JPH0418499A - Prevention of caking of collagen - Google Patents

Abstract

PURPOSE:To prevent caking of a collagen powder with time and improve reagitation properties by dispersing the collagen powder in a resin using a surfactant of a nitrogen-containing compound or a silicone-based compound. CONSTITUTION:In a resin such as polyurethane, polybutadiene or urethane rubber, (A) 100 pts.wt. collagen powder containing >=85wt.% collagen powder having <=80mum particle size is dispersed using (B) 0.5-5.5 pts.wt. (preferably 1.5-4.0 pts.wt.) surfactant consisting of a nitrogen-containing compound such as an ethylene-bis-fatty monocarboxylic acid amide or a silicone-based compound.

Description

Detailed Description of the Invention (1) Industrial Application Field The present invention is suitable for producing resin materials in the form of solutions or pastes containing fine collagen powder used for paints, coatings, film forming, etc. In more detail, the mixture of collagen powder and resin can be used for parts such as automobile steering wheels, grips for exercise equipment, sheets,
Resin solutions or resin pastes, etc., which are used for various purposes such as furniture and bags, contain fine collagen powders, and the fine collagen powders are evenly dispersed in these resins in the form of solutions or pastes. The present invention relates to a mixture of collagen powder and resin that is optimal for producing a resin composition.

(2) Conventional technology In recent years, with the trend toward luxury, sheets, nonwoven fabrics, furniture, automobile steering wheels, and other parts made of vinyl chloride, artificial leather, etc. have the appearance, feel, and functionality of natural leather. requested.

The above-mentioned automobile parts, furniture, etc. that have a leather-like appearance are molded products of synthetic resin, etc., molded products of steel, aluminum, etc. with leather pasted on them, or leather pasted on the surface of wood, etc. There were many things that were composed. However, as mentioned above, the leather is expensive and the pasting process is time-consuming, so the cost is high.Also, the elasticity of the leather and the underlying fabric is different depending on the temperature, so the fabric may shrink. There were problems such as the edges of the leather being exposed and the leather peeling off, making it unsightly.

Synthetic leather is woven fabric or based on woven fabric, and the surface of sponge leather made of foam such as vinyl chloride, polyamide, polyurethane, etc. is made of modified polyamide, polyurethane,
It is treated with a polyacrylic acid derivative. In addition, artificial leather has been developed that is made of a porous structure of a three-dimensional fiber entanglement of special fibers such as root-shaped hollow fibers and fine fiber bundled fibers and a binder mainly made of elastomer (polyurethane). These synthetic or artificial leathers have characteristics similar to natural leather and have excellent heat retention functions. However, these synthetic leathers or artificial leathers only have a water absorption function due to capillary phenomenon, and do not have a water absorption function associated with tissue swelling. In addition, it does not have the function unique to natural leather, which adjusts the amount of gaps between tissues and controls air permeability as the tissues swell.

In order to solve these problems, collagen powder that is insoluble collagen, tropocollagen, atelocollagen, a mixture or crosslinked product of these, or collagen powder obtained by crushing leather scraps generated during the production of leather products is used as a material for various synthetic resin materials. Various attempts have been made to form leather-like coatings and to produce sheets, films, etc. by mixing them with However, if the collagen powder to be mixed has a relatively coarse particle size, it will aggregate when incorporated into a resin, making it difficult to disperse uniformly and having low fluidity, making it difficult to obtain products with smooth surfaces or thin products. Furthermore, there was the disadvantage that the smooth feel of natural leather could not be obtained. Therefore, it was discovered that by making the collagen powder to be mixed in finer and improving its compatibility with synthetic resin materials, it is possible to mix the collagen powder with paint or various synthetic resin materials to obtain a feel that is very similar to natural leather. .

However, in such a method, if the resin and collagen powder are mixed and left to stand still, the collagen powder will gradually start to sink downward, forming a hard sedimentary layer that is difficult to redisperse over time, which is called caking. There were inconveniences such as difficulty in stirring and reuse.

By using a surfactant, the present invention eliminates the disadvantages of the conventional mixing method, allows the collagen powder to be evenly dispersed in the resin, and further prevents the collagen powder in the resin composition from caking over time, making it easy to re-stir. The present invention provides a method for improving .

(3) Problems to be Solved by the Invention The purpose of the present invention is to improve the above-mentioned problems of the prior art by using a surfactant, and to improve parts such as automobile handles, grips of communication devices, seats, furniture, etc. We improved the dispersibility of collagen powder in solution or paste form and resin, which can be used for bags etc. and can give properties close to those of natural leather, and further improve the aging of collagen powder in the resin composition. The purpose of the present invention is to provide a method for preventing caking and improving re-stirring performance.

(4) Means for Solving the Problems According to the present invention, collagen powder in which the collagen powder in the range of finer than 80 microns accounts for 85% or more of the total amount of collagen powder by weight is preliminarily dissolved in a resin. After mixing with an organic solvent or a small amount of resin and stirring it thoroughly, add a surfactant, which is a nitrogen-containing compound or a silicone compound, and apply the surfactant uniformly to the entire collagen powder. Thereafter, a method is provided in which the dispersibility of the collagen powder and the resin is improved by mixing the resin, and further the re-stirrability is improved by preventing the collagen powder in the resin composition from caking over time. .

In the present invention, the collagen powder mixed with the resin is
Based on the viewpoint that it itself needs to have leather-like properties such as touch, smooth surface layer, and high moisture absorption and desorption properties, for example, Japanese Patent Application No. 1-335991
As seen in the issue, animal tissues containing a large amount of collagen, such as the skin of pigs and cows, are purified using enzymes, wet-pulverized to form a collagen fiber dispersion, and then chromium compounds and zirconium are added to the collagen fiber dispersion. Cross-linking or tanning treatment is performed using a cross-linking agent such as a compound or a tanning agent, followed by dehydration, drying,
Collagen powder is produced through sequential pulverization, and the particle size is finer than 80 microns, which accounts for 85% or more of the total amount of collagen powder by weight, and has a water absorption of 150 to 500.
% by weight, and the apparent bulk density is 0.1 O to O, lOg
It is preferable to use a collagen powder that is /ce.

In addition, since there is no standardized measuring method for the water absorption of the powder, it was measured by the method described below.

1.0 to 2.5 g (W) of the powder sample was placed on a glass plate (approximately 25
0x 250x 5mm) and cyan blue to 0.
A 0.2% aqueous solution of sodium oleate containing 25% is dripped into the center of the sample little by little from a bilette, and the whole is thoroughly kneaded with a spoon each time. The dropping and kneading operations are repeated, and the end point is when the whole becomes a hard putty-like lump that can be rolled up into a spiral shape with a probe. The amount (V) of the aqueous solution is determined, and the water absorption (%) (G) is calculated using the following formula.

G-V/WX100 In order to smooth the surface layer of the molded product and give it a smooth feel, this collagen powder has a particle size smaller than 80 microns or a weight ratio of 85
% or more, and the water absorption is 15% for the purpose of increasing moisture absorption and desorption properties.
0 to 500% by weight, and further, in order to increase the rate of moisture absorption and desorption, the apparent bulk density is 0.10 to 0.30 g/cc.
That is. The smaller the particle size of the collagen powder, the better for the purpose of smoothing the surface layer, but if the collagen powder is smaller than 80 microns and accounts for 85% by weight or more of the total amount of collagen powder, it is sufficient to achieve the purpose. . If collagen powder with a particle size larger than 80 microns exceeds 15%, the surface smoothness will be lost, which is not preferable. The higher the water absorption is, the better in terms of improving moisture absorption and desorption properties, but if it is so high as to exceed 500% by weight, the volume of the powder increases more than necessary due to water absorption, which reduces the strength of the surface layer, which is not preferable. If it is less than 150% by weight, sufficient moisture absorption and desorption effects cannot be obtained, so it is not practical. The smaller the apparent bulk density is, the better in terms of increasing moisture absorption and desorption properties, but if it is less than 0.1 Og/cc, dust is likely to be generated and mixing with a binder becomes difficult, so it is not suitable for practical use. Moreover, if it exceeds 0.30 g/cc, the rate of moisture absorption and desorption will decrease significantly, which is not preferable.

However, from the viewpoint of imparting a leather-like appearance although sufficient moisture absorption and desorption properties and tactile effects cannot be obtained, for example, a material obtained by simply crushing conventional chrome-tanned natural leather scraps, that is, As seen in Publication No. 6399298, ordinary chrome-tanned leather scraps are shredded, heated and swollen in an autoclave at 110°C for several hours with heated steam, and then dried and crushed to produce leather powder, and Japanese Patent Publication No. 61-44.
As seen in Publication No. 19, a powder obtained by subjecting purified animal skin to coarse dispersion, crosslinking reaction, dispersion, dehydration, and drying in this order is also a collagen powder from the viewpoint of a crosslinked product of collagen, and the present invention served.

The resins used in the collagen powder of the present invention include polyurethane, polyethylene (low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer), polypropylene. Polyolefins such as polybutadiene, polystyrene, ABS resin, AC5 resin, polyvinyl chloride (including those containing plasticizers), polyamide,
Synthetic resins such as polycarbonate are used. moreover,
Various rubbers such as urethane rubber and ethylene-propylene-diene rubber can also be used.

If necessary, the resin can be used as a resin compound by containing plasticizers, stabilizers, curing agents, catalysts, fillers, colorants, reactive monomers, solvents, dispersants, and other various additives. can. Moreover, it may be solid or liquid.

The blending ratio when blending collagen powder with resin to make a resin composition is determined by the use, shape, requirements, etc. of the molded product obtained by molding the resin composition, but usually, the resin is added to the composition. Alternatively, it is preferable to blend the resin compound so as to contain 30 to 98% by weight, preferably 40 to 95% by weight, and the collagen powder to contain 2 to 70% by weight, preferably 5 to 60% by weight.

If the amount of collagen powder blended is less than 2% by weight, leather-like properties cannot be obtained, and if it is more than 70% by weight, it becomes impossible to uniformly disperse in the resin and the physical properties such as strength and abrasion resistance are significantly reduced, which is not preferable. .

When mixing the collagen powder and the resin, the collagen powder is mixed in an organic solvent in advance and stirred to evenly disperse it in the organic solvent. The above organic solvents may be soluble solvents for the resin to be used, and may be selected from toluene, methanol, isopropyl alcohol, benzyl alcohol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl Various solvents such as isobutyl ketone, cyclohexane, cyclohexanone, tetrahydrofuran, dioxane, xylene, dimethylformamide, trichloroethane, perchlorethylene, and others are used as practical organic solvents. The mixing ratio of collagen powder and organic solvent is 50 to 150 parts, preferably 80 to 1 part of organic solvent to 100 parts of collagen powder.
After mixing and stirring at a ratio of 20 parts, a surfactant which is a nitrogen-containing compound or a silicon-based compound is added. When the amount of organic solvent blended is less than 50 parts, the mixture of organic solvent and collagen powder exhibits high viscosity, making stirring difficult. Further, if the amount of the organic solvent is 150 parts or more, when the mixture of the organic solvent and collagen powder is mixed with the resin, the viscosity decreases, making it difficult to form a coating.

The mixing ratio of collagen powder and surfactant is 0.5 to 5.5 parts, preferably 1.5 to 4.0 parts, per 100 parts of collagen powder, and the mixture is stirred. Then, the dispersibility of the collagen powder in the resin was improved by mixing the resin so that the mixing ratio of the collagen powder and the resin was as described above, and furthermore, the composition of the resin and the collagen powder was caked orally. It has become clear that it has the effect of preventing If the amount of surfactant is less than 0.5 parts, dispersibility and re-stirrability will not be improved, and if it exceeds 5.5 parts, dispersibility and re-stirrability will not change, but weather resistance and This is not preferable because it causes a significant decrease in physical properties such as abrasion resistance.

When adding a surfactant, it is important to immerse the collagen powder in an organic solvent in advance to sufficiently swell the collagen powder and allow the organic solvent to penetrate into the inside of the collagen powder. By adding a surfactant to the surface and inside of the collagen powder and making it compatible with the resin, the specific gravity of the collagen powder in the resin is reduced, the dispersibility and re-stirrability are improved, and caking is prevented. It is. Therefore, after dispersing surfactant in an organic solvent, collagen powder is mixed and stirred, and then resin is added.Alternatively, collagen powder is kneaded with a small amount of resin and surfactant, and then the remaining resin is mixed and stirred. Almost the same effect can be seen depending on the mixing method, but
Of course, it is not limited to this.

The nitrogen-containing compounds used in the present invention include ethylene bis aliphatic monocarboxylic acid amide, N-alkyl-β-aminopropionic acid and its salts, lecithin, soybean protein, amino acid derivatives, imidacillin compounds, etc. that contain nitrogen in the molecule. A silicon-based compound refers to a surfactant characterized by containing silicon in its composition. For example, WOO2 (GERMAN^)
DDrTIVSi2; ionizing neutral long-chain polyaminoamide and polymeric acid ester salt), WO port 3 (GERMAN
Manufactured by ADDITIVS; Ionizing neutral long chain polyoxyalkylene amine fatty acid ester), Talen 7500-2
0 (manufactured by Kao; higher fatty acid nitrogen derivative), Fluonon S
A 1000 (manufactured by Kao; higher fatty acid nitrogen derivative), Lipomin LA (manufactured by Lion; N-alkyl (C8-24)
β-aminopropionic acid and its salts (Na, K.

Li, Ca)), -ssan cation AR4 (NOF Co., Ltd., alkylimidacillin type), Enadicol C
40H (manufactured by NOF; alkylimidazoline type), Enadicol CNS (manufactured by NOF; alkylimidazoline type), Lepon 105 (manufactured by Sanyo Chemical; imidacillin derived from coconut oil fatty acid), Lecithin DX (manufactured by Nisshin Oil; lecithin) ), Basis LP-20 (made by Nisshin Oil Co., Ltd.: food additive soybean lecithin 90% or more), Amisoft H3-1
1 (Ajinomoto diamino acid surfactant), Tsurupi 20
00 (Nissin Oil Co., Ltd.; soybean protein), Homogenol L
-100 (manufactured by Kao; special nonionic surfactant),
NUC-8ILICONEF Z-2000, NUC
-5ILICONE L-7601, NUC-5IL
ICONE L-7001, NUC-SILICON
Examples include EA-163 (manufactured by Nippon Unicar; silicone surfactant), but are not limited thereto.

Resin compositions produced in this way can have various flow characteristics, so depending on the purpose of use of the resin composition produced, for example, a paste-like resin composition is prepared, and this is applied to leather by calender roll molding. Provided for the production of various types of sheets or films. In addition, by preparing a relatively highly viscous resin composition in the form of a resin solution and applying it directly to the surface of woven or nonwoven fabric, paper, etc. using a doctor knife coater, etc., a leather-like surface can be created. Alternatively, by impregnating these woven fabrics, non-woven fabrics, paper, etc. with the solution-like resin composition, it could be used to fabricate fabrics that have a leather-like appearance as a whole. Furthermore, the resin composition in the form of a resin solution is applied to a thickness of 0.2 to 0.8 mm on a release paper surface with a smooth and glossy surface using a doctor knife coating method.
By drying, it was possible to produce an ultrathin leather-like film that could be peeled off. In addition, a leather-like film with a thickness of 0.2 to 0.8 cm, which is once coated on the release paper surface, is transferred and adhered to the surface of woven or non-woven fabric, paper, synthetic leather, etc., to create an ultra-thin film on the surface. It could be used to produce fabrics etc. having a leather-like film.

In addition, the resin composition could be used as a paint with its viscosity as low as possible. The resin composition prepared in the form of a solution was found to be most suitable for painting leather-like coatings by spraying with a spray gun, painting, brushing, or rolling.

Paint films, films, coatings, non-woven fabrics, etc. made from the above resin compositions are
Collagen powder, which is finer than microns, evenly contains more than 85% of the total amount of collagen powder by weight, so there is no roughness on the surface and it is smooth and moist, which is unique to natural leather. In addition, after preparing the resin composition, it prevents caking of the collagen powder in the resin composition and allows for smooth re-stirring. The characteristics and physical properties of the painted film, film, coating film or non-woven fabric are not compromised.

Therefore, it is used for surface coating of automobile steering wheels, automobile interior materials, various handles, furniture, etc., as well as cloth,
It is used for sheets and films that are pasted onto the surfaces of paper, metal plates, resin plates, etc., and it is also used to make nonwoven fabrics etc. into leather-like materials, etc., and its uses are directed to all areas of daily life.

In addition, since the coating surface that is formed has properties unique to natural leather, it can be subjected to cosmetic treatments similar to those normally applied to natural leather, and can also be used to create a grained leather pattern. , it is possible to create unique patterns on crocodile leather by embossing.

In addition, the properties of the mixed collagen powder can be brought out even more effectively by performing a sanding treatment on the surface of the coating film, film, or sheet made from the above-mentioned thermoplastic resin material.

(5) Function The present invention involves mixing and molding collagen powder, in which collagen powder finer than 80 microns accounts for 85% or more by weight, into a resin for the purpose of imparting a leather-like appearance, feel, and function. In this case, by using a surfactant characterized by being a nitrogen-containing compound or a silicone-based compound, the dispersibility of the collagen powder and the resin is enhanced, and furthermore, caking of the collagen powder in the resin composition over time is prevented. This improves the prevention and re-stirring properties of the molded product, which gives it smoothness on the surface, as well as high moisture absorption and desorption properties and speed. Furthermore, after mixing the resin and collagen powder, it is possible to prevent the collagen powder in the resin composition from caking over time, allowing smooth re-stirring and reuse. Due to its excellent feel, the leather-like molded product obtained by the present invention is widely used as flexible films, seats, chair armrests, furniture, console boxes, handle grips, etc.

The present invention will be explained in more detail with reference to Examples and Comparative Examples below, but it is of course not limited thereto.

In the Examples and Comparative Examples, "parts" indicate "parts by weight" unless otherwise specified.

(6) Examples Example 1 Bovine bedding skin is purified and wet-pulverized to produce a collagen fiber dispersion, which is then cross-linked with a zirconium compound and an aluminum compound, followed by dehydration, drying, and pulverization in order. Collagen powder 10, in which collagen powder with a particle size smaller than 80 microns accounts for 85% or more of the total amount of collagen powder by weight, has a water absorption of 175% by weight, and has an apparent key density of 0.268 g/cc.
Mix and stir 100 parts of cyclohexanone to 0 parts,
After that, the surfactant Homogenol L-100 (manufactured by Kao Co., Ltd.)
3. Special nonionic activator). (One part was added and mixed to form a collagen dispersion.

LLDPE (Showa Denko type; Shorex Linear M
I-23g/10min, density 0.916g/cd) 80
40% by weight of the above collagen dispersion was melt-kneaded in a kneader at 180° C., and then a 0.8 m+* sheet was formed by compression molding.

Example 2 To 50 parts of the collagen powder of Example 1, 1.2 parts of surfactant NUC-3ILICONE A163 and 10 parts of vinyl chloride resin (Shin-Etsu Chemical TK-1300) were added.
A resin composition containing 0 part of dioctyl phthalate and 90 parts of dioctyl phthalate was made into a 0.5-inch sheet by a calendering method.

Example 3 100 parts of collagen powder of Example 1, surfactant WOO
2 (GERMAN ADDITIVS; ionizing neutral long-chain polyaminoamide and polymeric acid ester salt) 3.0 parts,
100 parts of polyurethane resin (manufactured by Kuraray, solid content: 10%) was mixed to obtain a collagen dispersion. A resin composition consisting of 90 parts of the above polyurethane resin without the addition of collagen powder and 20 parts of the above collagen powder-added polyurethane resin was applied onto a vinyl chloride sheet using an applicator to form a sheet with a film thickness of approximately 35 AIIO) and 0.5 a+m after drying. .

Example 4 Normal chrome-tanned leather scraps were shredded, heated and swollen at 110°C for 3 hours in an autoclave with heated steam, and dehydrated using a screw breath dehydrator until the moisture content reached 67% by weight. After that, it is dried using a hot air tray dryer to a moisture content of 9.5% by weight, and then crushed using a hammer mill to a powder finer than 80 microns to a weight ratio of 85% or more of the total powder to obtain collagen. It was made into powder.

80 parts of methyl ethyl ketone was mixed and stirred with respect to 100 parts of the above collagen powder, and then 5.0 parts of surfactant homogenol L-100 was added and kneaded to obtain a collagen dispersion.

A resin composition consisting of 100 parts of the polyurethane resin of Example 3 and 20 parts of the above-mentioned Kolaken dispersion was applied onto a vinyl chloride sheet using an applicator, and after drying, the film thickness was about 35%.
T! n), a sheet of 0.5 m11.

Surface layer tests were conducted on the molded articles obtained in Examples 1 and 2, and the results shown in Table 1 were obtained.

Comparative Example 1 (Method without surfactant) A 0.5 mm sheet was produced by calendering a resin composition consisting of 80 parts of the collagen powder of Example 1, 100 parts of the vinyl chloride resin of Example 2, and 90 parts of dioctyl phthalate. Then, a surface layer test was conducted, and the results shown in Table 1 were obtained.

Comparative Example 2 (Other surfactants) 80 parts of methyl ethyl ketone was mixed and stirred with respect to 100 parts of the collagen powder of Example 1, and then the surfactant Contrasol (manufactured by GERMAN-ADDITIVES 13,
5.0 parts of 2% anionic active agent having a main chain of non-polar polymethylene was added and kneaded to obtain a collagen dispersion.

A resin composition consisting of 100 parts of the polyurethane resin of Example 3 and 20 parts of the above collagen dispersion was applied onto a vinyl chloride sheet using an applicator (film thickness after drying: approximately 35%).
-), 0.5+u sheet.

Surface layer tests were conducted on the molded products obtained in Comparative Examples 1 and 2, and the results shown in Table 1 were obtained.

From the results in Table 1, the leather-like molded products of the present invention have excellent appearance and feel, and have excellent moisture absorption and desorption properties, regardless of the resin used, compared to leather-like molded products produced by conventional mixing methods. The moisture release rate is higher than the practically necessary level of 2.50 g/rf, the moisture release rate is also maintained at less than 50 seconds, and caking does not occur over time after forming the resin composition. It has been shown that it can be reused, with little deterioration in the properties and physical properties of the resulting molded article. A preferred method for mixing collagen powder and resin is to wet the collagen powder in advance with an organic solvent, add a surfactant, and then knead it with the resin. The improvements in dispersibility and re-stirrability of collagen powder tend to diminish somewhat.

(7) Effects of the Invention According to the present invention, when using collagen powder in which the collagen powder in a range smaller than 80 microns accounts for 85% or more of the total amount of collagen powder by weight, it is confirmed that the collagen powder is a nitrogen-containing compound or a silicon-based compound. By using the characteristic surfactant, it is possible to obtain a leather-like molded product that has the same appearance, feel, and moisture absorption and desorption properties as natural leather, regardless of which resin is used, and a composition of collagen powder and resin. It features a method to prevent caking when mixing collagen powder and resin, which prevents caking when mixed with collagen powder and resin, improves re-stirring properties, and enables reuse.

Claims (1)

[Claims] Collagen characterized by using a surfactant that is a nitrogen-containing compound or a silicon-based compound when dispersing collagen powder containing 85% or more by weight of collagen powder in a range of particles finer than 80 microns into a resin. How to prevent powder caking.