JPH083444A - Modified polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. which is suitable for adhesion between the same or different metals, between a metal and a synthetic resin, between the same or different synthetic resins, between a synthetic resin and a plywood (a decorative laminate material, etc.), or between plywoods. CONSTITUTION:This compsn. is prepd. by mixing 100 pts.wt. polyamide resin obtd. by the reaction of a dimer acid with a polyamine with 0.1-20 pts.wt. polycarboxylic anhydride having a plurality of carboxylic anhydride groups in the molecule.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to adhesion of metals of the same kind or different kinds, adhesion of metals and various synthetic resins, adhesion of various kinds of synthetic resins of the same kind or different kinds, various synthetic resins and plywood (decorative plate, etc.) The present invention relates to a modified polyamide resin composition suitable for the adhesion of the above or the adhesion between plywoods. The polyamide resin composition of the present invention has excellent mechanical properties and is used as a hot melt adhesive having improved adhesiveness.

[0002]

Polyamide resin obtained by the reaction of dimer acid and polyamine is a thermoplastic resin excellent in flexibility, rubber elasticity, and low temperature characteristics. It is blended with wax, base resin for hot melt adhesive, and molded. Widely used as a product. A hot melt adhesive made by mixing a polyamide resin with an adhesive or wax such as rosin or petroleum resin does not always have sufficient adhesive force, and particularly adheres to a hard-to-adhere material such as soft PVC material. It has a weakness.

Conventionally, there has been known a method in which a saponified product of an ethylene-vinyl acetate copolymer and a polyamide resin are mixed to form a sheet (for example, JP-A-56-122880). However, it is difficult to obtain sufficient adhesive strength by this method, and the saponified product of the ethylene-vinyl acetate copolymer and the polyamide resin are melted during film forming, and the film is not formed into a film in a uniformly mixed state. As a result, pinholes are generated in the film, and the temperature dependence of the heat-melt viscosity of the polyamide resin is large, so that the film cannot be formed if the compatibility with the polyamide resin is poor.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have focused their attention on the excellent adhesion performance of polyamide resins, and as a result of diligent studies, as a result, a specific poly-carboxylic acid for a polyamide resin obtained by the reaction of dimer acid and polyamine was obtained. It was found that the mechanical properties and adhesiveness of the polyamide resin can be significantly improved by mixing an anhydride, and the present invention has been completed.

[0005]

The present invention is directed to a polyamide resin obtained by the reaction of a dimer acid and a polyamine, and a polycarboxylic acid having a plurality of carboxylic acid anhydrides in one molecule with respect to 100 parts by weight of the polyamide resin. A modified polyamide resin composition containing 0.1 to 20 parts by weight of a carboxylic anhydride.

The present invention will be described in more detail below. The polyamide resin used in the present invention is a polyamide resin composed of dimer acid and diamine, and preferably has an amine value of 3 to 30, and a softening point of 90 ° C., preferably 12
0 ℃ or more, viscosity 1000 (cps / 200 ℃) or more, preferably 50
A polyamide resin with a temperature of 00 (cps / 200 ° C) or higher.

Such polyamide resin is specifically formed by reaction of a dimer acid which is a dimer of fatty acid such as soybean oil, tung oil and tol oil with alkyl polyamines such as ethylenediamine and diethylenetriamine. Things are used. Specific examples include Tomide (trade name, manufactured by Fuji Kasei Kogyo Co., Ltd.) 390, 394, 500, 509, 5
35, 558, 560, 575, 1310, 1350,
1360, 1396, 1400, TXC-232C, Sunmide (trade name of Sanwa Chemical Industry Co., Ltd.) 15-K5, HT-
140PK-20, Evergrip (trade name of ACI Japan Co., Ltd.) PA131H, PA-79BT,
Newmide (Harima Chemicals trade name) 945, 215
2, 3008 and the like.

Among them, the polyamide resin preferably used in the present invention has a viscosity of 5000 (cps / 200 ° C.) or more, more preferably 8000 to 15000 (cps / 200 ° C.), or a softening point of 120 ° C. As mentioned above, a polyamide resin of 130 to 170 ° C. is preferable. Examples of polyamide resins belonging to these categories include Tomide TXC232C, Sunmide HT-140PK-20, and EVAGrip PA-7.
9BT, Newmide 3008 and the like are exemplified.

The poly-carboxylic acid anhydride used in the present invention is a poly-carboxylic acid anhydride having a plurality of carboxylic acid anhydrides in one molecule, and is, for example, a saturated or unsaturated one having 2 to 20 carbon atoms. Aliphatic poly-carboxylic acid anhydride,
Aromatic poly-carboxylic acid anhydrides having 8 to 20 carbon atoms, or derivatives containing these, for example, esters of the polycarboxylic acids with polyvalent alcohols such as alkylene glycol, or other maleic anhydride Examples thereof include a copolymer with an ethylene vinyl monomer, and specifically, pyromellitic dianhydride, a diester of pyromellitic dianhydride or trimellitic dianhydride and ethylene glycol, or a triester of glycerin, 3,3 ′. , 4,4'-benzophenone tetracarboxylic acid anhydride, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer,
A propylene-maleic anhydride copolymer or a methyl vinyl ether-maleic anhydride copolymer is mentioned.

As the aliphatic or aromatic poly-carboxylic acid anhydride particularly preferably used in the present invention, a diester of trimellitic anhydride or pyromellitic anhydride and ethylene glycol (for example, manufactured by Shin Nippon Rika Co., Ltd.) Ethylene glycol bis (anhydrotrimellitate)
Trade name RIKACID TMEG) or triester with glycerin, ethylene-maleic anhydride copolymer (eg,
Bondyne HX-814 manufactured by Sumitomo Chemical Co., Ltd.
0) or a methyl vinyl ether-maleic anhydride copolymer is preferably used.

The amount of the poly-carboxylic acid anhydride used in the present invention is 0.1 to 20 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polyamide resin.

The present invention is characterized in that the polyamide resin contains a predetermined amount of poly-carboxylic acid anhydride, and further, if necessary, other major additives such as other thermoplastic resins, adhesives, A thickener, a coloring agent, a filler, an antiaging agent, etc. can be added, and the composition of the present invention can be added to another adhesive for the purpose of modifying the other adhesive. . Specific examples of these additives include:
Sumitate MB-11 (ethylene-vinyl acetate copolymer; product name of Sumitomo Chemical Co., Ltd.), Neotor 125 (modified rosin; product name of Harima Kasei Co., Ltd.), super ester 125
(Modified rosin; trade name of Arakawa Chemical Co., Ltd.) and the like.

The method for producing the modified polyamide resin composition according to the present invention is only required to uniformly mix (disperse, mix or fuse) these two or further additives and the like. It is not particularly limited, but usually the above components are mixed by a blender or other means, a method of extruding using an extruder, a kneader, a Hensiel mixer, or the like,
As it is or a method using an extruder, other additives and the poly-carboxylic acid anhydride of the present invention are mixed in advance, a polyamide resin is mixed therein, a method of extrusion, a high-concentration master batch is produced, Examples thereof include a masterbatch method of mixing them. As for the mixing conditions, in the case of an extruder, the extrusion conditions of the polyamide resin can be used as they are. Mixing is usually carried out at room temperature or under heating, and it is preferable to fuse the materials under heating.

The modified polyamide resin composition of the present invention prepared by the above method is preferably used as a sheet-like adhesive or a film-like adhesive. When used as the sheet-like adhesive or film-like adhesive of the present invention, its thickness is not particularly limited, but is usually 10 to 10.
It is used at 500μ, preferably 50 to 200μ.

The materials to be adhered to which the modified polyamide resin composition of the present invention is applied include adhesion of metals of the same kind or different kinds, adhesion of metals and various synthetic resins, various kinds of synthetic resins of the same kind or different kinds. It is used as a hot-melt adhesive suitable for adhering each other, adhering various synthetic resins to plywood (decorative plate, etc.), or adhering plywood to each other.

Specific examples include adhesion of aluminum to each other, adhesion of aluminum to stainless steel (SUS), and the like, and adhesion of metal to various synthetic resins includes polyvinyl chloride and metal (iron, aluminum). , Copper, etc.), hard vinyl chloride and metal, soft vinyl chloride each other, soft vinyl chloride and metal (iron, aluminum, copper, etc.), soft vinyl chloride and plywood, polycarbonate and aluminum,
Nylon and aluminum, reinforced polyester fiber and aluminum, ABS resin and aluminum, acrylic resin and aluminum, polyethylene terephthalate (PET)
It is preferably used for adhesion of PET, metal and the like. Adhesion of vinyl chloride to each other or as a hot-melt adhesive for flooring made of soft vinyl floor sheet and stainless steel (SUS) or aluminum plate, or adhesion of soft vinyl chloride to metal (iron, aluminum, copper, etc.) or plywood It is preferably used for.

[0017]

EFFECTS OF THE INVENTION The modified polyamide resin composition of the present invention can be easily formed into a film or a sheet, and the same kind or different kinds of synthetic resin or the same kind or different kind of metal can be bonded.
It shows excellent adhesive strength for adhesion between metals and various synthetic resins or adhesion between various synthetic resins and plywood, and particularly shows excellent performance for adhesion between soft vinyl chlorides, and its industrial utility value is extremely large. is there.

[0018]

The present invention will be described below with reference to examples. In the examples, "parts" means "parts by weight" unless otherwise specified.

Example 1 Using a plastic coder manufactured by Brabender, 50 parts of Tomide TXC-232C (manufactured by Fuji Kasei Kogyo Co., Ltd.) and TME
Two parts of G (manufactured by Shin Nippon Rika Co., Ltd.) were melt mixed at 150 ° C. for 5 minutes. Then, using a table press manufactured by Tester Sangyo Co., Ltd., 10 parts of the obtained mixed melt is sandwiched between Teflon sheets and pressed at a temperature of 150 ° C. for 5 minutes at a gauge pressure of 200 kg to obtain a sheet having a thickness of 120 μ (A-1). Was produced.

Example 2 In Example 1, as the polyamide resin, Sunmide H was used.
40 parts of T-140PK-20 (manufactured by Sanwa Chemical Industry Co., Ltd.)
Bondine HX-814 as poly-carboxylic acid anhydride
A sheet (A-2) having a thickness of 105 μm was produced in the same manner as in Example 1 except that 4 parts of 0 (manufactured by Sumitomo Chemical Co., Ltd.) was used.

Example 3 In Example 1, 40 parts of Numid 3008 (trade name of Harima Chemicals Co., Ltd.) as a polyamide resin, 2 parts of TMEG as a poly-carboxylic acid anhydride, and 5 parts of Smitate MB-11 as an additive were used. A 110 μm-thick sheet (A-3) was produced in the same manner as in Example 1 except that it was used.

Example 4 In Example 1, as the polyamide resin, Sunmide H was used.
40 parts of T-140PK-20 (manufactured by Sanwa Chemical Industry Co., Ltd.)
A 115 μm-thick sheet (A-4) was produced in the same manner as in Example 1 except that 2 parts of Neotor 125 (modified rosin; trade name of Harima Kasei Co., Ltd.) of poly-carboxylic acid anhydride was used as an additive.

Comparative Example 1 A sheet (B-1) having a thickness of 105 μ was prepared in the same manner as in Example 1, except that 10 parts of the polyamide resin, Thomaid TXC-232C pellets were used.

Comparative Example 2 Sunamide HT-140PK-2 which is a polyamide resin
0 for 40 parts and Sumitate MB-11 for 5 parts only,
The rest is the same as in Example 1 and the sheet (B
-2) was produced.

Adhesive Performance Test Using the sheets prepared in the above Examples and Comparative Examples, an adhesive performance test was conducted according to the following method. The results are shown in Table-1. The bonding conditions and test method are as follows.

[Adhesion conditions] Using the sheet obtained by the above method, the temperature was 150 ° C. × 10 minutes / pressing pressure 0.05 kgf / cm ²
mm × 150 mm × 3.0 mm soft PVC sheets (manufactured by Nippon Test Panel Co., Ltd.) were bonded together.

[Test Conditions] One end of the bonded portion of the test piece was peeled off in advance by about 10 mm, both were attached to the grip portion of the tester, and the T peel strength (kgf / inch) was measured. Tensile speed = 50mm / min, measurement temperature = 25 ℃, 60 ℃

[0028]

[Table 1]

Claims (4)

[Claims] 1. A polyamide resin obtained by the reaction of dimer acid and polyamine, and poly-carboxylic acid anhydride 0.1 having a plurality of carboxylic acid anhydrides in one molecule with respect to 100 parts by weight of the polyamide resin. A modified polyamide resin composition comprising a mixture of ˜20 parts by weight. 2. A polyamide resin is a polymer obtained by the reaction of dimer acid and polyamine, and has an amine value of 3
~ 30, viscosity is 5000 (cps / 200 ℃) or more, softening point is 120
The modified polyamide resin composition according to claim 1, which has a temperature of not less than ° C. 3. The modified polyamide resin composition according to claim 1, wherein the poly-carboxylic acid anhydride is an anhydride of an aliphatic or aromatic polycarboxylic acid. 4. An aliphatic or aromatic polycarboxylic acid anhydride is pyromellitic dianhydride, diester of pyromellitic dianhydride or trimellitic dianhydride and ethylene glycol, or triester of glycerin, 3,3 ′. , 4,
4′-benzophenone tetracarboxylic acid anhydride, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer The modified polyamide resin composition according to claim 3.