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WO2008018184A1 - Résine thermoplastique - Google Patents

Résine thermoplastique Download PDF

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Publication number
WO2008018184A1
WO2008018184A1 PCT/JP2007/000873 JP2007000873W WO2008018184A1 WO 2008018184 A1 WO2008018184 A1 WO 2008018184A1 JP 2007000873 W JP2007000873 W JP 2007000873W WO 2008018184 A1 WO2008018184 A1 WO 2008018184A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
leather
acid
product
takenate
Prior art date
Application number
PCT/JP2007/000873
Other languages
English (en)
Japanese (ja)
Inventor
Yoshihiro Nomura
Toshihiko Kitaura
Original Assignee
Tokyo University Of Agriculture And Technology Tlo Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo University Of Agriculture And Technology Tlo Co., Ltd. filed Critical Tokyo University Of Agriculture And Technology Tlo Co., Ltd.
Priority to JP2007546360A priority Critical patent/JP5305320B2/ja
Publication of WO2008018184A1 publication Critical patent/WO2008018184A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C08G18/6446—Proteins and derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step

Definitions

  • the present invention relates to a thermoplastic resin that can be used as a leather-like material.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • the present invention relates to the following 1) to 3).
  • thermoplastic resin obtained by reacting a urethane precursor having a free isocyanate group at the terminal with a hard protein degradation product.
  • thermoplastic resin characterized by reacting a urethane precursor having a free isocyanate group at the terminal with a hard protein degradation product.
  • 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.
  • a biodegradable urethane prepolymer a biodegradable thermoplastic resin can be obtained and the environmental load can be reduced.
  • FIG. 1 is a chart of FT-IR of the product of the present invention and raw materials.
  • 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.
  • 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. .
  • 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).
  • 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.
  • 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.
  • 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.
  • Examples of the araliphatic polyisocyanate include xylylene diisocyanate and jetylbenzene diisocyanate.
  • 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.
  • 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.
  • polyol compound examples include polyether polyol, polyester polyol, polyolefin polyol, and mixed polyols thereof.
  • 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.
  • polyoxyalkylene glycols such as polypropylene glycol and polytetramethylene glycol
  • ethylene glycol diethylene glycol
  • propylene glycol dipropy
  • polyester polyol examples include condensation-type polyester polyols and lactone-type polyols.
  • 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.).
  • 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.
  • polyhydric alcohol examples include glycerin, bisphenol A, ethylene glycol, 1,2_propylene glycol, 1,4_butane diol, diethylene glycol, 1,6-hexane glycol, hexane diol, and cyclohexane.
  • polyhydric alcohol examples 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.
  • lactone-based polyol examples include ring-opening polymers such as propion lactone, valerolactone, one-strength prolacton, and one methyl one-strength prolacton.
  • polyolefin polyol examples include a polyol having an ethylene / polyolefin skeleton and a polyol having a polyisobutylene skeleton.
  • polystyrene resin 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • elastin, wool, pig hair, cow hair, etc. the dermis of cattle, pigs, sheep, goats, horses, chickens, ligaments, tendons, blood vessel walls, and the like.
  • 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.
  • the alkali used here include lime
  • 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.
  • 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.
  • alkali for example, 0.5 M sodium hydroxide solution
  • 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.
  • 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.
  • Inorganic such as sulfuric acid, hydrochloric acid, acetic acid, formic acid, oxalic acid, hydrogen bromide, perchloric acid, periodic acid, etc.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a medium such as a solvent that does not affect the reaction.
  • 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.
  • 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).
  • a catalyst such as a photocatalyst
  • a crosslinking agent such as stearic acid
  • a release agent such as stearic acid
  • the cross-linking agent include trifunctional isocyanate cross-linking agents (for example, TDI trimethylolpropane adducts).
  • the reaction temperature may be within the range where the hard protein degradation product is not denatured.
  • 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.
  • 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.
  • 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.
  • 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.
  • the fibers include pulps such as natural pulp and synthetic pulp, synthetic fibers such as polyester fibers, polyamide fibers, acrylic fibers, and acetate fibers.
  • 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.
  • thermoplastic resin of the present invention When 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.
  • DMF dimethylformamide
  • Hard protein degradation products and urethane prepolymers used the following: 1. Hard protein degradation products
  • Feather-derived hydrolyzed keratin "Hydrolyzed keratin” (Toyo Feather Industrial Co., Ltd.)
  • Cowhide gelatin with an average molecular weight of 240,000 (Nitsubi Corporation)
  • cowhide gelatin Cowhide gelatin with an average molecular weight of 120,000 (Natsubi Corporation)
  • cowhide peptide Cowhide gelatin with an average molecular weight of 5,500 (Nippi Corporation)
  • Viscosity 1 0000 mPa's / 25 ° C
  • Viscosity 360000 mP a-s / 25 ° C
  • Viscosity 1 80000 mP a-s / 25 ° C
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une résine thermoplastique innovante qui possède le toucher, l'aspect et la souplesse du cuir naturel et qu'il est possible de mouler en tant que matière semblable au cuir. La résine thermoplastique peut être produite en faisant réagir un pré-polymère d'uréthane ayant un groupe isocyanate libre à une extrémité et un produit de la digestion d'une protéine dure.
PCT/JP2007/000873 2006-08-10 2007-08-10 Résine thermoplastique WO2008018184A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007546360A JP5305320B2 (ja) 2006-08-10 2007-08-10 熱可塑性樹脂

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-218728 2006-08-10
JP2006218728 2006-08-10

Publications (1)

Publication Number Publication Date
WO2008018184A1 true WO2008018184A1 (fr) 2008-02-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/000873 WO2008018184A1 (fr) 2006-08-10 2007-08-10 Résine thermoplastique

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Country Link
JP (1) JP5305320B2 (fr)
WO (1) WO2008018184A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108586692A (zh) * 2018-01-23 2018-09-28 陕西科技大学 一种合成革用可抛光水性聚氨酯的制备方法及应用
CN113755002A (zh) * 2021-09-22 2021-12-07 莆田市涵江怡丰鞋业有限公司 一种耐水洗女鞋的制备方法
WO2023013638A1 (fr) * 2021-08-02 2023-02-09 Ｓｐｉｂｅｒ株式会社 Cuir synthétique, et procédé de fabrication de celui-ci

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4835001A (fr) * 1971-09-08 1973-05-23
JPS5113879A (en) * 1974-07-26 1976-02-03 Idemitsu Kosan Co Kaishitsutanpakuno seizohoho
JPS5391962A (en) * 1977-01-24 1978-08-12 Asahi Chem Ind Co Ltd Polyurethane composition
JPH09165431A (ja) * 1995-11-08 1997-06-24 Basf Ag 水溶性又は水分散性のグラフトポリマー及びこれより成る化粧品学における助剤
JPH10195169A (ja) * 1997-01-13 1998-07-28 Showa Denko Kk 重合性を付与した天然有機高分子化合物の製造方法
JP2000010242A (ja) * 1998-06-04 2000-01-14 Eastman Kodak Co ゼラチン改質ポリウレタンを含む画像形成用ベ―ス及び写真要素

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3095144B1 (ja) * 1999-05-10 2000-10-03 工業技術院長 生分解性ポリウレタン複合体及びその製造方法
JP3567286B2 (ja) * 2000-12-06 2004-09-22 独立行政法人産業技術総合研究所 生分解性エラストマーシート
JP4605491B2 (ja) * 2003-07-31 2011-01-05 日本ポリウレタン工業株式会社 １，４−ブタンジオールを主剤とするコポリカーボネートジオールの製造方法、およびそのコポリカーボネートジオールを用いたポリウレタン樹脂。

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4835001A (fr) * 1971-09-08 1973-05-23
JPS5113879A (en) * 1974-07-26 1976-02-03 Idemitsu Kosan Co Kaishitsutanpakuno seizohoho
JPS5391962A (en) * 1977-01-24 1978-08-12 Asahi Chem Ind Co Ltd Polyurethane composition
JPH09165431A (ja) * 1995-11-08 1997-06-24 Basf Ag 水溶性又は水分散性のグラフトポリマー及びこれより成る化粧品学における助剤
JPH10195169A (ja) * 1997-01-13 1998-07-28 Showa Denko Kk 重合性を付与した天然有機高分子化合物の製造方法
JP2000010242A (ja) * 1998-06-04 2000-01-14 Eastman Kodak Co ゼラチン改質ポリウレタンを含む画像形成用ベ―ス及び写真要素

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108586692A (zh) * 2018-01-23 2018-09-28 陕西科技大学 一种合成革用可抛光水性聚氨酯的制备方法及应用
WO2023013638A1 (fr) * 2021-08-02 2023-02-09 Ｓｐｉｂｅｒ株式会社 Cuir synthétique, et procédé de fabrication de celui-ci
EP4382661A4 (fr) * 2021-08-02 2025-08-27 Spiber Inc Cuir synthétique, et procédé de fabrication de celui-ci
CN113755002A (zh) * 2021-09-22 2021-12-07 莆田市涵江怡丰鞋业有限公司 一种耐水洗女鞋的制备方法

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JP5305320B2 (ja) 2013-10-02
JPWO2008018184A1 (ja) 2009-12-24

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