WO2022180897A1 - 合成皮革 - Google Patents
合成皮革 Download PDFInfo
- Publication number
- WO2022180897A1 WO2022180897A1 PCT/JP2021/033081 JP2021033081W WO2022180897A1 WO 2022180897 A1 WO2022180897 A1 WO 2022180897A1 JP 2021033081 W JP2021033081 W JP 2021033081W WO 2022180897 A1 WO2022180897 A1 WO 2022180897A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- urethane resin
- biomass
- mass
- synthetic leather
- derived
- Prior art date
Links
- 239000002649 leather substitute Substances 0.000 title claims abstract description 35
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 107
- 150000003077 polyols Chemical class 0.000 claims abstract description 89
- 229920005862 polyol Polymers 0.000 claims abstract description 60
- 125000000129 anionic group Chemical group 0.000 claims abstract description 56
- 239000004417 polycarbonate Substances 0.000 claims abstract description 46
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 46
- 239000011342 resin composition Substances 0.000 claims abstract description 45
- 239000010410 layer Substances 0.000 claims abstract description 40
- 239000002028 Biomass Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012790 adhesive layer Substances 0.000 claims abstract description 28
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 31
- 239000005056 polyisocyanate Substances 0.000 claims description 28
- 229920001228 polyisocyanate Polymers 0.000 claims description 28
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 19
- 150000004292 cyclic ethers Chemical group 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 6
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 4
- 229960002479 isosorbide Drugs 0.000 claims description 4
- 210000002615 epidermis Anatomy 0.000 claims 1
- 210000003491 skin Anatomy 0.000 claims 1
- 239000007858 starting material Substances 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 42
- -1 polyethylene Polymers 0.000 description 42
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 28
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 27
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 27
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 27
- 239000004970 Chain extender Substances 0.000 description 27
- 239000005642 Oleic acid Substances 0.000 description 27
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 27
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 20
- 239000004793 Polystyrene Substances 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
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- 239000000654 additive Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
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- 239000000835 fiber Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 4
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- D—TEXTILES; PAPER
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1678—Resistive to light or to UV
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Definitions
- the present invention relates to synthetic leather.
- Urethane resin compositions in which urethane resins are dispersed in water can reduce the burden on the environment compared to conventional organic solvent-based urethane resin compositions.
- it has begun to be suitably used as a material for manufacturing coating agents such as.
- global demand for biomass raw materials such as plants is increasing in order to reduce the amount of fossil resources such as petroleum used.
- the urethane resin composition is required to have high durability, especially when used for synthetic leather used as an interior material for vehicles.
- evaluation items for this durability include heat resistance, resistance to moist heat, light resistance, chemical resistance, and abrasion resistance (see, for example, Patent Document 1).
- synthetic leather since synthetic leather frequently comes into contact with the human body, it is strongly required to have resistance to oleic acid contained in sebum. was done.
- the problem to be solved by the present invention is to provide an environmentally friendly synthetic leather that uses biomass raw materials and has excellent oleic acid resistance, low-temperature flexibility, peel strength, and light resistance.
- the present invention is a synthetic leather having at least a substrate (i), an adhesive layer (ii), and a skin layer (iii), wherein the adhesive layer (ii) comprises an anionic urethane resin (X) and ,
- the anionic urethane resin (X) is formed of a urethane resin composition containing water (Y), and the anionic urethane resin (X) is a polyol (a) containing a biomass-derived polycarbonate polyol (a1) and a polyisocyanate (b ) and an alkanolamine (c) as essential raw materials
- the skin layer (iii) is formed of an anionic urethane resin (S) and a urethane resin composition containing water (T)
- the anionic urethane resin (S) is a polycarbonate polyol (A-1) made from biomass-derived decanediol, and a biomass-derived dihydroxy compound having a cyclic ether structure as raw materials.
- the synthetic leather of the present invention is an eco-friendly synthetic leather in which both the adhesive layer and the skin layer are made of a urethane resin composition containing water. Furthermore, both the adhesive layer and the skin layer use biomass raw materials, and in this respect as well, the synthetic leather is eco-friendly. Furthermore, the synthetic leather of the present invention is excellent in oleic acid resistance, low-temperature flexibility, peel strength, and light resistance.
- the synthetic leather of the present invention has at least a substrate (i), a specific adhesive layer (ii), and a specific skin layer (iii).
- Examples of the base material (i) include polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, Fiber base materials such as non-woven fabrics, woven fabrics, and knitted fabrics made of blended fibers thereof, etc.; non-woven fabrics impregnated with resin such as polyurethane resin; non-woven fabrics further provided with a porous layer; thermoplastic urethane (TPU) etc. can be used.
- the adhesive layer (ii) is formed of a urethane resin composition containing an anionic urethane resin (X) that essentially contains a specific raw material and water (Y).
- the anionic urethane resin (X) is a polyol (a) containing a biomass-derived polycarbonate polyol (a1) and a polyisocyanate (b) in order to obtain excellent oleic acid resistance, low-temperature flexibility, and peel strength. and alkanolamine (c) as essential raw materials.
- the biomass-derived polycarbonate polyol (a1) is an essential component particularly for obtaining excellent oleic acid resistance and low-temperature flexibility.
- polycarbonate polyol (a1) for example, a reaction product of a carbonate ester and/or phosgene and a glycol compound containing a biomass-derived glycol can be used. Those described in JP-A-2017-133024, JP-A-2011-225863, etc. can be used. These polycarbonate polyols may be used alone or in combination of two or more.
- polycarbonate polyol (a1) among the above-mentioned ones, a glycol compound made from biomass-derived decanediol is used as a raw material to obtain even more excellent oleic acid resistance and low-temperature flexibility. From this point of view, it is more preferable to use biomass-derived 1,10-decanediol as a raw material.
- butanediol more preferably 1,4-butanediol, from the viewpoint of obtaining even better oleic acid resistance and low-temperature flexibility.
- the total amount used is preferably 50 mol% or more, more preferably 70 mol% or more, and 80 mol of the glycol compound. % or more is more preferable.
- the molar ratio [(C4)/(C10)] is From the viewpoint of obtaining oleic acidity and low-temperature flexibility, the range is preferably 5/95 to 95/5, more preferably 50/50 to 98/2, and 75/25 to 95/5. A range is more preferred.
- the number average molecular weight of the polycarbonate diol (a1) is preferably in the range of 500 to 100,000 from the viewpoint of obtaining even better oleic acid resistance, low-temperature flexibility, and peel strength. A range of 000 to 3,000 is more preferred, and a range of 1,500 to 2,500 is even more preferred.
- the number average molecular weight of the polycarbonate diol (a1) is the value measured by gel permeation chromatography (GPC).
- polycarbonate polyol (a1) for example, "Beneviol NL-2010DB” manufactured by Mitsubishi Chemical Corporation can be obtained as a commercial product.
- the polyol (a) may be used in combination with other polyols as necessary.
- the content of the polycarbonate polyol (a1) in the polyol (a) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.
- polycarbonate polyols other than (a1) for example, polycarbonate polyols other than (a1), polyester polyols, polyether polyols, polyacrylic polyols, and the like can be used. These polyols may be used alone or in combination of two or more.
- polyisocyanate (b) examples include aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic polyisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and norbornene diisocyanate; and phenylene diisocyanate.
- aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate
- alicyclic polyisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and norbornene diisocyanate
- phenylene diisocyanate examples include phenylene
- toluene diisocyanate diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidated diphenylmethane polyisocyanate.
- These polyisocyanates may be used alone or in combination of two or more.
- polyisocyanate (b) among those mentioned above, an aliphatic polyisocyanate and/or Alicyclic polyisocyanates are preferred, and alicyclic polyisocyanates are more preferred.
- the amount of the polyisocyanate (b) used is preferably in the range of 2.5 to 5.0% by mass, more preferably 3.0 to 4.0% by mass, based on the total mass of the raw materials constituting the anionic urethane resin (X). % range is preferred.
- the alkanolamine (c) is an essential component for obtaining excellent peel strength.
- the alkanolamine has an amino group with fast reactivity and a hydroxyl group with slower reactivity than the amino group with respect to the isocyanate group derived from the polyisocyanate (b). Therefore, the alkanolamine (c) functions not only as a chain extender (contributes to high molecular weight and hard segment formation) in producing the urethane resin (X), but also as a stopper. As a result, it is possible to control the molecular weight of the urethane resin (X) while forming good hard segments, so that excellent peel strength, oleic acid resistance, and low-temperature flexibility can be achieved at the same time.
- alkanolamine (c) examples include primary alkanolamines such as monoethanolamine and monoisopropanolamine; diethanolamine, diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, and N-ethylethanolamine. , secondary alkanolamine such as N-benzylethanolamine, tertiary alkanolamine such as triethanolamine and tripropanolamine, and the like. These alkanolamines may be used alone or in combination of two or more. Among these, primary alkanolamine and/or secondary alkanolamine are preferred from the viewpoint of obtaining even better oleic acid resistance, low-temperature flexibility, and peel strength.
- primary alkanolamine and/or secondary alkanolamine are preferred from the viewpoint of obtaining even better oleic acid resistance, low-temperature flexibility, and peel strength.
- the amount of alkanolamine (c) used is preferably in the range of 0.1 to 0.95% by mass, more preferably 0.7 to 0.9% by mass, based on the total mass of raw materials constituting the anionic urethane resin (X). % range is preferred.
- the anionic urethane resin (X) used in the present invention includes, for example, the polyol (a), the polyisocyanate (b), the alkanolamine (c), and the compound having an anionic group (d ), and optionally a chain extender (e) reactant can be used.
- Examples of the compound (d) having an anionic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, 2,2 -Compounds having a carboxyl group such as valeric acid; 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2-aminoethyl)- 2-aminosulfonic acid, N-(2-aminoethyl)-2-aminoethylsulfonic acid, N-2-aminoethane-2-aminosulfonic acid, N-(2-aminoethyl)- ⁇ -alanine, salts thereof
- a compound having a sulfonyl group such as can be used. These compounds may be used alone or in
- the amount of the compound (d) having an anionic group is preferably in the range of 0.2 to 0.95% by mass of the total mass of raw materials constituting the anionic urethane resin (X). A range of 0.5% by weight is preferred.
- the chain extender (e) preferably has a molecular weight of less than 500, and more preferably has a molecular weight in the range of 50 to 450.
- chain extender (e) among the above-described ones, a chain extender (e1) having two or more amino groups is used as a raw material from the viewpoint of obtaining even more excellent low-temperature flexibility and peel strength, In addition, it is preferable not to use a chain extender (e2) having two or more hydroxyl groups as a starting material, and piperazine and/or hydrazine are more preferable as the chain extender (e1).
- the equivalent ratio [(c)/(e1)] between the alkanolamine (c) and the chain extender (e1) provides even better low-temperature flexibility .
- the range of 1.1/0.3 to 0.7/0.2 is preferable, and the range of 1.0/0.2 to 0.8/0.1 is more preferable.
- the amount used is preferably in the range of 0.001 to 0.1% by mass, preferably 0.01 to 0.1%, based on the total mass of the raw materials constituting the anionic urethane resin (X) A range of 0.050% by weight is preferred.
- the anionic urethane resin (X) for example, the raw material polyol (a), the polyisocyanate (b), the alkanolamine (c), the compound (d) having an anionic group, and the necessary
- the latter method is preferable because the reaction can be easily controlled.
- Any of the above reactions may be performed, for example, at 50 to 100°C for 30 minutes to 10 hours.
- an organic solvent may be used when producing the anionic urethane resin (X).
- the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetic ester compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; Amide compounds and the like can be used. These organic solvents may be used alone or in combination of two or more. It is preferable that the organic solvent is finally removed by a distillation method or the like.
- the weight-average molecular weight of the anionic urethane resin (X) is preferably in the range of 15,000 to 70,000, more preferably in the range of 15,000 to 35,000, from the viewpoint of obtaining even better peel strength. preferable.
- the weight average molecular weight of the anionic urethane resin (X) is the value measured by gel permeation chromatography (GPC).
- the content of the urethane resin (X) in the urethane resin composition is, for example, in the range of 10 to 60% by mass.
- water (Y) for example, ion-exchanged water, distilled water, or the like can be used. These waters may be used alone or in combination of two or more.
- the content of water (Y) is, for example, in the range of 35 to 85% by mass.
- the urethane resin composition of the present invention contains the anionic urethane resin (X) and the water (Y), but may contain other additives as necessary.
- additives examples include neutralizers, emulsifiers, cross-linking agents, thickeners, urethanization catalysts, fillers, foaming agents, pigments, dyes, oil repellents, hollow foams, flame retardants, and antifoaming agents. , leveling agents, anti-blocking agents and the like can be used. These additives may be used alone or in combination of two or more.
- the acid value of the anionic urethane resin (X) is 35 mgKOH/g or less from the viewpoint of obtaining even better hydrolysis resistance, oleic acid resistance, low-temperature flexibility, and peel strength. is preferred, preferably in the range of 1 to 20 mgKOH/g.
- the acid value of the anionic urethane resin (X) can be adjusted by adjusting the amount of the anionic group-containing compound (d) used as a raw material. The method for measuring the acid value of the anionic urethane resin (X) will be described later in Examples.
- the skin layer (iii) used in the present invention is formed of a urethane resin composition containing an anionic urethane resin (S) essentially containing specific raw materials and water (T).
- the anionic urethane resin (S) is a polycarbonate polyol (A-1) made from biomass-derived decanediol, and
- the essential raw material is a polycarbonate polyol (A-2) made from a dihydroxy compound having a cyclic ether structure.
- the mass ratio [(A-1)/(A-2)] between the polycarbonate polyol (A-1) and the polycarbonate polyol (A-2) provides even better oleic acid resistance, low-temperature flexibility, and , the range of 98/2 to 40/60 is preferable, and the range of 95/5 to 60/40 is more preferable, from the viewpoint of obtaining light resistance.
- polycarbonate polyol (A-1) made from biomass-derived decanediol for example, a reaction product of a glycol compound containing biomass-derived decanediol, a carbonate ester and/or phosgene can be used. Specifically, those described in JP-A-2018-127758 or the like can be used.
- 1,10-decanediol is preferable from the viewpoint of obtaining even better oleic acid resistance and low-temperature flexibility.
- butanediol is preferably used, and 1,4-butanediol is more preferable, from the viewpoint of obtaining even better oleic acid resistance and low-temperature flexibility.
- the total amount used is preferably 50 mol% or more, more preferably 70 mol% or more, and 80 mol of the glycol compound. % or more is more preferable.
- the biomass-derived decanediol (C10) and butanediol (C4) are used in combination
- the molar ratio [(C4)/(C10)] provides even better oleic acid resistance and , the range is preferably from 50/50 to 98/2, more preferably from 75/25 to 95/5, from the viewpoint of obtaining low-temperature flexibility.
- carbonate ester for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. can be used. These compounds may be used alone or in combination of two or more.
- the number-average molecular weight of the polycarbonate diol (A-1) is preferably in the range of 500 to 100,000, more preferably in the range of 700 to 10,000, from the viewpoint of obtaining even better oleic acid resistance and low-temperature flexibility. A range is more preferred, and a range of 1,500 to 4,000 is even more preferred.
- the number average molecular weight of the polycarbonate diol (A-1) is the value measured by gel permeation chromatography (GPC).
- polycarbonate polyol (A-1) for example, "Beneviol NL-3010DB” manufactured by Mitsubishi Chemical Corporation can be obtained as a commercial product.
- polycarbonate polyol (A-2) made from a biomass-derived dihydroxy compound having a cyclic ether structure examples include, for example, a glycol compound containing a biomass-derived dihydroxy compound having a cyclic ether structure, a carbonate ester and/or A reaction product with phosgene can be used, and specifically, those described in JP-A-2017-133024 and the like can be used.
- isosorbide As the dihydroxy compound having a cyclic ether structure, isosorbide, isomannide, isoidet, etc. can be used. These compounds may be used alone or in combination of two or more. Among these, isosorbide is preferable from the viewpoint of obtaining even more excellent light resistance and abrasion resistance.
- the total amount used is preferably 50 mol% or more in the glycol compound. , more preferably 70 mol % or more, and even more preferably 80 mol % or more.
- the biomass-derived glycol compound (ISB) that can be used other than the dihydroxy compound and butanediol (C4) and/or hexanediol (C6) are used in combination
- the molar ratio [(C4 + C6) /(ISB)] is preferably in the range of 30/70 to 90/10 from the viewpoint of obtaining even better oleic acid resistance, low-temperature flexibility, light resistance, and abrasion resistance.
- the range of /60 to 80/20 is more preferable, and the range of 50/50 to 70/30 is even more preferable.
- carbonate ester for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. can be used. These compounds may be used alone or in combination of two or more.
- the number average molecular weight of the polycarbonate diol (A-2) is preferably in the range of 400 to 100,000, more preferably in the range of 450 to 5,000, from the viewpoint of obtaining even better light resistance and abrasion resistance. is more preferred, and a range of 500 to 2,000 is even more preferred.
- the number average molecular weight of the polycarbonate diol (A-2) is the value measured by gel permeation chromatography (GPC).
- polycarbonate polyol (A-2) for example, "Beneviol HS0830B”, “Beneviol HS0840B”, “Beneviol HS0840H” and “Beneviol HS0850H” manufactured by Mitsubishi Chemical Corporation can be obtained as commercial products.
- the anionic urethane resin (S) includes, for example, the polyol (A), the polyisocyanate (B), the compound (C) having an anionic group, and, if necessary, a chain extender ( D) reactants can be used.
- polyols examples include polyester polyols, polyether polyols, polybutadiene polyols, the polycarbonate polyols (A-1 ) and polycarbonate polyols other than (A-2) can be used. These polyols may be used alone or in combination of two or more.
- the total amount of the polycarbonate polyol (A-1) and the polycarbonate polyol (A-2) used in the polyol (A) is preferably 60% by mass or more, more preferably 80% by mass, and 90% by mass. % is more preferred, and 95% by mass is particularly preferred.
- the amount of the polyol (A) used is preferably in the range of 73.4 to 85.3% by mass, more preferably in the range of 76.9 to 81.2% by mass, based on the total amount of raw materials constituting the anionic urethane resin (S). is more preferred.
- polyisocyanate (B) examples include aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic polyisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and norbornene diisocyanate; and phenylene diisocyanate.
- aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate
- alicyclic polyisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and norbornene diisocyanate
- phenylene diisocyanate examples include phenylene
- toluene diisocyanate diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidated diphenylmethane polyisocyanate, and the like can be used.
- These polyisocyanates may be used alone or in combination of two or more.
- the amount of the polyisocyanate (B) used is preferably in the range of 14.1 to 23.8% by mass of the total amount of raw materials constituting the anionic urethane resin (S), and 17.7 to 21.0% by mass. A range is more preferred.
- Examples of the compound (C) having an anionic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, 2,2 -Compounds having a carboxyl group such as valeric acid; 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2-aminoethyl)- 2-aminosulfonic acid, N-(2-aminoethyl)-2-aminoethylsulfonic acid, N-2-aminoethane-2-aminosulfonic acid, N-(2-aminoethyl)- ⁇ -alanine, salts thereof
- a compound having a sulfonyl group such as can be used. These compounds may be used alone or in
- the amount of the compound (C) having an anionic group used is preferably in the range of 1.3 to 3.9% by mass based on the total amount of raw materials constituting the anionic urethane resin (S). A range of 2 to 3.2% by mass is more preferred.
- the chain extender (D) has a molecular weight of less than 500 (preferably in the range of 50 to 450). ,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl-4,4′ -A chain extender (d1) having an amino group such as dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine;
- Ethylene glycol diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin, sorbitol , bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, trimethylolpropane, and other hydroxyl group-containing chain extenders (a2-1). These chain extenders may be used alone or in combination of two or more.
- the molecular weight of the chain extender (d) indicates the chemical formula weight calculated from the chemical formula.
- chain extender (D) a chain extender (d1) having an amino group is preferable from the viewpoint of obtaining even better oleic acid resistance and low-temperature flexibility, and piperazine and/or isophoronediamine is more preferred.
- the amount used is preferably in the range of 0.54 to 2.78% by mass based on the total amount of raw materials constituting the anionic urethane resin (S). A range of 20 to 2.04% by mass is more preferred.
- the method for producing the anionic urethane resin (S) includes, for example, the raw material polyol (A), the polyisocyanate (B), the compound (C) having an anionic group, and, if necessary, the chain extender A method of reacting (D) by charging it all at once; reacting the polyol (A), the polyisocyanate (B), and the compound (C) having an anionic group to obtain a urethane prepolymer having an isocyanate group, Next, a method of reacting the urethane prepolymer with the chain extender (D), and the like. Among these, the latter method is preferable because the reaction can be easily controlled.
- Any of the above reactions may be performed, for example, at 50 to 100°C for 30 minutes to 10 hours.
- the isocyanate groups remaining in the anionic urethane resin (X) may be deactivated.
- an alcohol having one hydroxyl group such as methanol.
- the amount of the alcohol used is in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the anionic urethane resin (S).
- an organic solvent may be used when producing the anionic urethane resin (S).
- the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetic ester compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; Amide compounds and the like can be used. These organic solvents may be used alone or in combination of two or more. It is preferable that the organic solvent is finally removed by a distillation method or the like.
- the content of the urethane resin (S) in the urethane resin composition is, for example, in the range of 10 to 60% by mass.
- water (T) for example, ion-exchanged water, distilled water, or the like can be used. These waters may be used alone or in combination of two or more.
- the content of water (T) is, for example, in the range of 35 to 85% by mass.
- the urethane resin composition of the present invention contains the anionic urethane resin (S) and the water (T), but may contain other additives as necessary.
- additives examples include neutralizing agents, cross-linking agents, thickeners, urethanization catalysts, fillers, foaming agents, pigments, dyes, oil repellents, hollow foams, flame retardants, antifoaming agents, and leveling agents. agents, antiblocking agents and the like can be used. These additives may be used alone or in combination of two or more.
- the urethane resin composition does not contain an emulsifier (U) in order to obtain even better hydrolysis resistance, oleic acid resistance, and low-temperature flexibility.
- Examples of the emulsifier (U) include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene/polyoxypropylene copolymer, and the like.
- Nonionic emulsifier fatty acid salt such as sodium oleate, alkyl sulfate, alkylbenzene sulfonate, alkyl sulfosuccinate, naphthalene sulfonate, polyoxyethylene alkyl sulfate, alkanesulfonate sodium salt, alkyldiphenyl ether sulfonate
- Anionic emulsifiers such as sodium salts
- cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts and alkyldimethylbenzylammonium salts.
- the acid value of the anionic urethane resin (S) is such that even better hydrolysis resistance, oleic acid resistance, and low-temperature flexibility can be obtained, and that the emulsifier (U) is not used. It is preferably in the range of 5 to 15 mgKOH/g from the viewpoint of obtaining good emulsifiability and liquid stability after emulsification.
- the acid value of the anionic urethane resin (S) can be adjusted by adjusting the amount of the anionic group-containing compound (c) used as a raw material. The method for measuring the acid value of the anionic urethane resin (S) will be described later in Examples.
- the synthetic leather of the present invention has at least a substrate (i), an adhesive layer (ii), and a skin layer (iii), and specifically has the following structure.
- substrate (i), adhesive layer (ii), skin layer (iii) (2) Base material (i), adhesive layer (ii), intermediate layer, skin layer (iii) (3) substrate (i), porous layer, adhesive layer (ii), skin layer (iii) (4) substrate (i), porous layer, adhesive layer (ii), intermediate layer, skin layer (iii)
- a solvent-based urethane resin composition formed by a known wet film forming method As the porous layer, a solvent-based urethane resin composition formed by a known wet film forming method; a water-based urethane resin composition made porous by a known method, or the like can be used.
- materials for forming the intermediate layer for example, known water-based urethane resins, solvent-based urethane resins, solvent-free urethane resins, water-based acrylic resins, silicone resins, polypropylene resins, polyester resins, and the like can be used. These resins may be used alone or in combination of two or more.
- a surface treatment layer may be further provided on the skin layer (iii) for scratch prevention and the like.
- materials for forming the surface treatment layer known water-based urethane resins, solvent-based urethane resins, solvent-free urethane resins, water-based acrylic resins, silicone resins, polypropylene resins, polyester resins, and the like can be used. These resins may be used alone or in combination of two or more.
- a urethane resin composition for forming a skin layer is applied on a release-treated base material, dried and processed to obtain a skin layer (iii), Then, on the skin layer (iii), a urethane resin composition for forming an adhesive layer is applied and dried to form an adhesive layer (ii), which is then laminated to the substrate (i). be done.
- a method of applying a urethane resin composition for forming an adhesive layer onto the skin layer (iii), bonding it to the substrate (i) and then drying it to form the adhesive layer (ii) may be used. .
- Examples of the method of applying the urethane resin composition for forming the skin layer and for forming the adhesive layer include methods using an applicator, roll coater, spray coater, T-die coater, knife coater, comma coater, and the like. be done.
- Examples of the method for drying the urethane resin composition include a method of drying at 40 to 130°C for 1 to 10 minutes.
- the thickness of the adhesive layer (ii) and skin layer (iii) to be obtained is appropriately determined according to the use of the synthetic leather, and is, for example, in the range of 0.5 to 100 ⁇ m.
- the synthetic leather After manufacturing the synthetic leather, it may be aged, for example, at 30 to 100°C for 1 to 10 days, if necessary.
- the synthetic leather of the present invention is an eco-friendly synthetic leather in which both the adhesive layer and the skin layer are made of a urethane resin composition containing water. Furthermore, both the adhesive layer and the skin layer use biomass raw materials, and in this respect as well, the synthetic leather is eco-friendly. Furthermore, the synthetic leather of the present invention is excellent in oleic acid resistance, low-temperature flexibility, peel strength, and light resistance.
- the obtained urethane resin had an acid value of 10.3 KOHmg/g and a weight average molecular weight of 30,000.
- HMDI dicyclohexylmethane diisocyanate
- the obtained urethane resin had an acid value of 10.3 KOHmg/g and a weight average molecular weight of 150,000.
- Measuring device high-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 Book “TSKgel G2000" (7.8 mm I.D.
- A (B x f x 5.611) / S (1)
- A is the solid acid value of the resin (mgKOH/g)
- B is the amount (mL) of the 0.1 mol/L potassium hydroxide aqueous solution used for titration
- f is the 0.1 mol/L potassium hydroxide aqueous solution.
- the factor S is the mass (g) of the resin particles
- 5.611 is the formula weight of potassium hydroxide (56.11/10).
- Example 1 Production of synthetic leather (1) 100 parts by mass of the urethane resin composition for forming a skin layer (S-1) obtained in Synthesis Example 3, black pigment (“Dylac HS-9530” manufactured by DIC Corporation) 10 parts by mass and 1 part by mass of a thickener ("Hydran Assister T10" manufactured by DIC Corporation) are placed on a flat release paper ("DN-TP-155T” manufactured by Ajinomoto Co., Inc.), and dried. It was applied to a film thickness of 30 ⁇ m and dried at 70° C. for 2 minutes and 120° C. for 2 minutes to obtain a skin layer.
- black pigment (“Dylac HS-9530” manufactured by DIC Corporation)
- a thickener (“Hydran Assister T10” manufactured by DIC Corporation)
- the 100% modulus value (hereinafter "100% M(2)") was measured in the same manner.
- a value obtained by dividing the 100% M(2) by the 100% M(1) was calculated as a retention rate and evaluated as follows. "A”: The retention rate is 50% or more. "B”: The retention rate is 30% or more and less than 50%. “C”: The retention rate is less than 30%.
- the synthetic leather of the present invention is environmentally friendly using water and biomass raw materials, and has excellent oleic acid resistance, low-temperature flexibility, peel strength, and light resistance.
- Comparative Example 1 uses a urethane resin composition that does not use alkanolamine (c) as the adhesive layer (ii), and uses a urethane resin composition that does not use the polycarbonate polyol (A-2) as the skin layer (iii).
- the oleic acid resistance, low-temperature flexibility, peel strength, and light resistance were all poor.
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Abstract
Description
ことを特徴とする合成皮革を提供するものである。
(1)基材(i)、接着層(ii)、表皮層(iii)
(2)基材(i)、接着層(ii)、中間層、表皮層(iii)
(3)基材(i)、多孔層、接着層(ii)、表皮層(iii)
(4)基材(i)、多孔層、接着層(ii)、中間層、表皮層(iii)
攪拌機、還流冷却器、温度計、及び、窒素導入管を備えた四つ口フラスコに、窒素気流下、ポリカーボネートポリオール(三菱化学株式会社製「ベネビオールNL-2010DB」、1,4-ブタンジオール、及び、バイオマス由来の1,10-デカンジールを原料とするもの、数平均分子量;2,000)300質量部、メチルエチルケトン380質量部、2,2-ジメチロールプロピオン酸9.2質量部を加え、十分に攪拌混合した。その後、イソホロンジイソシアネート68質量部、次いで、カルボン酸ビスマス0.1質量部を加え、75℃で4時間反応させることで、イソシアネート基を有するウレタンプレポリマーのメチルエチルケトン溶液を得た。
次いで、得られたウレタンプレポリマーのメチルエチルケトン溶液に、トリエチルアミン8.4質量部を加え、前記ウレタンプレポリマー中のカルボキシル基を中和した後、イオン交換水690質量部を加え、次いで、ピペラジン0.76質量部、モノエタノールアミン(以下「MEA」と略記する。)8.3質量部を加え、反応させた。反応終了後、MEKを減圧留去することによって、接着層形成用ウレタン樹脂組成物(X-1)を得た。得られたウレタン樹脂の酸価は、10.3KOHmg/g、重量平均分子量は、30,000であった。
MEAに代えて、ジエタノールアミンを用いた以外は、合成例1と同様にして接着層形成用ウレタン樹脂組成物(X-2)を得た。得られたウレタン樹脂の酸価は、10.3KOHmg/g、重量平均分子量は、25,000であった。
攪拌機、還流冷却器、温度計、及び、窒素導入管を備えた四つ口フラスコに、窒素気流下、1,4-ブタンジオール及びバイオマス由来の1,10-デカンジオールを原料とするポリカーボネートジオール(モル比[(C4)/(C10)]=90/10、数平均分子量;3,000、)100質量部、1,4-ブタンジオール及びバイオマス由来のイソソルバイドを原料とするポリカーボネートジオール(モル比[(C4)/(ISB)]=60/40、数平均分子量;800)11.1質量部を加え、メチルエチルケトン194質量部、2,2-ジメチロールプロピオン酸4.4質量部を加え、十分に撹拌混合した。その後、ジシクロヘキシルメタンジイソシアネート(以下「HMDI」と略記する。)29.4質量部、次いで、カルボン酸ビスマス0.03質量部を加え、75℃で約4時間反応させ、イソシアネート基を有するウレタンプレポリマーのメチルエチルケトン溶液を得た。
次いで、トリエチルアミン4.0質量部を加え、ウレタンプレポリマー中のカルボキシル基を中和した後、イオン交換水460質量部を加え、次いで、ピペラジン(以下「Pip」と略記する。)2.2質量部を加え反応させた。反応終了後、メチルエチルケトンを減圧留去することで、表皮層形成用ウレタン樹脂組成物(S-1)(酸価;13mgKOH/g)を得た。
実施例1において、HMDI29.4質量部を、イソホロンジイソシアネート24.9質量部、Pip2.2質量部を2.6質量部に変更した以外は合成例4と同様にして表皮層形成用ウレタン樹脂組成物(S-2)(酸価;13mgKOH/g)を得た。
攪拌機、還流冷却器、温度計、及び、窒素導入管を備えた四つ口フラスコに、窒素気流下、ポリカーボネートポリオール(三菱化学株式会社製「ベネビオールNL-2010DB」、1,4-ブタンジオール、及び、バイオマス由来の1,10-デカンジールを原料とするもの、数平均分子量;2,000)300質量部、メチルエチルケトン400質量部、2,2-ジメチロールプロピオン酸16質量部を加え、十分に攪拌混合した。その後、イソホロンジイソシアネート83質量部、次いで、カルボン酸ビスマス0.1質量部を加え、75℃で4時間反応させることで、イソシアネート基を有するウレタンプレポリマーのMEK溶液を得た。
次いで、得られたウレタンプレポリマーのメチルエチルケトン溶液に、トリエチルアミン14.3質量部を加え、前記ウレタンプレポリマー中のカルボキシル基を中和した後、イオン交換水630質量部を加え、次いで、PiP6.42質量部を加え、反応させた。反応終了後、MEKを減圧留去することによって、接着層形成用ウレタン樹脂組成物(XR-1)を得た。得られたウレタン樹脂の酸価は、10.3KOHmg/g、重量平均分子量は、150,000であった。
攪拌機、還流冷却器、温度計、及び、窒素導入管を備えた四つ口フラスコに、1,4-ブタンジオール及びバイオマス由来の1,10-デカンジオールを原料とするポリカーボネートジオール(モル比[(C4)/(C10)]=90/10、数平均分子量;3,000、)100質量部を加え、メチルエチルケトン170質量部、2,2-ジメチロールプロピオン酸4.0質量部を加え、十分に撹拌混合した。その後、ジシクロヘキシルメタンジイソシアネート23.1質量部、次いで、カルボン酸ビスマス0.03質量部を加え、75℃で約4時間反応させ、イソシアネート基を有するウレタンプレポリマーのメチルエチルケトン溶液を得た。
次いで、トリエチルアミン3.6質量部を加え、ウレタンプレポリマー中のカルボキシル基を中和した後、イオン交換水404質量部を加え、次いで、Pip1.7質量部を加え反応させた。反応終了後、メチルエチルケトンを減圧留去することで、表皮層形成用ウレタン樹脂組成物(SR-1)(酸価;17mgKOH/g)を得た。
合成例および比較合成例で用いたポリオールの数平均分子量、アニオン性ウレタン樹脂の重量平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー(GPC)法により、下記の条件で測定し得られた値を示す。
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A-500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A-2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F-1」
東ソー株式会社製「TSKgel 標準ポリスチレン F-2」
東ソー株式会社製「TSKgel 標準ポリスチレン F-4」
東ソー株式会社製「TSKgel 標準ポリスチレン F-10」
東ソー株式会社製「TSKgel 標準ポリスチレン F-20」
東ソー株式会社製「TSKgel 標準ポリスチレン F-40」
東ソー株式会社製「TSKgel 標準ポリスチレン F-80」
東ソー株式会社製「TSKgel 標準ポリスチレン F-128」
東ソー株式会社製「TSKgel 標準ポリスチレン F-288」
東ソー株式会社製「TSKgel 標準ポリスチレン F-550」
合成例及び比較合成例で得られたウレタン樹脂組成物を乾燥し、乾燥固化した樹脂粒子の0.05g~0.5gを、300mL三角フラスコに秤量し、次いで、テトラヒドロフランとイオン交換水との質量割合[テトラヒドロフラン/イオン交換水]が80/20の混合溶媒約80mLを加えそれらの混合液を得た。
次いで、前記混合液にフェノールフタレイン指示薬を混合した後、あらかじめ標定された0.1mol/Lの水酸化カリウム水溶液で滴定し、滴定に用いた水酸化カリウム水溶液の量から下記計算式(1)に従い、水性ウレタン樹脂(A)の酸価(mgKOH/g)を求めた。
計算式 A=(B×f×5.611)/S (1)
式中、Aは樹脂の固形分酸価(mgKOH/g)、Bは滴定に用いた0.1mol/L水酸化カリウム水溶液の量(mL)、fは0.1mol/L水酸化カリウム水溶液のファクター、Sは樹脂粒子の質量(g)、5.611は水酸化カリウムの式量(56.11/10)である。
合成例3で得られた表皮層形成用ウレタン樹脂組成物(S-1)100質量部、黒色顔料(DIC株式会社製「ダイラックHS-9530」)10質量部、増粘剤(DIC株式会社製「ハイドラン アシスターT10」)1質量部を配合した配合液を、フラット離型紙(味の素株式会社製「DN-TP-155T」)上に、乾燥後の膜厚が30μmとなるように塗布し、70℃で2分間、120℃で2分間乾燥させて、表皮層を得た。
次いで、合成例1で得られた接着層形成用ウレタン樹脂組成物(X-1)100質量部、増粘剤(DIC株式会社製「ハイドラン アシスターT10」)1質量部、ポリイソシアネート架橋剤(DIC株式会社製「ハイドラン アシスターC5」)9質量部を配合した配合液を、前記表皮層上に、乾燥後の膜厚が50μmとなるように塗布し、70℃で3分間乾燥させた。乾燥後、直ちにポリウレタン含浸不織布を貼り合わせた後、120℃で2分間熱処理し、次いで、50℃で2日間熟成させた後、離型紙を剥がして合成皮革を得た。
用いる表皮層形成用ウレタン樹脂組成物、及び、接着層形成用ウレタン樹脂組成物の種類を表1に示す通りに変更した以外は、実施例1と同様にして合成皮革(2)~(4)、(R1)を得た。
実施例及び比較例で得られた合成皮革を幅5mm、長さ50mmの短冊状に裁断し、試験片とした。この試験片を引張試験機(株式会社島津製作所製「オートグラフAG-I」)を使用して、チャック間距離;40mm、引張速度;10mm/秒、温度23℃の条件下で引張試験を行い、100%伸長した際の応力(100%モジュラス、以下「100%M(1)」)を測定した。
「A」:保持率が50%以上である。
「B」:保持率が30%以上50%未満である。
「C」:保持率が30%未満である。
実施例及び比較例で得られた合成皮革を、フレキソメーター(株式会社安田精機製作所製「低温槽付きフレキソメーター」)での屈曲性試験(-10℃、100回/毎分)を行い、合成皮革の表面に割れが生じるまでの回数を測定し、以下のように評価した。
「A」:30,000回以上
「B」:10,000回以上30,000回未満
「C」:10,000回未満
実施例及び比較例で得られた合成皮革を、島津オートグラフ「AG-1」(株式会社島津製作所製)を使用して、フルスケール5kg、ヘッドスピード20mm/分の条件にて剥離強度を測定し、以下のように評価した。
「A」;1.0kgf/cm以上
「B」;0.5kgf/cm以上1.0kgf/cm未満
「C」;0.5kgf/cm未満
実施例及び比較例で得られた合成皮革を、650ppmのNOxガスに1時間暴露し、暴露後の黄変度により以下のように評価した。
「A」;外観に黄変なし。
「B」;外観にわずかな黄変が確認された。
「C」;外観に濃黄色が確認された。
Claims (7)
- 少なくとも、基材(i)、接着層(ii)、及び、表皮層(iii)を有する合成皮革であって、
前記接着層(ii)が、
アニオン性ウレタン樹脂(X)、及び、水(Y)を含有するウレタン樹脂組成物により形成されたものであり、
前記アニオン性ウレタン樹脂(X)が、
バイオマス由来のポリカーボネートポリオール(a1)を含むポリオール(a)と、
ポリイソシアネート(b)と、アルカノールアミン(c)とを必須原料とするものであり、
前記表皮層(iii)が、
アニオン性ウレタン樹脂(S)、及び、水(T)を含有するウレタン樹脂組成物により形成されたものであり、
前記アニオン性ウレタン樹脂(S)が、
バイオマス由来のデカンジオ-ルを原料とするポリカーボネートポリオール(A-1)、及び、バイオマス由来の、環状エーテル構造を有するジヒドロキシ化合物を原料とするポリカーボネートポリオール(A-2)を原料とするものものである、
ことを特徴とする合成皮革。 - 前記バイオマス由来のポリカーボネートポリオール(a1)が、バイオマス由来のデカンジオールを原料とするものである、請求項1記載の合成皮革。
- 前記ポリカーボネートポリオール(A-1)が、更にブタンジオールを原料とするものである請求項1又は2記載の合成皮革。
- 前記ポリカーボネートポリオール(A-1)における、前記ブタンジオール(C4)と前記バイオマス由来のデカンジオール(C10)とのモル比[(C4)/(C10)]が、50/50~98/2の範囲である請求項3記載の合成皮革。
- 前記ポリカーボネートポリオール(A-2)が、更にブタンジオール、及び/又は、ヘキサンジオールを原料とするものである請求項1~4のいずれか1項記載の合成皮革。
- 前記ポリカーボネートポリオール(A-2)における、前記ブタンジオール(C4)及び前記ヘキサンジオール(C6)の合計と、前記バイオマス由来の、環状エーテル構造を有するジヒドロキシ化合物(ISB)とのモル比[(C4+C6)/(ISB)]が、30/70~90/10の範囲である請求項5記載の合成皮革。
- 前記前記バイオマス由来の、環状エーテル構造を有するジヒドロキシ化合物が、バイオマス由来のイソソルバイドである請求項1~6のいずれか1項記載の合成皮革。
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JPWO2022180897A1 (ja) | 2022-09-01 |
TW202233711A (zh) | 2022-09-01 |
JP7347711B2 (ja) | 2023-09-20 |
KR20230127279A (ko) | 2023-08-31 |
EP4299830A1 (en) | 2024-01-03 |
CN116829783A (zh) | 2023-09-29 |
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