JP7455131B2 - モノマーイソシアネートの放出量が少ないホットメルト接着剤の製造方法 - Google Patents
モノマーイソシアネートの放出量が少ないホットメルト接着剤の製造方法 Download PDFInfo
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- 239000004831 Hot glue Substances 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000012948 isocyanate Substances 0.000 title description 25
- 150000002513 isocyanates Chemical class 0.000 title description 24
- 239000000178 monomer Substances 0.000 title description 16
- 238000000034 method Methods 0.000 claims description 41
- 229920005862 polyol Polymers 0.000 claims description 24
- 150000003077 polyols Chemical class 0.000 claims description 24
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 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 claims description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical group CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 235000013772 propylene glycol Nutrition 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 5
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 229960002479 isosorbide Drugs 0.000 claims description 3
- -1 methylene diphenyl Chemical group 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000012943 hotmelt Substances 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 239000012467 final product Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004823 Reactive adhesive Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 208000005333 pulmonary edema Diseases 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
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- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- 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
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
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- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- C09J2475/00—Presence of polyurethane
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
(i)2,4'-トルエンジイソシアネート(2,4'-TDI)をポリオールと反応させ、その後のステップにおいて、
(ii)ステップ(i)の反応混合物にメチレンジフェニルジイソシアネート(MDI)を加え、
ここで、ホットメルト接着剤の塗布温度は、80~160℃、好ましくは90~140℃である。
プレポリマー:
ポリプロピレングリコール(487.5g、ヒドロキシル価237mgKOH/g)とアジピン酸、イソフタル酸/PPG/ジエチレングリコールのポリエステル(56.2g、ヒドロキシル価137mgKOH/g)を2,4'-TDI(269gと混合して、プレポリマーを得た。約80℃に加熱すると、NCO値は6.8%となった。続いて、4,4'-MDI(57.5g)を加え、80℃で撹拌を続けた。NCO終了値は約6.41%であった。
NCO:OH (ステップ(i)) = 1.38:1
NCO:OH (ステップ(ii)) = 2.2:1
450gのプレポリマーを80℃に加熱し、7.12gの1,3-ブタンジオールを添加した。
450gのプレポリマーを80℃に加熱し、8.67gの1,2-プロパンジオールを添加した。
TDIおよびMDIの必要量の計算は、上記のプレポリマーの調製と同様に行った。
本発明の好ましい態様は以下を包含する。
〔1〕ポリウレタンプレポリマーを含むホットメルト接着剤の製造方法であって、ここで、ポリウレタンプレポリマーは鎖延長剤と反応しており、ポリウレタンプレポリマーは以下の反応によって得られ、第1ステップにおいて
(i)2,4'-トルエンジイソシアネート(2,4'-TDI)をポリオールと反応させ、その後のステップにおいて
(ii)ステップ(i)の反応混合物にメチレンジフェニルジソシアネート(MDI)を添加する;
ここで、ホットメルト接着剤は、80~160℃、好ましくは90~140℃の塗布温度を有し、鎖延長剤は、1,3-ブタンジオール、1,2-プロパンジオール、2-エチル-1-ヘキサノール、ジエチレングリコール、トリプロピレングリコール、イソソルビド、レゾルシノール、1,4-ジメチロールシクロヘキサン、およびこれらの混合物からなる群から選択される、方法。
〔2〕前記方法のステップ(i)および(ii)は、触媒、好ましくは金属有機化合物およびアミン含有有機化合物からなる群から選択される触媒の存在下で実施されることを特徴とする、〔1〕に記載の方法。
〔3〕ステップ(i)で使用されるポリオールは、GPCにより測定される数平均分子量Mnが100~10000g/mol、好ましくは500~5000g/molであることを特徴とする、前記項のいずれかに記載の方法。
〔4〕ポリオールとして、ポリエーテルポリオールおよび/またはポリエステルポリオールを使用することを特徴とする、前記項のいずれかに記載の方法。
〔5〕ポリオールは、50~1500mgKOH/g、好ましくは250~1500mgKOH/g、最も好ましくは500~1500mgKOH/gのヒドロキシル価(OH価)を有することを特徴とする、前記項のいずれかに記載の方法。
〔6〕ステップ(i)および/またはステップ(ii)におけるイソシアネート基とヒドロキシル基の比率(NCO:OH)は1.1:1~4:1、好ましくは1.5:1~3:1であることを特徴とする、前記項のいずれかに記載の方法。
〔7〕ホットメルト接着剤中のモノマートルエンジイソシアネートの含有量は、ホットメルト接着剤の総重量を基準にして0.02重量%未満であることを特徴とする、前記項のいずれかに記載の方法。
〔8〕ホットメルト接着剤中のモノマーメチレンジフェニルジイソシアネートの含有量は、ホットメルト接着剤の総重量を基準にして0.1重量%未満であることを特徴とする、前記項のいずれかに記載の方法。
〔9〕環球法により測定されるホットメルト接着剤の軟化点は40℃超であることを特徴とする、前記項のいずれかに記載の方法。
〔10〕ホットメルト接着剤中のモノマートルエンジイソシアネートの含有量は、ホットメルト接着剤の総重量を基準にして0.02重量%未満であることを特徴とする、〔1〕~〔10〕のいずれかに記載の方法で得られるホットメルト接着剤。
〔11〕ホットメルト接着剤中のモノマーメチレンジフェニルジイソシアネートの含有量は、ホットメルト接着剤の総重量を基準にして0.1重量%未満であることを特徴とする、〔10〕に記載のホットメルト接着剤。
〔12〕ホットメルト接着剤は、塗布温度で2時間保持する間に20%以下の粘度増加を示すことを特徴とする、〔10〕または〔11〕のいずれかに記載のホットメルト接着剤。
〔13〕トルエンジイソシアネートの放出率は2ppb未満、好ましくは1ppb未満、特に0.5ppb未満であることを特徴とする、〔10〕~〔12〕のいずれかに記載のホットメルト接着剤。
Claims (9)
- ポリウレタンプレポリマーを含むホットメルト接着剤の製造方法であって、ここで、ポリウレタンプレポリマーは鎖延長剤と反応しており、ポリウレタンプレポリマーは以下の反応によって得られ、第1ステップにおいて
(i)2,4'-トルエンジイソシアネート(2,4'-TDI)をポリオールと反応させ、その後のステップにおいて
(ii)ステップ(i)の反応混合物にメチレンジフェニルジソシアネート(MDI)を添加する;
ここで、ホットメルト接着剤は、80~160℃の塗布温度を有し、鎖延長剤は、1,3-ブタンジオール、1,2-プロパンジオール、2-エチル-1-ヘキサノール、ジエチレングリコール、トリプロピレングリコール、イソソルビド、レゾルシノール、1,4-ジメチロールシクロヘキサン、およびこれらの混合物からなる群から選択される、方法。 - 前記方法のステップ(i)および(ii)は、触媒の存在下で実施されることを特徴とする、請求項1に記載の方法。
- ステップ(i)で使用されるポリオールは、GPCにより測定される数平均分子量Mnが100~10000g/molであることを特徴とする、請求項1~2のいずれかに記載の方法。
- ポリオールとして、ポリエーテルポリオールおよび/またはポリエステルポリオールを使用することを特徴とする、請求項1~3のいずれかに記載の方法。
- ポリオールは、50~1500mgKOH/gのヒドロキシル価(OH価)を有することを特徴とする、請求項1~4のいずれかに記載の方法。
- ステップ(i)および/またはステップ(ii)におけるイソシアネート基とヒドロキシル基の比率(NCO:OH)は1.1:1~4:1であることを特徴とする、請求項1~5のいずれかに記載の方法。
- ホットメルト接着剤中のモノマートルエンジイソシアネートの含有量は、ホットメルト接着剤の総重量を基準にして0.02重量%未満であることを特徴とする、請求項1~6のいずれかに記載の方法。
- ホットメルト接着剤中のモノマーメチレンジフェニルジイソシアネートの含有量は、ホットメルト接着剤の総重量を基準にして0.1重量%未満であることを特徴とする、請求項1~7のいずれかに記載の方法。
- 環球法により測定されるホットメルト接着剤の軟化点は40℃超であることを特徴とする、請求項1~8のいずれかに記載の方法。
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