JP3432788B2 - Hybrid powder consisting of collagen and resin components - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hybrid powder for a leather-like molded article or a leather-like coating film, which comprises collagen and a resin component, and more particularly to a hybrid powder comprising collagen and a resin component, which have excellent affinity with a resin.

[0002]

2. Description of the Related Art Leather has been used as a material for daily necessities for a long time by taking advantage of the leather surface layer, which has an elegant appearance peculiar to each species, and has both flexibility and toughness due to the entanglement of collagen fiber bundles. In addition, it has the characteristics of excellent durability, hygroscopicity, heat resistance and cold resistance.

However, compared with natural fiber products and synthetic resin products, natural leather has the disadvantage that the physical properties of the leather are different when the parts of the leather taken from different organisms are different. It has the disadvantage that not all parts of leather taken from living organisms are necessarily available, as it reduces its value. Therefore, the natural leather product becomes a high cost material compared to other materials (natural fiber product and synthetic resin product). Further, natural leather is a by-product produced during the meat production process, and its supply is limited. Therefore, there is an attempt to pulverize natural leather and mix the leather powder with a resin material to provide a leather-like molded article that resembles natural leather.

For example, Japanese Patent Laid-Open No. 62-240400 discloses a leather made by kneading and molding dry leather powder having a particle size of 50 mesh (296 μm) to 250 mesh (59 μm), a thermoplastic resin and a pigment. In molded products like
A "leather-like molded article in which the above-mentioned mixed pigment is bound to a leather powder forming a molding material together with a thermoplastic resin" is disclosed (hereinafter referred to as "known art 1"). Also, JP-A-63-1131
No. 1 discloses "a leather-like molded product obtained by mixing dry leather powder having a particle size of 50 mesh to 250 mesh with a thermoplastic resin compound within a weight ratio of 60%, and injecting it into a molding metal and molding." Is disclosed (hereinafter referred to as "known art 2"). Further, Japanese Patent Laid-Open No. 63-22864 discloses "Leather-like molding in which dry leather powder having a particle size of 50 mesh to 250 mesh is mixed with a thermoplastic resin compound within a weight ratio of 60% and extrusion molding is performed. "Product" is disclosed (hereinafter referred to as "known art 3"). However, since the leather-like molded articles described in each of these publications use a relatively coarse (large particle size) powder as a leather powder, they have poor fluidity when blended with a thermoplastic resin, Leather powder cannot be uniformly dispersed in the plastic resin. As a result, the strength of the molded product is inferior, the leather-specific molded product cannot be given the characteristics peculiar to leather, and a molded product having a smooth surface cannot be obtained.

Further, Japanese Patent Application Laid-Open No. 3-195800 discloses, in order to provide a leather-like molded article composed of fine leather powder and a resin, "purified collagen tissue containing molecular collagen from the floor skin by the action of an enzyme. The collagen tissue is obtained by wet pulverization, and the collagen tissue after the wet pulverization is subjected to a crosslinking treatment by adding a crosslinking agent of an inorganic substance to produce a collagen fiber aggregate, and the collagen fiber aggregate is dehydrated and dried and then pulverized to obtain a collagen powder. And obtaining a leather-like molded article by molding a mixture of this collagen powder and a thermoplastic resin. "(Hereinafter referred to as" known art 4 "). However, since the collagen tissue containing molecular collagen is cross-linked with an inorganic cross-linking agent to obtain collagen fiber aggregates, the water resistance is poor, and when the collagen powder and the thermoplastic resin are mixed, the collagen powder is mixed in an aqueous solvent. Since the powder easily swells, it is not suitable for use as a leather-like paint.

[0006] Further, the tanned leather is heated with heated steam,
A method (hereinafter referred to as "known art 5") of swelling to fix collagen fibers by sticking them together, dehydration and drying, and then crushing the tanned leather to obtain collagen powder has also been proposed. Since a considerable part of the collagen fibers is modified into gelatinous substance, even if a leather-like water-based paint can be obtained from the collagen powder and thermoplastic resin obtained by this method, the viscosity of the paint increases and it cannot be applied well. In addition, the coating film is sticky and the coating film has poor water resistance.

[0007]

[Problems to be Solved by the Invention] Generally, crushing leather (non-tanned leather is called "leather" and tanned leather is called "leather") into fine particles. Since it is difficult to obtain a leather powder having a relatively coarse diameter in the conventional leather-like molded article as described in the known techniques 1 to 3, it is difficult to obtain the leather in the thermoplastic resin. The powder could not be dispersed uniformly, the strength of the molded product was poor, and a molded product having a smooth surface could not be obtained. Further, the leather-like coating film obtained from the collagen powder described in the known arts 4 and 5 has a drawback that it has poor water resistance.

The present invention has been made in view of such problems of the prior art, and an object thereof is a leather-like molded article having a tough and smooth surface and a leather-like coating excellent in water resistance. It is an object of the present invention to provide a fine hybrid powder composed of collagen and a resin component capable of obtaining a film.

[0009]

[Means for Solving the Problems] In order to achieve the above object, the present invention forms a collagen fiber bundle by stitching the side surface of a collagen coarse fiber with a resin component formed by non-catalytic graft copolymerization, By pulverizing this collagen fiber bundle after drying, a fine hybrid powder composed of collagen and a resin component can be obtained.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION That is, according to the present invention, a collagen fiber component is used in a weight ratio of 5 to the collagen fiber component.
A hybrid powder comprising collagen and a resin component, which can be obtained by drying and pulverizing a polymer obtained by graft-copolymerizing a resin having 0 to 200% by weight of the resin component, is defined as the first invention, and In the first invention, the hybrid powder has a particle size of 40 μm or less in an amount of 90% by weight or more and has an average particle size of 5
The second invention is a hybrid powder having a particle size of 20 μm.

According to the first aspect of the present invention, since collagen fiber bundles can be formed by stitching collagen fibers with a resin component formed by graft copolymerization, there is no entanglement between collagen fibers, and the collagen fibers are not entangled after drying. By pulverizing with a general-purpose pulverizer, a fine hybrid powder composed of collagen and a resin component can be obtained. When this hybrid powder is kneaded with a thermoplastic resin and an additive added as necessary, fine hybrid powder is uniformly dispersed in the kneaded product, and the kneaded product is molded by a conventional method to obtain a tough and smooth surface. It is possible to obtain a leather-like molded product having Further, when a mixture of the hybrid powder, a thermoplastic resin or a thermosetting resin, and an additive that is added as necessary is kneaded and applied onto leather, a coating film having excellent water resistance can be formed.

When the ratio of the resin component to the collagen fiber component is less than 50% by weight of the collagen fiber component, the surface of the collagen coarse fiber is graft-copolymerized but the interior of the fiber is not graft-copolymerized. However, this raw collagen fiber has a drawback that it is difficult to pulverize, and moreover, it produces thread-like collagen which is difficult to classify. On the other hand, the ratio of resin component to collagen fiber component is 200% by weight of collagen fiber component.
If it exceeds, that is, if the ratio of the collagen component in the hybrid powder decreases, there is a drawback that the moisture absorption / desorption ability, which is an important characteristic of the hybrid powder, decreases. Therefore, the ratio of the resin component to the collagen fiber component is preferably 50 to 200% by weight of the collagen fiber component. As such a resin component, a graft polymer obtained by copolymerization with a methyl methacrylate and a glycidyl methacrylate monomer, or a methyl methacrylate and a glycidyl methacrylate monomer and another monomer, for example, styrene, vinyl acetate, acrylonitrile, methacrylonitrile, methacryl A graft polymer obtained by copolymerization with a vinyl monomer copolymerizable with methyl methacrylate such as acid hydroxyester can be used.

Examples of the thermoplastic resin include polyethylene, polypropylene, polybutadiene, polystyrene, polyvinyl chloride, polyamide, polycarbonate,
Known substances such as styrene-butadiene block copolymer can be used.

As the thermosetting resin, for example, known resins suitable for coating materials such as polyurethane resin, melamine resin and urea resin can be used.

As the additive, various kinds of additives such as a plasticizer, a stabilizer, a filler, a colorant, a solvent and a dispersant can be used.

The hybrid powder having a particle size of 40 μm or less is preferably 90% by weight or more because the surface of the molded product can be made smoother. Further, when the average particle size of the hybrid powder is less than 5 μm, not only the crushing cost becomes high, but also the denaturation and coloring of the collagen component occur with the increase of the crushing time.
If it exceeds m, there is a drawback that it becomes difficult to form a thin film and impart gloss to the film in forming a leather-like film. Therefore, the average particle size of the hybrid powder is preferably 5 to 20 μm.

[0017]

Embodiments of the present invention will be described below in the order of steps. 1. Manufacture of hybrid powder (a) Manufacture of collagen coarse fiber Living skin is limed, dehaired, and defatted in ordinary leather manufacturing.
After the steps such as decalcification, the dermis (so-called dermis) obtained by removing the epidermis and subcutaneous tissue from the naked dermis was coarsely crushed with a meat chopper equipped with a screen having a diameter of 2 mm.
After drying to a water content of 5% by weight, this coarsely crushed and dried skin was put into a wheelie type pulverizer composed of a fixed blade and a rotary blade to obtain a collagen coarse fiber which passed through a screen having a diameter of 1 mm. The particle size distribution of this collagen crude fiber is as follows. Those that passed 150 mesh = 0% Those that passed more than 50 mesh and less than 150 mesh =
23 wt% after passing through 50 mesh = 77 wt% (b) Polymerization treatment Then, in a polymerization reaction vessel equipped with a stirrer (not shown, internal volume: 1600 liters), 1000 parts by weight of water, 17 parts by weight of acetic acid, the above collagen 100 parts by weight of coarse fiber, 5 parts by weight of propylene oxide and 0.4 of glycidyl methacrylate
Parts by weight were added and the mixture was maintained at 35 ° C. for 24 hours while stirring. Then, 100 parts by weight of methyl methacrylate was added to the reaction vessel, and nitrogen gas was introduced into the reaction vessel to remove oxygen from the polymerization mother liquor. Then, the mixture was stirred while introducing nitrogen gas into the same reaction vessel, and kept at 35 to 40 ° C. for 48 hours. Then, after stopping the passage of nitrogen gas to terminate the polymerization, 15 parts by weight of aluminum sulfate and an appropriate amount of an aqueous solution of sodium hydroxide are added to the reaction vessel to adjust the pH of the polymerization mother liquor to 7 to 8. , And held for another 24 hours. (C) Dehydration treatment In order to reduce the water content of the polymer obtained by the above graft copolymerization treatment and shorten the time of the drying treatment described below, the water content becomes 75% by weight using a centrifuge. Dehydrated until. This water content is preferably 80% by weight or less in order to shorten the drying time described later. As a device used for dehydration, a known dehydration device such as a filter press or a screw press can be used in addition to the centrifugal separator. (D) Drying treatment To reduce the water content of the graft copolymer in the form of chips by further lowering the water content with a centrifuge, and to facilitate the pulverization process described later, place it in a well-ventilated and shaded place. The dehydrated graft copolymer was spread and air dried to a water content of about 20% by weight, and then dried using a hot air dryer at 50 ° C. to a water content of 3% by weight. This water content is preferably 10% by weight or less in order to facilitate the pulverization process described later. (E) Pulverizing treatment The dried chip-shaped graft copolymer was pulverized using a vibration mill to obtain a hybrid powder composed of collagen and resin having a particle size distribution as shown in Table 1 below.
The grinding conditions are as follows. Material of crushing cylinder = Stainless steel crushing cylinder Total volume = 3.6 liters Crushing method = Batch type crushing medium = General carbon steel rod (diameter 19 mm) Frequency = 1200 cycles / min. Amount of processing = 1.0 kg / Hr As a crusher Other than the vibration mill, a crusher such as a hammer mill, a jet mill or a ball mill can be used. If the average particle size of the hybrid powder is made to be less than 5 μm, the pulverization time becomes extremely long, and thermal denaturation and coloring of the powder are induced. Therefore, it is preferable that the average particle diameter of the hybrid powder is 5 μm or more in order to suppress the crushing cost and to prevent the thermal denaturation and coloring of the powder. The maximum diameter of the hybrid powder is preferably 50 μm or less, and more preferably 20 μm or less, for the reason that the leather-like film is likely to be thinned and the film is likely to be glossy.

[0018]

[Table 1]

The average particle size of those in Table 1 was 8 μm. 2. Production of leather-like molded article and formation of leather-like coating film (1) Examples 1 and 2 and Comparative Examples 1 and 2 [Example 1] 50 parts by weight of hybrid powder having a particle size distribution shown in Table 1 and dioctyl phthalate 30 By weight, 3 parts by weight of the stabilizer and 100 parts by weight of polyvinyl chloride were kneaded at 160 ° C. using a kneader (not shown), and then hot pressed to obtain a 0.5 mm thick sheet. The sheet had a natural leather texture with a smooth surface and gloss. [Example 2] Further, 30 parts by weight of a hybrid powder having a particle size distribution shown in Table 1, 30 parts by weight of dioctyl phthalate, 3 parts by weight of a stabilizer and 100 parts by weight of polyvinyl chloride were used at 160 ° C using the same kneader. After kneading and then hot pressing, a 0.5 mm thick sheet was obtained. The sheet had a natural leather texture with a smooth surface and gloss.

The mechanical properties of the molded sheets of Examples 1 and 2 are shown in Table 2, and the moisture absorption / desorption properties are shown in Table 3.

[0021]

[Table 2]

The coefficient of friction was measured by a conventional method using a surface tester "HEIDON-14R" to measure the coefficient of static friction and the coefficient of dynamic friction. The test conditions are as follows.

Indenter = 3 cm × 3 cm Flat indenter Indenter moving speed = 1000 mm / min Load = 100 g (11 g / cm ² ).

[0024]

[Table 3]

The characteristic values shown in Table 3 (and Table 5 below) relating to the moisture absorption and desorption characteristics were measured as follows.

A sample set in a moisture permeable cup so that its surface is exposed to the outside air was dried in advance at 80 ° C. overnight and then 3
The sample was transferred to an environment of 5 ° C. and a relative humidity of 85%, and the amount of weight increase with time was measured after 60 minutes (or 10 minutes) (hygroscopicity test). Immediately thereafter, the relative humidity is 30 at 35 ° C.
%, The amount of weight loss was measured 1 hour later (moisture release test).

The surface moisture absorption amount and the surface moisture release amount were calculated by the following equations.

Surface moisture absorption amount = ((Sample weight after 60 minutes or 10 minutes)-(Sample weight when dried)) / (Sample area) Surface moisture release amount = ((Sample weight at the start of moisture release test) -(Sample weight after 1 hour)) / (Sample area) As for the surface water absorption, after immersing only the surface of the sample of known weight in water for 2 minutes, the water adhering to the sample in the form of water droplets is measured. After wiping off, the weight gain of the sample was measured, and the weight gain was divided by the sample area to obtain the surface water absorption.

The degree of sweat absorption is measured by a skin surface stratum corneum moisture measuring device,
Using a model name “Model Skicon-200”, the water content on the skin surface of the inner part of the arm was measured in advance. Then, the sample was pressed against the inner part of the arm for 2 minutes, the water content on the skin surface was measured again, and the sweat absorption rate was calculated using the following formula. Table 3
The values shown in Table 5 and Table 5 are the averages of five measurements. The smaller the numerical value of the degree of sweat absorption, the better the sweat absorption.

Sweat absorbency = (water amount on skin surface after pressing sample) × 100 / (water amount on skin surface before pressing) [Comparative Example 1] In Comparative Example 1, the particle size distribution was 100.
To 0.3 μm, 30 parts by weight of dry leather powder having an average particle size of 40 μm, 30 parts by weight of dioctyl phthalate, 3 parts by weight of stabilizer and 100 parts by weight of polyvinyl chloride were used at 160 ° C. using the same kneader. And then hot pressed to obtain a 0.5 mm thick sheet. The sheet had a rather rough surface and could not be said to have a natural leather texture. [Comparative Example 2] As Comparative Example 2, the particle size distribution was 100.
Kneading 30 parts by weight of dry leather powder having an average particle size of 18 μm, 30 parts by weight of dioctyl phthalate, 3 parts by weight of stabilizer and 100 parts by weight of polyvinyl chloride over a range of up to 2 μm at 160 ° C. using the same kneader. Then, hot pressing was performed to obtain a sheet having a thickness of 0.5 mm. The sheet had a rather rough surface and could not be said to have a natural leather texture.

The mechanical properties of the molded sheets of Comparative Examples 1 and 2 are shown in Table 4, and the moisture absorption / desorption properties are shown in Table 5.

[0032]

[Table 4]

[0033]

[Table 5]

The following points are clear from Tables 2-5. The sheets of Examples 1 and 2 have higher strength than the sheets of Comparative Examples 1 and 2. Since the surfaces of the sheets of Examples 1 and 2 are smooth, both the static friction coefficient and the dynamic friction coefficient are lower than those of the sheets of Comparative Examples 1 and 2. The numerical values of the surface moisture absorption amount, the surface moisture release amount and the surface water absorption of the sheets of Examples 1 and 2 are all sufficiently higher than the numerical values of the sheets of Comparative Examples 1 and 2, while the numerical value of the sweat absorption is the comparative example. It is much lower than the numbers on the 1st and 2nd sheets. in this way,
It can be seen that the molded product made from the hybrid powder of the present invention has extremely excellent moisture absorption and desorption properties. (2) Example 3 100 parts by weight of one-component polyurethane resin solution (solid content: 33% by weight), 20 parts by weight of N, N dimethylformamide, 10 parts by weight of methyl ethyl ketone, and 20 parts by weight of the above hybrid powder were used on three paint rollers. The mixture was added and kneaded using the same kneader to obtain a paste. Next, the above paste was applied on the floor leather by a roll coater to a constant thickness. Then, the floor leather is dipped in water, and after the coating film is sufficiently cured, it is taken out of the water, and the floor leather is attached to a net dryer and air-dried.
When a leather-like embossing process was performed with, a leather-like molded product having a glossy natural leather texture could be obtained. (3) Examples 4 and 5 and Comparative Example 3 [Example 4] 200 parts by weight of an undercoating binder obtained by emulsifying an acrylic acid ester resin, 25 parts by weight of the hybrid powder, 200 parts by weight of water, and 100 parts by weight of an aqueous pigment. The mixture was emulsified using a homogenizer (not shown). Then, the above emulsion was coated on the floor leather with a roll coater to a constant thickness. Then, stick this floor leather to a net dryer and air dry,
When ironing was performed with an iron having a surface temperature set to 90 ° C., a leather-like molded product having a glossy natural leather texture could be obtained. Example 5 A mixture of 200 parts by weight of a binder for an undercoat obtained by emulsifying a butadiene polymer, 35 parts by weight of the hybrid powder, 200 parts by weight of water and 100 parts by weight of an aqueous pigment was emulsified using the same homogenizer. Then, the above emulsion was coated on the floor leather with a roll coater to a constant thickness. Then, this floor leather is attached to a net dryer and air-dried, and the surface temperature is 90%.
Ironing with an iron set to ℃ made it possible to obtain a leather-like molded product having a glossy natural leather texture. Comparative Example 3 As Comparative Example 3, in Examples 4 and 5,
An attempt was made to obtain a leather-like molded article in the same manner as in Examples 4 and 5 except that the collagen powder obtained by the method described in the known art 4 was used in place of the hybrid powder of the present invention. When the collagen powder was blended, a gelation phenomenon occurred, and the intended emulsion for forming a leather-like coating film could not be obtained. (4) Examples 6 and 7 and Comparative Examples 4 and 5 [Example 6] 150 parts by weight of acrylic resin-based tight coating agent A (trade name "LT-87" manufactured by Rohm & Haas Co.) and acrylic resin-based tight 120 parts by weight of coating agent B (trade name "Primal 892" manufactured by Rohm & Haas), 550 parts by weight of water, 120 parts by weight of penetrant (trade name "L-219" manufactured by Rohm & Haas), and the above hybrid powder 60 parts by weight of the same homogenizer was emulsified, the above emulsion was spray-painted on the floor leather with a spray coating machine, and ironing was carried out with an iron whose surface temperature was set to 90 ° C. It was possible to obtain a leather-like molded product having the texture of. [Example 7] A coating composed of an acrylic resin, a urethane resin and an inorganic filler (trade name "Rodabase T" manufactured by TFL).
AM ") 140 parts by weight and urethane resin binder (TF
L company's trade name "Dectane WBO") 70 parts by weight, acrylic resin binder (TFL's trade name "Rodacryl 155") 280 parts by weight, and pigment (Rohm &Haas' trade name "Dear Color") 130 parts by weight Parts and 300 parts by weight of water and penetrant (trade name "L-21 manufactured by Rohm & Haas Co., Ltd.
9 ") 30 parts by weight and 50 parts by weight of the above hybrid powder are emulsified using the same homogenizer, iron the floor leather with an iron whose surface temperature is set to 90 ° C., and then spray the above emulsion with a spray coater. By spray-painting on this floor leather, a leather-like molded product having a glossy natural leather texture could be obtained. Comparative Example 4 As Comparative Example 4, in Examples 6 and 7,
A leather-like molded article was sought to be obtained in the same manner as in Examples 6 and 7, except that the collagen powder obtained by the method described in the known art 4 was used instead of the hybrid powder of the present invention. As a result, in the case of the former (process corresponding to Example 6), the emulsion could be spray-painted on the floor leather, but in the case of the latter (process corresponding to Example 7), inside the homogenizer. It was not possible to obtain an emulsion in which collagen powder was uniformly dispersed in the above liquid, and it was made into a paste, so it was not possible to spray paint the floor leather with the emulsion. Comparative Example 5 As Comparative Example 5, in Examples 6 and 7,
Instead of the hybrid powder of the present invention, after cutting leather scraps that have been subjected to normal chrome tanning, collagen powder (corresponding to known technique 5) that has been heated and swelled in an autoclave with steam and dried and crushed is used. An attempt was made to obtain a leather-like molded article by the same method as in Examples 6 and 7 except that the leather-like molded article was used.
As a result, in the case of the former (process corresponding to Example 6), it was not possible to obtain an emulsion in which leather powder was evenly dispersed in the liquid in the homogenizer, and gelling occurred, so the emulsion was spray-painted on the floor leather. I couldn't. In the latter case (process corresponding to Example 7), the emulsion could be spray-coated on the floor leather. (5) Compounding test into floor leather finishing agent 10 parts by weight of the hybrid powder of the present invention is shown below as 1
When added to 100 parts by weight of each of the floor leather finishes of item 0, the hybrid powder of the present invention was well dispersed, emulsified, and did not gel in any of the floor leather finishes.

However, in the case of the collagen powders obtained by the methods described in the publicly known techniques 4 and 5, all of the gelling agents were gelled in 9 kinds of finishing agents (the following Nos. 2 to 10), and It was judged that the above-mentioned finishing agent cannot be used as a leather-like paint. 10 floor leather finishing agents (No. 1 to No. 10 below)
No. 1 = Product name “1761” manufactured by Star Finish Co., Ltd.
-A "(acrylic water-soluble resin) No. 2 = product name" RA-2 "manufactured by Star Finnish
353 "(water-soluble acrylic resin) No. 3 = product name" LT-76 "manufactured by Rohm & Haas Co.
(Acrylic Copolymer Emulsion) No. 4 = Rohm & Haas brand name "Hydrac PC" (acrylic top coat) No. 5 = Rohm & Haas brand name "Primal H"
PB-980 "(acrylic emulsion binder) No. 6 = product name" Primal E "manufactured by Rohm & Haas
863 "(acrylic emulsion binder No. 7 = trade name" ST-84 "manufactured by Rohm & Haas)
(Thermoplastic acrylic copolymer emulsion binder) No. 8 = Product name "SB150" manufactured by Rohm & Haas Co.
(Acrylic binder) No. 9 = product name "SB" manufactured by Rohm & Haas (flexible base binder) No. 10 = product name "Primal S-1" manufactured by Rohm & Haas (acrylic copolymer emulsion) (6) Water resistance test Leather-like molded article obtained in Example 6 and leather-like molded article obtained in Comparative Example 4 (by the process corresponding to Example 6),
The leather-like molded article obtained in Comparative Example 5 (by the process corresponding to Example 7) was subjected to a water resistance test, and the results are shown in Table 6 below.

[0036]

[Table 6]

As is clear from Table 6, the leather-like molded products obtained in Example 6 have extremely excellent water resistance as compared with the leather-like molded products of Comparative Examples 4 and 5.

[0038]

Since the present invention is constructed as described above, it has the following effects. (1) By using the hybrid powder of the present invention,
It is possible to obtain a leather-like molded product having a tough, smooth surface and a texture of natural leather. (2) By using the hybrid powder of the present invention,
A leather-like coating film having excellent water resistance can be formed.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields investigated (Int.Cl. ⁷ , DB name) D06N 3/00-3/18 C14B 7/04

Claims (2)

(57) [Claims] 1. A polymer obtained by graft-copolymerizing a collagen fiber component and a resin component having a weight ratio of 50 to 200% by weight with respect to the collagen fiber component is dried and then pulverized. A hybrid powder composed of collagen and a resin component that can be obtained. 2. The hybrid powder has a particle size of 40 μm or less in an amount of 90% by weight or more and has an average particle size of 5%.
The hybrid powder according to claim 1, which has a size of -20 μm.