether 2-ethylhexyl diglycidyl ether trimethylolpropane di (or tri) glycidyl ether monoglycidyl ether of glycerin di (or tri) glycidyl ether alcohols R = C _{4 to} C ₁₈ alkyl group] Phenol or its derivative monoglycidyl ether R = H or C _{1 to} C ₁₈ alkyl group] Monoglycidyl ester of carboxylic acid Alkyl] N of R = H or C ₄ to C _18, N'-diglycidyl aniline derivative Or a C _{1 to} C ₈ alkyl group] The compounding agent, which is optionally compounded, may be added at the same time as or prior to the dissolution of the component (b) by heating, or the curing agent component (c). It may be added at the same time as the compounding, and can be added at any stage.

(Effects of the Invention) According to the present invention, an adhesive having excellent adhesiveness to vinyl halide resins such as vinyl chloride resin, vinylidene chloride resin and copolymer resins thereof, without using any solvent. An agent composition is obtained.

Further, the adhesive composition of the present invention can be cured at an extremely low temperature, for example, a temperature lower than the glass transition point (Tg) of a hard vinyl chloride resin, and the thermal deformation of the cured vinyl chloride resin during its use. It also has the advantage that it can be effectively prevented.

Thus, the adhesive composition of the present invention becomes a suitable adhesive for a vinyl chloride resin or vinylidene chloride resin molded body in a solventless form.

(Examples) Examples 1 to 12 and Comparative Example 1 As epoxy resin, bisphenol AD type epoxy resin, epoxy equivalent 173, viscosity (25 ° C) 3000cps As diluent, polypropylene glycol diglycidyl ether, epoxy equivalent 309, viscosity (25 ° C) 150cps Mutual prosperity Epolite 400 P manufactured by Yushi Co., Ltd. and vinyl chloride-based terpolymer resin as vinyl chloride / vinyl acetate / maleic anhydride copolymerized resin Average degree of polymerization 440 Vinyl acetate content 6% Maleic anhydride content 4% ZEON manufactured by Zeon Corporation 400 × 110A or vinyl chloride / vinyl acetate / maleic anhydride copolymer resin Average degree of polymerization 330 Vinyl acetate content 13% Maleic anhydride content 1% Denka Vinyl CS manufactured by Denki Kagaku Kogyo Co., Ltd. is used.

According to the blending amounts shown in Table 1, these were added to a 200 cm ³ serable flask, dissolved under stirring in an oil bath heated to 135 ° C, and cooled to room temperature to prepare a sample of the main ingredient.

Also, for comparison, a sample was prepared in which no vinyl chloride terpolymer was blended.

Each of these samples was treated with 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] -undecane modified with butyl glycidyl ether as a hardener component (activity Hydrogen equivalent 95, viscosity at 25 ℃
3000 cps) was blended to obtain an adhesive composition.

Apply each adhesive composition to a white opaque hard vinyl chloride sheet (12 cm in length, 7 cm in width, 0.28 mm in thickness) used in telephone cards, cash cards, IC cards, etc. with a bar coater at a thickness of 12.5 μm. Applied.

The adhesive composition was removed from the periphery of this hard vinyl chloride sheet over 4 mm, and a 12.5 μm-thick Mylar film was placed on the portion to form a spacer.

After sticking the same hard vinyl chloride sheet without adhesive applied to this, 85 ℃, 70 minutes (pressure 20gf / c
m ² ) Heat curing was performed.

The obtained adhesive sheet was cut into a width of 1.0 cm, and the T-peel adhesive strength was measured with a tensile tester.

The measurement was performed under the conditions of 21 ° C. and a pulling speed of 50 mm / min. Each measurement was performed 3 times, and the average value was adopted.

 The measurement results are shown in Table 1.

Examples 13 to 18 Example 1 except that the same curing agent as in Examples 1 to 12 was used as the main component and the types of epoxy resin and diluent were changed.
The T-peel adhesion strength was measured in exactly the same manner as ~ 12.

 The results are shown in Table 2.

Examples 19 to 27, Comparative Examples 2 to 7 Main ingredient component of Example 4, namely, bisphenol AD type epoxy resin 70.0 g polypropylene glycol diglycidyl ether 30.0 g vinyl chloride / vinyl acetate / maleic anhydride copolymer resin 5.0 g vinyl acetate content Example 4 Using a 6% maleic anhydride content of 4% and an average degree of polymerization of 400, various curing agents were used.
The T-type peel adhesive strength was measured in the same manner as in.

 Table 3 shows the measurement results and the type of curing agent used.

Claims (5)

(57) [Claims] 1. A composition comprising (a) an epoxy resin, 100 parts by weight, and (b) vinyl chloride / vinyl acetate / unsaturated carboxylic acid or an anhydride thereof, having an average degree of polymerization of 200 to 800 and a vinyl acetate content. Terpolymer resin having a content of 2 to 25% by weight and an unsaturated carboxylic acid or its anhydride content in the range of 0.1 to 10% by weight, 0.5 to 40 parts by weight, and (c) an alicyclic compound as a curing agent component. Polyamine or the following formula: In the formula, R ₁ , R ₂ , and R ₃ represent a hydrogen atom, a methyl group, an ethyl group, or halogen, x, y, and z are numbers from 0 to 12, and their total value (x + y + z) is 2 A solvent-free adhesive composition for a vinyl halide resin, which comprises an alkylenediamine represented by a number in the range from 1 to 12. 2. The adhesive for vinyl halide resin according to claim 1, wherein the terpolymer resin (b) is a vinyl chloride / vinyl acetate / maleic anhydride terpolymer resin. Agent composition. 3. The adhesive composition for vinyl halide resin according to claim 1, wherein the alicyclic polyamine as the component (c) has a ring number of 1 to 3. 4. The adhesive composition for vinyl halide resins according to claim 1, wherein the alicyclic polyamine contains at least one primary amino group or secondary amino group. 5. The alkylenediamine of the component (c) is
The adhesive composition for vinyl halide resins according to claim 1, which is ethylenediamine, propylenediamine, or 1,6-diamino-2,2,4-trimethylhexane.