JP3080095B2 - Curable adhesive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention relates to a curable adhesive resin composition, more specifically, it is cured by heat or light, and is particularly useful as a sealing agent. A curable adhesive resin composition.

(Prior Art and Problems to be Solved by the Present Invention) The pressure-sensitive adhesive tape has tackiness at room temperature and can be attached to an object without any preliminary operation. In addition, they are used in various fields because of the advantage that they can be reattached. However, adhesive tapes have the disadvantage that their adhesive strength is generally weaker than adhesives. In addition, since the tape is usually formed by applying an adhesive to the tape base, the part having a complicated shape, for example, a stepped part, a dent, or a part that is protruding, is provided with a base material. Due to the thickness, hardness, waist and the like, it is impossible to attach without gaps. The adhesive tape also has problems in water resistance, solvent resistance and heat resistance.

On the other hand, paints, adhesives, sealants, etc. have complex shapes,
It is applicable to curved surfaces, holes, protrusions, steps, gaps, and the like, and can also utilize a curing reaction, which is advantageous in improving water resistance, solvent resistance, and heat resistance. However, these require a pretreatment such as mixing a curing agent before use, and are usually in the form of a sol or paste containing a solvent. It is troublesome because you have to be in a container on a flat surface. In addition, attention must be paid to the contamination of parts other than the target location due to flow, dripping, and splashing during construction, and once contaminated, removal is extremely complicated and often impossible.

Solving the problems of the prior art, combining the advantages of adhesives, paints, adhesives, and sealers,
As a result of diligent research into developing a curable composition which is tacky under normal conditions, the present applicant filed a patent application (Japanese Patent Application No. 62-266899).

The present inventors have further researched, and have a composition different from the reactive pressure-sensitive adhesive composition according to the above-mentioned patent application, and have properties equal to or higher than that of the pressure-sensitive adhesive, which is a heat or light-curable pressure-sensitive adhesive. We succeeded in developing a resin composition.

[Constitution of the Invention] (Means for Solving the Problems) The present invention relates to a liquid crystal composition having at least one thermoplastic resin selected from an ethylene-vinyl acetate copolymer and a polyamide and having a viscosity of 500 poise or more at room temperature. It is a curable adhesive resin composition obtained by melt-kneading a (meth) acrylic urethane oligomer and a heat and / or photoreaction initiator in the absence of a solvent.

As the thermosetting resin used in the present invention, for example,
Epoxy resins, alkyd resins, unsaturated polyester resins, acrylic resins, xylene resins, urea resins, melamine resins, diallyl phthalate resins, and the like. Among these resins, those having good stability over time under normal conditions (especially those such as two-component epoxy resins) and having a curing temperature of 50 to 300 ° C, preferably 80 to 180 ° C For the liquid resin, those having a viscosity of 500 poise or more, preferably 2000 poise or more are used.

Examples of the photocurable resin include acryloyl polybutadiene oligomers at both ends, urethane acrylates such as epoxy acrylic oligomers and urethane acrylic oligomers, polyester acrylic oligomers, alkyd acrylic oligomers, silicone acrylic oligomers,
(Meth) acrylic monomer trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, neopentyl glycol di (meth) acrylate,
Diacryloxyethyl phosphate and the like.

More specific photocurable resins include, for example, modified acrylic epoxy oligomers (Grace Japan, Amicon UV300), modified acrylic oligomers (Sankyo Pharmaceutical, Superdyne AE), epoxy (meth) acrylates (Shin Nakamura Chemical Industries, NK ester EA800H), urethane (meta)
Acrylate (Shin Nakamura Chemical, NK Ester U6H; Toa Gosei, Aronix M-1100), Acrylate Prepolymer (ThreeBond, ThreeBond 3056), Polyester (Sony Chemical, Sony Bond UV1001), Modified Polyester (Electrochemical, Modified Polyester) ), Modified oligoacrylates, HI-LOCK UV-500), and acrylic resins (Toyo Ink, Multi-cure).

As the curable resin of the present invention, of course, a resin having both thermosetting and photocurable properties can also be used, and a thermosetting resin and a photocurable resin can be used in combination, Further, two or more kinds of different thermosetting resins or two or more kinds of different photocurable resins can be used in combination.

Among the above-mentioned curable resins, the present invention is used, in particular,
Preferred is a urethane acrylate resin.

Next, the thermoplastic resin used in the present invention usually has a softening point or a heat distortion temperature (° C., 18.6 kg / cm ² ) of 200 ° C.
If it is less than about, it can be used. Specifically, for example, the following resins are used.

Polyethylene (eg, Idemitsu Petrochemical, Moretec 0628
G); Polyester (eg, Unitika, Elitel UE3221); Polypropylene (eg, Chisso, Chisso Polypro K101)
6); polybutylene; polybutadiene (eg, Japan Synthetic Rubber, JSRRB820); polybutene (eg, Mitsui Petrochemical Industries, M8340); polyisoprenevinyl butyral; polyphenylene ether (oxide) (eg, Asahi Kasei, G0
10H); Polysulfone (eg, Amoco Chemicals Japan Limited, UDEL polysulfone P-1700); Polycarbonate (eg, Teijin Chemicals, Panlite G313)
0); poly-p-xylene (eg, Mitsubishi Gas Chemical, Nicanol NP
-140); polyvinyl acetate (eg, Nippon Gohsei, Gohsenil M50)
-Y5); polyvinyl chloride (eg, Nippon Zeon, Zeon 101EP); polyvinylidene chloride (eg, Asahi Kasei, Saran Resin F21)
6); Chlorinated polyvinyl chloride (partially chlorinated polyvinyl chloride); Chlorinated polyethylene (partially chlorinated polyethylene)
(Example: Showa Denko, Eraslen 301E); Chlorinated polypropylene (partially chlorinated polypropylene); Fluororesins: [Example: Polytetrafluoroethylene (eg, Daikin Industries, Polyflon TFEM-31); Polychlorotrifluoroethylene (Eg, Daikin Industries,
NEOFLON CTFE M-300H); polyvinylidene fluoride (eg, Showa Denko, Foraphron 10)
0HD); polyvinyl fluoride]; polyacetal (eg, DuPont Japan Limited, Delrin 500CL); polyarylate (eg, Unitika, U-Polymer UM-8400-)
30); polystyrene (eg, Nippon Steel Chemical, Estyrene GP); methacrylic resin (eg, Mitsubishi Rayon, Acrypet IR-)
H50); Polymethylpentene (eg, Mitsui Petrochemical, MX002); Polyacrylonitrile; Polyethers (eg, IC Japan, VICT)
REX PEEK 450G); Silicones; Polyamide (eg, MMS Japan, Grillamide LKN-5)
H); polyamide derivatives; polyketones (eg, Arakawa Chemical, Ketone Resin K-90); polyvinyl butyral; thermoplastic epoxy resins; and copolymers of these thermoplastic resins.

These thermoplastic resins may be used alone or in combination of two or more.

The compounding ratio of the curable resin to the thermoplastic resin, which is a component of the composition of the present invention, is 5:95 to 99: 1 by weight, and preferably 30:70 to 80:20.

In the composition of the present invention, it is advantageous to use a reaction initiator in order to accelerate the curing reaction.

The reaction initiator includes a thermal reaction initiator and a photoreaction initiator. Examples of the thermal reaction initiator include benzoyl peroxide, di-2-ethylhexyl peroxydicarbonate, and di-3-methoxybutyl peroxydicarbonate. Benzoyl peroxide, cyclohexane peroxide and the like.

Examples of the photoreaction initiator include benzoin compounds such as benzoin methyl ether and benzoin isooctyl ether, benzylacetyl, diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, methylanthraquinone, acetophenone, benzophenone, and benzoylformic acid. Examples include carbonyl compounds such as methyl, sulfur compounds such as diphenyl disulfide and dithiocarbamate, naphthalene compounds such as α-chloromethylnaphthalene, metal salts such as iron chloride, and anthracene.

The addition amount of the above-mentioned reaction initiator is about 0.01 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, based on 100 parts by weight of the photocurable resin and / or the thermosetting resin. The photoreaction initiator or the thermal reaction initiator may be used alone or in combination.

The composition of the present invention may further contain, as a filler, for example, calcium carbonate (eg, calcium shiraishi, whiten SS)
B), aluminum silicate (eg, Showa Mining, Suwanee Z), Saran hollow spheres (eg, DowChem. Saran Microspher)
e) 0.1 to 95 parts by weight, preferably 1 to 100 parts by weight of an organic or inorganic filler such as cellulose powder (eg, Sanyo Kokusai Parve, Pulp Floc W-1) based on 100 parts by weight of the resin component.
10 parts by weight can be added.

Other additives include, for example, lubricants (eg, Mobil Oil, Mobil Crystalwax; Sanyo Chemical, Sunwax 161)
-P) and a plasticizer [eg, dioctyl phthalate (eg, Shin Nippon Rika, Sansocizer); dimethyl malate (eg, Kurokin Kasei, Solver DMM); isodecyl diphenyl phosphate (eg, Monsanto, Santicizer 148)] Can also be used.

The composition of the present invention can be obtained by mixing the above-described components, and dispersing or dissolving them uniformly by melting or dissolving each other.

The curable pressure-sensitive adhesive composition of the present invention thus obtained does not have fluidity at room temperature and has appropriate tackiness and cohesive strength, so that it can be supplied in any form. For example, string, pellet, sheet, tape, tube,
It can be supplied in block form.

Further, the composition of the present invention can be spread, for example, on a release yarn to form a sheet of a curable pressure-sensitive adhesive. To cure the composition of the present invention, the composition is applied to an appropriate place, and then cured by applying heat or light (the light includes electromagnetic waves such as visible light, UV light, and X-rays).

In the case of photocuring, a photosensitizer or the like may be added. In the case of thermal curing, the temperature is adjusted to control the curing rate. In the case of a composition spread on release paper, a thick coating can be formed by peeling off the release paper and applying heat or light.

(Example) [Example 1] Polyacrylate ester resin 100 parts by weight Modified polyphenylene oxide 80 parts by weight (Mitsubishi Gas Chemical Co., Ltd.) Dicyandiamide 5 parts by weight (Nippon Carbide Co., Ltd.) Aerosil No. 300 10 parts by weight ( Nippon Aerosil Co., Ltd. The above ingredients were kneaded, made uniform, and extruded into a tape having a width of 2 cm and a thickness of 0.5 mm using an extruder to obtain a sealer material. This was pressed against a place where two cold-rolled steel sheets having a thickness of 0.3 mm overlapped each other. Then 160
When heated at 30 ° C. for 30 minutes, the sealer material was cured. Further, coating was performed from above, and heating was performed at 160 ° C. for 30 minutes. As a result, the adhesion to the paint was good. Even when this sample was immersed in boiling water for 5 hours, no rusting or paint cracking was observed at the place where the sealer material was applied.

[Example 2] Acrylic urethane resin 30 parts by weight (Aronix M-1100: Toagosei Co., Ltd.) Nylon 6 (Ube Industries, Ltd.) 70 parts by weight Talc 1 part by weight Perbutyl IF (Nippon Oil & Fats Co., Ltd.) 1 part by weight Part The above ingredients are kneaded, made uniform, extruded into a sheet with a width of 30 cm and a thickness of 1 mm, cooled, punched out with a punching machine to an inner diameter of 6 mm and an outer diameter of 10 mm, and sealed. Material. This is a cold-rolled steel plate with a diameter of 8 mm.
Then, when heat treatment and coating treatment were performed in the same manner as in Example 1, the rustability and paint adhesion were good.

[Example 3] Acrylic urethane resin 60 parts by weight (Aronix M-1100: Toagosei Co., Ltd.) Ethylene vinyl acetate copolymer 40 parts by weight (EVA-150: Mitsui Polychemicals Co., Ltd.) Irgacure 184 2 parts by weight ( (Nippon Ciba Geigy Co., Ltd.) The above blended raw material was molded in the same manner as in Example 1 and affixed to the edge of a cold-rolled steel sheet having a thickness of 1 mm. Upon irradiation, the sealer material hardened.

[Example 4] Xylene resin 70 parts by weight (Nicanol NP-140: Mitsubishi Gas Co., Ltd.) Polyarylate 30 parts by weight (U Polymer AX-1500: Unitika Ltd.) Polyamide 5 parts by weight (Versamide 125: Henkel Japan ( Co., Ltd.) The above blended raw materials were kneaded, made uniform, and formed into a tape having a width of 30 cm and a thickness of 0.1 mm by an extruder to obtain a sealer material. This was applied so as to cover a cold-rolled steel plate having a thickness of 0.3 mm, a length of 15 cm and a width of 5 cm. After that, 160 ℃ × 30
After heating for 1 minute, the sealer material was hardened, and the coating was further performed from above. After heating at 160 ° C. for 30 minutes, the adhesion to the coating was good. Even if this sample was immersed in boiling water for 5 hours, no cracking of the paint was observed.
Even after a salt spray test for 48 hours, no rust was generated on the cold-rolled steel sheet covered with the sealer material.

[Comparative Example 1] Xylene resin 70 parts by weight (Nicanol NP-140: Mitsubishi Gas Corporation) Polyamide 5 parts by weight (Versamide 125: Henkel Japan K.K.) Was applied to the place where two cold-rolled steel sheets having a thickness of 0.3 mm overlapped each other with a sealer gun. With a sealer gun, it was difficult to move while discharging at a constant speed, and the discharged sealer did not ride on both sides of the edge, only on the edge. In addition, since the moving speed of the gun was not constant, the discharge amount was different in each part, and the sealer was wavy and the appearance was poor. Furthermore, since the viscosity was low, the steel plate was sagged during the heat treatment, and the steel plate was exposed in the sagged portion, and rust was observed in the salt spray test.

[Comparative Example 2] Acrylic urethane resin 100 parts by weight (Aronix M-8060: Toagosei Co., Ltd.) 1 part by weight of perbutyl O (Nippon Oil & Fats Co., Ltd.) It was formed into a tape shape having a width of 2 cm and a thickness of 0.3 mm to obtain a sealer material. This was pressed against a place where two cold-rolled steel sheets having a thickness of 0.3 mm overlapped each other, but the adhesive was so strongly adhered to the hand that it could not be placed at an appropriate position. In addition, a mark was left on a portion of the surface touched by hand during construction, and a uniform surface could not be obtained.

Example 5 50 parts by weight of phenolic resin (CY4711, Matsushita Electric Works) 50 parts by weight of vinyl acetate resin (Gosenil M50-Y5, Nippon Gohsei) 5 parts by weight of calcium carbonate (whiten SSB, calcium shiraishi) 10 parts by weight of formaldehyde hexamethylenetetramine 2 parts by weight (Sumitomo Chemical) The above ingredients were kneaded, made uniform, and extruded into a tape having a width of 15 mm, a thickness of 1.0 mm, and a length of 100 mm to obtain a sealer material. This is affixed to an electrodeposition coated plate,
After heating and curing for 0 minutes, the sealer material of the present invention was well fixed to the coated plate.

Example 6 60 parts by weight of diallyl phthalate (Dapol D500, Fudo Chemical Industry) 30 parts by weight of methacrylic acid resin (Acrypet IR-H50, Mitsubishi Rayon) 10 parts by weight of polyvinyl chloride (Zeon 101EP, Zeon Japan) 8 parts by weight of aluminum silicate Part (Showa Mining Co., Suwanee Z) Organic peroxide 1 part by weight (perbutyl O, Japanese oil and fat) The above blended raw material was molded in the same manner as in Example 5 to obtain a sealer material, which was likewise electrodeposited coated plate When heated (140 ° C., 30 minutes), similarly good results were obtained.

Example 7 50 parts by weight of photocurable acrylic resin (Toyo Ink, Multi-cure) 30 parts by weight of polycarbonate (Teijin Kasei, Panlite G3130) 20 parts by weight of chlorinated polyethylene (Showa Denko, Eraslen 301E) Cellulose powder 5 parts by weight ( Sanyo Kokusaku pulp, pulp floc W-1) 2 parts by weight of photoreaction initiator (Nippon Ciba Geigy, Irgacure 184) The above blended raw material was molded in the same manner as in Example 5 to obtain a sealer material, which was similarly electrodeposited. When attached to a painted plate and heated (140 ° C., 30 minutes), similarly good results were obtained.

Example 8 50 parts by weight of a phenolic resin (Gunei Chemical Industry Co., Ltd., resin top PL-2312) 30 parts by weight of a polyamide resin (MS Japan, Grillamide LKN-5H) 20 parts by weight of polybutadiene (Nippon Synthetic Rubber, JSR RB820) 10 parts by weight of talc The compounding raw material was molded in the same manner as in Example 5 to obtain a sealer material, which was similarly affixed to an electrodeposition coated plate and heated (140 ° C., 30 minutes) to obtain similarly good results. Was.

Example 9 Melamine resin 60 parts by weight (Sumitomo Bakelite, HA204) Polyvinylidene fluoride 40 parts by weight (Showa Denko, Foraphron 100HD) The above compounding raw material was molded in the same manner as in Example 5 to obtain a sealer material. Was heated (140 ° C., 30 minutes), and similarly good results were obtained.

Example 10 Urethane polyol 70 parts by weight (Sankyo Pharmaceutical, Superdyne UA-A) Polymethylpentene 30 parts by weight (Mitsui Petrochemical, MX002) Calcium carbonate 5 parts by weight (Takehara Chemical, Sunlight # 100) Molding was performed in the same manner as in Example 5, to obtain a sealer material, which was similarly affixed to an electrodeposition coated plate and heated (140 ° C., 30 minutes), and similarly good results were obtained.

(Effect of the Invention) The composition of the present invention, particularly when used as a sealant, has been difficult to use with a gun until now,
Sealing can be performed easily. In addition, even if the construction fails once, the workability is good, such as no contamination because it can be peeled off cleanly. Furthermore, the composition of the present invention has good adhesion to paint even when trace coating is used as a sealing agent, and furthermore has excellent rust prevention, and is useful for industrial use.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Yoshio Kishimoto 2-4-2, Kudanminami, Chiyoda-ku, Tokyo Nichiban Co., Ltd. (72) Junjiro Saito 2-4-2, Kudanminami, Chiyoda-ku, Tokyo (56) References JP-A-58-125773 (JP, A) JP-A-51-125138 (JP, A) JP-A-57-42779 (JP, A) JP-A-61-101583 (JP) , A) JP 49-1623 (JP, B1)

Claims (1)

(57) [Claims] 1. A thermal and / or photoreaction with at least one thermoplastic resin selected from ethylene-vinyl acetate copolymer and polyamide, and a liquid (meth) acrylic urethane oligomer having a viscosity of 500 poise or more at room temperature. A curable adhesive resin composition obtained by melt-kneading an initiator with no solvent.