JPH05156092A - Synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of giving a surface skin material having improved light-resistance and heat-resistance by adding a specific stabilizer to a composition composed of a rubber latex, an adsorbent and a surfactant. CONSTITUTION:The objective composition is produced by compounding (A) a rubber latex (preferably latex of a butadiene copolymer), (B) an adsorbent (e.g. active carbon or hydrated magnesium silicate clay mineral), (C) a surfactant (preferably a mixture of polymeric compounds having weight-average molecular weights of 150-10,000 and >=10,000, e.g. a mixture of an alkylnaphthalenesulfonic acid sodium salt, etc., and polyvinyl alcohol, etc.), (D) a stabilizer consisting of a semicarbazide compound of formula [R is (CH2)n ((n) is 1-12) or C6H4CH2C6 H4; R1 to R4 are H or 1-12C alkyl] (the amount of the component D is preferably 1-5 pts.wt. based on 100 pts.wt. of the solid component of the rubber latex) and (E) other additives such as flame-retardant and conductivity imparting agent and dispersing the obtained composition in an aqueous medium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin composition used for fabrics such as vehicle seat skins and skins used for door linings.

[0002]

2. Description of the Related Art Conventionally, a synthetic resin composition is laminated on a fabric such as a skin material of a vehicle. It is known that in the synthetic resin composition used here, rubber latex, activated carbon and hydrous magnesium silicate clay mineral as additives, and the like are dispersed in an aqueous medium by a surfactant (Japanese Patent Laid-Open No. HEI-2). No. 145864). The skin material has deodorizing properties and antistatic properties due to these additives. However, since the rubber latex, which is the main component of this synthetic resin composition, has insufficient heat resistance and light resistance of the film formed by coating and drying, it deteriorates with time when exposed to heat, sunlight, etc., and the texture of the skin material. And the adhesive strength of the resin component applied to the cloth is reduced, resulting in peeling.

[0003]

Therefore, this skin material is limited in its use in a region affected by heat, light, oxygen and the like. On the other hand, it has been attempted to add a benzotriazole-based compound or a benzophenone-based compound as a stabilizer to a synthetic resin composition for the purpose of improving the light resistance, but the light resistance is insufficient but the heat resistance is not sufficient. There are also stabilizers that increase heat resistance, but the improvement of light resistance is not sufficient, and in order to satisfy both, it is necessary to add expensive light stabilizers and heat stabilizers in combination. There's a problem.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a synthetic resin composition capable of forming a skin material having improved heat resistance and light resistance by adding one stabilizer. To do.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above circumstances, and when a semicarbazide compound is used as a stabilizer, a synthetic resin composition is applied to a cloth, and a dried resin film has a light resistance, It has been completed by finding out that the heat resistance is remarkably improved, the texture is soft for a long time, the strong adhesive strength between the cloth and the resin film is maintained, and the malodor is absorbed.

The synthetic resin composition of the present invention is a synthetic resin composition in which a rubber latex and an adsorbent such as activated carbon or hydrous magnesium silicate clay mineral are dispersed in an aqueous medium by a surfactant. It is characterized by having a stabilizer composed of a semicarbazide compound. The semicarbazide compound is a compound represented by the following general formula.

R₁R₂NNHCONH (R) NHNCONHNR₃R_Four (Where R is (CH₂)_nOr C₆H_FourCH₂C₆H_Four
R₁, R₂, R₃, R _FourIs a hydrogen atom or 1 to 1 carbon atoms
12 alkyl groups, n represents the integer of 1-12. ) Stable
Examples of semicarbazide compounds used as agents
Is 1,6-hexamethylenebis (N, N-dimethylsemi)
Carbazide) [shown in the formula (1)],

[0008]

[Chemical 1]

1,1,1 ', 1'-tetramethyl 4,
For example, 4 '-(methylenedi-P-phenylene) disemicarbazide [shown in the formula (2)] can be used.

[0010]

[Chemical 2]

A plurality of these semicarbazide compounds may be mixed and used. Although the mechanism of the resin film formed from the synthetic resin composition by adding the semicarbazide compound is unknown, it is possible to improve light resistance and heat resistance,
The light resistance and heat resistance of the skin material can be improved. The rubber latex used in the present invention may be natural rubber or synthetic rubber latex. A latex of a butadiene-based copolymer is particularly preferable. The butadiene copolymer is preferably one containing 20 to 80% by weight of butadiene and 20 to 80% by weight of an ethylenically unsaturated monomer copolymerizable therewith. Examples of the ethylenically unsaturated monomer include methacrylic acid ester, acrylic acid ester, styrene, acrylonitrile, methacrylonitrile, acrylamide, N-methylol acrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, acrylic acid, itaconic acid, fumaric acid, croton. Acid, maleic acid, etc. can be used.

The copolymer composition of the butadiene copolymer preferably contains 20 to 70% by weight of butadiene. Considering heat resistance and light resistance required as a rubber component for a vehicle skin material, butadiene 20 to 60% by weight, (meth) acrylic acid ester 40 to 80% by weight, other ethylenically unsaturated monomer 0 to 20% by weight % Is desirable. To the adsorbent used in the present invention, activated carbon, hydrous magnesium silicate clay mineral, etc. are added in order to impart deodorizing property and antistatic property of the skin material.

As the activated carbon, those obtained by using coconut shell, charcoal, briquette, peat, coal, pulp, etc. as raw materials can be used, but from the viewpoint of adsorption performance, it is preferable to use activated carbon made from coconut shell. . Examples of hydrated magnesium silicate clay minerals include sepiolite, silotile, raffinite, falconite, and valigorskite. Among them, sepiolite is particularly preferable.
These have a highly reactive hydroxyl group and fine pores on the surface, and have the property of adsorbing malodor and water vapor in the atmosphere.

The surfactant is used for stably dispersing the additive in the rubber latex. The surfactant has a weight average molecular weight of 150 to 100.
A mixture of No. 00 and a polymer compound having a weight average molecular weight of 10,000 or more is preferable. Weight average molecular weight is 150
Examples of the sodium hydroxide of 1 to 10,000 include sodium alkylnaphthalene sulfonate, sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, sodium polyacrylate and polyvinyl alcohol. As the one having a weight average molecular weight of 10,000 or more, polyvinyl alcohol, sodium polyacrylate, styrene-maleic acid copolymer, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose can be used.

The use ratio of these rubber latex, stabilizer, activated carbon and hydrous magnesium silicate clay mineral is 1 to 100 parts by weight of the solid content of the rubber latex.
10 parts by weight, more preferably 1 to 5 parts by weight, and the total amount of activated carbon and hydrous magnesium silicate clay mineral is 50 to 50 parts by weight.
The range of 200 weight is preferable, and the activated carbon content is preferably 10 to 80 weight%.

On the other hand, the ratio of the surfactant used is such that when the weight average molecular weight is 150 to 10,000, it is 0.3 to 10 parts by weight based on 100 parts by weight of the total amount of activated carbon and hydrous magnesium silicate clay mineral. Is preferred. The weight average molecular weight of 10,000 is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of activated carbon and hydrous magnesium silicate clay mineral.

The non-volatile content of the synthetic resin composition is in the range of 35 to 50%, more preferably 35 to 45%, in terms of productivity, workability and storage stability in the steps of applying and drying on the fabric. It is adjusted in and used. Other additives such as flame retardants and conductive agents may be added to the composition of the present invention. Examples of the flame retardant include phosphorus compounds, chlorine compounds, bromine compounds, guanidine compounds, antimony compounds, and boron compounds.

As the conductive agent, conductive carbon black, conductive polymers such as polyacetylene and polypyrrole, metal powders such as copper, aluminum and stainless steel, and conductive fiber substances such as carbon fibers and metal fibers can be used. The synthetic resin composition can be used not only as a vehicle skin material but also as a residential carpet, wallpaper, ceiling material and the like.

[0019]

In the synthetic resin composition of the present invention, a semicarbazide compound is added as a stabilizer as one component of the additive. Although the mechanism of stabilization of this semicarbazide compound is unknown, the resin film of the skin material formed by applying the synthetic resin composition containing this stabilizer to the fabric has improved light resistance and heat resistance. Therefore, the texture of the skin material is maintained for a long period of time, and the performance of the adsorbent such as antistatic property and deodorant property is not deteriorated.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples. (Example 1) (Synthesis of rubber latex) In a pressure-resistant reaction vessel equipped with a stirrer, lined with glass, 140 parts by weight of deionized water, 1 part by weight of sodium alkylbenzene sulfonate, 0.05 part by weight of EDTA, 50 parts by weight of butadiene,
Acrylic acid 3 parts by weight, styrene 47 parts by weight, t-dodecyl mercaptan 0.1 parts by weight, and potassium persulfate 0.3 parts by weight were added, and the inside of the container was replaced with nitrogen and sealed, and polymerization was performed at 65 ° C. for 10 hours. I did it. Thereafter, aqueous ammonia was added to the contents to adjust the pH to 8-9. Next, the contents were put into a stripper, and the pressure was reduced while blowing steam at 100 ° C. to simultaneously remove unreacted residual monomers and concentrate them. The solid content concentration of the obtained rubber latex is 50%
And

(Preparation of Synthetic Resin Composition) 90 parts by weight of -100 mesh sepiolite and 90 parts by weight of -250 mesh activated carbon were dry-mixed, and 0.9 part by weight of sodium alkylnaphthalene sulfonate (molecular weight 342) was added. Parts, 5 parts by weight of carboxymethyl cellulose having a weight average molecular weight of 13,000, 1,6-hexamethylenebis (N,
N-dimethylsemicarbazide) [shown in formula (1)] 5
And 370 parts by weight of a liquid dissolved in 370 parts by weight of water were added and mixed using a twin-screw mixer.

Then, 200 parts by weight of the above rubber latex was added to and mixed with this mixed solution. The obtained synthetic resin composition (solid content 38%) was applied to the back surface of a fabric made of polyester fiber using a doctor blade so that the basis weight was 110 g / m ² in terms of solid content ratio.
It was dried with a hot air dryer at ℃ for 20 minutes to prepare a vehicle skin material. Comparative Example 1 For comparison, the composition is exactly the same as that of Example 1 except that the stabilizer 1,6-hexamethylenebis (N, N′-dimethylsemicarbazide) is removed from the composition of Example 1 above. A synthetic resin composition was prepared. In the same manner as in Example 1, a fabric made of polyester fiber was applied and dried to prepare a vehicle skin material. (Example 2) A rubber latex was produced in the same manner as in Example 1 except that methyl methacrylate was used in place of styrene as a copolymerization component in the polymerization of the rubber latex of Example 1, and all the copolymerization components were methyl methacrylate. . This rubber latex also had a solid content of 50%.

Then, the stabilizers 1, 6-in Example 1 were used.
Instead of hexamethylenebis (N, N′-dimethylsemicarbazide), the same amount of 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-P-phenylene) disemicarbazide [(2 A synthetic resin composition was prepared in the same manner as in Example 1, except that 5 parts by weight of the formula) was used.

Then, the fabric was applied and dried in the same manner as in Example 1 to prepare a vehicle skin material. (Example 3) In the synthetic resin composition of Example 2, the stabilizer 1,1,1 ', 1'-tetramethyl-4,4'-
2.5 parts by weight of (methylene-di-P-phenylene) disemicarbazide, 1,6-hexamethylenebis (M, M ′)
-Dimethylsemicarbazide) was used in a mixture of 2.5 parts by weight, and a synthetic resin composition was prepared in the same manner as in Example 2 to prepare a vehicle skin material. Further, when the obtained synthetic resin composition was allowed to stand at room temperature (25 ° C.), no change was observed even after one month or more. (Comparative Example 2) A synthetic resin composition having the same composition as in Example 2 except that the stabilizer is not added to the synthetic resin composition of Example 2 is prepared, applied to a fabric, and dried to produce a vehicle skin material. did. (Comparative Example 3) In Example 1, the same amount of 2- (5-methyl-2-hydroxyphenyl) benzotriazole was used in place of the stabilizer 1,6-hexamethylenebis (N, N'dimethylsemicarbazide). Others were made to have the same composition and method as in Example 1 to produce a vehicle skin material.

[0025]

[Table 1]

As shown in Table 1, the following evaluations were carried out for each of the above vehicle skin materials. Flexibility (feel): The feel was compared by touch with the initial, light resistance (after irradiation with a fade meter) test, and heat resistance test. Adhesive strength (seam fatigue): Skin material width 10 cm, length 10
2 pieces of test pieces, each of which is cut into cm
A set of two or more sets is taken, the surfaces of two test pieces are overlapped, a sewing machine is sewn at a position 10 mm from the end of the long piece, and a notch having a length of 88 mm is made at a position 25 mm from both ends of the test piece. (The width of the center should be 50 mm). The test piece was repeatedly pulled by an Amsra type woven fabric abrasion tester under a load of 3 kg and the state of slipping of the seam 2500 times was observed. In the table, ◯ represents 1.7 mm or less, Δ represents 1.7 to 2.2 mm, and x represents 2.2 mm or more.

Antistatic performance: A test piece was placed on an insulated sheet at low temperature and low humidity, and a subject wearing 100% wool clothes sat on the sheet, stood after frictional movement, and stood indoors. The electric shock sensation when touching the metal part of was measured. Deodorization performance: In order to evaluate the deodorization performance of the obtained skin material, the adsorption amount to ammonia and the toluene adsorption amount were determined by an adsorption test.

With the skin materials of Examples 1 and 2, the texture was almost the same as the initial stage even after the light resistance and heat resistance tests, and there was no change and was soft. On the other hand, in Comparative Examples 1 and 2 containing no stabilizer, the texture became slightly hard after 150 hours in the light resistance test, and the texture became hard after 400 hours. It shows that the texture became hard and the resin film deteriorated even after the heat resistance test. When the known light stabilizer of Comparative Example 3 was added, the texture after the light resistance test for 150 hours did not change, but the texture became harder after 200 hours or longer. Further, after the heat resistance test, the texture becomes hard and the heat resistance is not sufficient, so that the stabilizer of the present invention does not show the light resistance and heat resistance.

Further, the adhesive strength between the skin material and the resin film is also indicated by a circle in the Examples, which shows almost no change even after the light resistance and heat resistance tests. However, in the comparative example, after the light resistance and heat resistance tests, the slipped state of the seam was large, and the mark Δ indicates that the resin film was deteriorated. Therefore, the stabilizer of the semicarbazide compound can improve the light resistance and heat resistance of the resin film and contribute to the light resistance and heat resistance of the skin material. Further, the light resistance and heat resistance of the skin material can be maintained without reducing the effects of additives such as antistatic agents and deodorants added to the synthetic resin composition.

[0030]

Since the skin material formed from the synthetic resin composition of the present invention is superior in heat resistance and light resistance to the conventional one, the initial texture and adhesive strength can be maintained for a long period of time. Further, an adsorbent such as a deodorant additive or an antistatic substance is added to this synthetic resin composition, and since the resin component does not deteriorate, the performance of the skin material can be retained for a long time without deteriorating. Therefore, the skin material coated with this synthetic resin composition can be used at a site affected by light, heat, and the like.

 ─────────────────────────────────────────────────── ─── Continuation of front page (71) Applicant 000002886 Dainippon Ink and Chemicals, Inc. 3-35-58, Sakashita, Itabashi-ku, Tokyo (72) Inventor Mitsumasa Horii, Nagakute-cho, Aichi-gun, Aichi Prefecture 41 No. 1 Toyota Central Research Institute Co., Ltd. (72) Inventor Masahiro Sugiura No. 41, Nagakute-cho, Aichi-gun, Aichi-gun, Nagakute 1 Toyota Central Research Institute No. 1 (72) Inventor Yoshio Yamada Toyota City, Aichi Prefecture Toyota Town No. 1 Toyota Motor Co., Ltd. (72) Inventor Araki Osamu Toyota City, Aichi Prefecture Toyota Town No. 1 Toyota Motor Co., Ltd. (72) Inventor Akihiro Matsuyama 1-1, Kariya City Aichi Prefecture Toyota Boshoku Ori Co., Ltd. (72) Inventor Takatoshi Sekihara 1-1, Toyota-cho, Kariya city, Aichi Toyobo Co., Ltd. (72) Inventor Toru Umehara 2-5-25 Takashihama, Takaishi-shi, Osaka (72) Inventor Reisaburo Tomioka 2-3, Chiyoda, Takaishi-shi, Osaka

Claims (2)

[Claims] 1. A synthetic resin composition in which a rubber latex and an adsorbent such as activated carbon or hydrous magnesium silicate clay mineral are dispersed in an aqueous medium by a surfactant, the stabilizer comprising a semicarbazide compound. A synthetic resin composition characterized by having 2. A semicarbazide compound is a compound represented by the following general formula:
The synthetic resin composition according to claim 1, which is a compound represented by the formula:
Stuff. R₁R₂NNHCONH (R) NHNCONHNR₃R_Four (Where R is (CH₂)_nOr C₆H_FourCH₂C₆H_Four
R₁, R₂, R₃, R _FourIs a hydrogen atom or 1 to 1 carbon atoms
12 alkyl groups, n represents the integer of 1-12. )