JPH01178571A - Adhesive composition for vinyl halide resin - Google Patents

Abstract

PURPOSE:To obtain the title composition which contains no solvent and has excellent adhesiveness to vinyl halide resin, by mixing an epoxy resin, a specified terpolymer resin, and an alicyclic polyamine or alkylenediamine. CONSTITUTION:Vinyl chloride (a) is copolymerized with 2-25wt.% vinyl acetate (b) and 0.1-10wt.% unsaturated carboxylic acid (c) (e.g., maleic anhydride) to give a terpolymer resin (B) having an average degree of polymerization of 200-800. 100pts.wt epoxy resin (A) containing at least two epoxy groups per molecule is mixed with 0.5-40pts.wt. component B. The mixture is melted by heating and then mixed with a curing agent (C) comprising an alicyclic polyamine having 1-3 rings or alkylenediamine (e.g., ethylenediamine), in such an amount that the content of the primary and secondary amino groups is approximately stoichiometrically equivalent in relation to the glycidyl groups of component A.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an adhesive composition used for halogenated vinyl resins such as vinyl chloride resins and vinylidene chloride resins.

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

Such vinyl chloride resins are used by being laminated or bonded with other resins, paper, etc., depending on the above-mentioned uses, for example, but the bonding means poses a practical problem.

That is, as the adhesive means, (1) a solution type adhesive in which vinyl chloride/vinyl acetate copolymer resin, acrylic ester copolymer, cocondensed polyester resin, thermoplastic polyurethane, etc. is dissolved in a solvent is used; (2) Dissolve the surface of the adherend (vinyl chloride resin) with a solvent and bond without the solvent completely scattering (3) Dope cement (vinyl chloride resin dissolved in a solvent) Methods such as bonding using a solvent are often used, but since a solvent is used in either case, there is a problem that the vinyl chloride resin is susceptible to whitening, embrittlement, cracking, etc.

In addition, in order to avoid the above problems, solvent-free epoxy resins, reactive acrylic resins, polyurethane adhesives, etc. have been proposed, but vinyl chloride resins contain
Since large amounts of stabilizers, various stabilizers, antistatic agents, etc. are usually blended, it is difficult to obtain a satisfactory adhesive strength.

(Means for Solving the Problems) As a result of intensive studies on solvent-free adhesive compositions, the inventors of Wood have developed a composition consisting of epoxy resin and vinyl chloride/vinyl acetate/unsaturated carboxylic acid or its anhydride. An adhesive composition containing a terpolymer resin as a main component and using a specific amine curing agent to exhibit adhesion of 1 to 1 to a vinyl halide resin such as a vinyl chloride resin. I found out that it can be obtained.

That is, the adhesive composition of the present invention comprises (a) an epoxy resin, (b) a terpolymer resin consisting of vinyl chloride/vinyl acetate/unsaturated carboxylic acid or its anhydride, and (c) a curing agent component. It contains an alicyclic polyamine or an alkylene cyamine.

(Function) In the adhesive composition of the present invention, the epoxy resin of component (a) and the terpolymer resin of component (b) are adhesive components, but especially the terpolymer resin of component (b) The resin acts like a surfactant and improves the affinity between the epoxy resin of component (a) and the surface of the vinyl halide resin that is the adherend.

In addition, by blending a specific polyamine compound of component (c) as a curing agent to the combination of components (a) and (b) above, as shown in the examples below,
An adhesive composition having excellent adhesive strength can be obtained.

For example, the T-type beer adhesive strength of the adhesive structure constructed using the adhesive composition of the present invention shows a value of 1.0 Kgf/cm or more, whereas the adhesive strength of the adhesive composition of the comparative example shows a value of 0.1 Kgf/cm or more.
~Q, only about 3 Kgf/am.

Furthermore, 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 be bonded at a temperature that does not deform the adherend. It also has advantages.

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

As such epoxy resins, for example, the following are used.

Bisphenol A, 2.2-bis(4-hydroxyphenylbutane (bisphenol B), 1゜bis(4-
Hydroxyphenyl)ethane (sometimes abbreviated as bisphenol AD), bis(4-hydroxyphenyl)
A glycidyl ether-based epoxy resin of novophenol compounds such as methane (bisphenol F), 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 4-hydroxyphenyl ether, and P-(4-hydroxy)phenol.

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

Glycidyl ether-based epoxy resin of polyhydric phenols such as catechol, resorcinol, hydroquinone, and phloroglucin.

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

Novolac type epoxy resin.

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

A polyglycidyl ester-based epoxy resin of an ester condensate of polycarboxylic acids such as phthalic acid and cyclohexane-1,2-dicarboxylic acid.

Polyglycidylamine-based epoxy resin.

Methyl epicro type epoxy resin.

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

(b) Vinyl chloride terpolymer resin In the present invention, vinyl chloride/vinyl acetate/vinyl acetate/vinyl chloride/vinyl acetate/ A terpolymer resin consisting of an unsaturated carboxylic acid or its anhydride is used.

This terpolymer resin is prepared by adding the epoxy resin, finger (a), etc.
It is blended by melting the parts.

Such terpolymer resins have an average degree of polymerization of 200 to 800, from the viewpoint of compatibility with epoxy resin J resin (a) and affinity with halogenated vinyl resins.
In particular, those in the range of 300 to 600 are suitable,
Also, the vinyl acetate content is 2 to 25% by weight, especially 4 to 2% by weight.
The content of unsaturated carbonic acid is in the range of 0% by weight and 0.2% by weight.
A range of 1 to 10% by weight, particularly 0.5 to 7% by weight, is preferred.

Examples of unsaturated carboxylic acids or anhydrides thereof for copolymerization include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo(2,2゜1)hept-2- en-5,6
-Unsaturated carboxylic acids such as dicarboxylic acids, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo(2,2,1)hept-2-2:
Examples include anhydrides of unsaturated carbonic acids such as /-5,6-dicarboxylic anhydrides, and maleic anhydride, acrylic acid, and methacrylic acid are particularly preferred.

In the present invention, the terpolymer resin is used in an amount of 5 to 40 parts by weight, particularly 1.0 to 350 parts by weight, per 100 parts by weight of the epoxy resin of component ja).

If the total 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 resulting adhesive composition tends to be extremely high, resulting in a decrease in workability. It is in.

In the present invention, an alicyclic polyamine or an alkylene diamine is used as a curing agent.

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

The amino group contained in this compound must be a -class or secondary amino group, and compounds containing only a -class amino group or a compound containing a primary amine group and a secondary amino group are particularly preferred. Therefore, those containing only tertiary amino groups are not suitable.

Specifically, the following can be used.

Isophorone diamine, menthene diamine, (wherein n is a number from 0 to 6 and R represents H1CH3,C2)I5 or C1) N-aminoethylpiperazine, 3.9-bis(3-aminopropyl) ) −2,4,8,
10-tetraoxaspiro(5,5)-undecane, diamine having a decane skeleton, dimer acid (a fatty acid obtained by the Diels-Alder reaction of unsaturated fatty acids whose main components are linoleic acid and oleic acid, A polyamide amine obtained by dehydrating and condensing an unsaturated carboxylic acid containing a cyclohexene ring and having 36 carbon atoms as a main component with diethylenetriamine or triethylenetetramine.

In addition, among the above-mentioned alicyclic polyamines, some of those having a plurality of -class amino groups are solid at room temperature,
For those that are difficult to use as curing agents for adhesives, add a small amount of mono (or di) glycidyl ether compound,
Those modified with acrylonitrile, phenol/formalin, etc. to adjust liquefaction or reactivity can be used.

In addition, as the alkylene diamine, the following H2'+
+ (,H2−)−−+ CI+÷=+ c −h−
NH21' R, R3 In the formula, R1, R2, R3 represent a hydrogen atom, a methyl group, an ethyl group, or a halogen, x, y, and z are numbers from O to 12, and their total value (x+y+z) is a number in the range of 2 to 12, such as ethylenediamine, propylene diamine, 1,6-diamino-2.2°4-trimethylhexane, etc. are used.

These polyamines are blended in such a way that the primary and secondary amino groups are stoichiometrically approximately equal to the glycidyl groups in the epoxy resin of component (a), but usually, They are blended in proportions that satisfy the following formula.

≦1.3 Other compounding agents In the present invention, in addition to the above-mentioned components (a) to (c), various compounding agents known per se may be blended as necessary.

For example, stabilizers for vinyl chloride resin such as organic acid metal salts, lead sulfate, and organic tin salts; antistatic agents such as surfactants, conductive carbon, and boron-based antistatic agents: Aerosil, bentonites, bisamides, and waxes. Fluidity modifiers such as silicone-based and organic acid salt-based thixotropic agents: silicone-based and titanium-based coupling agents can be blended as long as they do not impair properties such as adhesiveness.

In addition, fillers or reinforcing agents that are known per se may also be blended.

For example, silica, calcium carbonate, talc, alumina,
Inorganic fillers such as aluminum hydroxide, magnesium hydroxide, iron oxide, magnesium oxide, magnesium silicate, aluminum silicate, mica, barium sulfate, carbon black, graphite, asbestos, aluminum, copper, silver, nickel, chromium, Metal powders such as stainless steel, flakes, glass fibers, ceramic fibers such as alumina and zirconia, carbon fibers, aramid fibers, metal fibers, etc. can be blended.

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

In this case, the vinyl chloride copolymer resin of component (b) is replaced with (a
) When heated and dissolved in the epoxy resin component, the viscosity of the mixture increases significantly, which may lead to a decrease in workability.

In such a case, for example, the viscosity at 25°C is 100
An epoxy diluent having a concentration of 0 cps or less may be blended in an amount of 5 to 100 parts by weight per 100 parts by weight of the epoxy resin.

Examples of such diluents include those listed below.

Polyethylene glycol diglycidyl ether n=1~
22] Polypropylene glycol diglycidyl ether CH.

n=1-15) Polytetramethylene glycol diglycidyl ether n=1-20] Neopentyl glycol diglycidyl ether 1.6-
Hexanesiol diglycidyl ether 2-ethylhexyl diglycidyl ether trimethylolpropane di(or tri)glycidyl ether glycerin monoglycidyl etherkyl group of di(or tri)glycidyl ether alcohols] Monoglycidyl ether of phenol or its derivatives to CI8 Alkyl group of carboxylic acid monoglycidyl ester C+a] N,N'-diglycidylaniline derivative C1 to C8
[Alkyl group of] In addition, compounding agents blended as necessary may be added at the same time as or prior to heating and dissolving component (b), or may be added at the same time as blending curing agent component (c). It can be added at any stage.

(Effect of the invention) According to the present invention, without using any solvent,
An adhesive composition is obtained that exhibits superior adhesion to vinyl halogenated resins such as vinyl chloride resin, vinylidene chloride resin, and copolymer resins thereof.

Further, the adhesive composition of the present invention can be cured at an extremely low temperature, for example, a temperature lower than the glass inversion point (Tg) of a hard vinyl chloride resin. It also has the advantage of effectively preventing deformation.

As described above, the adhesive composition of the present invention becomes a suitable adhesive for vinyl chloride resin or vinylidene chloride resin molded articles in a solvent-free form. It is also possible to dilute it with a solvent, various cellosolves, ketone solvents, etc. before use.

(Example) Examples 1 to 12 and Comparative Example 1 As an epoxy resin: Bisphenol AD type epoxy resin Epoxy equivalent: 173 Viscosity (25°C) 3000 cps As a diluent: Polypropylene glycol diglycidyl ether epoxy equivalent: 309 Viscosity (25°C) 150 cps Epolite 400P manufactured by Kyoei Yushi Co., Ltd. and vinyl chloride terpolymer resin: ■ Vinyl chloride/vinyl acetate/maleic anhydride copolymer resin Average degree of polymerization 440 Vinyl acetate content 6% Maleic anhydride content 4% Nikki Zeon Use Zeon 400x 110A manufactured by Denki Kagaku Kogyo Co., Ltd. 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.

These were added to a 200 cm3 separable flask in accordance with the blending amounts shown in Table 1, dissolved under stirring in an oil bath heated to 135°C, and cooled to room temperature to prepare a sample of the main component.

For comparison, a sample containing no vinyl chloride ternary copolymer resin was prepared.

Each of these samples contained a modified product of 3,9-bis(3-aminopropyl)-2,4,8°10-tetraoxaspiro(5,5)-undecane with butyl glycidyl ether (activated) as a curing agent component. is the hydrogen equivalent of 95.25℃
(viscosity of 3,000 ps) was combined to form an adhesive composition.

Each adhesive composition was applied to a white opaque hard vinyl chloride sheet (length 12 cm, width 7 cm, thickness 0.28 m) used for telephone cards, cash carts, IC cards, etc.
M) was coated to a thickness of 12.5 μm using a bar coater.

The adhesive composition was removed over a 4 mm area around this hard vinyl chloride sheet, and a 12.5 μm thick Mylar film was placed on that area to serve as a spacer.

After bonding the same hard vinyl chloride sheet with no adhesive applied to this, it was heated at 85℃ for 70 minutes (pressure 20℃).
gf/cm2) heat curing was performed.

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

The measurements were carried out at 21° C. and at a tensile speed of 50 mm/min. Each sample was measured three times, and the average value was used.

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 type of diluent was changed.
T-type beer adhesive strength was measured in exactly the same manner as in 12.

The results are shown in Table 2.

Examples 19-27. Comparative Examples 2 to 7 The main components of Example 4, namely: Bisphenol AD type epoxy resin 70.0 g Polypropylene glycol diglycidyl ether 30.0 g Vinyl acetate content 6% Maleic anhydride content 4% Average degree of polymerization 400 This was mixed with various curing agents to obtain Example 4.
The T-type beer adhesive strength was measured in the same manner as above.

The measurement results and the types of hardeners used are shown in Table 3.

Claims (8)

[Claims] (1) (a) Epoxy resin; (b) terpolymer resin consisting of vinyl chloride/vinyl acetate/unsaturated carboxylic acid or its anhydride; (c) alicyclic polyamine or alkylene as a curing agent component. An adhesive composition for a halogenated vinyl resin, comprising a diamine. (2) The terpolymer resin (component (b)) is a component (
The adhesive composition according to claim 1, wherein the adhesive composition is blended in a proportion of 0.5 to 40 parts by weight per 100 parts by weight of the epoxy resin a). (3) The terpolymer resin (b) has an average degree of polymerization of 2
00 to 800, the content of vinyl acetate is in the range of 2 to 25% by weight, and the content of unsaturated carboxylic acid or its anhydride is in the range of 0.1 to 10% by weight. adhesive composition. (4) The adhesive composition according to claim 3, wherein the terpolymer resin (b) is a vinyl chloride/vinyl acetate/maleic anhydride terpolymer resin. (5) The adhesive composition according to claim 1, wherein the alicyclic polyamine of component (c) has a number of rings in the range of 1 to 3. (6) The adhesive composition according to claim 1, wherein the alicyclic polyamine contains at least a primary amino group or a secondary amino group. (7) The alkylene diamine of component (c) has the following formula, ▲ mathematical formula, chemical formula, table, etc. ▼ In the formula, R_1, R_2, R_3 represent a hydrogen atom, a methyl group, an ethyl group, or a halogen, and x , y, and z are numbers from 0 to 12, and their total value (x+y+z) is a number in the range from 2 to 12. (8) The alkylene diamine is ethylene diamine,
Propylene diamine, or 1,6-diamino-2,2,
The adhesive composition according to claim 7, which is 4-trimethylhexane.