TWI842947B - Moisture-curing polyurethane hot-melt resin composition, adhesive and laminate - Google Patents
Moisture-curing polyurethane hot-melt resin composition, adhesive and laminate Download PDFInfo
- Publication number
- TWI842947B TWI842947B TW109131188A TW109131188A TWI842947B TW I842947 B TWI842947 B TW I842947B TW 109131188 A TW109131188 A TW 109131188A TW 109131188 A TW109131188 A TW 109131188A TW I842947 B TWI842947 B TW I842947B
- Authority
- TW
- Taiwan
- Prior art keywords
- moisture
- resin composition
- blank
- melt resin
- curing polyurethane
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- 239000012943 hotmelt Substances 0.000 title claims abstract description 29
- 239000004814 polyurethane Substances 0.000 title claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 29
- 238000013008 moisture curing Methods 0.000 title claims description 34
- 239000000853 adhesive Substances 0.000 title claims description 11
- 230000001070 adhesive effect Effects 0.000 title claims description 11
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 32
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 23
- 150000003077 polyols Chemical class 0.000 claims abstract description 23
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 239000001361 adipic acid Substances 0.000 claims abstract description 13
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 9
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims abstract description 7
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000005871 repellent Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 10
- 229920005749 polyurethane resin Polymers 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 239000004793 Polystyrene Substances 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 230000003075 superhydrophobic effect Effects 0.000 description 4
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 3
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 2
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- -1 polymethylene Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- ZJWDJIVISLUQQZ-UHFFFAOYSA-N 2,4-dimethylpentane-1,5-diol Chemical compound OCC(C)CC(C)CO ZJWDJIVISLUQQZ-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- AJKXDPSHWRTFOZ-UHFFFAOYSA-N 2-ethylhexane-1,6-diol Chemical compound CCC(CO)CCCCO AJKXDPSHWRTFOZ-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- AAAWJUMVTPNRDT-UHFFFAOYSA-N 2-methylpentane-1,5-diol Chemical compound OCC(C)CCCO AAAWJUMVTPNRDT-UHFFFAOYSA-N 0.000 description 1
- XWFCJSXTVSOIDN-UHFFFAOYSA-N 2-propan-2-ylbutane-1,4-diol Chemical compound CC(C)C(CO)CCO XWFCJSXTVSOIDN-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001442234 Cosa Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- BQWORYKVVNTRAW-UHFFFAOYSA-N heptane-3,5-diol Chemical compound CCC(O)CC(O)CC BQWORYKVVNTRAW-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
本發明所欲解決的課題在於提供一種與坯料(尤其是撥水性坯料)的接著性優異的濕氣硬化型聚胺基甲酸酯樹脂組成物。本發明提供一種濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物,其特徵在於含有具有異氰酸酯基的胺基甲酸酯預聚物(i),所述具有異氰酸酯基的胺基甲酸酯預聚物(i)為包含聚酯多元醇(a1)的多元醇(A)與聚異氰酸酯(B)的反應產物,所述聚酯多元醇(a1)為包含己二酸的多元酸與化合物(x)的反應產物,所述化合物(x)數量平均分子量未滿500且具有分支結構並且具有兩個~四個羥基。所述化合物(x)較佳為選自由2-甲基-1,3-丙二醇、3-甲基-1,5-戊二醇及新戊二醇所組成的群組中的一種以上。 The problem to be solved by the present invention is to provide a moisture-hardening polyurethane resin composition having excellent adhesion to a blank (especially a hydrophobic blank). The present invention provides a moisture-hardening polyurethane hot-melt resin composition, which is characterized by containing a urethane prepolymer (i) having an isocyanate group, wherein the urethane prepolymer (i) having an isocyanate group is a reaction product of a polyol (A) including a polyester polyol (a1) and a polyisocyanate (B), wherein the polyester polyol (a1) is a reaction product of a polyacid including adipic acid and a compound (x), wherein the compound (x) has a number average molecular weight of less than 500, has a branched structure, and has two to four hydroxyl groups. The compound (x) is preferably one or more selected from the group consisting of 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol and neopentyl glycol.
Description
本發明是有關於一種濕氣硬化型聚胺基甲酸酯樹脂組成物、接著劑及積層體。 The present invention relates to a moisture-curing polyurethane resin composition, an adhesive and a laminate.
兼具透濕性以及防水性的透濕防水功能性衣料為藉由接著劑將透濕性膜與坯料貼合而成的結構體,作為所述接著劑,就與透濕性膜以及坯料此兩者的密接性良好的方面而言,通常使用胺基甲酸酯系接著劑。另外,所述胺基甲酸酯系接著劑中,根據近來的世界性溶劑排出限制或殘留溶劑限制,作為無溶劑型的濕氣硬化型聚胺基甲酸酯樹脂組成物的使用量逐漸不斷增加(例如,參照專利文獻1)。 The moisture-permeable and waterproof functional clothing having both moisture-permeability and waterproofness is a structure formed by bonding a moisture-permeable film to a base material by an adhesive. As the adhesive, a urethane adhesive is generally used in terms of good adhesion to both the moisture-permeable film and the base material. In addition, among the urethane adhesives, the use of solvent-free moisture-curing polyurethane resin compositions has been gradually increasing due to the recent global solvent emission restrictions or residual solvent restrictions (for example, refer to Patent Document 1).
另一方面,指出所使用的坯料由於高功能化而細纖度化以及撥水度提高,從而與之對應地與接著劑的接著性變差的課題,於現行的濕氣硬化型聚胺基甲酸酯樹脂組成物中,現狀為未發現顯現出尤其是相對於超撥水坯料而言的高密接性者。 On the other hand, it is pointed out that the use of the blank material has become finer and more hydrophobic due to its high functionality, which in turn leads to poor adhesion with the adhesive. In the current moisture-curing polyurethane resin composition, there is currently no one that exhibits high adhesion, especially compared to the super hydrophobic blank material.
[現有技術文獻] [Prior art literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開2017-202608號公報 [Patent document 1] Japanese Patent Publication No. 2017-202608
本發明所欲解決的課題在於提供一種與坯料(尤其是撥水性坯料)的接著性優異的濕氣硬化型聚胺基甲酸酯樹脂組成物。 The problem to be solved by the present invention is to provide a moisture-curing polyurethane resin composition with excellent adhesion to blanks (especially water-repellent blanks).
本發明提供一種濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物,其含有具有異氰酸酯基的胺基甲酸酯預聚物(i),所述具有異氰酸酯基的胺基甲酸酯預聚物(i)為包含聚酯多元醇(a1)的多元醇(A)與聚異氰酸酯(B)的反應產物,所述聚酯多元醇(a1)為包含己二酸的多元酸與化合物(x)的反應產物,所述化合物(x)數量平均分子量未滿500且具有分支結構並且具有兩個~四個羥基。 The present invention provides a moisture-curing polyurethane hot-melt resin composition, which contains an isocyanate-containing urethane prepolymer (i), wherein the isocyanate-containing urethane prepolymer (i) is a reaction product of a polyol (A) containing a polyester polyol (a1) and a polyisocyanate (B), wherein the polyester polyol (a1) is a reaction product of a polyacid containing adipic acid and a compound (x), wherein the compound (x) has a number average molecular weight of less than 500, has a branched structure, and has two to four hydroxyl groups.
另外,本發明提供一種接著劑,其含有所述濕氣硬化型聚胺基甲酸酯樹脂組成物。進而,本發明提供一種積層體,其至少具有坯料(i)及所述濕氣硬化型聚胺基甲酸酯樹脂組成物的硬化物。 In addition, the present invention provides an adhesive containing the moisture-curing polyurethane resin composition. Furthermore, the present invention provides a laminate having at least a blank (i) and a cured product of the moisture-curing polyurethane resin composition.
本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物不包含溶劑,且是環境應對型的材料。另外,本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物相對於各種坯料而言的接著性優異,且相對於撥水性坯料亦具有優異的接著性。 The moisture-curing polyurethane hot-melt resin composition of the present invention does not contain a solvent and is an environmentally resistant material. In addition, the moisture-curing polyurethane hot-melt resin composition of the present invention has excellent adhesion to various blanks and also has excellent adhesion to water-repellent blanks.
本發明中所使用的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物為包含特定的聚酯多元醇的多元醇(A)與聚異氰酸酯(B)的反應產物,且含有具有異氰酸酯基的胺基甲酸酯預聚物(i)。 The moisture-curing polyurethane hot-melt resin composition used in the present invention is a reaction product of a polyol (A) containing a specific polyester polyol and a polyisocyanate (B), and contains a urethane prepolymer (i) having an isocyanate group.
於獲得優異的對坯料的接著性的方面,所述多元醇(A)必須包含聚酯多元醇(a1),所述聚酯多元醇(a1)為包含己二酸的多元酸與數量平均分子量未滿500且具有分支結構並且具有兩個~四個羥基的化合物(x)的反應產物。 In order to obtain excellent adhesion to the blank, the polyol (A) must contain a polyester polyol (a1), which is a reaction product of a polybasic acid containing adipic acid and a compound (x) having a number average molecular weight of less than 500, a branched structure and two to four hydroxyl groups.
作為所述多元酸,可單獨使用己二酸,但亦可併用其他多元酸。作為所述其他多元酸,例如可使用:草酸、丙二酸、琥珀酸、己二酸、癸二酸、壬二酸、十二烷二羧酸、戊二酸、庚二酸、辛二酸、二聚酸、十一烷二羧酸、六氫對苯二甲酸、鄰苯二甲酸、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸等。該些多元酸既可單獨使用亦可併用兩種以上。作為所述多元酸中的己二酸的使用率,較佳為50質量%以上,更佳為70質量%以上,進而佳為80質量%以上。 As the polyacid, adipic acid can be used alone, but other polyacids can also be used in combination. As the other polyacids, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, undecanedicarboxylic acid, hexahydroterephthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc. can be used. These polyacids can be used alone or in combination of two or more. The usage rate of adipic acid in the polyacid is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.
作為所述數量平均分子量未滿500且具有分支結構並且具有兩個~四個羥基的化合物(x),例如可使用:2-甲基-1,3-丙二醇、2-甲基-1,5-戊二醇、3-甲基-1,5-戊二醇、2,2,4-三甲基-1,3-戊二醇、1,2-丁二醇、1,3-丁二醇、2-丁基-2-乙基-1,3-丙二醇、1,2-丙二醇、2-甲基-1,3-丙二醇、新戊二醇、2-異丙基-1,4-丁二醇、2,4- 二甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、2-乙基-1,3-己二醇、2-乙基-1,6-己二醇、3,5-庚二醇、2-甲基-1,8-辛二醇、三羥甲基丙烷等。該些化合物既可單獨使用亦可併用兩種以上。該些中,就可獲得更優異的對坯料的接著性的方面而言,較佳為使用選自由2-甲基-1,3-丙二醇、3-甲基-1,5-戊二醇及新戊二醇所組成的群組中的一種以上的化合物。再者,所述化合物(x)的數量平均分子量表示根據化學結構式算出的值。 As the compound (x) having a number average molecular weight of less than 500, a branched structure and two to four hydroxyl groups, for example, 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-butanediol, 1,3-butanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, 2-methyl-1,8-octanediol, trihydroxymethylpropane, etc. These compounds may be used alone or in combination of two or more. Among these, in terms of obtaining better adhesion to the blank, it is preferred to use one or more compounds selected from the group consisting of 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol and neopentyl glycol. Furthermore, the number average molecular weight of the compound (x) refers to the value calculated based on the chemical structure formula.
視需要,亦可於所述化合物(x)中併用其他具有兩個以上羥基的化合物。作為所述其他具有兩個以上羥基的化合物,例如可使用:乙二醇、二乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、戊二醇、2,4-二乙基-1,5-戊二醇、3-甲基-1,5-戊二醇、己二醇、新戊二醇、六亞甲基二醇、甘油、三羥甲基丙烷、雙酚A或雙酚F及其環氧烷加成物等。該些化合物既可單獨使用亦可併用兩種以上。作為所述化合物(x)的使用率,於所述化合物(x)及所述其他具有兩個以上羥基的化合物的合計質量中,較佳為50質量%以上,更佳為70質量%以上,進而佳為80質量%以上。 If necessary, other compounds having two or more hydroxyl groups may be used in combination with the compound (x). As the other compounds having two or more hydroxyl groups, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopentyl glycol, hexamethylene glycol, glycerol, trihydroxymethylpropane, bisphenol A or bisphenol F and their oxirane adducts, etc. These compounds may be used alone or in combination of two or more. The usage rate of the compound (x) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more in the total mass of the compound (x) and the other compounds having two or more hydroxyl groups.
作為所述聚酯多元醇(a1)的數量平均分子量,就可獲得更優異的對坯料的接著性及機械強度的方面而言,較佳為500~100,000的範圍,更佳為700~10,000的範圍。再者,所述聚酯多元醇(a1)的數量平均分子量表示藉由凝膠滲透層析(gel permeation chromatography,GPC)法測定的值。 The number average molecular weight of the polyester polyol (a1) is preferably in the range of 500 to 100,000, and more preferably in the range of 700 to 10,000, in order to obtain better adhesion to the blank and mechanical strength. The number average molecular weight of the polyester polyol (a1) refers to a value measured by gel permeation chromatography (GPC).
所述多元醇(A)必須含有所述聚酯多元醇(a1),但視 需要亦可含有其他多元醇。作為所述其他多元醇,例如可使用所述聚酯多元醇(a1)以外的其他聚酯多元醇(a2)、聚碳酸酯多元醇、聚醚多元醇、聚丁二烯多元醇、聚丙烯酸多元醇等。該些多元醇既可單獨使用亦可併用兩種以上。該些中,就可獲得更優異的對坯料的接著性的方面而言,較佳為使用所述其他聚酯多元醇(a2)。作為所述多元醇(A)中的所述聚酯多元醇(a1)的使用率,就可獲得更優異的對坯料的接著性的方面而言,於多元醇(A)中,較佳為30質量%以上,更佳為40質量%以上,進而佳為40質量%~60質量%的範圍。 The polyol (A) must contain the polyester polyol (a1), but may contain other polyols as needed. As the other polyols, for example, other polyester polyols (a2), polycarbonate polyols, polyether polyols, polybutadiene polyols, polyacrylic polyols, etc. other than the polyester polyol (a1) can be used. These polyols can be used alone or in combination of two or more. Among them, in terms of obtaining better adhesion to the blank, it is preferred to use the other polyester polyol (a2). As for the usage rate of the polyester polyol (a1) in the polyol (A), in terms of obtaining better adhesion to the blank, it is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably in the range of 40% by mass to 60% by mass in the polyol (A).
作為所述其他聚酯多元醇(a2),例如可使用所述化合物(x)以外的具有兩個以上羥基的化合物與多元酸的反應產物。 As the other polyester polyol (a2), for example, a reaction product of a compound having two or more hydroxyl groups other than the compound (x) and a polybasic acid can be used.
作為所述化合物(x)以外的具有兩個以上羥基的化合物,例如可使用:乙二醇、二乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、戊二醇、2,4-二乙基-1,5-戊二醇、3-甲基-1,5-戊二醇、己二醇、新戊二醇、六亞甲基二醇、甘油、三羥甲基丙烷、雙酚A或雙酚F及其環氧烷加成物等。該些化合物既可單獨使用亦可併用兩種以上。 As compounds having two or more hydroxyl groups other than the above compound (x), for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopentyl glycol, hexamethylene glycol, glycerol, trihydroxymethylpropane, bisphenol A or bisphenol F and their alkylene oxide adducts can be used. These compounds can be used alone or in combination of two or more.
作為所述多元酸,例如可使用:草酸、丙二酸、琥珀酸、己二酸、癸二酸、壬二酸、十二烷二羧酸、戊二酸、庚二酸、辛二酸、二聚酸、十一烷二羧酸、六氫對苯二甲酸、鄰苯二甲酸、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸等。該些多元酸既可單獨使用亦可併用兩種以上。該些中,就可獲得更優異的對坯料的 接著性的方面而言,較佳為使用鄰苯二甲酸(選自由鄰苯二甲酸、鄰苯二甲酸酐、間苯二甲酸及對苯二甲酸所組成的群組中的一種以上的化合物)。 As the polyacid, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, undecanedicarboxylic acid, hexahydroterephthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc. can be used. These polyacids can be used alone or in combination of two or more. Among them, phthalic acid (one or more compounds selected from the group consisting of phthalic acid, phthalic anhydride, isophthalic acid and terephthalic acid) is preferably used in terms of obtaining better adhesion to the blank.
作為所述聚酯多元醇(a2)的數量平均分子量,就可獲得更優異的對坯料的接著性及機械強度的方面而言,較佳為500~100,000的範圍,更佳為700~10,000的範圍。再者,所述聚酯多元醇(a2)的數量平均分子量表示藉由凝膠滲透層析(GPC)法測定的值。 The number average molecular weight of the polyester polyol (a2) is preferably in the range of 500 to 100,000, and more preferably in the range of 700 to 10,000, in order to obtain better adhesion to the blank and mechanical strength. The number average molecular weight of the polyester polyol (a2) is a value measured by gel permeation chromatography (GPC).
作為使用所述聚酯多元醇(a2)時的使用率,就可獲得更優異的對坯料的接著性的方面而言,於所述多元醇(A)中,較佳為30質量%以上,更佳為40質量%以上,進而佳為40質量%~60質量%的範圍。 The usage rate of the polyester polyol (a2) is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably in the range of 40% by mass to 60% by mass in the polyol (A) in order to obtain better adhesion to the blank.
作為所述聚異氰酸酯(B),可使用:聚亞甲基聚苯基聚異氰酸酯、二苯基甲烷二異氰酸酯、碳二醯亞胺改質二苯基甲烷二異氰酸酯、二甲苯二異氰酸酯、苯二異氰酸酯、甲苯二異氰酸酯、萘二異氰酸酯等芳香族聚異氰酸酯;六亞甲基二異氰酸酯、環己烷二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷二異氰酸酯、四甲基二甲苯二異氰酸酯等脂肪族或脂環族聚異氰酸酯等。該些聚異氰酸酯既可單獨使用亦可併用兩種以上。該些中,就可獲得更優異的反應性及對坯料的接著性的方面而言,較佳為使用芳香族聚異氰酸酯,更佳為二苯基甲烷二異氰酸酯。 As the polyisocyanate (B), aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, xylene diisocyanate, phenyl diisocyanate, toluene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylene diisocyanate can be used. These polyisocyanates can be used alone or in combination of two or more. Among these, aromatic polyisocyanate is preferred, and diphenylmethane diisocyanate is more preferred, in terms of obtaining better reactivity and adhesion to the blank.
作為所述聚異氰酸酯(B)的使用量,於構成胺基甲酸 酯預聚物(i)的原料的合計質量中,較佳為5質量%~40質量%的範圍,更佳為10質量%~30質量%的範圍。 The amount of the polyisocyanate (B) used is preferably in the range of 5% to 40% by mass, and more preferably in the range of 10% to 30% by mass, based on the total mass of the raw materials constituting the urethane prepolymer (i).
所述胺基甲酸酯預聚物(i)是使所述多元醇(A)與所述聚異氰酸酯(B)反應而獲得者,且具有可與空氣中或塗佈有濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的基材中所存在的水分反應而形成交聯結構的異氰酸酯基。 The urethane prepolymer (i) is obtained by reacting the polyol (A) with the polyisocyanate (B), and has an isocyanate group that can react with moisture in the air or in a substrate coated with a moisture-curing polyurethane hot-melt resin composition to form a cross-linked structure.
作為所述胺基甲酸酯預聚物(i)的製造方法,例如可藉由如下方式來製造,於放入了所述多元醇(A)的反應容器中放入所述聚異氰酸酯(B),於所述聚異氰酸酯(B)所具有的異氰酸酯基相對於所述多元醇(A)所具有的羥基而過剩的條件下進行反應。 As a method for producing the urethane prepolymer (i), for example, the urethane prepolymer (i) can be produced by placing the polyisocyanate (B) in a reaction container containing the polyol (A) and reacting the polyisocyanate (B) under the condition that the isocyanate group of the polyisocyanate (B) is in excess relative to the hydroxyl group of the polyol (A).
作為製造所述胺基甲酸酯預聚物(i)時所述聚異氰酸酯(B)所具有的異氰酸酯基與所述多元醇(A)所具有的羥基的當量比(異氰酸酯基/羥基),就可獲得更優異的對坯料的接著性的方面而言,較佳為1.1~5的範圍,更佳為1.5~3的範圍。 When producing the urethane prepolymer (i), the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (A) is preferably in the range of 1.1 to 5, and more preferably in the range of 1.5 to 3, in order to obtain better adhesion to the blank.
作為藉由以上方法而獲得的胺基甲酸酯預聚物(i)的異氰酸酯基含有率(以下,簡稱為「NCO%」),就可獲得更優異的接著性的方面而言,較佳為1.7~5的範圍,更佳為1.8~3的範圍。再者,所述胺基甲酸酯預聚物(i)的NCO%表示依據日本工業標準(Japanese Industrial Standards,JIS)K1603-1:2007並藉由電位差滴定法測定的值。 The isocyanate group content (hereinafter referred to as "NCO%") of the urethane prepolymer (i) obtained by the above method is preferably in the range of 1.7 to 5, and more preferably in the range of 1.8 to 3, in order to obtain better adhesion. The NCO% of the urethane prepolymer (i) is a value measured by potentiometric titration in accordance with Japanese Industrial Standards (JIS) K1603-1: 2007.
本發明中所使用的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物含有所述胺基甲酸酯預聚物(i)作為必需成分,但視需要 亦可使用其他添加劑。 The moisture-curing polyurethane hot-melt resin composition used in the present invention contains the urethane prepolymer (i) as an essential component, but other additives may also be used as needed.
作為所述其他添加劑,例如可使用:耐光穩定劑、硬化觸媒、黏著賦予劑、塑化劑、穩定劑、填充材料、染料、顏料、螢光增白劑、矽烷偶合劑、蠟(wax)、熱塑性樹脂等。該些添加劑既可單獨使用亦可併用兩種以上。 As the other additives, for example, light-resistant stabilizers, hardening catalysts, adhesives, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent brighteners, silane coupling agents, waxes, thermoplastic resins, etc. can be used. These additives can be used alone or in combination of two or more.
以上,本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物不包含溶劑,且是環境應對型的材料。另外,本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物相對於各種坯料而言的接著性優異,且相對於撥水性坯料亦具有優異的接著性。 As mentioned above, the moisture-curing polyurethane hot-melt resin composition of the present invention does not contain a solvent and is an environmentally resistant material. In addition, the moisture-curing polyurethane hot-melt resin composition of the present invention has excellent adhesion to various blanks and also has excellent adhesion to water-repellent blanks.
接下來,對本發明的積層體進行說明。 Next, the laminate of the present invention will be described.
本發明的積層體至少具有坯料(i)及所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的硬化物。 The laminate of the present invention comprises at least a blank (i) and a cured product of the moisture-curing polyurethane hot-melt resin composition.
作為所述坯料(i),例如可使用:聚酯纖維、聚乙烯纖維、尼龍纖維、丙烯酸纖維、聚胺基甲酸酯纖維、乙酸酯纖維、嫘縈纖維、聚乳酸纖維、棉、麻、絹、羊毛、玻璃纖維(glass fibre)、碳纖維、由該些的混紡纖維等所形成的不織布、織布、編織物等纖維基材;使聚胺基甲酸酯樹脂等樹脂含浸於所述不織布中而成者;於所述不織布進而設置多孔質層者;樹脂基材等。 As the blank (i), for example, the following fiber substrates can be used: polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, linen, silk, wool, glass fiber, carbon fiber, non-woven fabrics, woven fabrics, knitted fabrics, etc. formed by blended fibers thereof; non-woven fabrics impregnated with resins such as polyurethane resin; non-woven fabrics further provided with a porous layer; resin substrates, etc.
另外,於本發明中,作為所述坯料(i),即使為對以上所述坯料實施了撥水處理而成者(以下,簡稱為「撥水性坯料」)亦顯示出優異的接著性。再者,於本發明中,所述撥水性坯料的「撥水性」表示藉由下述計算而獲得的表面自由能為50mJ/m2以 下。 In the present invention, the blank (i) exhibits excellent adhesion even if the blank is subjected to a water-repellent treatment (hereinafter referred to as a "water-repellent blank"). Furthermore, in the present invention, the "water-repellent" of the water-repellent blank means that the surface free energy obtained by the following calculation is 50 mJ/ m2 or less.
使用接觸角計(協和界面科學公司製造的「DM500」)測定所述坯料(i)上的測定用液(水及二碘甲烷)的接觸角。基於所述結果,使用下述式(1)算出坯料(i)的表面自由能。 The contact angle of the measuring liquid (water and diiodomethane) on the blank (i) was measured using a contact angle meter ("DM500" manufactured by Kyowa Interface Science Co., Ltd.). Based on the results, the surface free energy of the blank (i) was calculated using the following formula (1).
(1+cosA).γL/2=(γsd.γLd)1/2+(γsp.γLp)1/2 (1+cosA). γL/2=(γsd.γLd)1/2+(γsp.γLp)1/2
A:坯料(i)上的測定用液的接觸角 A: Contact angle of the measuring liquid on the blank (i)
γL:測定用液的表面張力 γL: Surface tension of the measuring liquid
γLd:測定用液的表面自由能的分散力成分 γLd: Dispersion force component of the surface free energy of the measurement liquid
γLp:測定用液的表面自由能的極性力成分 γLp: Polar force component of the surface free energy of the measurement liquid
γsd:坯料(i)的表面自由能的分散力成分 γsd: Dispersion force component of the surface free energy of the blank (i)
γsp:坯料(i)的表面自由能的極性力成分 γsp: Polar force component of the surface free energy of the blank (i)
作為塗敷所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的方法,例如可列舉使用輥式塗佈機、刮刀式塗佈機、噴塗機、凹版輥式塗佈機、缺角輪塗佈機、T字模塗佈機、敷料器、分配器等的方法。 As a method for applying the moisture-curing polyurethane hot melt resin composition, for example, there can be cited methods using a roller coater, a scraper coater, a spray coater, a gravure roller coater, a notched wheel coater, a T-die coater, an applicator, a dispenser, etc.
塗敷所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物後,藉由公知的方法進行乾燥、固化。 After applying the moisture-curing polyurethane hot-melt resin composition, it is dried and cured by a known method.
作為所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的硬化物的厚度,例如為5μm~300μm的範圍。 The thickness of the cured product of the moisture-curing polyurethane hot-melt resin composition is, for example, in the range of 5μm to 300μm.
再者,於將本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂 組成物用作透濕防水功能性衣料的接著劑的情況下,所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物較佳為藉由凹版輥式塗佈機、分配器進行間歇塗佈,使坯料(i)與公知的透濕膜貼合。作為所述情況下的所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的硬化物的厚度,例如為5μm~50μm的範圍。 Furthermore, when the moisture-curing polyurethane hot-melt resin composition of the present invention is used as an adhesive for moisture-permeable and waterproof functional clothing, the moisture-curing polyurethane hot-melt resin composition is preferably intermittently coated by a gravure roller coating machine or a dispenser to bond the blank (i) to a known moisture-permeable film. The thickness of the cured product of the moisture-curing polyurethane hot-melt resin composition in the above case is, for example, in the range of 5μm to 50μm.
[實施例] [Implementation example]
以下,使用實施例對本發明進行更詳細的說明。 The present invention is described in more detail below using an embodiment.
[實施例1] [Implementation Example 1]
於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中,裝入聚酯多元醇(使己二酸與2-甲基-1,3-丙二醇反應而得者,數量平均分子量:2,000,以下簡稱為「AA/2MPD」)40質量份、聚酯多元醇(使鄰苯二甲酸酐、二乙二醇與新戊二醇反應而得者,數量平均分子量:1,000,以下簡稱為「PA系PEs(1)」)40質量份,於110℃下減壓乾燥,脫水至水分量成為0.05質量%以下。接著,冷卻至60℃後,加入二苯基甲烷二異氰酸酯(以下,簡稱為「MDI(diphenyl methane diisocyanate)」)27質量份,升溫至110℃,反應2小時直至異氰酸酯基含量達到一定,藉此獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。 In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux cooler, 40 parts by mass of a polyester polyol (obtained by reacting adipic acid with 2-methyl-1,3-propanediol, number average molecular weight: 2,000, hereinafter referred to as "AA/2MPD") and 40 parts by mass of a polyester polyol (obtained by reacting phthalic anhydride, diethylene glycol and neopentyl glycol, number average molecular weight: 1,000, hereinafter referred to as "PA-based PEs (1)") were placed and dried under reduced pressure at 110°C to dehydrate until the moisture content became 0.05% by mass or less. Then, after cooling to 60°C, 27 parts by weight of diphenylmethane diisocyanate (hereinafter referred to as "MDI") was added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content reached a certain level, thereby obtaining a moisture-curing polyurethane hot-melt resin composition.
[實施例2] [Example 2]
代替所述AA/2MPD,使用聚酯多元醇(使己二酸與3-甲基-1,5-戊二醇反應而得者,數量平均分子量:2,000,以下簡稱為「AA/3MPD」),除此以外,與實施例1同樣地獲得濕氣硬化型聚 胺基甲酸酯熱熔樹脂組成物。 A moisture-curing polyurethane hot-melt resin composition was obtained in the same manner as in Example 1 except that polyester polyol (obtained by reacting adipic acid with 3-methyl-1,5-pentanediol, number average molecular weight: 2,000, hereinafter referred to as "AA/3MPD") was used instead of the AA/2MPD.
[實施例3] [Implementation Example 3]
代替所述AA/2MPD,使用聚酯多元醇(使己二酸與新戊二醇反應而得者,數量平均分子量:2,000,以下簡稱為「AA/NPG」),除此以外,與實施例1同樣地獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。 Instead of the AA/2MPD, a polyester polyol (obtained by reacting adipic acid with neopentyl glycol, number average molecular weight: 2,000, hereinafter referred to as "AA/NPG") was used. A moisture-curing polyurethane hot-melt resin composition was obtained in the same manner as in Example 1.
[實施例4] [Implementation Example 4]
代替所述PA系PEs(1),使用聚酯多元醇(使鄰苯二甲酸與乙二醇反應而得者,數量平均分子量:1,000,以下簡稱為「PA系PEs(2)」),除此以外,與實施例1同樣地獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。 A moisture-curing polyurethane hot-melt resin composition was obtained in the same manner as in Example 1 except that polyester polyol (obtained by reacting phthalic acid and ethylene glycol, number average molecular weight: 1,000, hereinafter referred to as "PA-based PEs (2)") was used instead of the PA-based PEs (1).
[比較例1] [Comparison Example 1]
於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中,裝入聚酯多元醇(己二酸、鄰苯二甲酸、對苯二甲酸與乙二醇的反應產物,數量平均分子量:2,000,以下簡稱為「AA/PA/EG」)40質量份、聚酯多元醇(鄰苯二甲酸與1,6-己二醇的反應產物,數量平均分子量:2,000,以下為「PA/HG」)40質量份,於110℃下減壓乾燥,脫水至水分量成為0.05質量%以下。接著,冷卻至60℃後,加入MDI 21質量份,升溫至110℃,反應2小時直至異氰酸酯基含量達到一定,藉此獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。 In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux cooler, 40 parts by mass of polyester polyol (a reaction product of adipic acid, phthalic acid, terephthalic acid and ethylene glycol, number average molecular weight: 2,000, hereinafter referred to as "AA/PA/EG") and 40 parts by mass of polyester polyol (a reaction product of phthalic acid and 1,6-hexanediol, number average molecular weight: 2,000, hereinafter referred to as "PA/HG") were placed and dried under reduced pressure at 110°C to dehydrate until the moisture content became less than 0.05% by mass. Then, after cooling to 60°C, 21 parts by weight of MDI was added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content reached a certain level, thereby obtaining a moisture-curing polyurethane hot-melt resin composition.
[數量平均分子量的測定方法] [Method for determining number average molecular weight]
實施例及比較例中所使用的多元醇的數量平均分子量表示藉由凝膠滲透層析(GPC)法並於下述條件下測定的值。 The number average molecular weight of the polyol used in the examples and comparative examples represents the value measured by gel permeation chromatography (GPC) under the following conditions.
測定裝置:高速GPC裝置(東曹(Tosoh)股份有限公司製造的「HLC-8220GPC」) Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Co., Ltd.)
管柱:將東曹股份有限公司製造的下述管柱串聯連接來使用。 Column: Use the following columns manufactured by Tosoh Corporation by connecting them in series.
「TSKgel G5000」(7.8mmI.D.×30cm)×1根 "TSKgel G5000" (7.8mmI.D.×30cm)×1
「TSKgel G4000」(7.8mmI.D.×30cm)×1根 "TSKgel G4000" (7.8mm I.D. × 30cm) × 1 piece
「TSKgel G3000」(7.8mmI.D.×30cm)×1根 "TSKgel G3000" (7.8mmI.D.×30cm)×1
「TSKgel G2000」(7.8mmI.D.×30cm)×1根 "TSKgel G2000" (7.8mmI.D.×30cm)×1
檢測器:RI(示差折射計) Detector: RI (differential refractometer)
管柱溫度:40℃ Column temperature: 40℃
溶離液:四氫呋喃(tetrahydrofuran,THF) Solvent: Tetrahydrofuran (THF)
流速:1.0mL/分鐘 Flow rate: 1.0mL/min
注入量:100μL(試樣濃度為0.4質量%的四氫呋喃溶液) Injection volume: 100μL (sample concentration is 0.4 mass% tetrahydrofuran solution)
標準試樣:使用下述標準聚苯乙烯來製作標準曲線。 Standard sample: Use the following standard polystyrene to prepare the standard curve.
(標準聚苯乙烯) (Standard Polystyrene)
東曹股份有限公司製造的「TSKgel標準聚苯乙烯A-500」 "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯A-1000」 "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯A-2500」 "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯A-5000」 "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-1」 "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-2」 "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-4」 "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-10」 "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-20」 "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-40」 "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-80」 "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-128」 "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-288」 "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-550」 "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation
[與坯料的接著性的評價方法] [Evaluation method of adhesion to blank]
將實施例及比較例中所獲得的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物於100℃下熔融後,使用凹版輥式塗佈機(40L/英吋(L/inch)、深度(depth)為130、附著量:10g/m2)塗敷於透濕膜(加平股份有限公司製造的「維特科思(VENTEX)」)上,分別與以下3種坯料貼合,於溫度23℃、濕度50%的環境下放置2天而獲得加工布。 The moisture-curing polyurethane hot-melt resin composition obtained in the examples and comparative examples was melted at 100°C and coated on a moisture-permeable film (VENTEX manufactured by Gapyeong Co., Ltd.) using a gravure roll coater (40 L/inch, depth 130, adhesion amount: 10 g/m 2 ), and then laminated with the following three types of blanks, and left in an environment of temperature 23°C and humidity 50% for 2 days to obtain processed fabrics.
坯料(1):非撥水坯料(表面自由能:超過50mJ/m2) Blank (1): Non-hydrophobic blank (surface free energy: more than 50mJ/m 2 )
坯料(2):撥水坯料(表面自由能:10mJ/m2~50mJ/m2的範圍) Blank (2): Water-repellent blank (surface free energy: range of 10mJ/m 2 ~50mJ/m 2 )
坯料(3):超撥水坯料(表面自由能:低於10mJ/m2) Blank (3): Superhydrophobic blank (surface free energy: less than 10mJ/m 2 )
將所獲得的加工布切成1英吋(inch)的寬度,使用島津製作所股份有限公司製造的「奧特古拉夫(Autograph)AG-1」,測定透濕膜與坯料的剝離強度(N/inch)。 The processed fabric was cut into 1 inch width and the peel strength (N/inch) between the moisture permeable film and the blank was measured using the "Autograph AG-1" manufactured by Shimadzu Corporation.
可知本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物具有與坯料的接著性。尤其可知相對於撥水坯料或超撥水坯料亦具有優異的接著性。 It can be seen that the moisture-curing polyurethane hot-melt resin composition of the present invention has good adhesion to the blank. In particular, it can be seen that it also has excellent adhesion to the hydrophobic blank or super hydrophobic blank.
另一方面,比較例1為代替聚酯多元醇(a1)而使用了作為己二酸與直鏈狀的二醇的反應產物的聚酯多元醇的形態,尤其是相對於超撥水坯料而言的接著性不良。 On the other hand, in Comparative Example 1, a polyester polyol which is a reaction product of adipic acid and a linear diol is used instead of polyester polyol (a1), and the adhesion to the super hydrophobic base material is poor.
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019171609 | 2019-09-20 | ||
JP2019-171609 | 2019-09-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW202116963A TW202116963A (en) | 2021-05-01 |
TWI842947B true TWI842947B (en) | 2024-05-21 |
Family
ID=
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201936686A (en) | 2018-02-21 | 2019-09-16 | 日商迪愛生股份有限公司 | Moisture-curable polyurethane hot melt resin composition |
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201936686A (en) | 2018-02-21 | 2019-09-16 | 日商迪愛生股份有限公司 | Moisture-curable polyurethane hot melt resin composition |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI689568B (en) | Moisture-curable urethane hot-melt resin composition and laminate | |
KR102220758B1 (en) | Moisture-curable polyurethane hot melt resin composition, and laminate | |
CN111741992A (en) | Moisture-curable polyurethane hot-melt resin composition | |
KR20220029712A (en) | Moisture-curable polyurethane resin composition, adhesive, and laminate | |
CN114222772B (en) | Moisture-curable polyurethane hot-melt resin composition, adhesive, and laminate | |
TWI842947B (en) | Moisture-curing polyurethane hot-melt resin composition, adhesive and laminate | |
JP6631863B1 (en) | Moisture-curable polyurethane hot melt resin composition and cured product thereof | |
KR20210151915A (en) | Moisture-curable polyurethane resin composition, adhesive, and laminate | |
TW202348669A (en) | Moisture-curable urethane hot melt resin composition, multilayer body and synthetic artificial leather | |
WO2020116305A1 (en) | Synthetic leather | |
JP7400257B2 (en) | Moisture-curable polyurethane hot melt resin composition and cured product thereof | |
JP6836735B2 (en) | Synthetic leather | |
WO2023097571A1 (en) | Moisture-curable polyurethane hot-melt resin composition, adhesive, and laminate | |
TW202323401A (en) | Moisture-curable polyurethane resin composition, adhesive, and laminate excellent in adhesion to fabrics (especially water-repellent fabrics) and washing resistance | |
JP7517622B2 (en) | Method for manufacturing polyurethane foam sheet and method for manufacturing synthetic leather | |
WO2024095530A1 (en) | Moisture-curable polyurethane hot melt resin composition, adhesive, and synthetic leather | |
TW202424030A (en) | Moisture-curing polyurethane resin composition, adhesive and laminate | |
KR20210062084A (en) | Synthetic Leather | |
CN116333662A (en) | Moisture-curable polyurethane hot-melt resin composition, adhesive, and synthetic leather |