WO2023085209A1 - ポリウレタン鎖延長剤、ポリウレタン系樹脂形成用組成物、ポリウレタン系樹脂、ポリウレタン系樹脂組成物、成形体及び物品 - Google Patents
ポリウレタン鎖延長剤、ポリウレタン系樹脂形成用組成物、ポリウレタン系樹脂、ポリウレタン系樹脂組成物、成形体及び物品 Download PDFInfo
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- WO2023085209A1 WO2023085209A1 PCT/JP2022/041164 JP2022041164W WO2023085209A1 WO 2023085209 A1 WO2023085209 A1 WO 2023085209A1 JP 2022041164 W JP2022041164 W JP 2022041164W WO 2023085209 A1 WO2023085209 A1 WO 2023085209A1
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- WIPO (PCT)
- Prior art keywords
- polyurethane
- chain extender
- polyurethane resin
- resin
- composition
- Prior art date
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- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 description 1
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- LWJWGXUXSVJWBY-UHFFFAOYSA-N dihydroxy-phenoxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)OC1=CC=CC=C1 LWJWGXUXSVJWBY-UHFFFAOYSA-N 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 210000003709 heart valve Anatomy 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- 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
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/02—Polyureas
Definitions
- the present invention relates to polyurethane chain extenders, polyurethane-based resin-forming compositions, polyurethane-based resins, polyurethane-based resin compositions, molded articles, and articles.
- Polyurethane resins are excellent in, for example, mechanical strength, flexibility, abrasion resistance, oil resistance, etc., and are widely used in various industrial fields.
- a polyurethane resin can be obtained, for example, by reacting a polyisocyanate, a polyol and a chain extender.
- Various physical properties of the resulting polyurethane-based resin can be adjusted by changing the types and blending ratios of the polyisocyanate, polyol and chain extender. Techniques related to such polyurethane-based resins include those described in Patent Documents 1 and 2, for example.
- Patent Document 1 an isocyanate group-terminated prepolymer in a non-aqueous dispersion medium is blended with a chain extender dispersion containing a chain extender, a non-aqueous dispersion medium, and a dispersion stabilizer, and a chain extension reaction is performed.
- the resulting thermoplastic polyurethane resin is described.
- US Pat. No. 5,300,000 comprises a polyisocyanate and a molecule having a hydrogen-active moiety, and optionally a chain extender and/or a mixture of surfactants, wherein the polyisocyanate comprises a bis(isocyanatomethyl)cyclohexane compound.
- Polyurethane dispersions are described.
- JP 2009-91519 A Japanese Unexamined Patent Application Publication No. 2011-46968
- the present invention has been made in view of the above circumstances, and provides a polyurethane chain extender and a polyurethane resin-forming composition capable of improving the mechanical properties of the obtained polyurethane resin, and a polyurethane resin having improved mechanical properties. , a polyurethane resin composition, a molded article and an article.
- the present inventors have found that the mechanical properties of the resulting polyurethane resin can be improved by using a specific amine compound as a polyurethane chain extender, and have completed the present invention.
- polyurethane chain extenders polyurethane resin-forming compositions, polyurethane resins, polyurethane resin compositions, molded articles, and articles are provided.
- R 1 to R 12 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, p and q are each independently an integer of 0 to 4, and p and at least one of q is 1 or more.
- a composition for forming a polyurethane-based resin comprising a polyisocyanate compound (A), a polyol compound (B), and the polyurethane chain extender (C) according to any one of [1] to [3].
- the ratio of the number of active hydrogen groups in the polyurethane chain extender (C) to the total number of active hydrogen groups in the polyol compound (B) and the number of active hydrogen groups in the polyurethane chain extender (C) is 0.01 or more.
- the polyurethane resin according to the above [6] or [7] which is 0.5 or less. [9] 1.
- the ratio of the number of isocyanate groups in the polyisocyanate compound (A) to the total number of active hydrogen groups in the polyol compound (B) and the number of active hydrogen groups in the polyurethane chain extender (C) is 0.5 or more. 5 or less, the polyurethane resin according to any one of the above [6] to [8].
- the tensile strength of the polyurethane resin is 1.0 MPa or more, measured under the conditions of a tensile speed of 200 mm / min and a distance between chucks of 50 mm.
- the polyurethane-based resin according to any one of the above.
- the tensile modulus of elasticity of the polyurethane-based resin is 2.5 MPa or more, measured under conditions of a tensile speed of 200 mm/min and a distance between chucks of 50 mm.
- the polyurethane-based resin according to any one of [6] to [12] which is a polyurethane urea resin.
- a polyurethane resin composition comprising the polyurethane resin according to any one of [6] to [13].
- a polyurethane chain extender and a composition for forming a polyurethane resin that can improve the mechanical properties of the resulting polyurethane resin, as well as a polyurethane resin, a polyurethane resin composition, and a molding with improved mechanical properties. Bodies and articles can be provided.
- this embodiment The form for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail.
- the following embodiments are exemplifications for explaining the present invention, and do not limit the content of the present invention.
- the present invention can be appropriately modified and implemented within the scope of the gist thereof.
- the rules that are considered preferable can be arbitrarily adopted, and it can be said that a combination of preferable ones is more preferable.
- the description of "XX to YY" means "XX or more and YY or less”.
- the polyurethane chain extender of the present invention contains an amine compound (X) represented by the following formula (1), and the ratio of the trans isomer in the amine compound (X) is 50 mol% or more.
- R 1 to R 12 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms
- p and q are each independently an integer of 0 to 4
- p and At least one of q is 1 or more.
- the polyurethane chain extender of the present invention can improve the mechanical properties of the obtained polyurethane resin by using it as a chain extender when producing a polyurethane resin.
- mechanical properties include tensile strength, tensile modulus, hardness, and the like.
- Amine compound (X) is a compound represented by the above formula (1).
- R 1 to R 12 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
- R 1 and R 2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, It is a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, still more preferably a hydrogen atom, still more preferably both R 1 and R 2 are hydrogen atoms.
- R 3 to R 12 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, It is a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, still more preferably a hydrogen atom, and still more preferably all of R 3 to R 12 are hydrogen atoms.
- p and q are each independently an integer of 0 or more and 4 or less, preferably 1 or more and preferably 3 or less, more preferably 3 or less, from the viewpoint of further improving the mechanical properties of the resulting polyurethane resin. It is 2 or less, more preferably 1, and more preferably both p and q are 1. However, at least one of p and q is an integer of 1 or more and 4 or less.
- the amine compound (X) preferably contains at least one selected from 1,4-bis(aminomethyl)cyclohexane and derivatives thereof from the viewpoint of further improving the mechanical properties of the resulting polyurethane resin.
- 1,4-bis(aminomethyl)cyclohexane is more preferred.
- the derivative of 1,4-bis(aminomethyl)cyclohexane for example, at least one of the hydrogen atoms of R 1 to R 12 in the above formula (1) is a carbonized derivative having 1 to 4 carbon atoms. Compounds substituted with hydrogen groups are mentioned.
- the hydrocarbon group in the 1,4-bis(aminomethyl)cyclohexane derivative is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group, from the viewpoint of further improving the mechanical properties of the resulting polyurethane resin.
- amine compounds (X) can be used alone or in combination of two or more.
- Amine compound (X) can be produced by a known method.
- the ratio of the trans isomer in the amine compound (X) is 50 mol% or more, and from the viewpoint of further improving the mechanical properties of the resulting polyurethane resin, it is preferably 55 mol% or more, more preferably 58 mol% or more, and further It is preferably 60 mol % or more, and from the same viewpoint, preferably 100 mol % or less, more preferably less than 100 mol %, still more preferably 99 mol % or less.
- the ratio of the trans isomer in the amine compound (X) is more preferably 97 mol% or less, more preferably 95 mol% or less, still more preferably 93 mol% or less, still more preferably is 90 mol % or less, more preferably 88 mol % or less.
- the amine compound (X) includes both cis- and trans-amine compounds represented by the formula (1), and the total amount of cis- and trans-isomers in the amine compound (X) is 100. in mol %.
- the cis amine compound (X) means an amine compound in which the two amino group-containing groups in the formula (1) are in the cis position on the cyclohexane ring
- the trans amine compound (X) is means an amine compound in which two amino group-containing groups in the above formula (1) are in the trans position on the cyclohexane ring.
- the ratio of the trans isomer in the amine compound (X) can be measured by the method described in Examples.
- the content of the amine compound (X) in the polyurethane chain extender according to the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of further improving the mechanical properties of the resulting polyurethane resin. , More preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably 99% by mass or more , from the same point of view, it is preferably 100% by mass or less.
- the polyurethane chain extender according to the present invention may appropriately contain a chain extender other than the amine compound (X) as long as the object of the present invention is not impaired.
- Chain extenders other than the amine compound (X) include, for example, chain extenders commonly used as chain extenders for polyurethane resins. Examples of such a chain extender include conventionally known polyhydric alcohols and amine compounds other than the amine compound (X).
- the polyurethane-based resin-forming composition of the present invention is a composition for forming a polyurethane-based resin, comprising a polyisocyanate compound (A), a polyol compound (B), and the above-described polyurethane chain extension according to the present invention.
- agent hereinafter also referred to as "polyurethane chain extender (C)"
- the composition for forming a polyurethane-based resin of the present invention comprises an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound (A) and a polyol compound (B), and a polyurethane chain extender (C). It can be a thing. Since the polyurethane-based resin-forming composition according to the present invention contains the polyurethane chain extender (C) according to the present invention described above, the mechanical properties of the obtained polyurethane-based resin can be improved.
- the polyisocyanate compound (A) is not particularly limited as long as it has two or more isocyanate groups, and conventionally known compounds can be used.
- Diisocyanate compounds having two isocyanate groups include, for example, 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, lysine diisocyanate methyl ester, Chain aliphatic diisocyanate compounds such as 1,5-octylene diisocyanate; 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), norbornane diisocyanate, hydrogenated tolylene diisocyanate, methylcyclohexane diisocyanate, isopropylidene bis(4- cyclohexy
- Polyisocyanate compounds having 3 or more isocyanate groups include, for example, triphenylmethane triisocyanate, triisocyanate phenylthiophosphate, polymethylene polyphenylene polyisocyanate (polymeric MDI), isocyanurate modified body which is a trimer of HDI or TDI, and biuret. Modified forms and the like can be mentioned.
- Polyisocyanate compound (A) can be used individually by 1 type or in combination of 2 or more types.
- the polyisocyanate compound (A) is preferably a diisocyanate having two isocyanate groups, more preferably an alicyclic structure-containing diisocyanate compound, and still more preferably isophorone diisocyanate.
- the polyol compound (B) is not particularly limited, and conventionally known compounds can be used.
- Examples of the polyol compound (B) include polyester-based polyols, polyether-based polyols, polycarbonate-based polyols, and polylactone-based polyols.
- the polyester polyol is not particularly limited as long as it is a condensation product of a polycarboxylic acid or a reactive derivative thereof and a polyhydric alcohol, and examples thereof include those obtained by condensation polymerization of a dicarboxylic acid and a glycol. .
- Dicarboxylic acids include chain aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, and maleic acid; orthophthalic acid, terephthalic acid, isophthalic acid; ,6-naphthalenedicarboxylic acid and other aromatic dicarboxylic acids; and reactive derivatives thereof; 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acids and the like are included.
- chain aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid,
- glycols include dimethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, neopentyl glycol, 2,2- diethyl-1,3-propanediol, butylethylpropanediol, 1,2-butanediol, butylene glycol, 1,4-butanediol, dimethylbutanediol, 1,5-pentanediol, 2,4-diethylpentanediol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,
- glycols chain aliphatic glycols
- alicyclic glycols such as 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane
- m- Aromatic ring-containing glycols such as xylylene glycol, p-xylylene glycol, bisphenol A, bisphenol F, bisphenol S, and the like are included. These glycols can be used individually by 1 type or in combination of 2 or more types.
- polyester polyols include condensation polyester polyols such as polyethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, and polyethylene butylene adipate glycol.
- polyether-based polyols include aliphatic polyether polyols such as polytetramethylene glycol, polyethylene glycol and polypropylene glycol.
- polycarbonate-based polyols examples include low-molecular-weight polyols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, nonanediol, and 1,4-cyclohexanedimethanol, diethylene carbonate, dipropylene carbonate, Examples thereof include polyols obtained by dealcoholization with carbonate compounds such as diphenyl carbonate.
- polylactone-based polyols examples include polylactone diols obtained by ring-opening polymerization of lactones using the above low-molecular-weight polyols as initiators, polycaprolactone diols, and lactone polyester diols such as polymethylvalerolactone diol.
- polyols used for water-based polyurethane resins may be used.
- the polyol used in the water-based polyurethane resin is not particularly limited, but examples thereof include polyols having anionic groups, preferably dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid and the like. and polyols containing groups.
- the polyol compound (B) can be used singly or in combination of two or more.
- the polyol compound (B) is preferably at least one selected from the group consisting of polyester polyols and polyether polyols, more preferably polyether polyols, polytetramethylene glycol, polyethylene glycol and polypropylene glycol. At least one selected from the group consisting of is more preferable, and polytetramethylene glycol is more preferable.
- the total number of active hydrogen groups in the polyol compound (B) and the number of active hydrogen groups in the polyurethane chain extender (C) is The ratio of the number of active hydrogen groups is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.04 or more, from the viewpoint of further improving the mechanical properties of the resulting polyurethane resin. From the viewpoint, it is preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less, still more preferably 0.2 or less, and even more preferably 0.15 or less.
- Radix ratio is preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, still more preferably 0.8, from the viewpoint of further improving the mechanical properties of the resulting polyurethane resin. above, more preferably 0.9 or more, and from the same viewpoint, preferably 1.5 or less, more preferably 1.4 or less, still more preferably 1.3 or less, even more preferably 1.2 or less, still more preferably is less than or equal to 1.1.
- the polyurethane-based resin-forming composition according to the present invention may contain one or more solvents, if necessary.
- a known solvent can be used, and examples thereof include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone and water.
- the solid content concentration of the polyurethane-based resin-forming composition is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass.
- composition for forming a polyurethane-based resin according to the present invention contains water as a solvent
- the composition for forming a polyurethane-based resin may be an emulsion.
- the total content of the polyisocyanate compound (A), the polyol compound (B) and the polyurethane chain extender (C), or the polyisocyanate compound (A) and the polyol compound, in the composition for forming a polyurethane resin according to the present invention The total content of the isocyanate group-terminated prepolymer obtained by reacting with (B) and the polyurethane chain extender (C) is 100% by mass of the total solid content contained in the composition for forming a polyurethane-based resin according to the present invention.
- the polyurethane-based resin of the present invention is formed from the polyurethane-based resin-forming composition of the present invention described above. Further, the polyurethane-based resin of the present invention may be obtained by reacting the polyisocyanate compound (A), the polyol compound (B), and the polyurethane chain extender (C) according to the present invention described above. Since the polyurethane-based resin according to the present invention contains the polyurethane chain extender (C) according to the present invention described above, the mechanical properties can be improved. Here, since the polyurethane-based resin according to the present invention uses the amine compound (X) as the polyurethane chain extender (C), it has urea bonds in its structure. Therefore, the polyurethane-based resin according to the present invention includes a polyurethane urea resin, preferably a polyurethane urea resin.
- the polyurethane-based resin according to the present invention can be produced by heating the composition for forming a polyurethane-based resin according to the present invention described above. Further, the polyurethane-based resin according to the present invention, for example, reacts an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound (A) and a polyol compound (B) in advance with a polyurethane chain extender (C).
- a so-called prepolymer method or a so-called one-shot method in which the polyol compound (B) and the urethane chain extender (C) are premixed and then this mixture is reacted with the polyisocyanate compound (A). can be done.
- the tensile strength of the polyurethane-based resin according to the present invention is preferably 1.0 MPa or higher, more preferably 1.1 MPa or higher, still more preferably 1.2 MPa or higher, from the viewpoint of further improving the mechanical properties of the polyurethane-based resin. It is preferably 1.3 MPa or more, more preferably 1.4 MPa or more. From the viewpoint of further improving the mechanical properties of the polyurethane-based resin, the higher the tensile strength, the better. Therefore, the upper limit is not particularly limited. 0 MPa or less.
- the tensile strength can be measured according to JIS K 6251:2017 under conditions of a tensile speed of 200 mm/min and a distance between chucks of 50 mm. Specifically, it can be measured by the method described in Examples below. can.
- the tensile modulus of the polyurethane-based resin according to the present invention is preferably 2.5 MPa or higher, more preferably 2.6 MPa or higher, and still more preferably 2.7 MPa or higher, from the viewpoint of further improving the mechanical properties of the polyurethane-based resin. More preferably 2.8 MPa or more, more preferably 2.9 MPa or more. From the viewpoint of further improving the mechanical properties of the polyurethane-based resin, the higher the tensile modulus, the better. It may be 3.5 MPa or less.
- the tensile modulus can be measured in accordance with JIS K 6251:2017 under the conditions of a tensile speed of 200 mm/min and a distance between chucks of 50 mm. Specifically, it can be measured by the method described in Examples below. can be done.
- the Shore A hardness of the polyurethane resin according to the present invention is preferably 50 or more, more preferably 53 or more, still more preferably 55 or more, still more preferably 56 or more, from the viewpoint of further improving the mechanical properties of the polyurethane resin. More preferably 58 or more, more preferably 59 or more. From the viewpoint of further improving the mechanical properties of the polyurethane-based resin, the higher the Shore A hardness, the better. may be The Shore A hardness can be measured according to JIS K 6253:2012, and specifically, it can be measured by the method described in Examples below.
- the polyurethane-based resin composition of the present invention contains the polyurethane-based resin of the present invention described above. Since the polyurethane-based resin composition according to the present invention contains the above-described polyurethane-based resin according to the present invention, the mechanical properties can be improved.
- the content of the polyurethane-based resin according to the present invention in the polyurethane-based resin composition according to the present invention is 100% of all resin components contained in the polyurethane-based resin composition according to the present invention, from the viewpoint of further improving mechanical properties.
- % by mass preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass % or more, more preferably 98 mass % or more, still more preferably 99 mass % or more, and from the same viewpoint, preferably 100 mass % or less.
- the polyurethane-based resin composition according to the present invention can contain one or more solvents, if necessary.
- a known solvent can be used, and examples thereof include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone and water.
- the solid content concentration of the polyurethane-based resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more. It is preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 65% by mass or less, and even more preferably 60% by mass or less.
- the polyurethane-based resin composition according to the present invention contains water as a solvent, the polyurethane-based resin composition may be an emulsion.
- the polyurethane-based resin composition according to the present invention is not particularly limited, but examples include foams, elastomers, paints, fibers, fiber processing agents, adhesives, adhesives, binders, inks, flooring materials, sealants, caulks, medical materials, It can be widely used for leather materials, tire materials, coating agents, active energy ray-curable resin compositions, and the like.
- the polyurethane-based resin composition according to the present invention may include, for example, a silane coupling agent, a filler, a thixotropic agent, a tackifier, a wax, a plasticizer, a heat stabilizer, an antioxidant, and an ultraviolet absorbing agent, depending on the application and need.
- a silane coupling agent for example, a silane coupling agent, a filler, a thixotropic agent, a tackifier, a wax, a plasticizer, a heat stabilizer, an antioxidant, and an ultraviolet absorbing agent, depending on the application and need.
- the method for producing the polyurethane-based resin composition according to the present invention is not particularly limited.
- the obtained mixture is supplied to an extruder, melt-kneaded at a general temperature for extruding a general thermoplastic polyurethane resin (for example, 150 to 250 ° C.), and then made into a pellet shape by strand cutting or underwater cutting.
- Method of preparation a method of preparing by dispersing, dissolving or emulsifying the polyurethane-based resin according to the present invention in a solvent, and the like.
- the molded article of the present invention is obtained by molding the polyurethane-based resin composition of the present invention described above.
- the article of the present invention includes the polyurethane-based resin composition of the present invention or the molded article of the present invention. That is, the polyurethane-based resin composition according to the present invention described above can be suitably used for producing various molded articles and articles. Since the molded article and article according to the present invention contain the polyurethane-based resin composition according to the present invention described above, the mechanical properties can be improved.
- the article according to the present invention may be wholly composed of the polyurethane-based resin composition or molded article of the present invention, or partially composed of the polyurethane-based resin composition or molded article of the present invention.
- aspects in which a part is constituted by the polyurethane-based resin composition or molded article according to the present invention include, for example, a configuration in which a layer of the polyurethane-based resin composition or molded article according to the present invention is provided on the surface or inside; A structure having a layer impregnated with the polyurethane-based resin composition according to the present invention is included.
- thermoplastic polyurethane-based resins As a method for molding the polyurethane-based resin composition according to the present invention, general molding methods for thermoplastic polyurethane-based resins can be applied. Examples include extrusion molding, injection molding, inflation molding, blow molding, vacuum molding, centrifugal molding, Forming methods such as rotational molding, calendering, roll processing, and press processing can be used. By these molding methods, moldings of various shapes such as resin plates, films, sheets, irregular shaped articles, etc. can be produced from the polyurethane resin composition according to the present invention.
- Molded bodies and articles include, for example, belts, tubes, hoses, wire covering materials, cable covering materials, fire hoses, gears, casters, packings, mechanical industrial parts such as wind turbines for wind power generation; tires, tire parts, bumpers, Vehicle parts such as side moldings, tail lamp seals, snow chains, ball joint seals, constant velocity joint boots, bellows, spring cover materials, ABS cables, ABS cable plugs, instrument panel skins, gear knobs, console boxes, door seal covers, seat materials, knobs, etc.
- 1,3-BAC 1,3-bis(aminomethyl)cyclohexane (ratio of trans isomer: 25 mol%, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
- 1,4-BAC 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 43 mol%, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
- 1,4-BAC 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 85 mol%, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
- 1,4-BAC 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 100 mol%, manufactured by Tokyo Chemical Industry Co., Ltd.)
- 1,4-BAC 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 99 mol%, prepared according to Production Example 1 below.)
- 1,4-BAC 1,4-bis(aminomethyl)cyclo
- Example 1 (1) Synthesis of isocyanate group-terminated prepolymer 1 Add 101 g of PTMG (OH group equivalent: 500 g/eq.) to a 500 mL four-necked separable flask equipped with a stirring blade and a thermocouple, and heat at 100° C./degree of pressure reduction of 100 to 200 hPa. Dehydration treatment was performed for 1 hour under the conditions of Then, after air-cooling to 70°C, a cooling pipe was provided, 79 g of MEK and 0.045 g of dibutyltin dilaurate were added, and the mixture was heated to 70°C in a nitrogen atmosphere.
- PTMG OH group equivalent: 500 g/eq.
- the resulting solution was poured into a stainless steel mold coated with a mold release agent, cured under conditions of 23° C./50% RH for 1 week, and then cured in an oven at an internal temperature of 60° C. for 1 hour to obtain a thickness of 1.5.
- a 5 mm polyurethane urea resin test panel was obtained. The following evaluations were carried out on the obtained polyurethane urea resin test plates. The results obtained are shown in the table.
- the hardness (Shore A) of the test plates was measured. Specifically, according to the method described in JIS K 6253:2012, a hardness meter (Durometer Type A GS-719N manufactured by Teclock Co., Ltd.) was pressed against the test plate to read the value.
- a hardness meter (Durometer Type A GS-719N manufactured by Teclock Co., Ltd.) was pressed against the test plate to read the value.
- Examples 4-6, Comparative Examples 1-2 Polyurethane urea resin test plates were obtained in the same manner as in Example 1, except that the polyurethane chain extender 1,4-BAC (ratio of trans isomer: 85 mol%) was changed to the polyurethane chain extender shown in the table. rice field. Each of the above evaluations was performed on the obtained polyurethane urea resin test plate. The results obtained are shown in the table.
- Comparative example 3 Polyurethane urea resin test plates were prepared in the same manner as in Example 1 except that 0.51 g of 1,4-BAC (ratio of trans isomer: 85 mol %), which is a polyurethane chain extender, was changed to 0.61 g of IPDA shown in the table. Got each. Each of the above evaluations was performed on the obtained polyurethane urea resin test plate. The results obtained are shown in the table.
- Example 2 (1) Synthesis of isocyanate group-terminated prepolymer 2 Add 90 g of PTMG (OH group equivalent: 500 g/eq.) to a 500 mL four-necked separable flask equipped with a stirring blade and a thermocouple, and heat at 100° C./pressure reduction of 100 to 200 hPa. Dehydration treatment was performed for 1 hour under the conditions of Then, after air-cooling to 70°C, a cooling tube was provided, 77 g of MEK and 0.045 g of dibutyltin dilaurate were added, and the mixture was heated to 70°C in a nitrogen atmosphere.
- PTMG OH group equivalent: 500 g/eq.
- the resulting solution was poured into a stainless steel mold coated with a mold release agent, cured under conditions of 23° C./50% RH for 1 week, and then cured in an oven at an internal temperature of 60° C. for 1 hour to obtain a thickness of 1.5.
- a test panel of 5 mm polyurethane urea was obtained. Each of the above evaluations was performed on the obtained polyurethane urea resin test plate. The results obtained are shown in the table.
- Comparative example 4 112.5 g of PTMG (OH group equivalent: 500 g/eq.) was added to a 500 mL four-necked separable flask equipped with a stirring blade and a thermocouple, and dehydration was performed for 1 hour under the conditions of 100° C. and a reduced pressure of 100 to 200 hPa. rice field. Then, after air-cooling to 70°C, a cooling tube was provided, 77 g of MEK and 0.045 g of dibutyltin dilaurate were added, and the mixture was heated to 70°C under a nitrogen atmosphere.
- PTMG OH group equivalent: 500 g/eq.
- a dropping funnel was attached and 25 g of IPDI was added dropwise over 30 minutes, followed by stirring at 70°C for 3 hours. Thereafter, 200 g of MEK was added to adjust the solid content concentration to 30% by mass, and the solution was taken out as a polyurethane resin solution.
- the resulting solution was poured into a stainless steel mold coated with a mold release agent, cured under conditions of 23° C./50% RH for 1 week, and then cured in an oven at an internal temperature of 60° C. for 1 hour to obtain a thickness of 1.5.
- a test panel of 5 mm polyurethane resin was obtained.
- Comparative Examples 5 and 6 Polyurethane urea resin test plates were obtained in the same manner as in Example 2, except that the polyurethane chain extender 1,4-BAC (ratio of trans isomer: 85 mol%) was changed to the polyurethane chain extender shown in the table. rice field. Each of the above evaluations was performed on the obtained polyurethane urea resin test plate. The results obtained are shown in the table.
- Comparative example 7 Polyurethane urea resin test plates were prepared in the same manner as in Example 2, except that 1.28 g of 1,4-BAC (ratio of trans isomer: 85 mol%), which is a polyurethane chain extender, was changed to 1.53 g of IPDA shown in the table. Got each. Each of the above evaluations was performed on the obtained polyurethane urea resin test plate. The results obtained are shown in the table.
- Example 3 (1) Synthesis of isocyanate group-terminated prepolymer 3 Add 107 g of PTMG (OH group equivalent: 500 g/eq.) to a 500 mL four-necked separable flask equipped with a stirring blade and a thermocouple, and heat at 100° C./pressure reduction of 100 to 200 hPa. Dehydration treatment was performed for 1 hour under the conditions of Then, after air-cooling to 70°C, a cooling tube was provided, 88 g of MEK and 0.045 g of dibutyltin dilaurate were added, and the mixture was heated to 70°C in a nitrogen atmosphere.
- PTMG OH group equivalent: 500 g/eq.
- the resulting solution was poured into a stainless steel mold coated with a mold release agent, cured under conditions of 23° C./50% RH for 1 week, and then cured in an oven at an internal temperature of 60° C. for 1 hour to obtain a thickness of 1.5.
- a test panel of 5 mm polyurethane urea was obtained. Each of the above evaluations was performed on the obtained polyurethane urea resin test plate. The results obtained are shown in the table.
- Comparative Examples 8 and 9 Polyurethane urea resin test plates were obtained in the same manner as in Example 3, except that the polyurethane chain extender 1,4-BAC (ratio of trans isomer: 85 mol%) was changed to the polyurethane chain extender shown in the table. rice field. Each of the above evaluations was performed on the obtained polyurethane urea resin test plate. The results obtained are shown in the table.
- Comparative example 10 Polyurethane urea resin test plate in the same manner as in Example 3, except that 0.14 g of 1,4-BAC (ratio of trans isomer: 85 mol%), which is a polyurethane chain extender, was changed to 0.17 g of IPDA shown in the table. obtained respectively. Each of the above evaluations was performed on the obtained polyurethane urea resin test plate. The results obtained are shown in the table.
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Abstract
Description
ポリウレタン系樹脂は、例えばポリイソシアネート、ポリオール及び鎖延長剤の反応により得ることができる。ポリイソシアネート、ポリオール及び鎖延長剤の種類や配合割合を変更することにより、得られるポリウレタン系樹脂の各種物性を調整することができる。
このようなポリウレタン系樹脂に関する技術としては、例えば、特許文献1及び2に記載のものが挙げられる。
本発明は上記事情に鑑みてなされたものであり、得られるポリウレタン系樹脂の機械的特性を向上できるポリウレタン鎖延長剤及びポリウレタン系樹脂形成用組成物、並びに、機械的特性が向上したポリウレタン系樹脂、ポリウレタン系樹脂組成物、成形体及び物品を提供するものである。
下記式(1)で示されるアミン化合物(X)を含むポリウレタン鎖延長剤であって、
前記アミン化合物(X)におけるトランス体の比率が50モル%以上であるポリウレタン鎖延長剤。
(上記式(1)中、R1~R12はそれぞれ独立に水素原子又は炭素数1以上4以下の炭化水素基を示し、p及びqはそれぞれ独立に0以上4以下の整数であり、p及びqの少なくとも一方は1以上である。)
[2]
前記アミン化合物(X)が1,4-ビス(アミノメチル)シクロヘキサン及びその誘導体から選択される少なくとも一種を含む、前記[1]に記載のポリウレタン鎖延長剤。
[3]
前記アミン化合物(X)におけるトランス体の比率が100モル%以下である、前記[1]又は[2]に記載のポリウレタン鎖延長剤。
[4]
ポリイソシアネート化合物(A)と、ポリオール化合物(B)と、前記[1]~[3]のいずれかに記載のポリウレタン鎖延長剤(C)とを含む、ポリウレタン系樹脂形成用組成物。
[5]
ポリイソシアネート化合物(A)とポリオール化合物(B)とが反応してなるイソシアネート基末端プレポリマーと、前記[1]~[3]のいずれかに記載のポリウレタン鎖延長剤(C)とを含む、ポリウレタン系樹脂形成用組成物。
[6]
前記[4]又は[5]に記載のポリウレタン系樹脂形成用組成物により形成されたポリウレタン系樹脂。
[7]
ポリイソシアネート化合物(A)、ポリオール化合物(B)、及び前記[1]~[3]のいずれかに記載のポリウレタン鎖延長剤(C)を反応させてなる、ポリウレタン系樹脂。
[8]
前記ポリオール化合物(B)中の活性水素基数と前記ポリウレタン鎖延長剤(C)中の活性水素基数との合計量に対する前記ポリウレタン鎖延長剤(C)中の活性水素基数の比が0.01以上0.5以下である、前記[6]又は[7]に記載のポリウレタン系樹脂。
[9]
前記ポリオール化合物(B)中の活性水素基数と前記ポリウレタン鎖延長剤(C)中の活性水素基数との合計量に対する前記ポリイソシアネート化合物(A)中のイソシアネート基数の比が0.5以上1.5以下である、前記[6]~[8]のいずれかに記載のポリウレタン系樹脂。
[10]
JIS K 6251:2017に準拠し、引張速度200mm/min、チャック間距離50mmの条件で測定される、前記ポリウレタン系樹脂の引張強度が1.0MPa以上である、前記[6]~[9]のいずれかに記載のポリウレタン系樹脂。
[11]
JIS K 6251:2017に準拠し、引張速度200mm/min、チャック間距離50mmの条件で測定される、前記ポリウレタン系樹脂の引張弾性率が2.5MPa以上である、前記[6]~[10]のいずれかに記載のポリウレタン系樹脂。
[12]
JIS K 6253:2012に準拠して測定される、前記ポリウレタン系樹脂のショアA硬度が50以上である、前記[6]~[11]のいずれかに記載のポリウレタン系樹脂。
[13]
ポリウレタンウレア樹脂である、前記[6]~[12]のいずれかに記載のポリウレタン系樹脂。
[14]
前記[6]~[13]のいずれかに記載のポリウレタン系樹脂を含むポリウレタン系樹脂組成物。
[15]
前記[14]に記載のポリウレタン系樹脂組成物を成形してなる成形体。
[16]
前記[14]に記載のポリウレタン系樹脂組成物又は前記[15]に記載の成形体を含む物品。
本発明のポリウレタン鎖延長剤は、下記式(1)で示されるアミン化合物(X)を含み、アミン化合物(X)におけるトランス体の比率が50モル%以上である。
アミン化合物(X)は、上記式(1)で示される化合物である。
上記式(1)中、R1~R12は、それぞれ独立に、水素原子又は炭素数1以上4以下の炭化水素基を示す。
R1及びR2は、得られるポリウレタン系樹脂の機械的特性をより向上させる観点から、それぞれ独立に、好ましくは水素原子又は炭素数1以上4以下のアルキル基であり、より好ましくは水素原子、メチル基又はエチル基であり、更に好ましくは水素原子又はメチル基であり、更に好ましくは水素原子であり、更に好ましくはR1及びR2の両方が水素原子である。
R3~R12は、得られるポリウレタン系樹脂の機械的特性をより向上させる観点から、それぞれ独立に、好ましくは水素原子又は炭素数1以上4以下のアルキル基であり、より好ましくは水素原子、メチル基又はエチル基であり、更に好ましくは水素原子又はメチル基であり、更に好ましくは水素原子であり、更に好ましくはR3~R12のすべてが水素原子である。
ここで、1,4-ビス(アミノメチル)シクロヘキサンの誘導体としては、例えば、上記式(1)中のR1~R12の水素原子のうちの少なくとも1つが、炭素数1以上4以下の炭化水素基で置換された化合物が挙げられる。1,4-ビス(アミノメチル)シクロヘキサンの誘導体における前記炭化水素基としては、得られるポリウレタン系樹脂の機械的特性をより向上させる観点から、好ましくは炭素数1以上3以下のアルキル基、より好ましくはメチル基又はエチル基、更に好ましくはメチル基である。
ここで、アミン化合物(X)には、前記式(1)で示される、シス体及びトランス体のアミン化合物の両方が包含され、アミン化合物(X)中のシス体及びトランス体の合計は100モル%である。また、シス体のアミン化合物(X)とは、前記式(1)における2つのアミノ基含有基が、シクロヘキサン環においてシス位にあるアミン化合物を意味し、トランス体のアミン化合物(X)とは、前記式(1)における2つのアミノ基含有基が、シクロヘキサン環においてトランス位にあるアミン化合物を意味する。
アミン化合物(X)におけるトランス体の比率は、実施例に記載の方法により測定することができる。
本発明に係るポリウレタン鎖延長剤は、本発明の目的を損なわない範囲でアミン化合物(X)以外の鎖延長剤を適宜含有してもよい。アミン化合物(X)以外の鎖延長剤としては、例えば、ポリウレタン系樹脂の鎖延長剤として一般的に使用される鎖延長剤が挙げられる。このような鎖延長剤としては、例えば、従来公知の多価アルコール類やアミン化合物(X)以外のアミン化合物が挙げられる。
本発明のポリウレタン系樹脂形成用組成物は、ポリウレタン系樹脂を形成するための組成物であって、ポリイソシアネート化合物(A)と、ポリオール化合物(B)と、前述した本発明に係るポリウレタン鎖延長剤(以下、「ポリウレタン鎖延長剤(C)」ともいう。)と、を含む。
また、本発明のポリウレタン系樹脂形成用組成物は、ポリイソシアネート化合物(A)とポリオール化合物(B)とが反応してなるイソシアネート基末端プレポリマーと、ポリウレタン鎖延長剤(C)とを含む組成物であってもよい。
本発明に係るポリウレタン系樹脂形成用組成物は、前述した本発明に係るポリウレタン鎖延長剤(C)を含むため、得られるポリウレタン系樹脂の機械的特性を向上させることができる。
ポリイソシアネート化合物(A)としては、イソシアネート基を2個以上有するものであれば特に限定されず、従来公知のものを使用できる。
イソシアネート基を2個有するジイソシアネート化合物としては、例えば、1,6-ヘキサメチレンジイソシアネート(HDI)、2,2,4-トリメチルヘキサメチレンジイソシアネート、メチレンジイソシアネート、イソプロピレンジイソシアネート、リジンジイソシアネート、リジンジイソシアネートメチルエステル、1,5-オクチレンジイソシアネート等の鎖状脂肪族ジイソシアネート化合物;4,4’-ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート(IPDI)、ノルボルナンジイソシアネート、水添トリレンジイソシアネート、メチルシクロヘキサンジイソシアネート、イソプロピリデンビス(4-シクロヘキシルイソシアネート)、ダイマー酸ジイソシアネート等の脂環式構造含有ジイソシアネート化合物;2,4-もしくは2,6-トリレンジイソシアネート(TDI)、4,4’-ジフェニルメタンジイソシアネート(MDI)、1,5-ナフチレンジイソシアネート、p-もしくはm-キシリレンジイソシアネート(XDI)、トリジンジイソシアネート、p-フェニレンジイソシアネート、ジフェニルエーテルジイソシアネート、ジフェニルスルホンジイソシアネート、ジアニシジンジイソシアネート、テトラメチル-m-キシリレンジイソシアネート等の芳香環含有ジイソシアネート化合物等が挙げられる。
イソシアネート基を3個以上有するポリイソシアネート化合物としては、例えば、トリフェニルメタントリイソシアネート、トリイソシアネートフェニルチオフォスフェート、ポリメチレンポリフェニレンポリイソシアネート(ポリメリックMDI)、HDIやTDIのトリマーであるイソシアヌレート変性体、ビウレット変性体等が挙げられる。
ポリイソシアネート化合物(A)は、1種を単独で又は2種以上を組み合わせて用いることができる。
ポリオール化合物(B)としては、特に限定されず、従来公知のものを使用できる。
ポリオール化合物(B)としては、例えば、ポリエステル系ポリオール、ポリエーテル系ポリオール、ポリカーボネート系ポリオール、ポリラクトン系ポリオール等が挙げられる。
ジカルボン酸としては、例えば、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸、フマル酸、マレイン酸等の鎖状脂肪族ジカルボン酸;オルトフタル酸、テレフタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸等の芳香族ジカルボン酸;及びこれらの反応性誘導体;1,3-シクロペンタンジカルボン酸、1,2-シクロヘキサンジカルボン酸、1,3-シクロヘキサンジカルボン酸、1,4-シクロヘキサンジカルボン酸等の脂環式ジカルボン酸等が挙げられる。これらのジカルボン酸は、1種を単独で又は2種以上を組み合わせて用いることができる。
グリコール類としては、例えば、ジメチレングリコール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、1,3-プロパンジオール、ネオペンチルグリコール、2,2-ジエチル-1,3-プロパンジオール、ブチルエチルプロパンジオール、1,2-ブタンジオール、ブチレングリコール、1,4-ブタンジオール、ジメチルブタンジオール、1,5-ペンタンジオール、2,4-ジエチルペンタンジオール、1,6-ヘキサンジオール、3-メチル1,5-ペンタンジオール、1,8-オクタンジオール、1,9-ノナンジオール、1,10-デカンジオール、1,12-ドデカンジオール、ポリエチレンブチレングリコール等の鎖状脂肪族グリコール;1,3-シクロペンタンジオール、1,4-シクロヘキサンジオール、1,4-シクロヘキサンジメタノール、2,2-ビス(4-ヒドロキシシクロヘキシル)プロパン等の脂環式グリコール;m-キシリレングリコール、p-キシリレングリコール、ビスフェノールA、ビスフェノールF、ビスフェノールS等の芳香環含有グリコール等が挙げられる。
これらのグリコール類は、1種を単独で又は2種以上を組み合わせて用いることができる。
ポリエーテル系ポリオールとしては、例えば、ポリテトラメチレングリコール、ポリエチレングリコール、ポリプロピレングリコール等の脂肪族ポリエーテルポリオール等が挙げられる。
ポリカーボネート系ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、ノナンジオール、1,4-シクロヘキサンジメタノール等の低分子ポリオールと、ジエチレンカーボネート、ジプロピレンカーボネート、ジフェニルカーボネート等のカーボネート化合物との脱アルコール反応により得られるポリオール等が挙げられる。
ポリラクトン系ポリオールとしては、例えば、上記低分子ポリオール等を開始剤としてラクトンを開環重合させて得られるポリラクトンジオール、ポリカプロラクトンジオール、ポリメチルバレロラクトンジオール等のラクトン系ポリエステルジオール等が挙げられる。
本発明に係るポリウレタン系樹脂形成用組成物が溶媒を含む場合、ポリウレタン系樹脂形成用組成物の固形分濃度は、好ましくは5質量%以上、より好ましくは10質量%以上、更に好ましくは15質量%以上、更に好ましくは20質量%以上であり、そして、好ましくは80質量%以下、より好ましくは65質量%以下、更に好ましくは50質量%以下、更に好ましくは40質量%以下である。
本発明に係るポリウレタン系樹脂形成用組成物が溶媒として水を含む場合、ポリウレタン系樹脂形成用組成物はエマルションであってもよい。
本発明のポリウレタン系樹脂は、前述した本発明に係るポリウレタン系樹脂形成用組成物により形成される。
また、本発明のポリウレタン系樹脂は、ポリイソシアネート化合物(A)、ポリオール化合物(B)、及び前述した本発明に係るポリウレタン鎖延長剤(C)を反応させてなるものであってもよい。
本発明に係るポリウレタン系樹脂は、前述した本発明に係るポリウレタン鎖延長剤(C)を含むため、機械的特性を向上させることができる。
ここで、本発明に係るポリウレタン系樹脂は、ポリウレタン鎖延長剤(C)としてアミン化合物(X)を用いているため、構造中にウレア結合を有する。そのため、本発明に係るポリウレタン系樹脂は、ポリウレタンウレア樹脂を含み、好ましくはポリウレタンウレア樹脂である。
また、本発明に係るポリウレタン系樹脂は、例えば、ポリイソシアネート化合物(A)とポリオール化合物(B)とを予め反応させたイソシアネート基末端プレポリマーと、ポリウレタン鎖延長剤(C)とを反応させる、いわゆるプレポリマー法や、ポリオール化合物(B)とウレタン鎖延長剤(C)とを予め混合し、次いでこの混合物とポリイソシアネート化合物(A)とを反応させる、いわゆるワンショット法を用いて製造することができる。
前記引張強度はJIS K 6251:2017に準拠し、引張速度200mm/min、チャック間距離50mmの条件で測定することができ、具体的には、後述の実施例に記載の方法により測定することができる。
前記引張弾性率はJIS K 6251:2017に準拠し、引張速度200mm/min、チャック間距離50mmの条件で測定することができ、具体的には、後述の実施例に記載の方法により測定することができる。
前記ショアA硬度はJIS K 6253:2012に準拠して測定することができ、具体的には、後述の実施例に記載の方法により測定することができる。
本発明のポリウレタン系樹脂組成物は、前述した本発明に係るポリウレタン系樹脂を含むものである。本発明に係るポリウレタン系樹脂組成物は、前述した本発明に係るポリウレタン系樹脂を含むため、機械的特性を向上させることができる。
本発明に係るポリウレタン系樹脂組成物中の本発明に係るポリウレタン系樹脂の含有量は、機械的特性をより向上させる観点から、本発明に係るポリウレタン系樹脂組成物に含まれる全樹脂成分を100質量%としたとき、好ましくは50質量%以上、より好ましくは60質量%以上、更に好ましくは70質量%以上、更に好ましくは80質量%以上、更に好ましくは90質量%以上、更に好ましくは95質量%以上、更に好ましくは98質量%以上、更に好ましくは99質量%以上であり、同様の観点から、好ましくは100質量%以下である。
本発明に係るポリウレタン系樹脂組成物が溶媒を含む場合、ポリウレタン系樹脂組成物の固形分濃度は、好ましくは5質量%以上、より好ましくは10質量%以上、更に好ましくは15質量%以上、更に好ましくは20質量%以上であり、そして、好ましくは80質量%以下、より好ましくは70質量%以下、更に好ましくは65質量%以下、更に好ましくは60質量%以下である。
本発明に係るポリウレタン系樹脂組成物が溶媒として水を含む場合、ポリウレタン系樹脂組成物はエマルションであってもよい。
本発明の成形体は、前述した本発明に係るポリウレタン系樹脂組成物を成形してなるものである。また、本発明の物品は、前述した本発明に係るポリウレタン系樹脂組成物、又は本発明に係る成形体を含むものである。すなわち、前述した本発明に係るポリウレタン系樹脂組成物は、各種成形体及び物品の作製に好適に用いることができる。
本発明に係る成形体及び物品は、前述した本発明に係るポリウレタン系樹脂組成物を含むため、機械的特性を向上させることができる。
本発明に係る物品は、本発明に係るポリウレタン系樹脂組成物又は成形体により全体が構成されていてもよいし、本発明に係るポリウレタン系樹脂組成物又は成形体により一部が構成されていてもよい。本発明に係るポリウレタン系樹脂組成物又は成形体により一部が構成されている態様としては、例えば、表面又は内部に本発明に係るポリウレタン系樹脂組成物又は成形体の層を備える構成;表面又は内部に本発明に係るポリウレタン系樹脂組成物が含浸した層を備える構成等が挙げられる。
GC装置Agilent 7890B GC(Agilent Technologies,inc.製)を使用し、トランス体の比率を測定した。具体的には、FID検出強度(面積値)の比からトランス体の比率を算出した。
1,3-BAC:1,3-ビス(アミノメチル)シクロヘキサン(トランス体の比率:25モル%、三菱瓦斯化学株式会社製)
1,4-BAC:1,4-ビス(アミノメチル)シクロヘキサン(トランス体の比率:43モル%、三菱瓦斯化学株式会社製)
1,4-BAC:1,4-ビス(アミノメチル)シクロヘキサン(トランス体の比率:85モル%、三菱瓦斯化学株式会社製)
1,4-BAC:1,4-ビス(アミノメチル)シクロヘキサン(トランス体の比率:100モル%、東京化成工業株式会社製)
1,4-BAC:1,4-ビス(アミノメチル)シクロヘキサン(トランス体の比率:99モル%、以下の製造例1に従って作製した。)
1,4-BAC:1,4-ビス(アミノメチル)シクロヘキサン(トランス体の比率:70モル%、以下の製造例2に従って作製した。)
1,4-BAC:1,4-ビス(アミノメチル)シクロヘキサン(トランス体の比率:60モル%、以下の製造例3に従って作製した。)
IPDA:イソホロンジアミン(東京化成工業株式会社製)
トランス体の比率が43モル%の1,4-BAC(2質量部)と、トランス体の比率が100モル%の1,4-BAC(98質量部)と、を混合することにより作製した。
トランス体の比率が43モル%の1,4-BAC(35質量部)と、トランス体の比率が85モル%の1,4-BAC(65質量部)と、を混合することにより作製した。
トランス体の比率が43モル%の1,4-BAC(58質量部)と、トランス体の比率が85モル%の1,4-BAC(42質量部)と、を混合することにより作製した。
IPDI:イソホロンジイソシアネート(東京化成工業株式会社製)
(ポリオール化合物)
PTMG:ポリテトラメチレングリコール(富士フイルム和光純薬株式会社製)
(その他の化合物)
MEK:メチルエチルケトン(関東化学株式会社製)
(1)イソシアネート基末端プレポリマー1の合成
攪拌翼及び熱電対を備えた500mLの4口セパラブルフラスコにPTMG(OH基当量:500g/eq.)を101g加え、100℃/減圧度100~200hPaの条件で1時間脱水処理を行った。その後、70℃まで空冷した後、冷却管を備え付け、MEK79g、ジブチル錫ジラウレート0.045g加え、窒素雰囲気下、70℃になるまで加熱した。70℃に到達後、滴下漏斗を備え付け、IPDI25gを60分かけて滴下し、その後70℃で3時間攪拌した。その後、MEK210gを加えて固形分濃度を30質量%とし、イソシアネート基末端プレポリマー(プレポリマー1)の溶液として取り出した。
窒素雰囲気下で、攪拌翼、窒素導入管、熱電対、冷却管及び滴下漏斗を備えた500mLの4口セパラブルフラスコに前記プレポリマー1の溶液150gを加え、60℃になるまで加熱した。60℃に到達後、ポリウレタン鎖延長剤である1,4-BAC(トランス体の比率:85モル%)0.51gを1分かけて滴下し、その後60℃で30分撹拌した。得られた溶液を離型剤を塗布したステンレス製の型に流し入れ、23℃/50%RHの条件で1週間養生した後、庫内温度60℃のオーブンにて1時間養生し、厚み1.5mmのポリウレタンウレア樹脂の試験板を得た。
得られたポリウレタンウレア樹脂の試験板について、以下の各評価をおこなった。得られた結果を表に示す。
試験板の引張試験を実施し、引張強度(MPa)及び引張弾性率(MPa)をそれぞれ測定した。具体的には、JIS K 6251:2017に記載の方法に準拠し、試験板から幅10mmのサンプルを切り出し、引張試験機(株式会社東洋精機製作所製、ストログラフEII-L05)にて、引張速度200mm/min、チャック間距離50mmの条件で測定した。なお、引張弾性率は下記式より算出した。
E=(σ2-σ1)/(ε2-ε1)
E:引張弾性率(MPa)
σ1:ひずみε1=0.05において測定された引張応力
σ2:ひずみε2=0.1において測定された引張応力
試験板の硬度(ショアA)を測定した。具体的には、JIS K 6253:2012に記載の方法に準拠し、硬度計(株式会社テクロック製、デュロメータ タイプA GS―719N)を試験板に押し付け、値を読み取った。
ポリウレタン鎖延長剤である1,4-BAC(トランス体の比率:85モル%)を表に示すポリウレタン鎖延長剤に変更した以外は実施例1と同様にしてポリウレタンウレア樹脂の試験板をそれぞれ得た。
得られたポリウレタンウレア樹脂の試験板について、上記の各評価をおこなった。得られた結果を表に示す。
ポリウレタン鎖延長剤である1,4-BAC(トランス体の比率:85モル%)0.51gを表に示すIPDA0.61gに変更した以外は実施例1と同様にしてポリウレタンウレア樹脂の試験板をそれぞれ得た。
得られたポリウレタンウレア樹脂の試験板について、上記の各評価をおこなった。得られた結果を表に示す。
(1)イソシアネート基末端プレポリマー2の合成
攪拌翼及び熱電対を備えた500mLの4口セパラブルフラスコにPTMG(OH基当量:500g/eq.)を90g加え、100℃/減圧度100~200hPaの条件で1時間脱水処理を行った。その後、70℃まで空冷した後、冷却管を備え付け、MEK77g、ジブチル錫ジラウレート0.045g加え、窒素雰囲気下、70℃になるまで加熱した。70℃に到達後、滴下漏斗を備え付け、IPDI25gを30分かけて滴下し、その後70℃で3時間攪拌した。その後、MEK199gを加えて固形分濃度を30質量%とし、イソシアネート基末端プレポリマー(プレポリマー2)の溶液として取り出した。
窒素雰囲気下で、攪拌翼、窒素導入管、熱電対、冷却管及び滴下漏斗を備えた500mLの4口セパラブルフラスコに前記プレポリマー2の溶液156gを加え、60℃になるまで加熱した。60℃に到達後、ポリウレタン鎖延長剤である1,4-BAC(トランス体の比率:85モル%)1.28gを1分かけて滴下し、その後60℃で30分撹拌した。得られた溶液を離型剤を塗布したステンレス製の型に流し入れ、23℃/50%RHの条件で1週間養生した後、庫内温度60℃のオーブンにて1時間養生し、厚み1.5mmのポリウレタンウレアの試験板を得た。
得られたポリウレタンウレア樹脂の試験板について、上記の各評価をおこなった。得られた結果を表に示す。
攪拌翼及び熱電対を備えた500mLの4口セパラブルフラスコにPTMG(OH基当量:500g/eq.)を112.5g加え、100℃/減圧度100~200hPaの条件で1時間脱水処理を行った。その後、70℃まで空冷した後、冷却管を備え付け、MEK77g、ジブチル錫ジラウレート0.045g加え、窒素雰囲気下、70℃になるまで加熱した。70℃に到達後、滴下漏斗を備え付け、IPDI25gを30分かけて滴下し、その後70℃で3時間攪拌した。その後、MEK200gを加えて固形分濃度を30質量%とし、ポリウレタン樹脂の溶液として取り出した。得られた溶液を離型剤を塗布したステンレス製の型に流し入れ、23℃/50%RHの条件で1週間養生した後、庫内温度60℃のオーブンにて1時間養生し、厚み1.5mmのポリウレタン樹脂の試験板を得た。
ポリウレタン鎖延長剤である1,4-BAC(トランス体の比率:85モル%)を表に示すポリウレタン鎖延長剤に変更した以外は実施例2と同様にしてポリウレタンウレア樹脂の試験板をそれぞれ得た。
得られたポリウレタンウレア樹脂の試験板について、上記の各評価をおこなった。得られた結果を表に示す。
ポリウレタン鎖延長剤である1,4-BAC(トランス体の比率:85モル%)1.28gを表に示すIPDA1.53gに変更した以外は実施例2と同様にしてポリウレタンウレア樹脂の試験板をそれぞれ得た。
得られたポリウレタンウレア樹脂の試験板について、上記の各評価をおこなった。得られた結果を表に示す。
(1)イソシアネート基末端プレポリマー3の合成
攪拌翼及び熱電対を備えた500mLの4口セパラブルフラスコにPTMG(OH基当量:500g/eq.)を107g加え、100℃/減圧度100~200hPaの条件で1時間脱水処理を行った。その後、70℃まで空冷した後、冷却管を備え付け、MEK88g、ジブチル錫ジラウレート0.045g加え、窒素雰囲気下、70℃になるまで加熱した。70℃に到達後、滴下漏斗を備え付け、IPDI25gを30分かけて滴下し、その後70℃で3時間攪拌した。その後、MEK222gを加えて固形分濃度を30質量%とし、イソシアネート基末端プレポリマー(プレポリマー3)の溶液として取り出した。
窒素雰囲気下で、攪拌翼、窒素導入管、熱電対、冷却管及び滴下漏斗を備えた500mLの4口セパラブルフラスコに前記プレポリマー3の溶液80gを加え、60℃になるまで加熱した。60℃に到達後、ポリウレタン鎖延長剤である1,4-BAC(トランス体の比率:85モル%)0.14gを1分かけて滴下し、その後60℃で30分撹拌した。得られた溶液を離型剤を塗布したステンレス製の型に流し入れ、23℃/50%RHの条件で1週間養生した後、庫内温度60℃のオーブンにて1時間養生し、厚み1.5mmのポリウレタンウレアの試験板を得た。
得られたポリウレタンウレア樹脂の試験板について、上記の各評価をおこなった。得られた結果を表に示す。
ポリウレタン鎖延長剤である1,4-BAC(トランス体の比率:85モル%)を表に示すポリウレタン鎖延長剤に変更した以外は実施例3と同様にしてポリウレタンウレア樹脂の試験板をそれぞれ得た。
得られたポリウレタンウレア樹脂の試験板について、上記の各評価をおこなった。得られた結果を表に示す。
ポリウレタン鎖延長剤である1,4-BAC(トランス体の比率:85モル%)0.14gを表に示すIPDA 0.17gに変更した以外は実施例3と同様にしてポリウレタンウレア樹脂の試験板をそれぞれ得た。
得られたポリウレタンウレア樹脂の試験板について、上記の各評価をおこなった。得られた結果を表に示す。
Claims (16)
- 前記アミン化合物(X)が1,4-ビス(アミノメチル)シクロヘキサン及びその誘導体から選択される少なくとも一種を含む、請求項1に記載のポリウレタン鎖延長剤。
- 前記アミン化合物(X)におけるトランス体の比率が100モル%以下である、請求項1又は2に記載のポリウレタン鎖延長剤。
- ポリイソシアネート化合物(A)と、ポリオール化合物(B)と、請求項1~3のいずれかに記載のポリウレタン鎖延長剤(C)とを含む、ポリウレタン系樹脂形成用組成物。
- ポリイソシアネート化合物(A)とポリオール化合物(B)とが反応してなるイソシアネート基末端プレポリマーと、請求項1~3のいずれかに記載のポリウレタン鎖延長剤(C)とを含む、ポリウレタン系樹脂形成用組成物。
- 請求項4又は5に記載のポリウレタン系樹脂形成用組成物により形成されたポリウレタン系樹脂。
- ポリイソシアネート化合物(A)、ポリオール化合物(B)、及び請求項1~3のいずれかに記載のポリウレタン鎖延長剤(C)を反応させてなる、ポリウレタン系樹脂。
- 前記ポリオール化合物(B)中の活性水素基数と前記ポリウレタン鎖延長剤(C)中の活性水素基数との合計量に対する前記ポリウレタン鎖延長剤(C)中の活性水素基数の比が0.01以上0.5以下である、請求項6又は7に記載のポリウレタン系樹脂。
- 前記ポリオール化合物(B)中の活性水素基数と前記ポリウレタン鎖延長剤(C)中の活性水素基数との合計量に対する前記ポリイソシアネート化合物(A)中のイソシアネート基数の比が0.5以上1.5以下である、請求項6~8のいずれかに記載のポリウレタン系樹脂。
- JIS K 6251:2017に準拠し、引張速度200mm/min、チャック間距離50mmの条件で測定される、前記ポリウレタン系樹脂の引張強度が1.0MPa以上である、請求項6~9のいずれかに記載のポリウレタン系樹脂。
- JIS K 6251:2017に準拠し、引張速度200mm/min、チャック間距離50mmの条件で測定される、前記ポリウレタン系樹脂の引張弾性率が2.5MPa以上である、請求項6~10のいずれかに記載のポリウレタン系樹脂。
- JIS K 6253:2012に準拠して測定される、前記ポリウレタン系樹脂のショアA硬度が50以上である、請求項6~11のいずれかに記載のポリウレタン系樹脂。
- ポリウレタンウレア樹脂である、請求項6~12のいずれかに記載のポリウレタン系樹脂。
- 請求項6~13のいずれかに記載のポリウレタン系樹脂を含むポリウレタン系樹脂組成物。
- 請求項14に記載のポリウレタン系樹脂組成物を成形してなる成形体。
- 請求項14に記載のポリウレタン系樹脂組成物又は請求項15に記載の成形体を含む物品。
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JP2023509521A JP7468780B2 (ja) | 2021-11-15 | 2022-11-04 | ポリウレタン鎖延長剤、ポリウレタン系樹脂形成用組成物、ポリウレタン系樹脂、ポリウレタン系樹脂組成物、成形体及び物品 |
KR1020247015115A KR20240065332A (ko) | 2021-11-15 | 2022-11-04 | 폴리우레탄 쇄연장제, 폴리우레탄계 수지 형성용 조성물, 폴리우레탄계 수지, 폴리우레탄계 수지 조성물, 성형체 및 물품 |
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Citations (5)
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JPS559699A (en) * | 1978-07-03 | 1980-01-23 | Akzo Nv | Polyurethane consisting of transscyclohexane 1*44diisocyanate and preparing same |
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JP2009091519A (ja) | 2007-10-11 | 2009-04-30 | Mitsui Chemicals Polyurethanes Inc | 粒子状ポリウレタン樹脂組成物、その製造方法および成形品 |
WO2014141475A1 (ja) * | 2013-03-15 | 2014-09-18 | 三井化学株式会社 | 低反発性ポリウレタンフォームおよびその製造方法 |
CN107663670A (zh) * | 2017-08-16 | 2018-02-06 | 东华大学 | 一种聚氨酯弹性纤维及其制备方法 |
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DE3739480A1 (de) * | 1987-11-21 | 1989-06-01 | Huels Chemische Werke Ag | Verfahren zur herstellung von blockierten harnstoffgruppenhaltigen polyisocyanaten sowie die danach hergestellten produkte |
JP6046576B2 (ja) * | 2013-09-02 | 2016-12-21 | 三井化学株式会社 | 蒸着重合材料、ポリウレタンウレア膜、積層体および蒸着重合方法 |
EP3388416B1 (en) | 2015-12-09 | 2020-07-01 | Mitsui Chemicals, Inc. | Method for producing trans-rich-1,4-bis(aminomethyl)cyclohexane |
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JPS559699A (en) * | 1978-07-03 | 1980-01-23 | Akzo Nv | Polyurethane consisting of transscyclohexane 1*44diisocyanate and preparing same |
JP2006504849A (ja) * | 2002-10-31 | 2006-02-09 | ダウ グローバル テクノロジーズ インコーポレイティド | ポリウレタン分散液及びそれから製造した物品 |
JP2011046968A (ja) | 2002-10-31 | 2011-03-10 | Dow Global Technologies Inc | ポリウレタン分散液及びそれから製造した物品 |
JP2009091519A (ja) | 2007-10-11 | 2009-04-30 | Mitsui Chemicals Polyurethanes Inc | 粒子状ポリウレタン樹脂組成物、その製造方法および成形品 |
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CN107663670A (zh) * | 2017-08-16 | 2018-02-06 | 东华大学 | 一种聚氨酯弹性纤维及其制备方法 |
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