JP2939031B2 - Synthetic resin composition - Google Patents

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 a skin material for a seat of a vehicle and a door lining, and the like.

[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 or the like. It is known that the synthetic resin composition used here has rubber latex and additives such as activated carbon and hydrated magnesium silicate clay mineral dispersed in an aqueous medium by a surfactant (Japanese Patent Laid-Open No. Hei 2 (1994) -208). -145864). The skin material has a deodorizing property and an antistatic property by these additives. However, the rubber latex, which is the main component of this synthetic resin composition, does not have sufficient heat resistance and light resistance of the film formed by coating and drying. Or the adhesive strength of the resin applied to the cloth is reduced to cause peeling.

[0003]

For this reason, the use of this skin material in a site affected by heat, light, oxygen, etc. is limited. On the other hand, attempts have been made to add a benzotriazole-based compound or a benzophenone-based compound as a stabilizer to a synthetic resin composition for the purpose of improving light resistance, but heat resistance is not sufficient even if light resistance is improved. There are also stabilizers that increase heat resistance, but the improvement of light resistance is not enough and it is necessary to add expensive light stabilizers and heat stabilizers in combination to satisfy both. There's a problem.

[0004] The present invention has been made in view of the above circumstances, and by adding one type of stabilizer, the deodorizing function.
An object of the present invention is to provide a synthetic resin composition capable of forming a skin material having improved heat resistance and light resistance while maintaining the same.

[0005]

Means for Solving the Problems The present inventors diligently studied in view of the above circumstances, and found that when a semicarbazide compound was used as a stabilizer, a resin film obtained by applying a synthetic resin composition to a cloth and drying was light-resistant, The heat resistance is remarkably improved, the fabric has a soft touch for a long period of time, and the strong adhesive strength between the fabric and the resin film is maintained, and it has been found that it has an odor absorbing ability and completed.

The synthetic resin composition of the present invention contains activated carbon and
From at least one of the magnesium silicate clay minerals
Adsorbents and semicarbazide compounds become surfactants
An aqueous dispersion dispersed in a more aqueous medium;
And a box . The semicarbazide compound is a compound represented by the following general formula.

R ₁ R ₂ NNHCONH (R) N HC ONHNR ₃ R _{4 wherein} R is (CH ₂ ) _n or C ₆ H ₄ CH ₂ C ₆ H ₄
R ₁ , R ₂ , R ₃ , R ₄ represent a hydrogen atom or a carbon atom
12 alkyl groups and n represents an integer of 1 to 12. Examples of semicarbazide compounds used as stabilizers include 1,6-hexamethylenebis (N, N-dimethylsemicarbazide) [shown in formula (1)],

[0008]

Embedded image

[0009] 1, 1, 1 ', 1'-tetramethyl - 4,
4 ′-(methylene - di-P-phenylene) disemicarbazide [shown in the formula (2)] can be used.

[0010]

Embedded image

The semicarbazide compound may be used as a mixture of two or more kinds. The mechanism of the resin film formed from the synthetic resin composition by the addition of the semicarbazide-based compound is unknown, but light resistance and heat resistance can be improved.
The light resistance and heat resistance of the skin material can be improved. As the rubber latex used in the present invention, natural rubber or synthetic rubber latex can be used. Particularly, a latex of a butadiene copolymer is preferred. The butadiene copolymer preferably contains 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-methylolacrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, acrylic acid, itaconic acid, fumaric acid, croton Acids, maleic acid, etc. can be used.

The copolymer composition of the butadiene copolymer preferably contains 20 to 70% by weight of butadiene. Considering the heat resistance and light resistance required as a rubber component for a skin material for vehicles, butadiene 20 to 60% by weight, (meth) acrylate 40 to 80% by weight, and other ethylenically unsaturated monomers 0 to 20% by weight. % Is desirable. The present invention
As an adsorbent , activated carbon and hydrous magnesium silicate clay are used to impart the deodorant and antistatic properties of the skin material.
At least one of the earth minerals is used.

As the activated carbon, those made from coconut shell, charcoal, lignite, peat, coal, pulp and the like can be used, but from the viewpoint of adsorption performance, it is preferable to use activated carbon made from coconut shell. . Examples of the hydrous magnesium silicate clay mineral include sepiolite, silotile, laphrinite, falconite, and valigorskite, and of these, sepiolite is particularly preferred.
They have highly reactive hydroxyl groups and pores on the surface and have the property of adsorbing bad smell 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 00 and a polymer compound having a weight average molecular weight of 10,000 or more is preferred. Weight average molecular weight is 150
Examples of those having a molecular weight of 10,000 to 10,000 include sodium alkylnaphthalene sulfonate, sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, sodium polyacrylate, and polyvinyl alcohol. As those having a weight average molecular weight of 10,000 or more, cellulose derivatives such as polyvinyl alcohol, sodium polyacrylate, styrene-maleic acid copolymer, 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 such that the stabilizer 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, the total amount of activated carbon and hydrous magnesium silicate clay mineral is 50 to
A range of 200 weight is preferable, and a content of activated carbon of 10 to 80 weight% is preferable.

On the other hand, the ratio of the surfactant used is such that the weight average molecular weight of 150 to 10,000 is 0.3 to 10 parts by weight with respect to 100 parts by weight of the total of activated carbon and hydrous magnesium silicate clay mineral. Is preferred. Further, those having a weight average molecular weight of 10,000 or more preferably have a range of 0.1 to 20 parts by weight based on 100 parts by weight of the total of activated carbon and hydrous magnesium silicate clay mineral. Of the present invention
The synthetic resin composition contains the activated carbon and the hydrated magnesium silicate described above.
At least one kind of calcium clay mineral and a cercarbazide
The compound is dispersed in the aqueous medium by the surfactant.
And a rubber latex.

The non-volatile content of this synthetic resin composition is in the range of 35 to 50%, more preferably 35 to 45%, from the viewpoints of productivity, workability and storage stability in the steps of coating and drying the fabric. And adjusted for use. The composition of the present invention may further contain additives such as a flame retardant and a conductive agent. Examples of the flame retardant include phosphorus compounds, chlorine compounds, bromine compounds, guanidine compounds, antimony compounds, and boron compounds.

As the conductive agent, conductive polymers such as conductive carbon black, polyacetylene and polypyrrole, metal powders such as copper, aluminum and stainless steel, and conductive fiber materials such as carbon fiber and metal fiber can be used. This synthetic resin composition can be used for carpets, wallpapers, ceiling materials and the like for houses in addition to the use as a skin material for vehicles.

[0019]

The synthetic resin composition of the present invention contains a semicarbazide compound as one of the additives as a stabilizer. The mechanism of stabilization of the semicarbazide compound is unknown, but the resin film of the skin material formed by applying a synthetic resin composition containing the stabilizer to a cloth has improved light resistance and heat resistance. Therefore, the texture of the skin material is maintained for a long time, and the performance of the adsorbent such as antistatic property and deodorizing property is not reduced.

[0020]

The present invention will be specifically described below with reference to examples. (Example 1) (Synthesis of rubber latex) 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 were placed in a pressure-resistant reaction vessel equipped with a glass-lined stirrer.
3 parts by weight of acrylic acid, 47 parts by weight of styrene, 0.1 parts by weight of t-dodecylmercaptan, and 0.3 parts by weight of potassium persulfate were added, the inside of the vessel was replaced with nitrogen, and the vessel was sealed and polymerized at 65 ° C. for 10 hours. I did it. Thereafter, the pH was adjusted to 8 to 9 by adding aqueous ammonia to the contents. Next, the content was put into a stripper, and the pressure was reduced while blowing steam at 100 ° C., thereby simultaneously removing and concentrating unreacted residual monomers. The solid 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 parts by weight of sodium alkylnaphthalene sulfonate (molecular weight: 342) was added thereto. Parts, 5 parts by weight of carboxymethyl cellulose having a weight average molecular weight of 13000, 1,6-hexamethylenebis (N,
N｀-dimethylsemicarbazide) [shown in formula (1)] 5
Was added to 370 parts by weight of water and mixed using a twin-screw mixer.

Thereafter, 200 parts by weight of the above rubber latex was added to the mixed solution and mixed. The obtained synthetic resin composition (solid content 38%) was applied to the back surface of the fabric made of polyester fiber using a doctor blade so that the basis weight was 110 g / m ² at a solid content ratio, and 130
It dried for 20 minutes with the hot air dryer of ° C, and produced the skin material for vehicles. Comparative Example 1 For comparison, the composition was exactly the same as in Example 1 except that the stabilizer 1,6-hexamethylenebis (N, N｀-dimethylsemicarbazide) was omitted from the composition of Example 1 described above. A synthetic resin composition was prepared. In the same manner as in Example 1, it was applied to a polyester fiber fabric and dried to produce a vehicle skin material. (Example 2) A rubber latex was produced in the same manner as in Example 1 except that in the polymerization of the rubber latex of Example 1, methyl methacrylate was used instead of styrene as a copolymer component, and the entire copolymer component was methyl methacrylate. . This rubber latex also had a solid content of 50%.

Next, the stabilizers 1,6-
Instead of hexamethylenebis (N, N'-dimethylsemicarbazide), the same amount of 1,1,1 ', 1'-tetramethyl-4,4'-(methylene-di-P-phenylene) disemicarbazide [(2 ) Was used in the same manner as in Example 1 except that 5 parts by weight of the formula (1) was used to prepare a synthetic resin composition.

After that, it was applied to the fabric and dried in the same manner as in Example 1 to produce a skin material for a vehicle. (Example 3) In the synthetic resin composition of Example 2, the stabilizers 1, 1,
2.5 parts by weight of 1 ', 1'-tetramethyl-4,4'-(methylene-di-P-phenylene) disemicarbazide,
Except that 2.5 parts by weight of 1,6-hexamethylenebis ( N, N'-dimethylsemicarbazide) was mixed and used, a synthetic resin composition was prepared in the same manner as in Example 2 by the same method, and a vehicle was prepared. A skin material was prepared. 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 that of Example 2 except that no stabilizer was added to the synthetic resin composition of Example 2, was prepared.
It was applied to the fabric and dried to produce a vehicle skin material. Comparative Example 3 In Example 1, the same amount of 2- (5-methyl-2-hydroxyphenyl) benzotriazole was used in place of 1,6-hexamethylenebis (N, N ′ dimethylsemicarbazide) as a stabilizer. Except for this, a vehicle skin material was manufactured in the same composition and method as in Example 1.

[0025]

[Table 1]

As shown in Table 1, the following evaluations were performed on the above-mentioned vehicle skin materials. Flexibility (feel): The feel was compared by the touch between the initial stage, the light resistance test (after irradiation with a fade meter), and the heat resistance test. Adhesive strength (seam fatigue): Skin material is 10cm in width and 10 in length
cm of test specimens, each set of two
Take two or more pairs of test pieces, superpose the surfaces of two test pieces, perforate the sewing machine at a position 10 mm from the end of the long piece, and make a cut of 88 mm in length at 25 mm from both ends of the test piece. (The width at the center is 50 mm). The test piece was repeatedly pulled under a load of 3 kg with an Amsula-type woven cloth abrasion tester, and the state of slippage of the seam was observed 2500 times. In the table, ○ indicates 1.7 mm or less, Δ indicates 1.7 to 2.2 mm, and X indicates 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 clothing was seated on the sheet, and after a frictional movement, stood up, Of the metal part when touching the metal part was measured. Deodorization performance: In order to evaluate the deodorization performance of the obtained skin material, was determined by adsorption test the ammonia adsorption Chakuryou toluene adsorption.

With the skin materials of Examples 1 and 2, even after the light resistance and heat resistance tests, the texture is almost the same as the initial one, and it is soft without any change. 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 became hard after 400 hours. The texture becomes hard even after the heat resistance test, indicating that the resin film is deteriorated. When the known light stabilizer of Comparative Example 3 was added, the texture after the 150-hour light resistance test did not change, but after 200 hours or more, the texture became hard. Further, after the heat resistance test, the texture becomes hard and the heat resistance is not sufficient, and the light resistance and heat resistance of the stabilizer of the present invention are not exhibited.

In the examples, the adhesion strength between the skin material and the resin film is also indicated by a circle with 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 slip-off state of the seam was large, and the mark "△" 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 improvement of the light resistance and heat resistance of the skin material. Furthermore, the light resistance and heat resistance of the skin material can be maintained without reducing the effects of additives such as an antistatic agent and a deodorant added to the synthetic resin composition.

[0030]

The skin material formed from the synthetic resin composition of the present invention has better heat resistance and light resistance than conventional ones, so that the initial texture and adhesive strength can be maintained for a long time. A skin material formed from the synthetic resin composition
Has excellent deodorizing properties and antistatic properties. Therefore,
The skin material to which the synthetic resin composition has been applied can be used in parts affected by light, heat, and the like and in parts requiring a deodorizing effect .

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08K 5:26) (72) Inventor Mitsumasa Horii 41, Chukumi Yokomichi, Daikakucho, Nagakute-cho, Aichi-gun, Aichi Prefecture 1 Toyota Chuo Research Inc. In-house (72) Inventor Masataka Sugiura 41 Toyota Chuo R & D Laboratories Co., Ltd. 1 at 41, Chuchu-Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture (72) Inventor Yoshio Yamada 1st Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Haru Araki 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Akihiro Matsuyama 1-1-1 Toyota Town, Kariya City, Aichi Prefecture Toyota Boshoku Corporation (72) Inventor Takatoshi Sekihara 1-1-1 Toyota-cho, Kariya City, Aichi Prefecture Inside Toyota Boshoku Corporation (72) Inventor Toro Umehara 2-5-25 Takashihama, Takaishi-shi, Osaka (72) Inventor Oka HajimuSaburo Osaka Prefecture Takaishi Chiyoda 2-3 (56) Reference Patent Sho 62-10145 (JP, A) (58 ) investigated the field (Int.Cl. ^6, DB name) C08L 7/00 - 21 / 02 C08K 3 / 04,3 / 34,5 / 26

Claims (2)

(57) [Claims] Activated carbon and hydrated magnesium silicate clay ore
Adsorbent comprising at least one of the following: a semicarbazide
Is dispersed in an aqueous medium by a surfactant
A synthetic resin composition comprising an aqueous dispersion and a rubber latex . 2. The synthetic resin composition according to claim 1, wherein the semicarbazide compound is a compound represented by the following general formula. R ₁ R ₂ NNHCONH (R) N HC ONHNR ₃ R _{4 wherein} R is (CH ₂ ) _n or C ₆ H ₄ CH ₂ C ₆ H ₄
R ₁ , R ₂ , R ₃ , R ₄ represent a hydrogen atom or a carbon atom
12 alkyl groups and n represents an integer of 1 to 12. )