WO2008018184A1

WO2008018184A1 - Thermoplastic resin

Info

Publication number: WO2008018184A1
Application number: PCT/JP2007/000873
Authority: WO
Inventors: Yoshihiro Nomura; Toshihiko Kitaura
Original assignee: Tokyo University Of Agriculture And Technology Tlo Co., Ltd.
Priority date: 2006-08-10
Filing date: 2007-08-10
Publication date: 2008-02-14
Also published as: JP5305320B2; JPWO2008018184A1

Abstract

Disclosed is a novel thermoplastic resin having the feel, appearance and flexibility like a natural leather and is moldable as a leather-like material. The thermoplastic resin can be produced by reacting an urethane prepolymer having a free isocyanate group at the terminus and a digestion product of a hard protein.

Description

Specification

Thermoplastic resin

Technical field

The present invention relates to a thermoplastic resin that can be used as a leather-like material.

Background art

[0002] Artificial leather and synthetic leather have been developed as substitutes for natural leather, and many proposals have been made so far. Synthetic leather is composed of a base material, an adhesive layer, and a skin layer. The appearance is similar to that of natural leather, but the structure and performance are different from those of natural leather. Artificial leather is composed of non-woven fabric entangled with fibers and an elastic polymer, and has an appearance, structure and performance close to those of natural leather. However, since human leather uses a technique in which a nonwoven fabric is formed and then impregnated with an elastic polymer and filled between fibers, a nonwoven fabric formation process and an elastic polymer filling process are required, making the production complicated and producing costs. There is a problem that the habit becomes high.

[0003] In addition, in synthetic leather and artificial leather, the degree of polymerization of an elastic resin such as polyurethane, which is a constituent component, is modified or modified in order to bring its feel and performance closer to natural leather, collagen, keratin, etc. Attempts have been made to produce materials that have a feel similar to natural leather. For example, a method of obtaining a leather-like material by blending natural leather powder with polyvinyl chloride and polyurethane (Patent Document 1), and a method of applying a dispersion of silk powder and natural leather powder in a synthetic resin solution to the surface of synthetic leather (Patent Document 2) and a method of using a collagen powder in a synthetic resin as a surface layer forming material (Patent Document 3).

[0004] However, artificial leather and synthetic leather blended with these proteins remain the same as the basic component of synthetic resin, and the leather-like feel is improved compared to materials using only synthetic resin. However, the moist feel of natural leather cannot be obtained.

Patent Document 1: Japanese Patent Application Laid-Open No. 60-0-2 1 5 8 75

Patent Document 2: Japanese Patent Laid-Open No. 3_4 5 7 8 5 Patent Document 3: Japanese Patent Laid-Open No. 3-1 2 4 8 0 0

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention relates to providing a novel thermoplastic resin that has a natural leather-like feel, appearance, and flexibility and can be molded as various leather-like materials.

Means for solving the problem

[0006] In view of such circumstances, the present inventors have studied a resin substance that can be a leather-like material. As a result, urethane prepolymers having a free isocyanate group at the terminal and hard protein degradation products are fixed. When mixing and stirring under the above conditions, it was found that both of them react unexpectedly and a thermoplastic resin that can be molded as a leather-like material is obtained.

That is, the present invention relates to the following 1) to 3).

1) A thermoplastic resin obtained by reacting a urethane precursor having a free isocyanate group at the terminal with a hard protein degradation product.

2) A leather-like material made of the above thermoplastic resin.

3) A method for producing a thermoplastic resin, characterized by reacting a urethane precursor having a free isocyanate group at the terminal with a hard protein degradation product.

[0008] Since the thermoplastic resin of the present invention has a natural leather-like feel, appearance and flexibility, it can be molded as it is as a leather-like material, or subjected to various molding processes and treatments, sheets, films, etc. It can be a raw material for producing various molded articles, fibers, synthetic leather surface coating layers, artificial leather, and the like. In addition, by using a biodegradable urethane prepolymer, a biodegradable thermoplastic resin can be obtained and the environmental load can be reduced.

Brief Description of Drawings

[0009] FIG. 1 is a chart of FT-IR of the product of the present invention and raw materials. (Production Example 1 2 to 1 BEST MODE FOR CARRYING OUT THE INVENTION

[0010] The thermoplastic resin of the present invention is obtained by reacting a urethane prepolymer having a free isocyanate group at the terminal with a decomposition product of a hard protein, and a urethane having a free isocyanate group at the terminal. Examples of the prepolymer include a reaction product obtained by reacting an excess of a polyisocyanate compound with a polyol compound, and usually contains 1 to 10% by weight of an isocyanate group at a molecular end. .

[0011] Examples of polyisocyanate compounds include aliphatic polyisocyanates having 2 to 12 carbon atoms (excluding carbon in the NCO group), and 4 to 15 carbon atoms (excluding carbon in the NCO group). Alicyclic polyisocyanate, aromatic aliphatic polyisocyanate having 8 to 12 carbon atoms (excluding carbon in the NCO group), aromatic polyisocynate having 6 to 20 carbon atoms (excluding carbon in the NCO group) Cyanates and their polyisocyanates-modified products (such as modified products containing force-positive groups, uretdione groups, uretoimine groups, urea groups, burette groups, and / or isocyanurate groups). You may use together.

[0012] Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2, 2, 4 _Trimethylhexane diisocyanate, trizine diisocyanate (TOD I), 2,6-diisocyanate methyl caproate, bis (2_isocyanatetoyl) fumarate, bis (2-isocyanatetoethyl) ) Force 1 Ponate, 2_isocyanate 1,2,6-diisocyanate 1 hexanoate, and the like.

[0013] Examples of the alicyclic polyisocyanate include isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isocyanate). (Netetyl) _4-cyclohexene _ 1, 2-dicarboxylate I can get lost.

[0014] Examples of the araliphatic polyisocyanate include xylylene diisocyanate and jetylbenzene diisocyanate.

[0015] Aromatic polyisocyanates include, for example, 2, 4_tolylene diisocyanate (2, 4-TDI), 2, 6_tolylene diisocyanate (2, 6-TDI), 4, 4 '— Diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MD I), p-phenylenediisocyanate, polymethylene poly Examples thereof include phenylene polyisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalenediisocyanate (NDI), and the like.

[0016] Of these, aromatic polyisocyanates are preferred from the standpoint of toughness and heat resistance of the reactants, especially tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MD I), and mixtures thereof. Is preferred.

[0017] Examples of the polyol compound include polyether polyol, polyester polyol, polyolefin polyol, and mixed polyols thereof.

[0018] Polyether polyols include, in addition to polyoxyalkylene glycols such as polypropylene glycol and polytetramethylene glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3_butanediol, 1,4_ Dihydric alcohols such as butanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxyphenylmethane, glycerin, 1, 1, 1_trimethylolpropane, 1, 2, 5-hexanetrio Le, pentaerythri! Polymerization obtained by adding one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. to one or more polyhydric alcohols such as Things.

Among these, polyoxyalkylene glycol having a number average molecular weight in the range of 500 to 10,000 is preferable. [001 9] Preferred examples of the polyester polyol include condensation-type polyester polyols and lactone-type polyols. Examples of the condensation-type polyester polyols include polyhydric acid and polyhydric alcohol obtained by dehydration condensation. And a condensate of hydroxycarboxylic acid and polyhydric alcohol (for example, castor oil, reaction product of castor oil and ethylene glycol, etc.). Here, examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid, and one or more of these are used. Examples of the polyhydric alcohol include glycerin, bisphenol A, ethylene glycol, 1,2_propylene glycol, 1,4_butane diol, diethylene glycol, 1,6-hexane glycol, hexane diol, and cyclohexane. Examples thereof include sandimethanol and neopentyl glycol, and one or more of these are used.

Examples of the lactone-based polyol include ring-opening polymers such as propion lactone, valerolactone, one-strength prolacton, and one methyl one-strength prolacton.

[0020] Examples of the polyolefin polyol include a polyol having an ethylene / polyolefin skeleton and a polyol having a polyisobutylene skeleton.

[0021] Other low molecular polyols such as polyols having an acrylic skeleton, hydrogenated polybutadiene polyols, etc., ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, etc. Also mentioned.

[0022] As such a polyol compound, polyether polyol and polyester polyol are preferable, and as the polyether polyol, polyoxyalkylene glycol such as polypropylene glycol is preferable, and as the polyester polyol, A dehydrated condensation polymer of adipic acid and diethylene glycol is preferred.

[0023] From the above-described polyol compound and polyisocyanate compound, terminal dissociation The mixing ratio of the polyol compound and the polyisocyanate compound in obtaining the nitrate group-containing urethane prepolymer is usually 1 to 2 to 5 equivalents of polyisocyanate compound (NCO equivalent) per equivalent of polyol compound (OH equivalent). ), Preferably 1.5 to 3 equivalents.

[0024] Such urethane prepolymers are produced by mixing the above-mentioned two compounds in a predetermined quantitative ratio and heating and stirring at 30 to 120 ° C, preferably 50 to 100 ° C for several hours. be able to. Commercially available products (Takenate D_7018, Takenate D-7028 (Mitsui Chemicals Polyurethane Co., Ltd.), etc.) may also be used.

[0025] Examples of the hard protein in the present invention include fibrous proteins such as collagen, keratin, elastin, hive mouth-in, sericin, and cuticle, and one or more of these may be mixed. From the viewpoint of processability and reactivity, collagen, keratin or elastin is preferred, and collagen and keratin are particularly preferred.

[0026] The degradation product of the hard protein includes a product obtained by hydrolyzing a part of the chemical bond present in the hard protein with an acid, an alkali, an enzyme or the like, and reducing the molecular weight of the protein. For example, the collagen degradation product has a molecular weight of 1,000 to 100,000, preferably 1,20,000 to 240,000, and 5,500 to 1,20,000, more preferably 2,000 to 10,000. Examples of keratin degradation products include those having a molecular weight of 1,000 to 1,3,000, preferably 2,000 to 3,000.

[0027] Such a hard protein degradation product can be obtained by extracting the hard protein from the hard protein-containing raw material, or directly hydrolyzing it with an acid, an alkali, an enzyme, or the like. Examples of hard protein-containing raw materials include collagen, cattle, pigs, sheep, goats, horses, chickens, fish, shark skin and bones, fish scales, keratin, waterfowl and chicken feathers. For elastin, wool, pig hair, cow hair, etc., the dermis of cattle, pigs, sheep, goats, horses, chickens, ligaments, tendons, blood vessel walls, and the like. [0028] For example, when preparing a degradation product of collagen, the collagen-containing raw material is degreased and impurities are removed, and then treated with acid or alkali, and heated with warm water (around 80 ° C) to obtain gelatin. It is preferable to extract it and subject it to hydrolysis. Preferred examples of the alkali used here include lime, and examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid. The treatment time is generally several hours to several days in the case of acid treatment, but in the case of lime treatment, one week when using animal skin or fish skin, and two to three months when using bone Cost.

[0029] Further, when preparing a degradation product of keratin, the raw material containing keratin may be subjected to degradation as it is, but it is applied to a low concentration alkali (for example, 0.5 M sodium hydroxide solution). It is preferable to hydrolyze after removing impurities by submerging.

In addition, after the keratin raw material has a water content of 20 to 80%, it is hydrolyzed in an alkaline solution, then neutralized, and the keratin degradation product extracted from the supernatant (international publication) No. 2 0 0 5/0 9 5 4 3 9 pamphlet) is also preferred.

[0030] Hydrolysis with acid or alcohol to obtain a hard protein degradation product is made from water and / or methanol, ethanol, propanol, butanol, propylene glycol, 1, 3 —Inorganic, such as sulfuric acid, hydrochloric acid, acetic acid, formic acid, oxalic acid, hydrogen bromide, perchloric acid, periodic acid, etc., dissolved in one or more mixtures such as butylene glycol, preferably water and / or ethanol It is performed by adding an acid, an organic acid or an alcohol.

[0031] Examples of the alkali power include those usually used for the hydrolysis of proteins and peptides, such as alkaline metal hydroxides such as sodium hydroxide and lithium hydroxide, and alkalis such as calcium hydroxide. Examples include earth metal hydroxides, ammonia, and the like, which may be appropriately selected depending on the properties of the target protein raw material. The alkaline solution is preferably an aqueous alkali solution, but a mixed solvent of alcohol and water may be used.

[0032] The concentration of acid or alcohol in the solution is appropriate for the protein material of interest. The conditions may be appropriately selected, but when using an acid, it is usually preferable to be 0.1 to 0.8 mo I / L, and in the case of an alkali, usually 0.2 to 0.5 mol / L. Is preferred.

[0033] The hydrolysis treatment is performed by shaking or stirring the protein raw material in the acid or alkaline solution. The reaction is preferably carried out within the range of 20 to 120 ° C. for 0.1 to 72 hours.

[0034] In the hydrolysis by an enzyme, a protein is usually made into a 0.1 to 40% by weight solution, and the enzyme may be allowed to act in the working pH range and working temperature range of the enzyme used.

[0035] As an enzyme used for hydrolysis, any enzyme capable of degrading hard proteins such as collagen, keratin, and elastin may be used. It may be any of the above, and may be of animal origin, plant origin or microbial origin. Specifically, for example, pepsin, papain, promeline, and ficin.

[0036] The hard protein hydrolyzate thus obtained is, for example, neutralized, filtered, desalted (ultrafiltration, ion exchange, dialysis membrane, electrodialysis, electrodialysis, gel filtration. Etc.), can be separated and purified using centrifugation, etc., and can be concentrated or powdered by removing water.

[0037] The reaction between the urethane prepolymer and the hard protein degradation product may be carried out directly or in the presence of a medium such as a solvent that does not affect the reaction. Preferably, the two are directly mixed and stirred using a table kneader or the like.

The ratio of hard protein degradation products is usually determined by using an equivalent urethane precursor to one free amino group contained in the molecular weight of the protein molecule 2500, and the reaction conditions, cost, and stability. It adjusts suitably according to etc.

[0038] In addition, the above reaction can be appropriately performed by adding various materials having a tanning effect, a catalyst such as a photocatalyst, a crosslinking agent, and a release agent (such as stearic acid). Examples of the cross-linking agent include trifunctional isocyanate cross-linking agents (for example, TDI trimethylolpropane adducts). By using this, the hardness of the resin And heat resistance can be improved.

[0039] The reaction temperature may be within the range where the hard protein degradation product is not denatured. For example, the reaction temperature is within the range of 50 ° C to 15 ° C, preferably 50 ° C to 120 ° C. be able to. The reaction time is usually preferably about 0.5 to 48 hours.

[0040] By the above reaction, a leather-like thermoplastic resin having a moldable temperature of about 80 to 130 ° C is obtained. The appearance varies depending on the type and origin of the hard protein used.For example, when a feather keratin degradation product is used, it is a brown skin, and when a pig skin collagen degradation product is used, it is a white skin. And the feel is similar to natural leather.

[0041] Accordingly, the thermoplastic resin can be used as a leather-like material as it is, and after being subjected to various molding processes and treatments, various molded products (films, sheets, etc.), fibers, and surface coating layers of synthetic leather Can be artificial leather and so on.

[0042] When the thermoplastic resin of the present invention is used as a leather-like material as it is, polymerization and molding may be performed simultaneously using a mold or other molding apparatus. In this case, in the polymerization reaction, In addition, by adding and mixing various fibers, animal hair or powder thereof, feathers or powder thereof, and the like, a leather-like material closer in strength and appearance to natural leather can be obtained. Here, examples of the fibers include pulps such as natural pulp and synthetic pulp, synthetic fibers such as polyester fibers, polyamide fibers, acrylic fibers, and acetate fibers. Animal hair obtained from sheep, goats, rabbits, camels, alpaca and other animals, and feathers obtained from poultry such as chickens, ducklings and geese, water birds such as duck, birds such as pigeons and ostriches These powders include those obtained by pulverizing animal hair and feathers to about several tens of microns.

[0043] When the thermoplastic resin of the present invention is used as a surface film layer of synthetic leather, for example, the resin solution of the present invention (for example, dimethylformamide (DMF) solution) is applied to a substrate such as a nonwoven fabric. A method of impregnating a DMF / water mixture to form a porous film, or applying the thermoplastic resin of the present invention as a mixed solution slurry of methyl ethyl ketone / water to a substrate and then drying. Use it. Example [0044] Hard protein degradation products and urethane prepolymers used the following: 1. Hard protein degradation products

(1) Feather-derived hydrolyzed keratin: "Hydrolyzed keratin" (Toyo Feather Industrial Co., Ltd.)

(2) Pig skin-derived hydrolyzed collagen: “Natsubi Peptide PRA” (Nitsubi Corporation)

(3) Crust derived hydrolyzed collagen: “Peptide PRA” (Nitsubi Corporation)

(4) High molecular weight cowhide gelatin: Cowhide gelatin with an average molecular weight of 240,000 (Nitsubi Corporation)

(5) Medium molecular weight cowhide gelatin: Cowhide gelatin with an average molecular weight of 120,000 (Natsubi Corporation)

(6) Medium molecular weight cowhide peptide: Cowhide gelatin with an average molecular weight of 5,500 (Nippi Corporation)

[0045] 2. Urethane prepolymer

(1) “Takenate D—701 8” (Mitsui Chemicals Polyurethanes)

Type: Polyurethane prepolymer consisting of polypropylene glycol and 2, 4-T D I

Viscosity: 1 0000 mPa's / 25 ° C

N C O%: 1. 68

N CO equivalent: 2498 g

[0046] (2) “Takenate D_7028” (Mitsui Chemicals Polyurethanes, Inc.)

Type: Polyurethane prepolymer consisting of polyester polyol (condensation polymer of adipic acid and diethylene glycol) and 2, 4_T D I

Viscosity: 360000 mP a-s / 25 ° C

N C O%: 1.82

N CO equivalent: 2236 g

[0047] (3) “Takenate D_7038” (Mitsui Chemicals Polyurethanes, Inc.) Type: Polyurethane prepolymer consisting of polyester polyol (condensation polymer of adipic acid and diethylene glycol) and 2, 4_T DI

Viscosity: 1 80000 mP a-s / 25 ° C

N C O%: 6. 24

N CO equivalent: 1 350 g

[0048] Production Example 1

47 g of “Takenate D—701 8” is added to 50 g of feather-derived hydrolyzed keratin and mixed and stirred at 80 ° C. for 24 hours in a table kneader to obtain a resin material (Product 1 of the present invention). It was.

Features: brown, leather-like substance

Moldable temperature: 100 ° C

[0049] Production Example 2

47 g of “Takenate D—7028” was added to 50 g of feather-derived hydrolyzed keratin, and the mixture was stirred and reacted at 80 ° C. for 2 hours with a table kneader to obtain a resin substance (Invention product 2).

Features: brown, strong leather-like substance

Moldable temperature: 1 1 0 ° C

[0050] Production Example 3

50 g of feather-derived hydrolyzed keratin, 25 g of “Takenate D—7028”, and a trifunctional isocyanate crosslinking agent consisting of trimethylolpropane and TDI (“Takenate D_ 1 03 H” (Mitsui Chemical Polyurethanes Co., Ltd.) g was mixed and stirred at 80 ° C. for 1 hour in a table kneader to obtain a resin substance (Invention product 3).

Features: brown, granular leather-like substance

Moldable temperature: 1 30 ° C

[0051] Production Example 4

47 g of “Takenate D—701 8” is added to 50 g of feather-derived hydrolyzed keratin, and mixed and stirred at 100 ° C for 5 hours with a table kneader. Quality (Invention product 4) was obtained.

Features: Brown, firm leather-like substance

Moldable temperature: 1 1 0 ° C

[0052] Production Example 5

Add 47 g of “Takenate D—7028” to 50 g of hydrolyzed collagen derived from pork skin, and mix and stir at 80 ° C for 4 hours with a table kneader to obtain a resin material (Invention product 5). It was.

Features: White, stretchy, strong leather-like substance, insoluble in water

Moldable temperature: 1 20 ° C

[0053] Production Example 6

Add 50 g of “Takenate D—7028” to 50 g of hydrolyzed collagen derived from crust, and mix and stir at 80 ° C for 6 hours with a table kneader to obtain a resin material (Invention product 6). It was.

Features: White, stretchy leather-like substance (stretchable from product 5), insoluble in water

Moldable temperature: 1 1 0 ° C

[0054] Production Example 7

To 50 g of feather-derived hydrolyzed keratin, 47 g of “Takenate D—7028” and 2.2 g of stearic acid were added. After mixing and stirring for 1 hour on the desktop, add 15 g of feathers, and then 1 hour The mixture was stirred and reacted to obtain a resin substance (Invention product 7).

Features: brown, stretchy leather-like substance

Moldable temperature: 1 1 0 ° C

[0055] Production Example 8

47 g of urethane tampreborima “Takenate D—7028” was added to 25 g of hydrolyzed collagen derived from pig skin and 25 g of hydrolyzed keratin, and the mixture was stirred and reacted at 80 ° C. for 2 hours. 8) got.

Features: light brown, strong leather-like substance Moldable temperature: 1 20 ° C

[0056] Production Example 9

Add 47 g of “Takenate D_7028” and 2.2 g of stearic acid to 25 g of hydrolyzed collagen derived from pork skin and 25 g of hydrolyzed keratin, mix and stir at 80 ° C for 1 hour, and then add 15 g of feathers. The mixture was further stirred and reacted for 1 hour to obtain a resin substance (Product 9 of the present invention).

Features: light brown, strong leather-like substance

Moldable temperature: 1 20 ° C

[0057] Production Example 1 0

50 g of hydrolyzed collagen derived from pig skin, add 47 g of “Takenate D—7028” and 2.2 g of stearic acid, mix and stir for 3 hours at 80 ° C, add 15 g of feathers, and mix and stir for another 2 hours Thus, a resin substance (invention product 10) was obtained.

Features: white, tough leather-like substance

Moldable temperature: 1 20 ° C

[0058] Production Example 1 1

Add 50 g of “Takenate D—7028” and 2.2 g of stearic acid to 50 g of hydrolyzed collagen derived from crust, mix and stir at 80 ° C for 3 hours, add 15 g of feathers, and stir for another 2 hours. Thus, a resin substance (Invention product 11) was obtained.

Features: White, stretchy, strong leather-like substance

Moldable temperature: 1 20 ° C

[0059] Production Example 1 2

Add 50 g of “Takenate D—7038” and 0.49 g of stearic acid to 50 g of high-molecular-weight cowhide gelatin (particle size 30 mesh), and mix and stir at 100 °° for 1 hour and a half with a table kneader. Resin material (Invention product 1 2).

Similarly, a resin material (Invention product 13) was obtained using high molecular weight cowhide gelatin having a particle size of 60 mesh. Features: light yellow, tough leather-like substance

Moldable temperature: 1 30 ° C

[0060] Production Example 1 3

47 g of “Takenate D—7038” and 0.49 g of stearic acid were added to 50 g of medium molecular weight cowhide gelatin, and the mixture was stirred and reacted at 100 ° C for 1 hour and a half. (Invention product 14) was obtained.

Features: light yellow, tough leather-like substance

Moldable temperature: 1 30 ° C

[0061] Production Example 1 4

Add 50 g of “Takenate D—7038” and 0.49 g of stearic acid to 50 g of medium molecular weight cowhide peptide, and mix and stir at 100 ° C for 1 hour and a half. (Invention product 15) was obtained.

Features: light yellow, tough leather-like substance

Moldable temperature: 1 30 ° C

[0062] Analysis by FT-IR>

The following samples were subjected to FT-IR measurement under the following conditions.

(1) Sample

1) Takenet D— 7038

2) High molecular weight cowhide gelatin (Production Example 1 2)

3) Invention product 1 2 (Production example 1 2)

4) Medium molecular weight cowhide gelatin (Production Example 1 3)

5) Invention product 1 4 (Production example 1 3)

6) Medium molecular weight cowhide peptide (Production Example 1 4)

7) Invention product 1 5 (Production Example 1 4)

[0063] (2) Conditions

(i) Detector: JEOL Ltd. Fourier Transform Infrared Spectrophotometer JIR-WINSPEG 5

0

(ii) Number of scans during sample measurement: 1 6 times [0064] (3) Operating procedure

(A) Takenate

a) Only the salt plate is put in the equipment and the background measurement is performed.

b) Apply Takenate to the rock salt board, put it in the apparatus and measure the sample. The number of scans during sample measurement is 16 times.

(B) Gelatin, peptide, resin substance (product of the present invention)

a) Crush KB r in a mortar

* The resin material and cowhide gelatin were crushed in advance with a pulverizer. b) Put the ground KBr into a disk with a hole, and remove air with a compressor. c) Place the disk in the instrument and measure the background.

d) Bring the KBr and sample to a mass ratio of 3: 1 and grind in a mortar.

e) Place the ground sample in a disk with holes and remove air with a compression device. f) Place the disk in the device and measure the sample.

[0065] (4) Results

Takenate and the resin material (the product of the present invention) have different peaks, and gelatin and peptide also have different peaks from the resin material, so that Takenate certainly reacts with gelatin and peptide. It is thought that there is. Also, all resin materials had similar peaks.

[0066] Test Example 1

About the thermoplastic resin obtained by the said manufacture example, the molding of 15cm x15cm and thickness about 3 countries was prepared using the compression molding machine. Tensile strength was measured using a universal material testing machine (INSTR0N 5565). The results are shown below. Thus, the thermoplastic resin of the present invention had sufficient strength without being reprocessed. It was confirmed that cowhide gelatin or cowhide peptide had a higher strength than hydrolyzed collagen, and that finer and higher molecular weight tend to increase strength.

[0067] [Table 1] Tensile cutting load Tensile strength Thickness

(kgf) (N) (kgf / thigh ² ) (Mpa)

2. 937 17. 41 170. 73 0. 593 5. 814 Product 5 2. 227 13. 657 133. 93 0. 613 6. 015 Average: 0. 603 Average: 5. 914

2. 472 10. 055 98. 61 0. 407 3. 989 Invention product 6

2. 698 9. 333 91. 53 0. 346 3. 392 Average: 0. 376 Average: 3. 691

3. 62 3. 363 32. 976 0. 093 0. 911 Invention product 7 3. 17 3. 556 34. 872 0. 113 1. 11 Average: 0. 103 Average: 1. 01 1 Invention product 12 2 99 3. 36 32. 97 0. 11 1. 11

(Use of high molecular weight gelatin *)

Invention product 14 2. 81 4. 86 47. 66 0. 17 1. 69

(Uses medium molecular weight gelatin)

Invention product 15 3. 15 5. 07 49. 77 0. 16 1. 58

(Uses medium molecular weight peptide)

Invention product 13 2. 96 9. 69 95. 04 0. 35 3. 44

(High molecular weight gelatin * * used)

*: Particle size 30 mesh

* *: Particle size 60 mesh

Claims

The scope of the claims

[1] A thermoplastic resin obtained by reacting a urethane precursor having a free isocyanate group at the terminal with a decomposition product of a hard protein.

[2] The thermoplastic resin according to claim 1, wherein the hard protein is at least one selected from collagen and keratin.

[3] The thermoplastic resin according to claim 1 or 2, wherein the urethane prepolymer is obtained by reacting an aromatic polyisocyanate or aliphatic polyisocyanate with a polyether polyol or a polyester polyol. .

[4] The thermoplastic resin according to claim 3, wherein the aromatic polyisocyanate is tolylene disulfonate (T D I).

[5] The reaction is carried out at 5 0 to 1 5 0 ° 0 for 0.5 hours to 48 hours.

5. The thermoplastic resin according to any one of 4.

6. The thermoplastic resin according to any one of claims 1 to 5, wherein one or more selected from fibers, animal hair and animal hair powder are further mixed and reacted.

[7] A leather-like material comprising the thermoplastic resin according to any one of claims 1 to 6.

[8] A method for producing a thermoplastic resin, comprising reacting a urethane precursor having a free isocyanate group at a terminal with a decomposition product of a hard protein.