JPH04304242A - Resin composition and molding made therefrom - Google Patents

Abstract

PURPOSE:To provide a synthetic resin composition excellent in properties and feeling and a molding obtained by processing the composition. CONSTITUTION:A resin composition containing 1-100 pts.wt., per 100 pts.wt. resin, vegetable protein powder, and a molding made by molding the composition or coating a substrate with the composition. A molding having excellent moisture permeability, pitch-blackness, scratch resistance, tensile strength, dry touch and suedo-tone feeling can be made from the resin composition.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to resin compositions and molded products using the same, and more specifically, synthetic leather, artificial leather, synthetic sheets such as moisture-permeable waterproof fabrics, three-dimensional molded products, and molded products such as thread. Useful for imparting a suede-like texture with excellent moisture permeability, jet blackness, scratch resistance, tensile strength, and dry touch without impairing the properties of the synthetic resin when used in the production of or as a coating agent for paints, etc. The present invention relates to a resin composition and a molded article using the same.

0002

BACKGROUND OF THE INVENTION Various surface treatment agents have been developed for giving the surfaces of synthetic leather, artificial leather, metal, plastic, ceramics, wood, etc. a suede feel. Typical examples include (1) polyurethane resin solution mixed with fatty acid ester and silica, (2) polyurethane resin solution or acrylic resin solution mixed with dimethylpolysiloxane and silica, and (3) polyurethane resin solution mixed with dimethylpolysiloxane and silica. Examples include those in which silica is blended with one of polyethylene fine powder, polybutylene fine powder, acrylic resin fine powder, urethane resin fine powder, nylon resin fine powder, or silicone resin fine powder.

[0003] However, the surface of the coating layer formed by surface treating synthetic leather, such as polyvinyl chloride leather (hereinafter referred to as PVC leather) or synthetic resin molded products, with these treatment agents using a gravure printer method, spray method, etc. It is easy to break or deform when scratched with a hand, and there are problems such as lack of scratch resistance, leaving fingerprints or the like on areas touched by hands, or having a sticky feel.

[0004]Also, a method has been proposed in which powders of acrylic resin, nylon resin, etc. are mixed with polyisocyanates in a polyurethane resin organic solvent solution and sprayed, but there are problems such as texture, pot life, baking temperature, etc. There is.

On the other hand, various methods for imparting moisture permeability have been developed, including (4) a method of forming a porous synthetic sheet using a polyurethane resin solution, a polyamino acid urethane resin solution, etc.; ) A method in which fine gelatin particles, or fine gelatin particles and fine leather powder are added to a polyurethane resin solution to form a film, and some of the gelatin particles are eluted with hot water (JP-A-1-222938, JP-A-1-222939) ), etc.

However, method (4) requires the film to be extremely thin, resulting in poor abrasion resistance, and also has a problem in that the film itself has a low moisture-absorbing function, resulting in a sticky feeling upon contact. be. In addition, method (5) has complicated steps, poor dispersibility in resin,
It also has the problem of being somewhat inferior in abrasion resistance, tensile strength, jet blackness, and texture.

[0007]

[Problems to be Solved by the Invention] The present invention was made in view of the above-mentioned problems, and has excellent moisture permeability, scratch resistance, abrasion resistance, tensile strength, soft and dry touch, and no sticky feeling. The object of the present invention is to obtain a synthetic resin composition with a suede-like texture and good dispersibility, and a molded article obtained by processing the same.

[0008]

[Means for Solving the Problems] In order to solve this problem, the present inventor has conducted extensive research on various synthetic resins, and has found that by incorporating vegetable protein powder into the synthetic resin, the desired characteristics are not impaired. We have discovered that a resin composition with excellent moisture permeability, scratch resistance, abrasion resistance, tensile strength, jet blackness, a soft, dry touch, no sticky feeling, and a suede-like texture with good dispersibility can be obtained,
This has led to the completion of the present invention.

Specifically, the present invention provides a resin composition comprising 1 to 100 parts by weight of vegetable protein powder per 100 parts by weight of a synthetic resin, and a resin composition comprising the resin composition or a resin composition based on the resin composition. Regarding molded products coated on materials. The present invention will be explained in detail below.

[0010] As the resin used in the present invention, any resin can be used regardless of its type, such as polyamino acids,
polyamino acid urethane, polyamide, polyurethane,
Polyester, polyesteramide, acrylonitrile polymer, polyvinyl chloride, polystyrene and its copolymer, polyvinyl alcohol and its derivative, polyvinyl acetate and its copolymer, polyacrylamide or polymethacrylamide and these derivatives, natural rubber and synthetic rubbers such as polyisoprene and polybutadiene, and mixtures thereof, polyethylene and copolymers thereof, polyprene and copolymers thereof, phenolic resins, melamine resins, urea resins, etc., or mixtures of two or more thereof, It can be used after being diluted with a solvent if necessary. Among these, polyurethane, polyamino acid urethane,
Polyvinyl chloride is preferred for reasons such as dispersibility of vegetable protein powder in resin, texture when molded, and scratch resistance.

[0011] The vegetable protein referred to in the present invention is
Saikachi, Modama, Clara, Fujiki, Enishida, Umagoyashi, Komatsumagi, Yamafuji, Natsubji, Muresuzume,
Astragalus, Harienju, Kusanemu, Yabuhagi, Yamahahagi, Yahazusou, peanut, broad bean, lentil,
Legumes such as peas, climbing beans, soybeans, sea cucumbers, azuki beans, Fuji beans, tankiri beans, Himeguzhu, Yabu beans, and Guzu, Japanese spinach, Madake, Mosouchiku, Okamezasa, Medake, Kumzasa, Yadake, Narihiradake, Kanchiku, Makomo, Iso, Azumagaya, Hama Garlic, kamojigusa, barley, wheat, dokumugi, foxglove,
Ushinokegusa, Loach Tsunagi, Strawberry Tsunagi, Hogaerigaya, Sasakusa, Seaweed, Komegaya, Japanese Calligraphy,
Japanese hyacinth, Urahagusa, reed, Tsuruyoshi, Yoshitake, Kamogaya, Oat, Azegaya, Ohishiba, Yamawa,
It refers to protein obtained from gramineous plants, such as grasshopper, millet, honey grass, foxtail millet, millet, silver grass, sorghum, cowweed, miscanthus, sugarcane, corn, and adlay; however, in practical terms, it refers to proteins obtained from grasses such as soybeans, adzuki beans, fava beans, etc. Edible beans and cereals such as rice, wheat, barley, and oats are preferred. The average particle size of the vegetable protein powder of the present invention is desirably 80 microns or less, preferably 20 microns or less, and more preferably 10 microns or less. If the average particle size is larger than 80 microns, the molded product obtained by processing will have a rough feel, which is unfavorable in terms of texture.

The vegetable protein powder may be used alone or in combination, but the total amount added to the resin is 1 to 100 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the resin. Department. If the amount added is less than 1 part by weight, the moisture permeability and suede-like texture will be insufficient, and if it is more than 100 parts by weight, it will be difficult to disperse in the resin, and the abrasion resistance, tensile strength, peel strength, texture, etc. This is not desirable. Note that there is no problem even if the vegetable protein powder and other fillers are used in combination and added to the resin.

[0013] The method of dispersing the vegetable protein powder in the resin can be selected as appropriate depending on the resin used.
Atomizer, dymo mill, ball mill, three rolls,
Examples include kneading using a universal mixer.

The resin composition of the present invention can be used as a base material for molded articles, as well as in paints, coating agents, and the like. Molded articles made of the resin composition of the present invention are in the form of synthetic sheets, three-dimensional molded articles, threads, etc. Examples of the synthetic sheets include synthetic leather, artificial leather, films, plates, elastic bodies, and the like. Examples of molding methods for the resin composition include compression molding, transfer molding, injection molding, lamination molding, extrusion molding, and calender molding, which can be appropriately selected depending on the resin.

In the case of a molded article coated with the resin composition of the present invention, examples of the base material that can be used for the coated molded article include cotton, linen, pulp, wood, bamboo, and bis. Cellulose and its derivatives such as Coss silk, Bemberg silk, cellulose acetate, silk, wool,
Natural leather, recycled leather, synthetic leather, artificial leather, polyamino acids, polyamino acid urethanes, polyamides, polyurethanes, polyesters, polyesteramides, acrylonitrile polymers, polyvinyl chloride, polystyrene and its copolymers, polyvinyl alcohol and its derivatives , polyvinyl acetate and its copolymers, polyacrylamide, or polymethacrylamide and their derivatives, natural rubber and synthetic rubbers such as polyytuprene and polybutadiene, and mixtures thereof, polyethylene and its copolymers, polypropylene and its copolymers , various plastics such as phenolic resin, melamine resin, urea resin,
Examples include one or more mixed materials such as quartz, glass, ceramics, cements, and various metals. Examples of molded products made from these base materials include fabrics, synthetic leathers, artificial leathers, films, papers, boards, elastic bodies, sheet-like molded products such as plastics, and plastic handles for automobiles. Furthermore, a molded article made of these base materials can be processed by applying the resin composition of the present invention in which vegetable protein powder is added to the resin, processing by coating, processing by dipping, spray processing, gravure processing, etc. It can also be used as a skin material by forming a film on release paper using a dry process and laminating it with the above-mentioned base material. In other words, the processing method itself can be a conventional method.

[0016]

[Examples] The present invention will be explained in more detail with reference to Examples below. Example 1 Method for producing soybean powders A and B Add 35 liters of water to 3.5 kg of defatted soybean flakes, adjust the pH to around 7 with a 20% aqueous sodium hydroxide solution while stirring, and remove insoluble matter using centrifugation. did. A 5% aqueous sulfuric acid solution was gradually added to this filtrate to adjust the pH to 4.
5 to precipitate soybean protein. This was centrifuged, the solid matter was washed with acetone, decolorized, and dried.
70g of soybean protein was obtained.

[0017] The obtained soybean protein was processed using a jet mill (AJP).
-1, manufactured by Nippon Pneumatic Co., Ltd.) and classified by a conventional method to obtain soybean powder A (average particle size 20±2 microns) and soybean powder B (average particle size 10±2 microns).

Example 2 Production of Wheat Flour Powders C and D After starch was removed from 10 kg of wheat flour (strong flour) using a large amount of water, 1.3 kg of gluten was obtained. Next, 2 liters of a 70% ethanol aqueous solution was added to the obtained gluten and stirred for 2 days using a shaker to remove gliadin and perform solid-liquid separation to obtain gummy glutenin. Then 5
% ammonia/acetic acid aqueous solution was added to dissolve the mixture, insoluble materials were removed using Celite, and the mixture was powdered by spray drying. Then, using an autoclave at 150℃
Heat treated in saturated steam for 3 hours, washed with water and dried for 30 minutes.
0g of wheat protein was obtained.

[0019] The obtained flour powder was passed through a jet mill (AJP).
-1, manufactured by Nippon Pneumatic Co., Ltd.) and classified by a conventional method to obtain flour powder C (average particle size 20±2 microns) and wheat flour powder D (average particle size 10±2 microns).

Example 3 Combination of polyurethane resin solution and soybean powder Soybean powders A and B obtained in Example 1 were added to a polyurethane resin solution (Luxkin 5005, manufactured by Seiko Kasei Co., Ltd.) at a resin solid content of 100 parts by weight. After adding 5, 30 and 100 parts by weight to the solution and stirring with a disper to uniformly disperse,
After defoaming, six types of resin compositions A11, A12, A13 were prepared.
, B11, B12 and B13 were obtained.

[0021] The dispersibility of soybean powder in the above six resin compositions was all good.

Example 4 Combination of polyamino acid urethane resin solution and soybean powder Soybean powders A and B obtained in Example 1 were added to a polyamino acid urethane resin solution (Luxkin A3571, manufactured by Seiko Kasei Co., Ltd.) as a resin solid content. 5, 30, and 100 parts by weight were added to 100 parts by weight, stirred with a disper to disperse them uniformly, and defoamed to form 6 types of resin compositions A21 and A2.
2, A23, B21, B22 and B23 were obtained.

[0023] The dispersibility of soybean powder in the above six resin compositions was all good.

Example 5 Combination of polyvinyl chloride resin solution and soybean powder Soybean powders A and B obtained in Example 1 were added to a polyvinyl chloride resin solution (Luxkin 301, manufactured by Seiko Kasei Co., Ltd.) as a resin solid content. After adding 5, 30, and 100 parts by weight to 100 parts by weight and uniformly dispersing them with three rolls, defoaming was performed to obtain six types of resin compositions A31, A32, A33, and B3.
1, B32 and B33 were obtained.

[0025] The dispersibility of soybean powder in the above six resin compositions was all good.

Example 6 Combination of polyurethane resin solution and flour powder Flour powders C and D obtained in Example 2 were added to a polyurethane resin solution (Luxkin 5005, manufactured by Seiko Kasei Co., Ltd.) at a resin solid content of 100 parts by weight. After adding 5, 30 and 100 parts by weight to the solution and stirring with a disper to uniformly disperse,
After defoaming, six types of resin compositions C11, C12, and C13 were prepared.
, D11, D12 and D13 were obtained.

[0027] The dispersibility of flour powder in the above six resin compositions was all good.

Example 7 Combination of polyamino acid urethane resin solution and flour powder Flour powders C and D obtained in Example 2 were added to a polyamino acid urethane resin solution (Luxkin A3571, manufactured by Seiko Kasei Co., Ltd.) as a resin solid content. 5, 30, and 100 parts by weight were added to 100 parts by weight, stirred with a disper to disperse them uniformly, and defoamed to form six types of resin compositions C21 and C2.
2, C23, D21, D22 and D23 were obtained.

[0029] The dispersibility of flour powder in the above six resin compositions was all good.

Example 8 Combination of polyvinyl chloride resin solution and flour powder Flour powders C and D obtained in Example 2 were added to a polyvinyl chloride resin solution (Seiko Kasei Co., Ltd., Ranokuskin 301) at a resin solid content of 100%. After adding 5, 30, and 100 parts by weight based on the weight part and uniformly dispersing them with three rolls, defoaming was performed to obtain six types of resin compositions C31, C32, C33, and D3.
1, D32 and D33 were obtained.

[0031] The dispersibility of flour powder in the above six resin compositions was all good.

Comparative Example 1 Combination of polyurethane resin solution and collagen powder Pulverized collagen powder (CX-240-1, manufactured by Showa Denko Co., Ltd.) was added to a polyurethane resin solution (Luxkin 5005, manufactured by Seiko Kasei Co., Ltd.). 5, 30, and 100 parts by weight were added to 100 parts by weight of resin solid content, and after uniformly dispersing with three rolls, defoaming was performed to obtain resin composition E1.
1, E12 and E13 were obtained.

Comparative Example 2 Combination of polyurethane resin solution and silica powder A polyurethane resin solution (Luxkin 5005, manufactured by Seiko Kasei Co., Ltd.) was mixed with pulverized silica powder (OK-412, manufactured by Degussa Japan Co., Ltd.) as a resin solid. The resin composition F11
, F12 and F13 were obtained.

Comparative Example 3 Combination of polyamino acid urethane resin solution and collagen powder A polyamino acid urethane resin solution (Luxkin A3571, manufactured by Seiko Kasei Co., Ltd.) was mixed with pulverized collagen powder (CX-240, manufactured by Showa Denko Co., Ltd.). 5, 30, and 100 parts by weight of -1) were added to 100 parts by weight of resin solid content, and after uniformly dispersing with three rolls, defoaming was performed to obtain resin compositions E21, E22, and E23. .

Comparative Example 4 Combination of polyamino acid urethane resin solution and silica powder A polyamino acid urethane resin solution (Seiko Kasei Co., Ltd., Luxkin A3571) was mixed with pulverized silica powder (Degussa Japan Co., Ltd., OK-412). ) to resin solid content 1
Adding 5, 30 and 100 parts by weight to 00 parts by weight,
After uniformly dispersing with three rolls, defoaming was performed to obtain resin compositions F21, F22, and F23.

Comparative Example 5 Combination of polyvinyl chloride resin solution and collagen powder Collagen powder (CX-240, manufactured by Showa Denko K.K., manufactured by Showa Denko KK) crushed into a polyvinyl chloride resin solution (Luxkin 301, manufactured by Seiko Kasei Co., Ltd.) 5, 30, and 100 parts by weight of -1) were added to 100 parts by weight of the resin solid content, and after uniformly dispersing with three rolls, defoaming was performed to form a resin composition E3.
1, E32 and E33 were obtained.

Comparative Example 6 Combination of polyvinyl chloride resin solution and silica powder A polyvinyl chloride resin solution (Seiko Kasei Co., Ltd., Luxkin 301) was mixed with pulverized silica powder (Degussa Japan Co., Ltd., OK-412). ) were added in 5, 30, and 100 parts by weight per 100 parts by weight of resin solid content, and after uniformly dispersing with three rolls, defoaming was performed to obtain resin composition F31.
, F32 and F33 were obtained.

Test Example 1 Evaluation of Moisture Permeability and Tensile Strength The resin compositions and powder-free resin solutions obtained in Examples 3 to 8 and Comparative Examples 1 to 6 were each placed on release paper to determine the thickness after removing the solvent. Apply with a roll coater to a thickness of 20 microns,
The film was dried at 0° C. for 5 minutes and at 120° C. for 10 minutes to obtain a membrane for evaluation, and its moisture permeability and tensile strength were evaluated.

The evaluation criteria are as follows. (1) Moisture permeability According to JIS L 1099 (calcium chloride method).

(2) Tensile strength Testing was conducted under the following conditions. Model Tensilon UTM-4-
Type 100 (manufactured by Orientec) Measurement conditions Film width 10mm
Film length 50mm (between chucks)
Tensile speed 50mm/mi
n

The results are shown in Tables 1-3. From Tables 1 to 3,
It is clear that the sheet obtained according to the present invention has excellent moisture permeability and tensile strength.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

Test Example 2 The resin compositions obtained in Examples 3 to 8 and Comparative Examples 1 to 6 and additive-free resin solutions were applied to a nylon fabric at 30 g/m2 using a roll coater, and dried at 120°C for 5 minutes. The sheet was surface-finished and used as an evaluation sheet, and its abrasion resistance and suede-like appearance were evaluated.

The evaluation criteria are as follows. (3) Abrasion resistance Gakushin type friction fastness tester (JIS
L 0823), JIS L 1084
(Friction tester method), friction was performed 1000 times under a load of 200 g, and the appearance of the film was observed and evaluated on the following three levels. ○ No abnormality △ Partial wear × Complete wear

(4) Suede-like appearance Judgment was made by visual inspection according to the following criteria. ○ It closely resembles natural leather. △ Slightly similar to natural leather. × It doesn't feel like natural leather.

The results are shown in Tables 4-6. From Tables 4 to 6, it is clear that the sheets obtained according to the present invention are excellent in both moisture permeability and tensile strength.

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

Test Example 3 Evaluation of Jet Blackness and Scratch Resistance The resin compositions obtained in Examples 3 to 8 and Comparative Examples 1 to 6 and the powder-free resin solution were applied to a black ABS sheet using a gravure printer at 30 g/g. m2 coated and 5 at 120℃
The sheet was dried for a few minutes and then surface-finished to obtain an evaluation sheet, and its jet blackness and scratch resistance were evaluated.

The evaluation criteria are as follows. (5) Jet blackness Judgment was made by visual inspection according to the following criteria. ○ Blackness is sufficient. △　　　　The blackness is slightly lacking. × Lack of blackness.

(6) Scratch Resistance The surface was scratched with a pencil of hardness H, and visually judged according to the following criteria. ○ No abnormalities △ Some scratches × Large scratches

The results are shown in Tables 7-9. From Tables 7 to 9, it is clear that the sheets obtained according to the present invention are excellent in both jet blackness and scratch resistance.

[0056]

[Table 7]

[0057]

[Table 8]

[0058]

[Table 9]

[0059]

Effects of the Invention: By using the resin composition of the present invention, it is possible to obtain excellent moisture permeability, jet blackness, scratch resistance,
It is possible to obtain a molded article with a suede-like texture in terms of tensile strength and dry touch. Therefore, the resin composition of the present invention can be used as a coating agent for paints, etc., and as a molding base material for a wide range of applications such as synthetic sheets such as synthetic leather and artificial leather, three-dimensional molded products, and various molded products such as thread. be.

Claims (5)

[Claims] 1. A resin composition comprising 1 to 100 parts by weight of vegetable protein powder per 100 parts by weight of resin. 2. The resin composition according to claim 1, wherein the vegetable protein powder has an average particle size of 20 microns or less. 3. The resin composition according to claim 1, wherein the vegetable protein is derived from a leguminous plant and/or a gramineous plant. 4. The resin composition according to claim 1, wherein the resin is mainly composed of polyurethane and/or polyamino acid urethane and/or polyvinyl chloride. 5. A molded article comprising the resin composition according to any one of claims 1 to 4, or having a substrate coated with the resin composition.