JPH01207373A - Adhesive for radically polymerizable resin - Google Patents
Adhesive for radically polymerizable resinInfo
- Publication number
- JPH01207373A JPH01207373A JP63033551A JP3355188A JPH01207373A JP H01207373 A JPH01207373 A JP H01207373A JP 63033551 A JP63033551 A JP 63033551A JP 3355188 A JP3355188 A JP 3355188A JP H01207373 A JPH01207373 A JP H01207373A
- Authority
- JP
- Japan
- Prior art keywords
- isocyanate groups
- water
- polyol
- compound
- reacting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 11
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 11
- 239000011347 resin Substances 0.000 title claims description 16
- 229920005989 resin Polymers 0.000 title claims description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 54
- 150000003077 polyols Chemical class 0.000 claims abstract description 40
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- -1 acrylic polyol Chemical class 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 20
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 15
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 15
- 239000002981 blocking agent Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 9
- 230000000903 blocking effect Effects 0.000 abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 21
- 229920000570 polyether Polymers 0.000 description 16
- 239000004721 Polyphenylene oxide Substances 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 14
- 239000012948 isocyanate Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000002987 primer (paints) Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 150000003509 tertiary alcohols Chemical class 0.000 description 3
- 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 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000015178 Asplenium bulbiferum subsp bulbiferum Nutrition 0.000 description 1
- 244000178908 Asplenium bulbiferum subsp bulbiferum Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000007788 liquid 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は各種基材へのラジカル重合性樹脂用接着剤に関
して、更に詳しくは各種基材の少なくとも一面に塗布し
、該基材にラジカル重合性樹脂に対する接着性と優れた
高温、耐湿ブロッキング性を付与する水溶性又は水分散
性の熱反応型ウレタンＡ［ｌ載物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to adhesives for radically polymerizable resins on various substrates, and more specifically, the present invention relates to adhesives for radically polymerizable resins on various substrates, and more specifically, the adhesives are applied to at least one surface of various substrates, and are applied to the substrates to provide excellent adhesion to radically polymerizable resins. This invention relates to a water-soluble or water-dispersible heat-reactive urethane A that provides high-temperature and moisture-resistant blocking properties.
従来より、ラジカル重合性樹脂としては１重合性二重結
合又は三重結合を含有する低分子量のモノマータイプと
中分子量のオリゴマータイプとがあり、これら樹脂の硬
化機構は、ラジカル重合機構を有し、熱重合、ラジカル
開始剤によるラジカル重合の他に、紫外線硬化、電子線
硬化などの極短時間での硬化が可能であること、及び一
般に無溶剤化が指向されていることより、エネルギーコ
スト面、環境汚染の観点より有効とされ、今後電子材料
関係、印刷、塗料関係などの用途に対して大きな期待の
もてるものとされている。Conventionally, radical polymerizable resins include low molecular weight monomer types containing monopolymerizable double bonds or triple bonds and medium molecular weight oligomer types, and the curing mechanism of these resins has a radical polymerization mechanism, In addition to thermal polymerization and radical polymerization using radical initiators, ultraviolet curing, electron beam curing, etc. can be used for curing in a very short time, and since there is a general trend towards solvent-free technology, energy costs are reduced. It is said to be effective in terms of environmental pollution, and holds great promise for future uses in electronic materials, printing, paints, and other fields.
しかし、これらラジカル重合性樹脂は、各種基材に対す
る接着性が悪く、未だこれら樹脂の各種基材に対する接
着性を向上させる化合物、手段（加工方法）が確立され
ていないのが現状である。However, these radically polymerizable resins have poor adhesion to various substrates, and currently no compounds or means (processing methods) have been established to improve the adhesion of these resins to various substrates.
よって１本発明の目的とするところは、ラジカル正合性
樹脂と各種基材との接着性を良好ならしめ、かつ、高温
、高湿下でのブロッキング性の良好な接着剤、プライマ
ーコート剤としてすぐれた性能を有する水溶性又は水分
散性、熱反応型つレタン組成物を提供することにある。Therefore, one object of the present invention is to provide an adhesive or primer coating agent that improves the adhesion between a radical polymerizable resin and various base materials and has good blocking properties under high temperature and high humidity conditions. The object of the present invention is to provide a water-soluble or water-dispersible, heat-reactive urethane composition having excellent performance.
即ち１本発明は、不飽和ポリエステルポリオール及び／
又は、ポリブタジェンポリオール及び／又は、アクリル
ポリオールを必須成分とする活性水素を２個以上有する
化合物と有機ポリイソシアネートを反応させることによ
り、遊離イソシアネート基を２個以上有するプレポリマ
ーとした後、熱処理によりイソシアネート′基を再生す
るブロック化剤又は熱処理によりイソシアネート基を再
生するブロック化剤と１分子中に活性水素を １個以上
有し、かつ親水性基を有する化合物とを反応して得られ
る水溶性又は水分散性、熱反応型ウレタン組成物を主成
分とすることを特徴とするラジカル重合性樹脂用接着剤
を提供するものである。That is, 1 the present invention provides an unsaturated polyester polyol and/or
Alternatively, a prepolymer having two or more free isocyanate groups is produced by reacting an organic polyisocyanate with a compound having two or more active hydrogens containing a polybutadiene polyol and/or an acrylic polyol as an essential component, and then heat-treated. A water-soluble compound obtained by reacting a blocking agent that regenerates isocyanate groups by heat treatment or a blocking agent that regenerates isocyanate groups by heat treatment with a compound that has at least one active hydrogen per molecule and has a hydrophilic group. The present invention provides an adhesive for radically polymerizable resins, characterized in that the main component is a water-dispersible, heat-reactive urethane composition.
次に本発明に用いられる水溶性又は水分散性、熱反応型
ウレタン組成物の製造について説明する。Next, the production of the water-soluble or water-dispersible, heat-reactive urethane composition used in the present invention will be explained.
本発明には、不飽和ポリエステルポリオール及び／又は
、ポリブタジェンポリオール及び／又は、アクリルポリ
オールを必須成分とする活性水素を ２個以上有する化
合物と有機ポリイソシアネートによるＭ蕩イソシアネー
トＸを ２個以上有するプレポリマーを製造した後、熱
処理によりイソシアネート基を再生するブロック化剤又
は熱処理によりイソシアネート基を再生するブロック化
剤と分子中に活性水素を １個以上有し、かつ親水性基
を有する化合物とを５反応して成る水溶性又は水分散性
、熱反応型ウレタン組成物が用いられる。The present invention has two or more M-isocyanate After producing the prepolymer, a blocking agent that regenerates isocyanate groups by heat treatment or a blocking agent that regenerates isocyanate groups by heat treatment and a compound having one or more active hydrogens and a hydrophilic group in the molecule are combined. A water-soluble or water-dispersible, heat-reactive urethane composition formed by five reactions is used.
前記不飽和ポリエステルポリオールとしては。As the unsaturated polyester polyol.
−分子中に少なくとも １個のエステル結合と少なくと
も １個の二重結合を有するものであり、例えばマレイ
ン酸、フマル酸及びこれらの無水物など、不飽和多価カ
ルボン酸及び同無水物及び／又は、フタル酸、イソフタ
ル酸などの芳香族多価カルボン酸類とエチレングリコー
ル、ジエチレングリコール、プロピレングリコール、ブ
チレンゲリコール、ネオペンチルグリコール、ヘキシレ
ングリコール、トリメチロールプロパンなどの多価アル
コール類及び／又はブチンジオールの様な不飽和多価ア
ルコール類との重縮合生成物が例示される。- having at least one ester bond and at least one double bond in the molecule, such as unsaturated polyhydric carboxylic acids and their anhydrides, such as maleic acid, fumaric acid, and their anhydrides; , aromatic polycarboxylic acids such as phthalic acid and isophthalic acid, and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene gellicol, neopentyl glycol, hexylene glycol, and trimethylolpropane, and/or butyne diol. Examples include polycondensation products with various unsaturated polyhydric alcohols.
前記ポリブタジェンポリオールとしては、１．２ポリブ
タジエンボリオール、 １．４ポリブタジエンポリオー
ルがあげられる。前記アクリルポリオールとしては、各
種アクリル酸系モノマーとヒドロキシエチルアクリレー
ト、ヒドロキシメタクリレートの如くヒドロキシル基を
有するアクリル酸系モノマーとの共重合により得られる
ヒドロキシル基を側鎖に有するアクリルポリオールがあ
げられる。Examples of the polybutadiene polyol include 1.2 polybutadiene polyol and 1.4 polybutadiene polyol. Examples of the acrylic polyol include acrylic polyols having hydroxyl groups in side chains obtained by copolymerizing various acrylic acid monomers with acrylic acid monomers having hydroxyl groups such as hydroxyethyl acrylate and hydroxymethacrylate.
前記活性水素を ２個以上有する化合物としては、通常
ウレタン製造に用いられる前記例示の多価アルコール、
前記例示の不飽和ポリエステルポリオール以外のポリエ
ステルポリオール。Examples of the compound having two or more active hydrogens include the above-mentioned polyhydric alcohols that are usually used in the production of urethane;
Polyester polyols other than the unsaturated polyester polyols listed above.
エチレンオキサイド、プロピレンオキサイド。Ethylene oxide, propylene oxide.
ブチレンオキサイド等のフルキレンオキサイド重付加に
よるポリエーテルポリオール、エタノールアミン、ジェ
タノールアミン、！・ジェタノールアミン等の７ミノア
ルコール、前記アミンアルコールにフルキレンオキサイ
ドを重付加させたポリエーテルポリオール等があげられ
。Polyether polyols, ethanolamine, jetanolamine, by polyaddition of fullylene oxide such as butylene oxide,! - Examples include 7-mino alcohols such as jetanolamine, and polyether polyols obtained by polyadding fullylene oxide to the above-mentioned amine alcohols.
更に、これら以外に通常ウレタン製造に用いられる活性
水素を ２個以上有する化合物はいずれも使用可能であ
る。Furthermore, in addition to these compounds, any compound having two or more active hydrogen atoms that is normally used in the production of urethane can be used.
前記不飽和ポリエステルポリオール、前記ポリブタジェ
ンポリオール、前記アクリルポリオールは、単独又は混
合しても用いられる。The unsaturated polyester polyol, the polybutadiene polyol, and the acrylic polyol may be used alone or in combination.
一方、前記不飽和ポリエステルポリオール、前記ポリブ
タジェンポリオール、 ｉｉ７＋記アクリアクリルポリ
オール記活性水素を２個以上有する化合物の使用割合は
、最終的に得られる本発明水溶性又は水分散性熱反応型
ウレタン組成物を塗！１ｊシ、熱処理して得られる各種
基材表面のブライマー層と、その上に塗布されるラジカ
ル重合性樹脂との接着性に影響をグーえ、不飽和ポリエ
ステルポリオール及び／又は、ポリブタジェンポリオー
ル及び／又は、アクリルポリオールの割合が多いほど好
ましく、即ちこれらポリオールを必須とするが、一部前
記活性水素を２個以上有する化合物を併用しても良い、
これら必須ポリオール成分は、それらを含めた出発原料
中の活性水素を２個以上有する全化合物の中に１０重量
％以上あることが好ましい。On the other hand, the proportions of the unsaturated polyester polyol, the polybutadiene polyol, and the acrylic acrylic polyol described in ii7+, which have two or more active hydrogen atoms, are determined based on the final water-soluble or water-dispersible heat-reactive urethane of the invention Apply the composition! 1j) To influence the adhesion between the brimer layer on the surface of various substrates obtained by heat treatment and the radical polymerizable resin applied thereon, unsaturated polyester polyol and/or polybutadiene polyol and /Or, the higher the proportion of acrylic polyol, the more preferable it is, that is, these polyols are essential, but some compounds having two or more of the above active hydrogens may be used in combination.
These essential polyol components are preferably present in an amount of 10% by weight or more in all compounds having two or more active hydrogen atoms in the starting materials including them.
前記有機ポリイソシアネートとしては、ジフェニルメタ
ンジイソシアネート、トルエンジイソシアネート等の芳
香族イソシアネート、ヘキサメチレンジイソシアネート
’Ｊの脂肪族イソシアネート、イソホロンジイソシアネ
ートの脂環族イソシアネート、キシリレンジイソシアネ
ートの芳香脂肪族イソシアネート等があげられ、更にこ
れらイソシアネート類とトリメチロールプロパン等の低
分子量ポリオールを予め反応させて得られるポリイソシ
アネート類があげられる。Examples of the organic polyisocyanate include aromatic isocyanates such as diphenylmethane diisocyanate and toluene diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate 'J, alicyclic isocyanates such as isophorone diisocyanate, and aromatic aliphatic isocyanates such as xylylene diisocyanate. Examples include polyisocyanates obtained by reacting these isocyanates with low molecular weight polyols such as trimethylolpropane in advance.
前記不飽和ポリエステルポリオール及び／又は、前記ポ
リブタジェンポリオール及び／又は、前記アクリルポリ
オール及び前記活性水素を ２個以上有する化合物と前
記有機ポリイシソアネートの反応は、無溶剤下又は有機
溶剤下で実施される。The reaction of the unsaturated polyester polyol and/or the polybutadiene polyol and/or the acrylic polyol and the compound having two or more active hydrogens with the organic polyisocyanate is carried out without a solvent or in an organic solvent. Implemented.
ただし、好ましい有機溶剤は、イソシアネートと不活性
であり、かつ最終工程で有機溶剤の留去を考慮すると、
洟点がｔ ｏ ｏ ’ｃ以下又は １００°Ｃ以下で水
と共沸する親水性の有機溶剤に溶解することが好ましく
、それら有機溶剤としては、ジオキサン、アセトン、テ
トラヒドロフラン。However, preferable organic solvents are inert with isocyanates, and considering the distillation of the organic solvent in the final step,
It is preferable to dissolve it in a hydrophilic organic solvent that is azeotropic with water at a temperature below 100°C or below 100°C, and examples of these organic solvents include dioxane, acetone, and tetrahydrofuran.
酢酸エチル、メチルエチルケトン等を例示することがで
きる。Examples include ethyl acetate and methyl ethyl ketone.
前記有機ポリイソシアネートのイソシアネート基と、前
記不飽和ポリエステルポリオール及び／又は、ポリブタ
ジェンポリオール及び／又は、アクリルポリオール及び
前記活性水素を ２個以上有する化合物の活性水素基の
モル数は、イソシアネート基が過剰系で任意に設定でき
るが、好ましくはインシアネー）！Ｓ；／活性水素基＝
１．１〜２．０の範囲で設定されることが好ましい、な
お、本工程は、常温〜 １００°Ｃ下で実施され、本工
程においては、有機酸、無機酸、金属及びアミン系触媒
等の通常のウレタン化触媒の適応ができる。The number of moles of the isocyanate groups of the organic polyisocyanate, the unsaturated polyester polyol and/or the polybutadiene polyol and/or the acrylic polyol, and the active hydrogen groups of the compound having two or more of the active hydrogens is determined by It can be set arbitrarily in excess system, but preferably incyane)! S;/active hydrogen group=
It is preferable to set it in the range of 1.1 to 2.0. This step is carried out at room temperature to 100°C, and in this step, organic acids, inorganic acids, metals, amine catalysts, etc. Can be used with ordinary urethanization catalysts.
以上の工程により、 ′ｉｉ９のイソシアネート基を２
個以上有するプレポリマーの調整ができる。Through the above steps, the isocyanate group of 'ii9 is converted to 2
It is possible to prepare prepolymers having more than 100%.
次に熱処理によりイソシアネート基を再生するブロック
化剤について例示する。Next, a blocking agent that regenerates isocyanate groups by heat treatment will be exemplified.
これらブロック化剤としては、重亜硫酸ソーダ等の重亜
硫酸塩、ブタンオキシム、シクロへキサノンオキシム等
のオキシム類、フェノール、アルキルフェノール等のフ
ェノール類、アセチルアセトン等の活性メチレン化合物
類、イソプロピルアルコール、第３ブチルアルコール等
の第２．第３アルコール類、イミダゾール。These blocking agents include bisulfites such as sodium bisulfite, oximes such as butane oxime and cyclohexanone oxime, phenols such as phenol and alkylphenol, active methylene compounds such as acetylacetone, isopropyl alcohol, and 2nd such as butyl alcohol. Tertiary alcohol, imidazole.
４．５位又は２位置換イミダゾール等のイミダゾール類
等があげられる。Examples include imidazoles such as imidazole substituted at the 4,5- or 2-position.
これらと前記遊離イソシアネート基を有するプレポリマ
ーのイソシアネート基の反応は、以下の様に実施される
０ｍ亜硫酸塩においては、１０〜３５％水溶液として添
加し実施されるが、その場合、エタノール、インプロピ
ルアルコール。The reaction between these and the isocyanate groups of the prepolymer having free isocyanate groups is carried out by adding 0m sulfite as a 10 to 35% aqueous solution as described below, but in that case, ethanol, inpropyl alcohol.
エチルセロソルブ等の親水性溶剤下で実施することが好
ましい、その他のオキシム類、フェノール類、活性メチ
レン化合物類、第２．第３アルコール類、イミダゾール
類は、非水系下で、常温〜 １００℃下で反応、実施さ
れ、必要であれば、前記した通常のウレタン化触媒を用
いることができる。更に必要であれば、ジオキサン、ア
セトン、テトラヒドロフラン１．酢酸エチル、メチルエ
チルケトン等の有機溶剤存在下で実施できる。Other oximes, phenols, active methylene compounds, which are preferably carried out in a hydrophilic solvent such as ethyl cellosolve; The tertiary alcohols and imidazoles are reacted and carried out in a non-aqueous system at room temperature to 100°C, and if necessary, the above-mentioned usual urethanization catalyst can be used. If necessary, dioxane, acetone, tetrahydrofuran 1. This can be carried out in the presence of an organic solvent such as ethyl acetate or methyl ethyl ketone.
上記ブロック化剤において、正亜硫酸塩類は、ウレタン
プレポリマーに水溶性又は水分散性を与え得るため、単
独での使用可能であるが、他のフェノール類、オキシム
類、活性メチレン化合物類、第２．第３アルコール類、
イミダゾール類は、ウレタンプレポリマーに水溶性又は
水分散性を与え得ないため１分子中に活性水素を１個以
上有し、かつ親水基を有する化合物と併用して用いられ
る。なお、これら水溶性又は水分散性を与え得ないブロ
ック化剤と分子中に活性水素を １個以上有し、かつ親
水基を有する化合物との使用量は、前記工程で得られた
Ｍ敲イソシアネート基を有するプレポリマーのイソシア
ネート基の５０重量％〜９５重量％を、前記水溶性又は
水分散性を与え得ないブロック化剤で反応し、残余のイ
ソシアネート基を、前記分子中に活性水素を １個以上
有し、かつ親水基を有する化合物と反応する様に設定さ
れる。上記以上に分子中に活性水素を １個以上有し、
かつ親水基を有する化合物の使用割合が多いと、それを
加工した各種基材表面のプライマー層の耐水性、耐溶剤
性が不良となる。In the above blocking agent, orthosulfites can impart water solubility or water dispersibility to the urethane prepolymer, so they can be used alone, but other phenols, oximes, active methylene compounds, secondary ．． tertiary alcohols,
Since imidazoles cannot impart water solubility or water dispersibility to the urethane prepolymer, they are used in combination with a compound having one or more active hydrogens in one molecule and having a hydrophilic group. In addition, the amount of the blocking agent that cannot provide water solubility or water dispersibility and the compound that has one or more active hydrogens in the molecule and has a hydrophilic group is based on the amount of the M-shaped isocyanate obtained in the above step. 50% to 95% by weight of the isocyanate groups of the prepolymer having groups are reacted with the blocking agent that cannot provide water solubility or water dispersibility, and the remaining isocyanate groups are converted to 1% by weight of active hydrogen in the molecule. or more, and is set to react with a compound having a hydrophilic group. It has one or more active hydrogens in its molecule than above,
Moreover, if the proportion of the compound having a hydrophilic group used is high, the water resistance and solvent resistance of the primer layer on the surface of various substrates processed therefrom will be poor.
前記分子中に活性水素を １個以上有し、かつ水溶性基
又は親水基を有する化合物を例示すると、モノ官能性化
合物と多官能性化合物に区分される。モノ官能性化合物
としては、タウリン、Ｎ−メチルタウリン、スルフアニ
ル酸等のアミノスルホン酸類、グリシン、アラニン等の
７ミノカルボン酸類、ジメチルエタノールアミンの四級
化合物等の四級化アルコール類、メタノール、エタノー
ルなどのモノアルコール、フェノール、アルキルフェノ
ールなどのモノフェノールにエチレンオキサイドを重付
加させて成るモノ官能性ポリエーテル類があげられる。Examples of compounds having one or more active hydrogens in the molecule and having a water-soluble group or a hydrophilic group are classified into monofunctional compounds and polyfunctional compounds. Examples of monofunctional compounds include aminosulfonic acids such as taurine, N-methyltaurine, and sulfanilic acid, 7-minocarboxylic acids such as glycine and alanine, quaternized alcohols such as quaternary compounds of dimethylethanolamine, methanol, and ethanol. Examples include monofunctional polyethers made by polyadding ethylene oxide to monophenols such as monoalcohols, phenols, and alkylphenols.
また、前記アミノアルコール付加して成るウレタン組成
物をアミン基と等量若しくは若干過剰量の有機酸及び／
又は無機酸で中和し・、アミン塩とし、親水性を行年す
ることも可能である。Further, the urethane composition obtained by adding the amino alcohol to the amine group may be mixed with an organic acid and/or an amount equivalent to or slightly in excess of the amine group.
Alternatively, it is also possible to neutralize it with an inorganic acid and make it an amine salt to increase its hydrophilicity.
上記アミノスルホン酸類、アミノカルボン酸類は、ソー
ダ塩、カリウム塩、トリエチルアミン塩の水溶液とした
後、イソシアネート基との反応に用いられ、３０〜５０
°Ｃの範囲で付加反応が実施される。上記四級化アルコ
ール類、モノ官能性ポリエーテル類は、常温〜 １００
℃の範囲でかつ非水系下でイソシアネート基との付加が
反応実施される。The above-mentioned aminosulfonic acids and aminocarboxylic acids are made into an aqueous solution of soda salt, potassium salt, and triethylamine salt, and then used for reaction with an isocyanate group.
The addition reaction is carried out in the °C range. The above-mentioned quaternized alcohols and monofunctional polyethers can be heated at room temperature to 100%
The addition with isocyanate groups is carried out in the temperature range 0.degree. C. and under non-aqueous conditions.
次に多官能性化合物としては、ジメチロールプロピオン
酸等ポリヒドロキシカルボン酸類。Next, examples of polyfunctional compounds include polyhydroxycarboxylic acids such as dimethylolpropionic acid.
モノメチルジェタノールアミンの四級化物、トリエタノ
ールアミンの四級化物等の四級化アミノアルコール類、
エチレンオキサイド重付加物であるポリエーテルポリオ
ール類があげられる、また、前記アミノアルコールを付
加して成るウレタン組成物を７ミノ基とｈＪ量若しくは
若干過剰量の有機酸及び／又は無機酸で中和し、アミン
塩とし、親水性を行年することも可能である。Quaternized amino alcohols such as quaternized products of monomethyl jetanolamine and quaternized products of triethanolamine,
Examples include polyether polyols which are ethylene oxide polyadducts, and the urethane composition obtained by adding the above amino alcohol is neutralized with 7mino groups and an amount of hJ or a slightly excess amount of organic acid and/or inorganic acid. However, it is also possible to improve the hydrophilicity by making it into an amine salt.
これらの反応は、常温〜 １００℃の範囲で、かつ非水
系下でイソシアネート基との付加反応が実施される。な
お、これら多官能性化合物は、第１段工程の遊離イソシ
アネート基を看するプレポリマー製造時に同時に反応し
ても良く、また前記プレポリマー製造後、すなわち、前
記ブロック他剤反応前にイソシアネートと反応しても良
い。In these reactions, addition reactions with isocyanate groups are carried out in a non-aqueous environment at a temperature ranging from room temperature to 100°C. Note that these polyfunctional compounds may be reacted at the same time during prepolymer production in which free isocyanate groups are monitored in the first stage step, or may be reacted with isocyanate after the prepolymer production, that is, before the block other agent reaction. You may do so.
上記のジメチロールプロピオン酸においては、前工程終
了後、ソーダ塩、カリウム用、トリエチルアミン塩とし
て水溶性基又は親水基に変換する。In the above dimethylolpropionic acid, after the previous step is completed, it is converted into a water-soluble group or a hydrophilic group as a sodium salt, a potassium salt, or a triethylamine salt.
特に使用する塩基がトリエチルアミンの場合は、熱処理
時に揮発してカルボキシル基の状態、即ち塩類状形態を
とらないため、又はカルボキシル基と再生イソシアネー
ト基との反応により、親水基の消失が起るため、該ウレ
タン組成物の耐水性向上に対しては、特に好ましい。In particular, when the base used is triethylamine, it volatilizes during heat treatment and does not form a carboxyl group, that is, a salt form, or the hydrophilic group disappears due to the reaction between the carboxyl group and the regenerated isocyanate group. It is particularly preferred for improving the water resistance of the urethane composition.
上記反応後、水稀釈することにより木１発明水溶性又は
水分散性の熱反応型ウレタン組成物が製造できる。After the above reaction, a water-soluble or water-dispersible heat-reactive urethane composition of the Moki 1 invention can be produced by diluting with water.
また、好ましくは反応した後、又は水稀釈した後、常圧
好ましくは減圧下で蒸留し、使用した有機溶剤を留去す
ることができる。Preferably, after the reaction or dilution with water, the organic solvent used can be distilled off under normal pressure, preferably reduced pressure.
かくして得られた水溶性又は水分散性の熱反応型ウレタ
ン組成物は、塩ビ、ポリオレフィン、ポリスチレン、ポ
リウレタン等の各種プラスチック、又はゴム類、アルミ
ニウム、鉄等の金属及び木材や紙類やガラス等の各種基
材の表面の一部又は全部に塗布し、前乾燥、更に熱処理
することにより、該各種基材にラジカル重合性樹脂に対
する接着性を付ケーすることができる。The water-soluble or water-dispersible heat-reactive urethane composition thus obtained can be used for various plastics such as vinyl chloride, polyolefin, polystyrene, and polyurethane, or metals such as rubber, aluminum, and iron, wood, paper, and glass. By coating a part or all of the surface of various base materials, pre-drying, and further heat-treating, it is possible to impart adhesion to the radically polymerizable resin to the various base materials.
なお、熱処理温度は、 １００〜２３０″Ｃで実施され
る。Note that the heat treatment temperature is 100 to 230''C.
この熱処理により１本発明ウレタン組成物の反応による
三次元架橋構造及び生成するウレタン結合が被着体との
接着性を向上させることに作用しているものと考えられ
、本発明前記ウレタン組成物のイソシアネート基が再生
さ、れ、架橋重合するため、得られたプライマー層は耐
水性、高温、高湿下でのブロッキング性の良好なものと
成る。It is thought that the three-dimensional cross-linked structure and the urethane bonds produced by the reaction of the urethane composition of the present invention act to improve the adhesion to the adherend by this heat treatment. Since the isocyanate groups are regenerated and cross-linked and polymerized, the resulting primer layer has good water resistance and blocking properties under high temperature and high humidity conditions.
ラジカル重合性樹脂との接着性の向上は、本発明ウレタ
ン組成物中の不飽和ポリエステル、ポリブタジェン中に
含まれる重合性二重結合とラジカル正合性樹脂の二重結
合との架橋及び本発明ウレタン組成物中のアクリルポリ
オール成分とラジカル重合性樹脂との親和性によるもの
と考える。The improvement in adhesion with the radically polymerizable resin is achieved by crosslinking the polymerizable double bonds contained in the unsaturated polyester and polybutadiene in the urethane composition of the present invention with the double bonds of the radically polymerizable resin and the urethane of the present invention. This is thought to be due to the affinity between the acrylic polyol component in the composition and the radically polymerizable resin.
なお、本発明、水溶性又は水分散性の熱反応型ウレタン
組成物には、得られるプライマー層の耐水性、高温、高
湿下でのブロッキング性に影響をもたらさない程度にア
クリル酸系ポリマーエマルジョンの配合使用も可能であ
り、その場合好ましくは本発明ウレタン組成物の熱処理
により再生するイソシアネート基と反応する官能基、例
えばヒドロキシル基を有するアクリル酸エステル系ポリ
マーエマルジョンの配合が適する。In addition, in the water-soluble or water-dispersible heat-reactive urethane composition of the present invention, an acrylic acid polymer emulsion is added to an extent that does not affect the water resistance of the resulting primer layer and the blocking property at high temperature and high humidity. In this case, it is preferable to use an acrylic ester polymer emulsion having a functional group, such as a hydroxyl group, which reacts with the isocyanate group regenerated by heat treatment of the urethane composition of the present invention.
次に本発明を実施例、効果例をあげて具体的に説明する
。Next, the present invention will be specifically explained by giving examples and examples of effects.
（なお、部１％は重量基準を示す、）
実施例１（合成例１）
ポリブタジエンボリオール７θ部（分子量２０００）
、ポリエーテルポリオール３０部（エチレンオキサイド
重付加体０公子ｉ ２０００）に系内温度６０°Ｃ下に
てヘキサメチレンジイソシアネート１８．８部を加え、
系内温度９５℃にて９０分反応を行ない、ｌａｌイソシ
アネート基３．６０％（ポリブタジェンポリオール、ポ
リエーテルポリオール、ヘキサメチレンジイソシアネー
ト総和に対して）有するウレタンプレポリマーを得た。(Note that part 1% indicates weight basis.) Example 1 (Synthesis Example 1) 7θ parts of polybutadiene boriol (molecular weight 2000)
, 18.8 parts of hexamethylene diisocyanate was added to 30 parts of polyether polyol (ethylene oxide polyadduct 2000) at an internal temperature of 60°C,
The reaction was carried out at a system internal temperature of 95° C. for 90 minutes to obtain a urethane prepolymer having 3.60% of lal isocyanate groups (based on the total of polybutadiene polyol, polyether polyol, and hexamethylene diisocyanate).
次にメチルエチルケトン５０部を添加した後。Then after adding 50 parts of methyl ethyl ketone.
ジメチロールプロピオン酸３．３０部を添加して、系内
温度７５°Ｃ下にて １８０分反応を行ない、遊離イソ
シアネート基 １．８％（ポリブタジェンポリオール、
ポリエーテルポリオール、ヘキサメチレンジイソシアネ
ート、ジメチロールプロピオン酸総和に対して）有する
ウレタンプレポリマーを得た。3.30 parts of dimethylolpropionic acid was added and the reaction was carried out for 180 minutes at an internal temperature of 75°C, resulting in 1.8% free isocyanate groups (polybutadiene polyol,
A urethane prepolymer containing polyether polyol, hexamethylene diisocyanate, and dimethylolpropionic acid was obtained.
次にブタノンオキシム ４．４部を添加して、６０℃下
で反応を行ない、イソシアネート基が完全に消失したこ
とを確認した後、トリエチルアミン２．４９部を添加、
後に水稀釈して、固型分１５％の乳白色の熱反応型ウレ
タン組成物を得た。Next, 4.4 parts of butanone oxime was added, the reaction was carried out at 60°C, and after confirming that the isocyanate group had completely disappeared, 2.49 parts of triethylamine was added.
It was then diluted with water to obtain a milky white heat-reactive urethane composition with a solids content of 15%.
次に６０℃／１００１１層Ｈｇ下で、 １８０分をかけ
使用したメチルエチルケトンの２倍量の水−メチルエチ
ルケトン混合溶剤を留去し、系内にメチルエチルケトン
の臭いがしなくなったことを確認した後、水で補正して
、固型分１５％とした。Next, at 60°C/10011 Hg, twice the amount of water-methyl ethyl ketone mixed solvent as the methyl ethyl ketone used was distilled off over 180 minutes, and after confirming that there was no longer any smell of methyl ethyl ketone in the system, the water The solid content was corrected to 15%.
実施例２（合成例２）
無水マレイン酸と １．６ヘキサンジオールより成るポ
リエステルポリオール７０部（分子ｍ１０００）と、ポ
リエーテルポリオール３０ｇｌ１（エチレンオキサイド
重付加体９公子ｍ ２０００）とトリメチロールプロパ
ン３．０部に系内温度６０℃下にてヘキサメチレンジイ
ソシアネート４０．４部を加え、系内温度８５℃にて６
０分反応を行ない、′Ｍ＃インシアネー１・６．２０％
（ボリエステルボリオール、ポリエーテルポリオール、
トリメチロールプロパン、ヘキサメチレンジイソシアネ
ート総和に対して）を有するウレタンプレポリマーを得
た。Example 2 (Synthesis Example 2) 70 parts of a polyester polyol (molecular m 1000) consisting of maleic anhydride and 1.6 hexanediol, 30 gl1 polyether polyol (9 molecules m 2000 of ethylene oxide polyadduct), and 3. Add 40.4 parts of hexamethylene diisocyanate to 0 parts at a system temperature of 60°C, and add 60.4 parts of hexamethylene diisocyanate at a system internal temperature of 85°C.
Perform the reaction for 0 minutes, 'M# incyanae 1.6.20%
(polyester polyol, polyether polyol,
A urethane prepolymer having trimethylolpropane and hexamethylene diisocyanate) was obtained.
次に、系内温度５０°Ｃ下にてエタノール５０部を添加
した後、１４７部の１５部濃度の重亜硫酸ソーダ水溶液
を系内温度３５℃にて添加し、同温にて９０分間反応を
行なった後、水稀釈して、固型分２０％の透明な熱反応
型ウレタン組成物を得た。Next, after adding 50 parts of ethanol at a system temperature of 50°C, 147 parts of a sodium bisulfite aqueous solution with a concentration of 15 parts was added at a system internal temperature of 35°C, and the reaction was continued at the same temperature for 90 minutes. After this, it was diluted with water to obtain a transparent heat-reactive urethane composition with a solids content of 20%.
次に５０℃／１０ｍｍＨｇにて １８０分をかけ使用し
たエタノールの２倍量の水−エタノール混合溶剤を留去
した後、エタノール臭のしないことを確認した後、水で
補正し、固型分２０％とした。Next, at 50℃/10mmHg, twice the amount of water-ethanol mixed solvent as the ethanol used was distilled off over 180 minutes, and after confirming that there was no ethanol odor, it was corrected with water and the solid content was 20%. %.
実施例３（合成例３）
アクリルポリオール １ｏｏｉ（アクリディックＡ−８
０１、固形分４９．５％、ＯＨＶ ４Ｂ、０．酢酸ブチ
ル液、大日木インキ化学社製）、ポリエーテルポリオー
ル３０部（エチレンオキサイド重付加俸０分子量＋００
０）に、ヘキサメチレンジインシアネー） ２３．２
１３部を添加して、系内温度９０°Ｃにて３０分反応を
行い、遊離イソシアネー１’！ｉ３．７ｏ％（アクリル
ポリオール、ポリエーテルポリオール、ヘキサメチレン
ジイソシアネート総和に対して）有するウレタンプレポ
リマーを得た。Example 3 (Synthesis Example 3) Acrylic polyol 1ooi (Acrydic A-8
01, solid content 49.5%, OHV 4B, 0. Butyl acetate liquid, manufactured by Dainichi Ink Chemical Co., Ltd.), 30 parts of polyether polyol (ethylene oxide polyaddition 0 molecular weight + 00
0), hexamethylene diine cyanide) 23.2
13 parts was added and the reaction was carried out for 30 minutes at a system internal temperature of 90°C, resulting in free isocyanate 1'! A urethane prepolymer having an i of 3.7o% (based on the total of acrylic polyol, polyether polyol, and hexamethylene diisocyanate) was obtained.
次にジメチロールプロピオン酸４．３０部を添加して、
９０°Ｃにて １８０分反応を行ない１Ｍ遊離ソシアネ
ート１．８５％（アクリルポリオール。Next, 4.30 parts of dimethylolpropionic acid was added,
The reaction was carried out at 90°C for 180 minutes and 1.85% of 1M free isocyanate (acrylic polyol).
ポリエーテルポリオール、ヘキサメチレンジイソシアネ
ート、ジメチロールプロピオン酸総和に対して）有する
ウレタンプレポリマーを得た。A urethane prepolymer containing polyether polyol, hexamethylene diisocyanate, and dimethylolpropionic acid was obtained.
次にメチルエチルケトオキシム８．２０部を添加して６
０°Ｃで反応を行ない、イソシア、ネート基を完全に消
失させた。Next, 8.20 parts of methyl ethyl ketoxime was added and 6
The reaction was carried out at 0°C to completely eliminate isocyanate and nate groups.
次に９０℃／２０ｍｍＨｇにて １８０分を要し系内酢
酸ブチルを留去した後、トリエチルアミン３．３０部を
添加し、後に水稀釈を行ない、固型分１５％、半透明、
熱反応型ウレタン組成物を得た。Next, after distilling off the butyl acetate in the system over 180 minutes at 90°C/20 mmHg, 3.30 parts of triethylamine was added, followed by dilution with water, and the solid content was 15%, translucent.
A heat-reactive urethane composition was obtained.
実施例４（合成例４）
実施例２（合成例２）で使用したポリエステルポリオー
ル７０部と、ポリエーテルポリオール３０部（エチレン
オキサイド重付勿体０分子量１０００）に、 ２．４−
トルエンジイソシアネート３３．１部を添加して、系内
温度７０℃にてＢＯ分反応を行ない、遊離イソシアネー
ト基５．８５％（ポリエステルポリオール、ポリエーテ
ルポリオール、 ２．４−）ルエンジイソシアネート総
和に対して）を有するブロック化ウレタンプレポリマー
を得た。Example 4 (Synthesis Example 4) 70 parts of the polyester polyol used in Example 2 (Synthesis Example 2) and 30 parts of polyether polyol (ethylene oxide weighted material 0 molecular weight 1000), 2.4-
33.1 parts of toluene diisocyanate was added and a BO reaction was carried out at a system internal temperature of 70°C, resulting in a total of 5.85% of free isocyanate groups (polyester polyol, polyether polyol, 2.4-) toluene diisocyanate total. ) was obtained.
次にメチルエチルケトオキシム７．９０部を添加し、６
０°Ｃ下で６０分反応を行ない、ｍ敲イソシアネート基
２．８０％（ポリエステルポリオール、ポリエーテルポ
リオール、２．４−）ルエンジイソシアネート総和に対
して）有するブロック化ウレタンプレポリマーを得た。Next, 7.90 parts of methyl ethyl ketoxime was added,
The reaction was carried out at 0°C for 60 minutes to obtain a blocked urethane prepolymer having 2.80% m isocyanate groups (based on the total of polyester polyol, polyether polyol, and 2.4-)luene diisocyanate).
次にメチルエチルケトン １００部、ジメチロールプロ
ピオン１９２．９７部を添加し、系内温度７０℃下にて
反応を行ない、イソシアネート基を完全に消失させた後
、トリエチルアミン２．２４部添加し、その抜水稀釈し
て、固型分１５％の白色系の熱反応型ウレタンｍ酸物を
得た。Next, 100 parts of methyl ethyl ketone and 192.97 parts of dimethylolpropion were added, and the reaction was carried out at an internal temperature of 70°C to completely eliminate the isocyanate groups. Then, 2.24 parts of triethylamine was added, and the water was drained. The mixture was diluted to obtain a white heat-reactive urethane m-acid having a solid content of 15%.
次に６０℃／１００ｍｍＨｇ下で １８０分を要し系内
メチルエチルケトンの２倍量の水−エチルケトン混合溶
剤を留去し、系内にメチルエチルケトン臭がしなくなっ
たことを確認した抜水で補正し、固型分１５％とした。Next, it took 180 minutes at 60°C/100 mmHg to distill off the mixed solvent of water and ethyl ketone, which was twice the amount of methyl ethyl ketone in the system, and corrected by draining water after confirming that there was no longer any methyl ethyl ketone odor in the system. The solid content was 15%.
効果例１〜４
実施例１〜４で得られたウレタン組成物を下記試験方法
に従って試験を行ない、その結果を第１表に示した。Effect Examples 1 to 4 The urethane compositions obtained in Examples 1 to 4 were tested according to the following test method, and the results are shown in Table 1.
接着性ニ
ガラス板に前記実施例１〜４で得られた本発明ウレタン
組成物を塗布し、加熱硬化（風乾−夜→熟処理 １５０
″ＣＸ＋Ｏ分）させることにより得られたガラス板に諸
星インキ■製、紫外線硬化型インキ（ｕｖｓ−ｐａｎ−
紅旬を厚さ ４ルに印刷し、日本電池鞠製ＵＶ照射装置
（ＡＳＥ−２０型）を用いて強度８０（ｖ／ｃｍ）及
び速度３（ｍ／鳳ｉｎ）で硬化させた。The urethane compositions of the present invention obtained in Examples 1 to 4 were applied to an adhesive glass plate, and heat-cured (air-drying-overnight->ripening treatment 150
``CX+O minutes)'' was coated with ultraviolet curing ink (uvs-pan-
Red season was printed to a thickness of 4 ml and cured using a UV irradiation device manufactured by Nippon Battery Mari (ASE-20 type) at a strength of 80 (v/cm) and a speed of 3 (m/in).
次いで、スコッチテープＮｏＥ１００ （３Ｍ社製。Next, Scotch Tape NoE100 (manufactured by 3M Company).
幅１９．４ｔｓ）を気泡の入らないように粘着し、この
上をＪＩＳ−０２７０１（１９７５）記載の手動式荷重
ロールでならし密着させる。更にこの試料の粘着させて
いない両端部を両手で持ち、急速剥離後の紫外線硬化イ
ンキの剥離状況を次の基準でａ察して評価した。(width 19.4ts) was adhered without air bubbles, and the top was smoothed and brought into close contact with a manual load roll as described in JIS-02701 (1975). Furthermore, both non-adhesive ends of this sample were held with both hands, and the peeling status of the ultraviolet curing ink after rapid peeling was observed and evaluated using the following criteria.
（評価基準）
×：紫外線硬化インキがほとんど粘着テープに移行した
もの
Δ：紫外線硬化インキの半分がガラス板上に残ったもの
Ｏ：紫外線硬化インキの全部がガ′ラス板上に残ったも
の
尚、効果例１〜４は、実施例１〜４に対応する。未処理
は未処理ガラス板に上記紫外線硬化インキを塗布し、硬
化させたものである。(Evaluation criteria) ×: Most of the UV-curable ink has transferred to the adhesive tape Δ: Half of the UV-curable ink remains on the glass plate O: All of the UV-curable ink remains on the glass plate , Effect examples 1 to 4 correspond to Examples 1 to 4. The untreated glass plate was coated with the above ultraviolet curing ink and cured.
第１表Table 1
Claims (1)
エンポリオール及び／又は、アクリルポリオールを必須
成分とする活性水素を２個以上有する化合物と有機ポリ
イソシアネートを反応させることにより、遊離イソシア
ネート基を２個以上有するプレポリマーとした後、熱処
理によりイソシアネート基を再生するブロック化剤又は
熱処理によりイソシアネート基を再生するブロック化剤
と分子中に活性水素を１個以上有し、かつ親水性基を有
する化合物とを反応して得られる水溶性又は水分散性、
熱反応型ウレタン組成物を主成分とすることを特徴とす
るラジカル重合性樹脂用接着剤。A prepolymer having two or more free isocyanate groups is produced by reacting an organic polyisocyanate with a compound having two or more active hydrogens, which includes an unsaturated polyester polyol and/or a polybutadiene polyol and/or an acrylic polyol as an essential component. After that, a blocking agent that regenerates isocyanate groups by heat treatment or a blocking agent that regenerates isocyanate groups by heat treatment is reacted with a compound having one or more active hydrogens in the molecule and a hydrophilic group. water-soluble or water-dispersible;
An adhesive for radically polymerizable resins characterized by containing a heat-reactive urethane composition as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63033551A JPH0730299B2 (en) | 1988-02-15 | 1988-02-15 | Adhesive for radical polymerizable resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63033551A JPH0730299B2 (en) | 1988-02-15 | 1988-02-15 | Adhesive for radical polymerizable resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01207373A true JPH01207373A (en) | 1989-08-21 |
| JPH0730299B2 JPH0730299B2 (en) | 1995-04-05 |
Family
ID=12389690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63033551A Expired - Fee Related JPH0730299B2 (en) | 1988-02-15 | 1988-02-15 | Adhesive for radical polymerizable resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730299B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1053636A (en) * | 1996-05-13 | 1998-02-24 | Elf Atochem North America Inc | Anionic aqueous polyurethane dispersion |
| US6492457B2 (en) | 2000-10-17 | 2002-12-10 | Solutia Austria Gmbh | Two-component systems based on water-soluble polyesters and blocked isocyanates for aqueous baking varnishes |
| CN109439268A (en) * | 2018-10-31 | 2019-03-08 | 烟台德邦科技有限公司 | A kind of photovoltaic imbrication component low Tg, the conducting resinl of low silver content |
| JP2019507817A (en) * | 2016-02-26 | 2019-03-22 | フィナ テクノロジー，インコーポレイティド | Modified polymer and stable emulsion comprising said modified polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5880320A (en) * | 1981-11-09 | 1983-05-14 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of heat-reactive water-soluble urethane resin |
| JPS606771A (en) * | 1983-06-27 | 1985-01-14 | Moon Star Co | Adhesive for footwear |
-
1988
- 1988-02-15 JP JP63033551A patent/JPH0730299B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5880320A (en) * | 1981-11-09 | 1983-05-14 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of heat-reactive water-soluble urethane resin |
| JPS606771A (en) * | 1983-06-27 | 1985-01-14 | Moon Star Co | Adhesive for footwear |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1053636A (en) * | 1996-05-13 | 1998-02-24 | Elf Atochem North America Inc | Anionic aqueous polyurethane dispersion |
| US6492457B2 (en) | 2000-10-17 | 2002-12-10 | Solutia Austria Gmbh | Two-component systems based on water-soluble polyesters and blocked isocyanates for aqueous baking varnishes |
| AT409967B (en) * | 2000-10-17 | 2002-12-27 | Solutia Austria Gmbh | TWO-COMPONENT SYSTEMS BASED ON WATER-SOLUBLE POLYESTERS AND CAPPED ISOCYANATES FOR THE FORMULATION OF WATER-THINNABLE BURNING LACQUERS |
| JP2019507817A (en) * | 2016-02-26 | 2019-03-22 | フィナ テクノロジー，インコーポレイティド | Modified polymer and stable emulsion comprising said modified polymer |
| US10584220B2 (en) | 2016-02-26 | 2020-03-10 | Fina Technology, Inc. | Modified polymers and stable emulsions comprising the same |
| CN109439268A (en) * | 2018-10-31 | 2019-03-08 | 烟台德邦科技有限公司 | A kind of photovoltaic imbrication component low Tg, the conducting resinl of low silver content |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0730299B2 (en) | 1995-04-05 |
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