JPH0123295B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for adhering plastic and a liquid rubber composition, and more specifically, the present invention relates to a method for adhering a plastic and a liquid rubber composition, and more specifically, a method for adhering a plastic and a liquid rubber composition by coating or pouring the liquid rubber composition after treating the plastic with a specific surface treatment agent. Concerning how to increase your power. Conventionally, the methods for bonding plastics and rubber compositions include (1) roughening the surface of polyolefin, applying an isocyanate group-containing compound and curing it by heating, and then applying a rubber adhesive containing an isocyanate compound; In the method of superimposing a rubber composition on top and heating and pressurizing it (Japanese Patent Publication No. 11814/1972), (2) the method of bonding a rubber or synthetic resin base material with a reactive adhesive, the surface of the base material is coated with alkyl hypohalide and A method of treating with a treatment agent containing a compound having a functional group capable of bonding to active hydrogen and a reactive adhesive (Japanese Patent Application Laid-open No. 49-57038) is known. However, in the conventional method as described above, the adhesion between the plastic and the rubber composition was insufficient and was not practical. Therefore, the present inventors have conducted extensive research in order to develop a method that can firmly bond plastic and rubber compositions. As a result, the inventors discovered that the object could be achieved by surface treating plastics with a hydroxyl group-containing ethylenically unsaturated monomer and an isocyanate, leading to the completion of the present invention. That is, the present invention surface-treats plastic or roughened plastic with a hydroxyl group-containing ethylenically unsaturated monomer and isocyanate,
The present invention provides a method for adhering plastic and a liquid rubber composition, which comprises applying or pouring the liquid rubber composition onto the surface-treated plastic and curing it. In the method of the present invention, the plastic may be used as it is, but it is preferable to roughen the surface in advance by conventional means such as blasting or solvent etching. Plastics to which the method of the present invention can be applied include various types, such as thermoplastic plastics such as polycarbonate, polystyrene, polymethyl methacrylate, polypropylene, and polyethylene, unsaturated polyesters, phenolic resins, melamine resins, Examples include thermosetting plastics such as acrylic resins. Among these, polycarbonate, polystyrene, polymethyl methacrylate, unsaturated polyester, etc. are particularly preferred. Next, in the method of the present invention, a hydroxyl group-containing ethylenically unsaturated monomer and an isocyanate are used in combination as the surface treating agent for the plastic. Examples of the hydroxyl group-containing ethylenically unsaturated monomer used here include hydroxyl group-containing acrylic esters such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate;
- Hydroxyl group-containing methacrylic esters such as -hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. On the other hand, as the isocyanate, aromatic isocyanates such as toluylene diisocyanate, polymethylene polyphenyl isocyanate, 4,4'-diphenylmethane diisocyanate, 4,4',4''-triphenylmethane triisocyanate, hexamethylene diisocyanate, 1 , 4-butane diisocyanate, and alicyclic isocyanates such as isophorone diisocyanate and cyclohexane diisocyanate.In the method of the present invention, as described above, a hydroxyl group-containing ethylenically unsaturated monomer is used as a surface treatment agent. It is necessary to use a polymer and an isocyanate in combination.If only one of them is used, sufficient adhesion cannot be developed and the purpose of the present invention cannot be achieved. Since it has good wettability with both plastics and liquid rubber compositions, the order of treatment is not particularly limited, but it is preferable to first treat with the hydroxyl group-containing ethylenically unsaturated monomer and then with the isocyanate. Surface treatment conditions may be selected appropriately depending on the type of surface treatment agent, type of plastic or rubber composition, etc., but usually the hydroxyl group-containing ethylenically unsaturated monomer is used directly or dispersed or dissolved in a solvent. Apply to the plastic surface by brushing, spraying, roll coating, etc. If a solvent is used, dry at room temperature to 80℃ to evaporate the solvent, then apply isocyanate to the surface in the same way. Here, the solvent for dissolving or decomposing the above-mentioned surface treatment agent includes ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetone, hydrocarbons such as pentane, hexane, octane, and cyclohexane, and chlorine such as methylene chloride, trichloroethylene, and trichloroethane. Examples include hydrogenated hydrocarbons and acetate esters such as ethyl acetate and butyl acetate.In the method of the present invention, plastics are surface-treated with the above-mentioned surface treatment agent, and if necessary, the plastic is heated at room temperature to 80°C. After sufficient drying, it is necessary to apply or pour a liquid rubber composition onto the surface-treated plastic and cure it. You can select the desired one, but usually (A) Telekylic liquid rubber, (B) Curing agent, (C) Reinforcing agent, (D) Inorganic filler, (E) Anti-aging agent, (F) Oil extender and (G ) A curing catalyst is used.In this liquid rubber composition, the blending ratio of each component (A) to (G) above is not particularly limited, but generally (A)
(B) for 100 parts by weight of Telekirik liquid rubber
Each component of (G) should be proportioned as follows: First, (B) the curing agent is 5 to 100 parts by weight, preferably 10 to 40 parts by weight.
Part by weight. For example, if (A) telechelic liquid rubber contains an OH group as a functional group, (B)
The curing agent preferably has an NCO group,
Regarding the OH group of this telekirik liquid rubber,
NCO group from 0.6 to 2.0 (equivalent ratio), preferably from 0.8 to 1.5
(equivalent ratio). Next, (C) reinforcing agent should be 0 to 100 parts by weight, preferably 10 to 50 parts by weight. If the amount of the reinforcing agent exceeds 100 parts by weight, the liquid rubber composition becomes brittle and has the opposite effect. The amount of inorganic filler (D) should be 0 to 300 parts by weight, preferably 10 to 100 parts by weight. If it exceeds 300 parts by weight, workability will drop significantly. Furthermore, (E) anti-aging agent is 0 to 10
It should be in parts by weight, preferably from 0.1 to 5 parts by weight. Even if it exceeds 10 parts by weight, there is no effect, and the physical properties etc. deteriorate, resulting in the opposite effect. Subsequently (F) the oil extender should be in an amount of 0 to 200 parts by weight, preferably 10 to 100 parts by weight.
If it exceeds 200 parts by weight, the strength of the entire liquid rubber composition decreases, and it also has an adverse effect on the adhesive surface, which is not preferable. The amount of curing catalyst (G) should also be from 0 to 3 parts by weight, preferably from 0.001 to 0.5 parts by weight. If it exceeds 3 parts by weight, the curing speed will be too high and the work will become impossible. The specific components of the liquid rubber composition having the above-mentioned mixing ratios are as follows. First of all, (A) Telekylic liquid rubber has fluidity at room temperature and forms a three-dimensional network structure through appropriate chemical treatment, such as curing treatment, and exhibits the same physical properties as ordinary vulcanized rubber. be. In the present invention, a liquid rubber having a functional group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a methoxy group, an aziridino group, or a halogen atom at the molecular end and having a number average molecular weight of 500 to 8,000 is preferred. Specific examples of the liquid rubber include butadiene homopolymer; butadiene copolymer such as butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-styrene copolymer, butadiene-pentadiene copolymer; isoprene homopolymer, etc. Among these, Butadiene homopolymer; butadiene-based liquid rubber such as butadiene copolymer is desirable. Moreover, those having a hydroxyl group as a functional group are desirable. Next, (B) the curing agent is a substance that acts to harden the liquid rubber by chemically bonding between the molecules of the liquid rubber and crosslinking it, specifically toluylene diisocyanate and 4,4'-diphenylmethane diisocyanate. , isocyanate compounds such as polymethylene polyphenyl isocyanate; 3,3'-dichlorobenzidine, 2,4-diamino-6-undecyl-
Amino compounds such as 1,3,5-triazine; tris[1-(2-methyl)-aziridinyl]phosphine oxide, bis[1-(2-ethyl)-aziridinyl]benzene-1,3-dicarboxylic acid amide, etc. Examples include glycidyl compounds such as glycerin glycidyl ether, bisphenol A glycidyl ether, and vinylcyclohexene dioxide. Among these, isocyanate compounds are preferred, and diisocyanate compounds are particularly preferred. On the other hand, the reinforcing agent (C) further increases the strength of the liquid rubber composition, and polyols, polyamines, and the like can be used. These polyols can be broadly classified into short chain polyols, polyester polyols, polyether polyols, acrylic polyols, castor oil, tall oil, and the like. Here, specific examples of short chain polyols include aromatic short chain diols such as N,N-bis-(2-hydroxypropyl)aniline and propylene oxide adduct of bisphenol A; 2-ethylhexanediol, 1,4
- Aliphatic diols such as butanediol; aliphatic triols such as glycerin and trimethylolpropane; and the like. Polyester polyols include polybasic acids (e.g. phthalic acid, adipic acid,
Organic acids such as dimerized linoleic acid and maleic acid) and hydroxy compounds (e.g. ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylolpropane, hexanetriol, glycerin, trimethylolethane, pentaerythritol, etc.) can be given. Examples of polyether polyols include poly(oxypropylene ether) polyol and poly(oxyethylene-propylene ether) polyol. Further, as a specific example of the polyamine, 4,4'-methylene-
Bis-2-chloroaniline, lauroguanamine,
Examples include polyoxypropylene amine and polyoxyethylene amine. Further, (D) inorganic fillers include carbon black, white carbon, metal oxides (aluminum hydroxide, etc.), metal carbonates (magnesium carbonate, etc.), metal sulfates (magnesium sulfate, etc.), and the like. Specifically, the anti-aging agent (E) in the above liquid rubber composition is an ultraviolet absorber, an antioxidant, etc. nylene diamine, etc.), alkylphenols (2,2'-methylenebis(4-methyl-6-tert-butylphenol), etc.), thiourea (1,3-bis(dimethylaminopropyl)-2-thiourea, etc.), benzene Imidazole (2-mercaptobenzimidazole, etc.) and the like can be used. Further, as the oil extender (F), aromatic process oils, naphthenic process oils, phthalic acid esters, adipic acid esters, etc. can be used. The curing reaction of the liquid rubber composition described above can normally be carried out without using a catalyst, but if shortening of the curing time is desired, (G) a curing catalyst.
For example, the usual urethane curing catalysts stannous chloride, dimethyltin dichloride, trimethyltin hydroxide, di-n-butyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, ferric chloride, and iron acetylacetonate. , cobalt naphthenate, bismuth nitrate, lead oleate,
Metal compounds such as antimony trichloride and amines such as triethylamine and tetramethylbutanediamine are used. In the method of the present invention, it is necessary to apply or pour the above-mentioned liquid rubber composition in a fluid state onto the surface-treated plastic, and to further cure the plastic. This curing is carried out at a temperature ranging from room temperature to 20-30°C below the melting temperature of the plastic, preferably 40-80°C.
This can be done for a predetermined period of time. The laminated adhesive of plastic and liquid rubber composition obtained by such an operation has extremely high adhesive strength and can sufficiently withstand various external forces. Furthermore, the method of the present invention has the advantage that the process is much simpler than conventional methods. Therefore, the method of the present invention can be effectively used for laminating and adhering liquid rubber compositions with polycarbonate, unsaturated polyester, etc., or manufacturing cast tires. Next, the method of the present invention will be explained in more detail with reference to Examples. Examples 1 to 8 A piece of polycarbonate with a thickness of 3 mm x 25 mm x 110 mm (manufactured by Idemitsu Petrochemical Co., Ltd., product name: Idemitsu Polycarbon A)
-2500) was roughened with a #400 sandpaper, and then degreased with hexane. Next, the first treatment agent shown in Table 1 was applied to this polycarbonate piece with a brush and left at room temperature for about 30 minutes. Next, a second treatment agent was applied with a brush and left at room temperature for about 60 minutes. The polycarbonate piece was then coated with about 1 portion of the liquid rubber composition shown below.
A 180° peel adhesion strength test piece was prepared by applying the adhesive to a thickness of mm and attaching a cotton canvas. Further, instead of the cotton canvas, a polycarbonate piece prepared by the above-mentioned treatment method was pasted together to prepare a tensile shear adhesive strength test piece. Next, these test pieces were heated and cured in an oven at 50°C for 48 hours, and then subjected to an adhesion test. The 180° peel adhesion strength test was based on JIS K 6301.
The tensile shear adhesive strength test was conducted in accordance with JIS K 6850 at a tensile speed of 25 mm/min. The results are shown in Table 1. The liquid rubber composition used as the adhesive had the following composition and was mixed using three paint mill rolls. Liquid rubber composition formulation No. 1 Hydroxyl group-terminated liquid polybutadiene (product name: Poly
bd R-45M, manufactured by ARCO, hydroxyl group content 0.76 meq/g) ...100 parts by weight ISAF-LS Carbon Black ...70 parts by weight Urethane polyol (Product name: Hiflex
750, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (reinforcing agent) ...34 parts by weight 2 (2'-hydroxy-3',5'-dithyabutyl phenyl) 5-chlorobenzotriazole (ultraviolet absorber) ... ...1 part by weight 2,2'-methylenebis(4-methyl-6-tertiarybutylphenol) (antioxidant)
...2 parts by weight dibutyltin dilaurate (curing catalyst)
...0.007 parts by weight Liquid modified 4,4'-diphenylmethane diisocyanate (curing agent) ...15.5 parts by weight No. 2 Hydroxyl group-terminated liquid polybutadiene (product name: Poly
bd R-45HT, manufactured by ARCO, hydroxyl group content 0.83 meq/g) ...100 parts by weight Calcium carbonate ...70 parts by weight N,N-bis(2-hydroxypropyl)aniline (reinforcing agent) ...1.7 parts by weight Dibutyltin dilaurate...0.02 parts by weight Liquid modified 4,4'-diphenylmethane diisocyanate...17.4 parts by weight No. 3 Tolylene diisocyanate prepolymer of hydroxyl-terminated liquid polybutadiene (product name: HTP-9,
Manufactured by Idemitsu Petrochemical Co., Ltd., NCO content 9% by weight)
...100 parts by weight N,N-bis(2-hydroxypropyl)aniline ...20.3 parts by weight dibutyltin dilaurate ...0.02 parts by weight Comparative example 1 Polycarbonate piece 3 mm x 25 mm x 110 mm thick (manufactured by Idemitsu Petrochemical Co., Ltd.) , Product name: Idemitsu Polycarbo A
-2500) was roughened with #400 sandpaper and then degreased with hexane. Next, the aforementioned No. 1 liquid rubber composition was applied to this polycarbonate piece to a thickness of about 1 mm, and a cotton canvas was attached to prepare a 180° peel adhesive strength test piece. In addition, a tensile shear adhesive strength test piece was prepared by pasting together a roughened and degreased polycarbonate piece instead of the cotton cloth. Next, these test pieces were heated and cured in an oven at 50°C for 48 hours, and then subjected to an adhesion test. The results are shown in Table 1. Comparative Example 2 Polycarbonate piece with a thickness of 3 mm x 25 mm x 110 mm (manufactured by Idemitsu Petrochemical Co., Ltd., product name: Idemitsu Polycarbon A)
-2500) was roughened with #400 sandpaper and then degreased with hexane. Next, a solution of about 20% triphenylmethane 4,4',4''-triisocyanate in methylene chloride (trade name: Desmodyur R, manufactured by Bayer AG) was applied to this polycarbonate piece and left at room temperature for about 60 minutes. Apply the above-mentioned No. 1 liquid rubber composition to a thickness of about 1 mm, and attach a cotton canvas.
A 180° peel adhesive strength test piece was prepared. In addition, instead of the cotton cloth, polycarbonate pieces prepared by the above-mentioned treatment method were pasted together to prepare tensile shear adhesive strength test pieces. Next, these test pieces were heated and cured in an oven at 50°C for 48 hours, and then subjected to an adhesion test. The results are shown in Table 1. Comparative Example 3 A piece of polycarbonate with a thickness of 3 mm x 25 mm x 110 mm (manufactured by Idemitsu Petrochemical Co., Ltd., product name: Idemitsu Polycarbon A)
-2500) was roughened with #400 sandpaper and degreased with hexane. Next, a 20% tetrahydrofuran solution containing 0.06 mol of tertiary butyl hypohalide and 0.06 mol of 2-methyl-2,4-pentenediol was applied to the polycarbonate piece, and after being left for 2 to 3 minutes, the surface was cleaned with methyl ethyl ketone. .
Thereafter, the above-mentioned No. 1 liquid rubber composition was applied to a thickness of about 1 mm, and a cotton canvas was attached to prepare a 180° peel adhesive strength test piece. In addition, instead of the cotton cloth, polycarbonate pieces prepared by the above-mentioned treatment method were pasted together to prepare tensile shear adhesive strength test pieces. Next, these test pieces were heated and cured in an oven at 50°C for 48 hours, and subjected to an adhesion test. The results are shown in Table 1. Comparative Example 4 Polycarbonate piece with a thickness of 3 mm x 25 mm x 110 mm (manufactured by Idemitsu Petrochemical Co., Ltd., product name: Idemitsu Polycarbon A)
-2500) was roughened with #400 sandpaper and then degreased with hexane. Next, a 5% by weight solution of polyphenylmethane polyisocyanate (trade name: PAPI, manufactured by Kagaku Upjiyon Co., Ltd.) in chlorinated naphtha (boiling point less than 250〓) was applied to this polycarbonate piece and dried for about 30 minutes at room temperature. A 1% by weight solution of triethylene diamine in methyl ethyl ketone was then applied and dried at room temperature for about 30 minutes. In addition to the above-mentioned No. 1
Apply the liquid rubber composition and paste the cotton canvas.
A 180° peel adhesive strength test piece was prepared. In addition, instead of the cotton canvas, polycarbonate pieces prepared by the above-mentioned treatment method were pasted together to prepare tensile shear adhesive strength test pieces. Next, these test pieces were heated and cured in an oven at 50°C for 48 hours, and then subjected to an adhesion test. The results are shown in Table 1. Examples 9 to 16 Using unsaturated polyester pieces with a thickness of 2 mm x 25 mm x 110 mm as adherends, adhesive test pieces were prepared in the same manner as in Examples 1 to 8, and subjected to an adhesive strength test. The results are shown in Table 2. Comparative Examples 5 to 8 Using an unsaturated polyester piece with a thickness of 2 mm x 25 mm x 110 mm as an adherend, adhesive test pieces were prepared in the same manner as in Comparative Examples 1 to 4, and subjected to an adhesive strength test. The results are shown in Table 2. Examples 17 to 20 Using a polystyrene piece with a thickness of 2 mm x 25 mm x 110 mm as an adherend, adhesive test pieces were prepared in the same manner as in Examples 1, 2, 5, and 6, and subjected to an adhesive strength test. did. The results are shown in Table 3. Comparative Examples 9 to 12 Using polystyrene pieces with a thickness of 2 mm x 25 mm x 110 mm as adherends, adhesive test pieces were prepared in the same manner as in Comparative Examples 1 to 4, and subjected to an adhesive strength test. The results are shown in Table 3. Examples 21 to 25 Using polymethyl methacrylate pieces with a thickness of 2 mm x 25 mm x 110 mm as adherends, Examples 1, 2,
Adhesive test pieces were prepared in the same manner as in Examples 5, 6, and 8, and subjected to an adhesive strength test. The results are shown in Table 4. Comparative Examples 13 to 16 Using polymethyl methacrylate pieces with a thickness of 2 mm x 25 mm x 110 mm as adherends, adhesive test pieces were prepared in the same manner as in Comparative Examples 1 to 4, and subjected to adhesive strength tests. . The results are shown in Table 4. The meanings of each symbol used in Tables 1 to 4 below are as follows. A...Cohesive failure, B...Interfacial peeling of adherend, C
...Destruction of adherend, D...Cohesive failure and interfacial peeling of adherend HEMA...20% by weight solution of 2-hydroxyethyl methacrylate in methyl ethyl ketone HEA...of 2-hydroxyethyl acrylate
20% by weight methyl ethyl ketone solution HEPA...20% by weight methyl ethyl ketone solution of 2-hydroxypropyl acrylate CONAP...CONAP1146C (product name, manufactured by CONAP, thermosetting polyurethane, solid content 25%, specific gravity
0.866) TDI...20% by weight solution of tolylene diisocyanate in methyl ethyl ketone MTL...30% of Millionate MTL (trade name, manufactured by Nippon Polyurethane Industries, NCO content 28.8% by weight)
Weight% ethyl acetate solution Desmodyur R...Triphenylmethane-4,
Approximately 20% methylene chloride solution of 4',4''-triisocyanate (trade name, manufactured by Bayer AG) N-75... Sumidyur N-75 (trade name, manufactured by Sumitomo Bayer Urethane, 75 weight of polyfunctional aliphatic isocyanate) % ethyl acetate, xylene solution) TBH/MPD...Tertiary butyl hypohalide
20% tetrahydrofuran solution of 0.06 mol and 0.06 mol of 2-methyl-2,4-pentenediol PAPI...5 wt% chlorinated naphtha solution of polyphenylmethane polyisocyanate TEDA...1 wt% methyl ethyl ketone solution of triethylene diamine

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Claims (1)

[Scope of Claims] 1. Surface-treating plastic or roughened plastic with a hydroxyl group-containing ethylenically unsaturated monomer and isocyanate, then applying or pouring a liquid rubber composition onto the surface-treated plastic and curing it. A method for adhering plastic and a liquid rubber composition, characterized by: 2. The method according to claim 1, wherein the plastic is polycarbonate, polystyrene, polymethyl methacrylate or unsaturated polyester. 3. The liquid rubber composition contains (A) 100 parts by weight of telechelic liquid rubber, (B) 5 to 100 parts by weight of a curing agent, (C) 0 to 100 parts by weight of a reinforcing agent, and (D) 0 to 300 parts by weight of an inorganic filler. ,(E)
The method according to claim 1, which comprises 0 to 10 parts by weight of an antiaging agent, (F) 0 to 200 parts by weight of an oil extender, and (G) 0 to 3 parts by weight of a curing catalyst. 4. The method according to claim 1, wherein the hydroxyl group-containing ethylenically unsaturated monomer is a hydroxyl group-containing acrylic ester or a hydroxyl group-containing methacrylic ester.