JP2012072292A - Releasability-treatment agent - Google Patents
Releasability-treatment agent Download PDFInfo
- Publication number
- JP2012072292A JP2012072292A JP2010218700A JP2010218700A JP2012072292A JP 2012072292 A JP2012072292 A JP 2012072292A JP 2010218700 A JP2010218700 A JP 2010218700A JP 2010218700 A JP2010218700 A JP 2010218700A JP 2012072292 A JP2012072292 A JP 2012072292A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polysiloxane
- treatment agent
- peelable
- modified
- 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
- -1 polysiloxane Polymers 0.000 claims abstract description 78
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 46
- 239000001569 carbon dioxide Substances 0.000 claims description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 11
- 229920005749 polyurethane resin Polymers 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 238000013035 low temperature curing Methods 0.000 abstract 1
- 238000012423 maintenance Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 20
- 239000000123 paper Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011086 glassine Substances 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GHKSKVKCKMGRDU-UHFFFAOYSA-N 2-(3-aminopropylamino)ethanol Chemical compound NCCCNCCO GHKSKVKCKMGRDU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FPORYTZOLLHXDO-UHFFFAOYSA-N 2-amino-1-(ethylamino)ethanol Chemical compound CCNC(O)CN FPORYTZOLLHXDO-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Landscapes
- Adhesive Tapes (AREA)
- Polyurethanes Or Polyureas (AREA)
- Silicon Polymers (AREA)
Abstract
Description
本発明は、剥離性処理剤に関し、さらに詳しくは、粘着テープ、粘着ラベルおよび粘着シートなどの如く粘着剤を用いた製品において、粘着面に重なって接するテープやシートなどの基材裏面や剥離紙の表面に剥離性を付与することができる剥離性処理剤に関する。 The present invention relates to a releasable treatment agent, and more specifically, in a product using an adhesive such as an adhesive tape, an adhesive label, and an adhesive sheet, a substrate back surface such as a tape or a sheet that is in contact with the adhesive surface, and a release paper. It is related with the peelable processing agent which can provide peelability to the surface of this.
従来、上記目的に使用される剥離性処理剤としては、長鎖アルキル基を結合したアクリル酸系、ポリエステル系およびポリアミド系などの高分子化合物やポリシロキサン系化合物を主成分とするものが知られている。これらの化合物を用いることで、粘着テープや粘着シートの背面や、剥離紙の表面に剥離性を付与して、剥離面を形成することが行われている。そして、上記した中でも、ポリシロキサン系化合物は、剥離性および残留接着性などの特性に優れていることが知られている(例えば、特許文献1〜特許文献3など参照)。 Conventionally, as a releasable treatment agent used for the above-mentioned purpose, a polymer compound mainly composed of a polymer compound such as acrylic acid-based, polyester-based, or polyamide-based compound having a long-chain alkyl group or a polysiloxane-based compound is known. ing. By using these compounds, the release surface is formed by imparting peelability to the back surface of the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet or the surface of the release paper. And among the above-mentioned, it is known that a polysiloxane type compound is excellent in characteristics, such as peelability and residual adhesiveness (for example, refer patent documents 1-patent documents 3, etc.).
しかしながら、ポリシロキサン系化合物は、剥離性能が強過ぎ、適度な剥離力を得るのが難しく、また、基材へ塗工する際に、高温焼付けを必要とするため、熱可塑性の基材フィルムには使用できないという問題点があった。また、基材の種類によっては、基材に対する密着性が不十分であるために、あらゆる種類の基材には利用できないという欠点があった。 However, polysiloxane compounds have too strong peelability, making it difficult to obtain an appropriate peel force, and require high-temperature baking when applied to a substrate. There was a problem that could not be used. In addition, depending on the type of substrate, there is a drawback that it cannot be used for all types of substrates because of insufficient adhesion to the substrate.
又、剥離性能が強い従来のポリシロキサン系化合物は臨界表面張力が小さいために、該化合物を付与することで形成した剥離面に筆記することができず、また、該剥離面に感圧型或いは感熱型の粘着剤を塗布した場合には、しばしばハジキ現象を生じ、良好な塗布面を形成できないという課題があった。 In addition, since the conventional polysiloxane compound having a strong peeling performance has a small critical surface tension, it cannot be written on the peeling surface formed by applying the compound, and the pressure-sensitive type or heat-sensitive property is applied to the peeling surface. When a mold pressure-sensitive adhesive is applied, there is a problem that a repellency phenomenon often occurs and a good coated surface cannot be formed.
以上の如き問題点を解決する方法として、本出願人は以前に、シリコーン共重合体を使用することで、低温焼付けが可能で、且つ、基材に対する接着性および剥離面への筆記性などを兼ね備えた優れた剥離性処理剤を提案してきた(特許文献4および特許文献5等参照)。 As a method for solving the above-mentioned problems, the present applicant has previously been able to perform low-temperature baking by using a silicone copolymer, and has good adhesion to a substrate and writing on a release surface. An excellent releasability treatment agent that has been combined has been proposed (see Patent Document 4 and Patent Document 5).
一方、最近における環境問題の高まりから、環境対策に積極的に取り組むメーカーが多くなっており、環境保全性に優れた材料を用いて製品を構成する動きがある。上述した剥離性テープや剥離性シート、剥離紙などは、使用後にリサイクルすることが難しく大量の廃棄物となるため、地球環境の観点からも環境対応製品の開発が要望されている。これに対し、上記に挙げた特許文献4、5などの従来技術は、この地球環境問題という観点からは何も解決策を示しておらず、改善すべき余地がある。 On the other hand, due to the recent increase in environmental problems, many manufacturers are actively working on environmental measures, and there is a movement to construct products using materials with excellent environmental conservation. The above-described peelable tape, peelable sheet, release paper, and the like are difficult to recycle after use and become a large amount of waste. Therefore, development of environmentally friendly products is also demanded from the viewpoint of the global environment. On the other hand, the conventional techniques such as Patent Documents 4 and 5 listed above show no solution from the viewpoint of the global environmental problem, and there is room for improvement.
上記観点から従来技術をみた場合、例えば、非特許文献1、2に見られるように、二酸化炭素を原料として利用するポリヒドロキシポリウレタン樹脂は以前から知られている。しかし、その応用展開は進んでいないのが実情である。その理由は、同種系の高分子化合物として対比される、ポリウレタン系樹脂に比べて特性面で明らかに劣るからである(特許文献6、7参照)。
一方、近年、増加の一途をたどる二酸化炭素に起因すると考えられる地球の温暖化現象は、世界的な問題となっており、全世界的に二酸化炭素の排出量低減が重要な課題となっている。さらに、枯渇性石化資源(石油)問題の観点からも、バイオマス、メタンなどの再生可能資源への転換が世界的潮流となっており、地球環境問題という観点からの技術開発は極めて重要である。
When the prior art is viewed from the above viewpoint, for example, as can be seen in Non-Patent Documents 1 and 2, polyhydroxy polyurethane resins using carbon dioxide as a raw material have been known for some time. However, the actual situation is that the application development is not progressing. This is because the characteristics are clearly inferior to those of polyurethane-based resins, which are compared as high-molecular compounds of the same type (see Patent Documents 6 and 7).
On the other hand, the global warming phenomenon, which is thought to be caused by the ever-increasing carbon dioxide in recent years, has become a global problem, and the reduction of carbon dioxide emissions has become an important issue worldwide. . In addition, from the viewpoint of exhaustible petrochemical resources (petroleum), the shift to renewable resources such as biomass and methane has become a global trend, and technological development from the viewpoint of global environmental issues is extremely important.
上記のような背景下、再び、ポリヒドロキシポリウレタン樹脂が見直されている。すなわち、この樹脂の原料である二酸化炭素は、容易に入手可能で、しかも持続可能な炭素資源であり、さらに、二酸化炭素を原料とするプラスチックは、温暖化、資源枯渇などの問題を解決する有効な手段となり得るからである。 Against the background as described above, the polyhydroxy polyurethane resin has been reviewed again. In other words, carbon dioxide, the raw material for this resin, is an easily available and sustainable carbon resource, and plastics made from carbon dioxide are effective in solving problems such as global warming and resource depletion. This is because it can be a simple means.
近年、粘着テープ、粘着ラベルおよび粘着シートなどの利用分野は広がりつつあり、それにともなって剥離性処理剤に対する、さらなる性能の向上が求められている。一方、先にも述べたように、剥離性テープや剥離性シート、剥離紙などは、使用後にリサイクルすることが難しく、大量の廃棄物となってしまうため、地球環境保護の観点からも環境対応製品の開発が切望されている。 In recent years, fields of application such as pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, and pressure-sensitive adhesive sheets have been expanding, and accordingly, further improvement in performance with respect to releasable treatment agents has been required. On the other hand, as mentioned earlier, peelable tape, peelable sheet, release paper, etc. are difficult to recycle after use and become a large amount of waste. Product development is anxious.
したがって、本発明の目的は、適度な剥離力を有する剥離性処理層(剥離面)を形成することができるとともに、剥離面を形成する際に低温焼付可能であるので基材に対する選択性がなく、さらに、形成された剥離面にペンなどで筆記可能な優れたものでありながら、該剥離面を形成するための材料が環境保全性にも資するものである剥離性処理剤を提供することにある。 Accordingly, an object of the present invention is to form a peelable treatment layer (peeling surface) having an appropriate peeling force, and since it can be baked at a low temperature when forming the peeling surface, there is no selectivity for the substrate. Furthermore, the present invention provides a releasable treatment agent in which the material for forming the release surface also contributes to environmental conservation while being excellent in that it can be written on the formed release surface with a pen or the like. is there.
上記の目的は以下の本発明によって達成される。すなわち、本発明は、シロキサンセグメントを有する樹脂を含有してなる剥離性処理剤において、上記樹脂が、下記一般式(1)で表せる5員環環状カーボネートポリシロキサン化合物と、アミン化合物との反応から誘導されてなるポリシロキサン変性ポリヒドロキシポリウレタン樹脂であることを特徴とする剥離性処理剤を提供する。
式中のR1は、炭素数1〜12のアルキレン基(該基中にO、S、又はNの各元素および/又は−(C2H4O)b−で連結されていてもよい)を表す。式(1)中のR2は、ないか、又は、炭素数2〜20のアルキレン基を表し、R2は、脂環族基又は芳香族基に連結していてもよい。式(1)中のbは1〜300の数を表わし、aは1〜300の数を表す。]
The above object is achieved by the present invention described below. That is, the present invention relates to a releasable treatment agent comprising a resin having a siloxane segment, wherein the resin is obtained by reacting a 5-membered cyclic carbonate polysiloxane compound represented by the following general formula (1) with an amine compound. Provided is a releasable treating agent which is a polysiloxane-modified polyhydroxypolyurethane resin derived.
R 1 in the formula is an alkylene group having 1 to 12 carbon atoms (which may be linked to each element of O, S, or N and / or — (C 2 H 4 O) b —). Represents. R 2 in Formula (1) is not present or represents an alkylene group having 2 to 20 carbon atoms, and R 2 may be linked to an alicyclic group or an aromatic group. In formula (1), b represents a number from 1 to 300, and a represents a number from 1 to 300. ]
さらには、以下の形態であることが好ましい。前記5員環環状カーボネートポリシロキサン化合物が、エポキシ変性ポリシロキサン化合物と二酸化炭素を反応させて得られる剥離性処理剤。前記ポリシロキサン変性ポリヒドロキシポリウレタン樹脂が二酸化炭素を1〜25質量%含有する剥離性処理剤。前記ポリシロキサン変性ポリヒドロキシポリウレタン樹脂が、その樹脂分子中に、ポリシロキサンセグメントを10〜75質量%の割合で含有している剥離性処理剤。更に、他の樹脂をバインダーとして含む記載の剥離性処理剤。更に、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂が、該樹脂を構成する水酸基と反応する架橋剤で架橋されている剥離性処理剤。 Furthermore, the following forms are preferable. A peelable treatment agent obtained by reacting the 5-membered cyclic carbonate polysiloxane compound with an epoxy-modified polysiloxane compound and carbon dioxide. A peelable treatment agent, wherein the polysiloxane-modified polyhydroxypolyurethane resin contains 1 to 25% by mass of carbon dioxide. A stripping treatment agent, wherein the polysiloxane-modified polyhydroxypolyurethane resin contains a polysiloxane segment in a proportion of 10 to 75% by mass in the resin molecule. Furthermore, the peelable treatment agent according to the description containing another resin as a binder. Furthermore, a releasable treatment agent in which a polysiloxane-modified polyhydroxypolyurethane resin is crosslinked with a crosslinking agent that reacts with a hydroxyl group constituting the resin.
本発明によれば、シロキサンセグメントを有する樹脂として、特定のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を用いて剥離面を形成することで、低温焼付可能であるため基材に対する選択性がなく適用性に優れ、形成した剥離面は、ペンなどで筆記可能であり、しかも適度な剥離力を有するものとできる。また、本発明を特徴付ける上記樹脂は、その原料に地球温暖化ガスとされている二酸化炭素を利用することができるため、地球環境保全の観点からも有用な剥離性処理剤であり、該剥離性処理剤によって剥離性を付与された製品は、地球環境保全に資する環境対応製品となる。 According to the present invention, as a resin having a siloxane segment, a specific polysiloxane-modified polyhydroxypolyurethane resin is used to form a release surface, which can be baked at a low temperature and has excellent selectivity and no applicability to the substrate. The formed release surface can be written with a pen or the like and has an appropriate release force. In addition, the resin that characterizes the present invention is a releasable treatment agent that is also useful from the viewpoint of global environmental conservation because carbon dioxide, which is a global warming gas, can be used as a raw material. A product to which peelability is imparted by a treatment agent is an environmentally friendly product that contributes to global environmental conservation.
次に、好ましい実施の形態を挙げて本発明をさらに詳しく説明する。
本発明を特徴づけるポリシロキサン変性ポリヒドロキシポリウレタン樹脂は、前記一般式(1)で表される5員環環状カーボネートポリシロキサン化合物と、アミン化合物との反応から得られる。
Next, the present invention will be described in more detail with reference to preferred embodiments.
The polysiloxane-modified polyhydroxypolyurethane resin characterizing the present invention is obtained from a reaction between an amine compound and a 5-membered cyclic carbonate polysiloxane compound represented by the general formula (1).
本発明で使用する前記一般式(1)で表される5員環環状カーボネートポリシロキサン化合物は、下記[式−A]で示されるように、エポキシ変性ポリシロキサン化合物と、二酸化炭素とを反応させて製造することができる。さらに詳しくは、エポキシ変性ポリシロキサン化合物を、有機溶媒の存在下または不存在下、および触媒の存在下、40℃〜150℃の温度で、常圧または僅かに高められた圧力下、10〜20時間、二酸化炭素と反応させることによって得られる。
The five-membered cyclic carbonate polysiloxane compound represented by the general formula (1) used in the present invention is obtained by reacting an epoxy-modified polysiloxane compound with carbon dioxide as shown in the following [Formula-A]. Can be manufactured. More particularly, the epoxy-modified polysiloxane compound is prepared in the presence or absence of an organic solvent and in the presence of a catalyst at a temperature of 40 ° C. to 150 ° C. under normal pressure or slightly elevated pressure, for 10-20. Obtained by reacting with carbon dioxide for hours.
上記で使用し得る、エポキシ変性ポリシロキサン化合物としては、例えば、次の如き化合物が挙げられる。 Examples of the epoxy-modified polysiloxane compound that can be used above include the following compounds.
以上列記したエポキシ変性ポリシロキサン化合物は、本発明において使用する好ましい化合物であって、本発明はこれらの例示の化合物に限定されるものではない。従って、上述の例示化合物のみならず、その他、現在市販されており、市場から容易に入手し得る化合物は、いずれも本発明において使用することができる。 The epoxy-modified polysiloxane compounds listed above are preferable compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Therefore, not only the exemplified compounds described above, but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.
上記したようなエポキシ変性ポリシロキサン化合物と、二酸化炭素の反応において使用される触媒としては、塩基触媒およびルイス酸触媒が挙げられる。 Examples of the catalyst used in the reaction between the epoxy-modified polysiloxane compound as described above and carbon dioxide include a base catalyst and a Lewis acid catalyst.
塩基触媒として、トリエチルアミン、トリブチルアミンなどの第三級アミン類、ジアザビシクロウンデセン、ジアザビシクロオクタン、ピリジンなどの環状アミン、リチウムクロライド、リチウムブロマイド、フッ化リチウム、塩化ナトリウムなどのアルカリ金属塩類、塩化カルシウムなどのアルカリ土類金属塩類、テトラブチルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、ベンジルトリメチルアンモニウムクロライドなどの四級アンモニウム塩類、炭酸カリウム、炭酸ナトリウムなどの炭酸塩類、酢酸亜鉛、酢酸鉛、酢酸銅、酢酸鉄などの金属酢酸塩類、酸化カルシウム、酸化マグネシウム、酸化亜鉛などの金属酸化物、テトラブチルホスホニウムクロリドなどのホスホニウム塩類が挙げられる。 As base catalysts, tertiary amines such as triethylamine and tributylamine, cyclic amines such as diazabicycloundecene, diazabicyclooctane and pyridine, alkali metal salts such as lithium chloride, lithium bromide, lithium fluoride and sodium chloride , Alkaline earth metal salts such as calcium chloride, quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride, carbonates such as potassium carbonate and sodium carbonate, zinc acetate, lead acetate, copper acetate, Examples thereof include metal acetates such as iron acetate, metal oxides such as calcium oxide, magnesium oxide and zinc oxide, and phosphonium salts such as tetrabutylphosphonium chloride.
ルイス酸触媒としては、テトラブチル錫、ジブチル錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫オクトエートなどの錫化合物が挙げられる。 Examples of the Lewis acid catalyst include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin octoate.
上記触媒の量は、エポキシ変性ポリシロキサン化合物50質量部当たり、0.1〜100質量部、好ましくは0.3〜20質量部とすればよい。上記使用量が0.1質量部未満では、触媒としての効果が小さく、100質量部を超えると最終樹脂の諸性能を低下させる場合があるので好ましくない。しかし、残留触媒が重大な性能低下を引き起こすような場合は、純水で洗浄して除去してもよい。 The amount of the catalyst may be 0.1 to 100 parts by mass, preferably 0.3 to 20 parts by mass, per 50 parts by mass of the epoxy-modified polysiloxane compound. If the amount used is less than 0.1 parts by mass, the effect as a catalyst is small, and if it exceeds 100 parts by mass, various performances of the final resin may be deteriorated. However, if the residual catalyst causes a serious performance degradation, it may be removed by washing with pure water.
上記したエポキシ変性ポリシロキサン化合物と二酸化炭素の反応において、使用できる有機溶媒としては、ジメチルホルムアミド、ジメチルスルホオキシド、ジメチルアセトアミド、N−メチルピロリドン、N−エチルピロリドン、テトラヒドロフランなどが挙げられる。また、これら有機溶剤と他の貧溶剤、例えば、メチルエチルケトン、キシレン、トルエン、テトラヒドロフラン、ジエチルエーテル、シクロヘキサノンなどの混合系で使用してもよい。 Examples of the organic solvent that can be used in the reaction of the epoxy-modified polysiloxane compound with carbon dioxide include dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and tetrahydrofuran. These organic solvents and other poor solvents such as methyl ethyl ketone, xylene, toluene, tetrahydrofuran, diethyl ether, and cyclohexanone may be used in a mixed system.
本発明で用いるポリシロキサン変性ポリヒドロキシポリウレタン樹脂は、下記[式−B]で示されるように、上記のようにして得られた5員環環状カーボネートポリシロキサン化合物と、アミン化合物とを、有機溶媒の存在下、20℃〜150℃の温度下で反応させることで得ることができる。 The polysiloxane-modified polyhydroxypolyurethane resin used in the present invention comprises, as shown by the following [Formula-B], a 5-membered cyclic carbonate polysiloxane compound obtained as described above, an amine compound, and an organic solvent. It can obtain by making it react at the temperature of 20 to 150 degreeC in presence of this.
上記反応に使用するアミン化合物としては、ジアミンが好ましく、従来ポリウレタン樹脂の製造に使用されているものがいずれも使用でき、特に限定されない。例えば、メチレンジアミン、エチレンジアミン、トリメチレンジアミン、1,3−ジアミノプロパン、ヘキサメチレンジアミン、オクタメチレンジアミンなどの脂肪族ジアミン;フェニレンジアミン、3,3’−ジクロロ−4,4’−ジアミノジフェニルメタン、4,4’−メチレンビス(フェニルアミン)、4,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルスルホン、メタキシリレンジアミン、パラキシリレンジアミンなどの芳香族ジアミン;1,4−シクロヘキサンジアミン、4,4’−ジアミノシクロヘキシルメタン、1,4’−ジアミノメチルシクロヘキサン、イソホロンジアミンなどの脂環族ジアミン;モノエタノールジアミン、エチルアミノエタノールアミン、ヒドロキシエチルアミノプロピルアミンなどのアルカノールジアミンが挙げられる。更にその他現在市販されており、市場から容易に入手し得る化合物は、いずれも本発明において使用することができる。 As an amine compound used for the said reaction, a diamine is preferable and what was conventionally used for manufacture of a polyurethane resin can be used, and it is not specifically limited. For example, aliphatic diamines such as methylenediamine, ethylenediamine, trimethylenediamine, 1,3-diaminopropane, hexamethylenediamine, octamethylenediamine; phenylenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4 , 4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, metaxylylenediamine, paraxylylenediamine, and the like; 1,4-cyclohexanediamine, 4 , 4'-diaminocyclohexylmethane, 1,4'-diaminomethylcyclohexane, isophoronediamine and other alicyclic diamines; monoethanoldiamine, ethylaminoethanolamine, hydroxyethylaminopropylamine Like alkanol diamine is. Furthermore, any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.
上記のようにして得られたポリシロキサン変性ポリヒドロキシポリウレタン樹脂は、その樹脂分子中のポリシロキサンセグメントの占める割合が、樹脂分子に対して、その含有量が10〜75質量%となる量であることが好ましい。10質量%未満ではポリシロキサンセグメントに基づく表面エネルギーに伴う剥離性機能の発現が不十分となる。また、75質量%を超えるとポリヒドロキシウレタン樹脂の機械強度、耐磨耗性などの性能が不十分となるので好ましくはない。樹脂分子中のポリシロキサンセグメントの占める割合は、好ましくは20〜70質量%であり、より好ましくは30〜60質量%である。 In the polysiloxane-modified polyhydroxypolyurethane resin obtained as described above, the proportion of the polysiloxane segment in the resin molecule is such that the content is 10 to 75% by mass with respect to the resin molecule. It is preferable. If it is less than 10 mass%, the expression of the peelable function accompanying the surface energy based on the polysiloxane segment will be insufficient. On the other hand, if it exceeds 75% by mass, the performance of the polyhydroxyurethane resin such as mechanical strength and abrasion resistance becomes insufficient, such being undesirable. The proportion of the polysiloxane segment in the resin molecule is preferably 20 to 70% by mass, more preferably 30 to 60% by mass.
また、本発明のポリシロキサン変性ポリヒドロキシポリウレタン樹脂の数平均分子量(GPCで測定した、標準ポリスチレン換算値)は、2,000〜100,000程度であることが好ましく、より好ましくは5,000〜70,000程度である。 The number average molecular weight (standard polystyrene equivalent value measured by GPC) of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention is preferably about 2,000 to 100,000, more preferably 5,000 to About 70,000.
本発明で用いるポリシロキサン変性ポリヒドロキシポリウレタン樹脂は、5員環環状カーボネート基がアミン化合物と反応して生成する水酸基が、本発明の剥離性処理剤に対して更なる性能の向上をもたらすことになる。水酸基は親水性を有しているため、基材シートに対しての接着性を向上させるとともに、水酸基と架橋剤などとの反応を利用して更なる剥離性能の向上を図ることができる。 In the polysiloxane-modified polyhydroxypolyurethane resin used in the present invention, the hydroxyl group produced by the reaction of a 5-membered cyclic carbonate group with an amine compound brings about further improvement in the performance of the peelable treatment agent of the present invention. Become. Since the hydroxyl group has hydrophilicity, the adhesion to the base sheet can be improved, and further the peeling performance can be improved by utilizing the reaction between the hydroxyl group and the crosslinking agent.
本発明で用いるポリシロキサン変性ポリヒドロキシポリウレタン樹脂の水酸基価は、20〜300mgKOH/gであることが好ましい。水酸基の含有量が上記範囲未満であると、二酸化炭素削減効果が不足であり、一方、上記範囲を超えると、高分子化合物としての諸物性不足となる。 The hydroxyl value of the polysiloxane-modified polyhydroxypolyurethane resin used in the present invention is preferably 20 to 300 mgKOH / g. When the hydroxyl group content is less than the above range, the effect of reducing carbon dioxide is insufficient, while when it exceeds the above range, various physical properties as a polymer compound are insufficient.
上記したポリシロキサン変性ポリヒドロキシポリウレタン樹脂によって形成される被膜は、そのままでも剥離性処理層(剥離層)として十分に機能するものとなるが、さらに下記のように構成することで架橋被膜とすることも好ましい形態である。この際、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂中の水酸基と反応するような架橋剤と組み合わせることで、架橋被膜が形成されるようにすれば、剥離性処理層(剥離層)に、更に安定した剥離性能と耐熱性を付与することができる。この際に使用可能な架橋剤としては、水酸基と反応するような架橋剤はすべて使用でき、特に限定されない。例えば、アルキルチタネート化合物やポリイソシアネート化合物が挙げられるが、従来ポリウレタン樹脂の架橋に使用されている公知のポリイソシアネート化合物が好ましい。例えば、下記のような構造式のポリイソシアネートと他の化合物との付加体などが挙げられる。 The film formed from the polysiloxane-modified polyhydroxypolyurethane resin described above functions as a peelable treatment layer (peeling layer) even if it is as it is. Is also a preferred form. At this time, if a cross-linked film is formed by combining with a cross-linking agent that reacts with a hydroxyl group in the polysiloxane-modified polyhydroxy polyurethane resin, a more stable release can be achieved in the release treatment layer (release layer). Performance and heat resistance can be imparted. As the crosslinking agent that can be used in this case, any crosslinking agent that reacts with a hydroxyl group can be used and is not particularly limited. For example, an alkyl titanate compound or a polyisocyanate compound may be mentioned, but a known polyisocyanate compound conventionally used for crosslinking of a polyurethane resin is preferable. Examples include adducts of polyisocyanates having the following structural formula and other compounds.
また、本発明の剥離性処理剤は、使用する際における基材シートに対するコーティング適正や、成膜性の向上、更に、適度な剥離力とするためにポリシロキサンセグメントの含有量を調整するなどの目的で、従来公知の各種バインダー樹脂を混合して使用することができる。バインダー樹脂としては、上記のポリイソシアネート付加物などの架橋剤と化学的に反応し得るものが好ましいが、反応性を有していないものでも本発明では使用することができる。 In addition, the releasable treatment agent of the present invention is suitable for coating the base sheet when used, improving film formability, and adjusting the content of the polysiloxane segment to obtain an appropriate peel force. For the purpose, various conventionally known binder resins can be mixed and used. As the binder resin, those capable of chemically reacting with a crosslinking agent such as the above-mentioned polyisocyanate adduct are preferable, but those having no reactivity can also be used in the present invention.
これらのバインダー樹脂としては特に限定されない。例えば、アクリル樹脂、ポリウレタン樹脂、ポリエステル樹脂、ポリブタジエン樹脂、シリコーン樹脂、メラミン樹脂、フェノール樹脂、ポリ塩化ビニル樹脂、セルロース樹脂、アルキッド樹脂、変性セルロース樹脂、フッ素樹脂、ポリビニルブチラール樹脂、エポキシ樹脂、ポリアミド樹脂などを使用することができる。また、各種樹脂をシリコーンやフッ素で変性した樹脂なども使用することができる。これらのバインター樹脂を併用する場合、その使用量は、本発明で用いるポリシロキサン変性ポリヒドロキシポリウレタン樹脂に100質量部に対して5〜90質量部、より好ましくは、10〜60質量部程度を添加するとよい。 These binder resins are not particularly limited. For example, acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used. Also, resins obtained by modifying various resins with silicone or fluorine can be used. When these binder resins are used in combination, the amount used is 5 to 90 parts by mass, more preferably about 10 to 60 parts by mass, with respect to 100 parts by mass to the polysiloxane-modified polyhydroxypolyurethane resin used in the present invention. Good.
本発明の剥離性処理剤を用いて剥離性処理層(剥離面)を形成する対象となる基材は、特に制約されるものではなく、紙、ラミネート紙、合成樹脂フィルムなどの公知のものを任意に選択して用いることができる。 The base material to which the peelable treatment layer (peeling surface) is to be formed using the peelable treatment agent of the present invention is not particularly limited, and known materials such as paper, laminated paper, and synthetic resin film are used. It can be arbitrarily selected and used.
紙基材としては、上質紙、クラフト紙、セミグラシン紙、グラシン紙、模造紙、コピー用紙、新聞用紙などの紙類や各種の紙にプラスチック樹脂をラミネートした樹脂ラミネート紙、各種の紙に水溶性樹脂、防湿コートやサイズ剤処理を行った各種コート紙、合成紙などが挙げられる。 Paper base materials include high-quality paper, kraft paper, semi-glassine paper, glassine paper, imitation paper, copy paper, newspaper paper, resin-laminated paper in which plastic resin is laminated to various papers, and water-soluble in various papers. Examples include resin, moisture-proof coat, various coated papers subjected to sizing treatment, and synthetic paper.
フィルム基材としては、ポリオレフィン系フィルム、ポリエステル系フィルム、ポリアミド系フィルム、アセタート系フィルム、ポリカーボネートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、各種生分解性フィルム、各種植物由来フィルム、各種金属蒸着フィルム、各種金属酸化物蒸着フィルムなどが挙げられる。 Film base materials include polyolefin film, polyester film, polyamide film, acetate film, polycarbonate film, polyvinyl chloride film, polyvinylidene chloride film, various biodegradable films, various plant-derived films, and various metal-deposited films. And various metal oxide vapor-deposited films.
本発明の剥離性処理剤を用いて剥離性処理層(剥離面)を形成する際には、例えば、下記のような方法が挙げられる。本発明を特徴づけるポリシロキサン変性ポリヒドロキシポリウレタン樹脂を適当な有機溶剤に溶解又は分散させ、これを、例えば、ワイヤーバー方式、グラビア印刷法、スクリーン印刷法、グラビア版を用いたリバースロールコーティング法などの形成手段により塗工し、乾燥することで、良好な剥離性処理層(剥離面)が形成される。乾燥温度としては50〜120℃の範囲が好ましい。また、剥離性処理層の厚さは0.001〜5.00μmが好ましい。0.001μm未満では十分な剥離性能が得られにくく、5.00μm以上では剥離シートをロール状に巻いたり、積層した時の嵩張りによる不具合と、保存時に、剥離性処理層と塗工背面とがブロッキングを起こす恐れがあるので好ましくはない。より好ましくは0.01〜2.0μmである。 When forming a peelable treatment layer (peeled surface) using the peelable treatment agent of the present invention, for example, the following methods can be mentioned. The polysiloxane modified polyhydroxypolyurethane resin characterizing the present invention is dissolved or dispersed in a suitable organic solvent, and this is, for example, a wire bar method, a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, etc. A good peelable treatment layer (peeling surface) is formed by coating and drying with the forming means. The drying temperature is preferably in the range of 50 to 120 ° C. The thickness of the peelable treatment layer is preferably 0.001 to 5.00 μm. If it is less than 0.001 μm, it is difficult to obtain sufficient peeling performance, and if it is 5.00 μm or more, the release sheet is rolled or laminated, and there is a problem due to bulkiness when stored. Is not preferred because it may cause blocking. More preferably, it is 0.01-2.0 micrometers.
本発明の剥離性処理剤は、基材シートなどに塗工させた場合にポリシロキサンセグメントが表面に配向することから、ポリシロキサンセグメントの持つ非粘着性が付与されることで、優れた剥離性を示す剥離性処理層の形成が可能となる。それと共に、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂の有する水酸基が、基材シートと界面で強く相互作用することにより、基材に対する優れた接着性や可とう性といった性能を合わせて得ることができる。更に、地球温暖化ガス削減の観点からも、その構造中に二酸化炭素を取り入れた樹脂を用いることにより、本発明の剥離性処理剤によれば、従来品では到達できなかった環境対応の製品の提供が可能となる。 The releasable treatment agent of the present invention is excellent in releasability because the non-adhesiveness of the polysiloxane segment is imparted because the polysiloxane segment is oriented on the surface when applied to a substrate sheet or the like. It becomes possible to form a peelable treatment layer showing At the same time, the hydroxyl group of the polysiloxane-modified polyhydroxypolyurethane resin interacts strongly with the substrate sheet at the interface, so that performances such as excellent adhesion to the substrate and flexibility can be obtained. Furthermore, from the viewpoint of reducing global warming gas, by using a resin that incorporates carbon dioxide in its structure, according to the peelable treatment agent of the present invention, environmentally friendly products that could not be achieved with conventional products can be obtained. Provision is possible.
次に、参考例、具体的な製造例および実施例および比較例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。また、以下の各例における「部」および「%」は特に断りのない限り質量基準である。 Next, the present invention will be described in more detail with reference to reference examples, specific production examples, examples and comparative examples, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.
<製造例1>(5員環環状カーボネートポリシロキサン化合物の製造)
攪拌機、温度計、ガス導入管および還流冷却器を備えた反応容器中に、下記式Aで表される2価エポキシ変性ポリシロキサン(信越化学工業(株)製、X−22−163;エポキシ当量198g/mol)100部、N−メチルピロリドン100部、ヨウ化ナトリウム1.2部を加え、均一に溶解させた。図1は、2価エポキシ変性ポリシロキサンAの赤外吸収スペクトルである。その後、炭酸ガスを0.5リッター/分の速度でバブリングしながら、80℃で30時間加熱攪拌させた。
<Production Example 1> (Production of 5-membered cyclic carbonate polysiloxane compound)
In a reaction vessel equipped with a stirrer, a thermometer, a gas introduction pipe and a reflux condenser, a divalent epoxy-modified polysiloxane represented by the following formula A (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-163; epoxy equivalent) (198 g / mol) 100 parts, 100 parts of N-methylpyrrolidone and 1.2 parts of sodium iodide were added and dissolved uniformly. FIG. 1 is an infrared absorption spectrum of divalent epoxy-modified polysiloxane A. Thereafter, the mixture was heated and stirred at 80 ° C. for 30 hours while bubbling carbon dioxide at a rate of 0.5 liter / min.
反応終了後、得られた溶液に100部のn−ヘキサンを加えて希釈した後、分液ロートにて80部の純水で3回洗浄し、N−メチルピロリドンおよびヨウ化ナトリウムを除去した。n−ヘキサン液を硫酸マグネシウムで脱水後、濃縮して、無色透明の液状の5員環環状カーボネートポリシロキサン化合物(1−A)92部(収率89.7%)を得た。 After completion of the reaction, the resulting solution was diluted by adding 100 parts of n-hexane and then washed three times with 80 parts of pure water in a separatory funnel to remove N-methylpyrrolidone and sodium iodide. The n-hexane solution was dehydrated with magnesium sulfate and concentrated to obtain 92 parts (yield 89.7%) of a colorless and transparent liquid 5-membered cyclic carbonate polysiloxane compound (1-A).
得られた生成物(1−A)の赤外吸収スペクトル(堀場製作所 FT−720)は、図2で示したように、1,800cm-1付近に、図1に示した原料の赤外吸収スペクトルには存在しない環状カーボネート基のカルボニル基の吸収が確認された。また、生成物の数平均分子量は、図3に示したように、2,450(ポリスチレン換算値、東ソー;GPC−8220)であった。また、得られた5員環環状カーボネートポリシロキサン化合物(1−A)中には、18.1%の二酸化炭素が固定化されていた。 The infrared absorption spectrum (Horiba FT-720) of the obtained product (1-A) was near 1,800 cm −1 as shown in FIG. 2, and the infrared absorption of the raw material shown in FIG. Absorption of a carbonyl group of a cyclic carbonate group that does not exist in the spectrum was confirmed. Moreover, the number average molecular weight of the product was 2,450 (polystyrene conversion value, Tosoh; GPC-8220) as shown in FIG. Moreover, 18.1% of carbon dioxide was fixed in the obtained 5-membered cyclic carbonate polysiloxane compound (1-A).
<製造例2>(5員環環状カーボネートポリシロキサン化合物の製造)
製造例1で用いた2価エポキシ変性ポリシロキサンAの代わりに、下記式B(信越化学工業(株)製、KF−105;エポキシ当量485g/mol)で表わされる2価エポキシ変性ポリシロキサンBを用いた以外は、製造例1と同様に反応させて、無色透明の液状5員環環状カーボネートポリシロキサン化合物(1−B)99部(収率91%)を得た。生成物は、赤外吸収スペクトル、GPC、NMRで確認した。また、得られた5員環環状カーボネートポリシロキサン化合物(1−B)中には、8.3%の二酸化炭素が固定化されていた。
<Production Example 2> (Production of 5-membered cyclic carbonate polysiloxane compound)
Instead of the bivalent epoxy-modified polysiloxane A used in Production Example 1, divalent epoxy-modified polysiloxane B represented by the following formula B (manufactured by Shin-Etsu Chemical Co., Ltd., KF-105; epoxy equivalent 485 g / mol) is used. The reaction was conducted in the same manner as in Production Example 1 except that it was used to obtain 99 parts (yield 91%) of a colorless and transparent liquid 5-membered cyclic carbonate polysiloxane compound (1-B). The product was confirmed by infrared absorption spectrum, GPC and NMR. Further, 8.3% carbon dioxide was immobilized in the obtained 5-membered cyclic carbonate polysiloxane compound (1-B).
<製造例3>(5員環環状カーボネートポリシロキサン化合物の製造)
製造例1で用いた2価エポキシ変性ポリシロキサンAの代わりに、下記式C(信越化学工業(株)製、X−22−169AS;エポキシ当量533g/mol)で表わされる2価エポキシ変性ポリシロキサンCを用いた以外は、製造例1と同様に反応させて、無色透明の液状5員環環状カーボネートポリシロキサン化合物(1−C)71部(収率68%)を得た。生成物は、赤外吸収スペクトル、GPC、NMRで確認した。また、得られた5員環環状カーボネートポリシロキサン化合物(1−C)中には、7.6%の二酸化炭素が固定化されていた。
<Production Example 3> (Production of 5-membered cyclic carbonate polysiloxane compound)
In place of the divalent epoxy-modified polysiloxane A used in Production Example 1, a divalent epoxy-modified polysiloxane represented by the following formula C (X-122-169AS; epoxy equivalent: 533 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.) The reaction was conducted in the same manner as in Production Example 1 except that C was used to obtain 71 parts (yield 68%) of a colorless and transparent liquid 5-membered cyclic carbonate polysiloxane compound (1-C). The product was confirmed by infrared absorption spectrum, GPC and NMR. Further, 7.6% of carbon dioxide was immobilized in the obtained 5-membered cyclic carbonate polysiloxane compound (1-C).
<比較製造例1>(5員環環状カーボネート化合物の製造)
製造例1で用いた2価エポキシ変性ポリシロキサンAの代わりに、下記式Dで表される2価エポキシ化合物(ジャパンエポキシレジン(株)製、エピコート828;エポキシ当量187g/mol)を使い、製造例1と同様に反応させて、白色粉末の5員環環状カーボネート化合物(1−D)118部(収率95%)を得た。図4は、2価エポキシ化合物の赤外吸収スペクトルである。生成物は、赤外吸収スペクトル、GPC、NMRで確認した。また、得られた5員環環状カーボネート化合物(1−D)中には、19%の二酸化炭素が固定化されていた。
<Comparative Production Example 1> (Production of 5-membered cyclic carbonate compound)
Instead of the divalent epoxy-modified polysiloxane A used in Production Example 1, a divalent epoxy compound represented by the following formula D (manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 828; epoxy equivalent 187 g / mol) is used for production. Reaction was carried out in the same manner as in Example 1 to obtain 118 parts (yield 95%) of a white powder 5-membered cyclic carbonate compound (1-D). FIG. 4 is an infrared absorption spectrum of a divalent epoxy compound. The product was confirmed by infrared absorption spectrum, GPC and NMR. Further, 19% of carbon dioxide was immobilized in the obtained 5-membered cyclic carbonate compound (1-D).
<実施重合例1〜3>(ポリシロキサン変性ポリヒドロキシポリウレタン樹脂の製造)
製造例1〜3で得られた5員環環状カーボネートポリシロキサン化合物をそれぞれに用いて、下記のような手順で、実施例で用いるポリシロキサン変性ポリヒドロキシポリウレタン樹脂を、それぞれ合成した。先ず、攪拌機、温度計、ガス導入管および還流冷却器を備えた反応容器を窒素置換し、該容器内に、各5員環環状カーボネートポリシロキサン化合物、更に液の固形分が35%になるようにN−メチルピロリドンを加え均一に溶解した。次に、表1に記載した各アミン化合物を所定当量加え、90℃の温度で10時間攪拌し、アミン化合物が確認できなくなるまで反応させた。このようにして得られた3種類のポリシロキサン変性ポリヒドロキシポリウレタン樹脂の、固形分35%溶液の性状は、表1に記載の通りであった。
<Exemplary polymerization examples 1 to 3> (Production of polysiloxane-modified polyhydroxypolyurethane resin)
Using the 5-membered cyclic carbonate polysiloxane compounds obtained in Production Examples 1 to 3, polysiloxane-modified polyhydroxypolyurethane resins used in the examples were respectively synthesized by the following procedure. First, a reaction vessel equipped with a stirrer, a thermometer, a gas introduction pipe and a reflux condenser is purged with nitrogen, and each 5-membered cyclic carbonate polysiloxane compound and the solid content of the liquid are 35% in the vessel. N-methylpyrrolidone was added to and uniformly dissolved. Next, a predetermined equivalent amount of each amine compound described in Table 1 was added, and the mixture was stirred at a temperature of 90 ° C. for 10 hours until the amine compound could not be confirmed. The properties of the 35% solid content solution of the three types of polysiloxane-modified polyhydroxypolyurethane resins thus obtained were as shown in Table 1.
<比較重合例1>(ポリヒドロキシポリウレタン樹脂の製造)
攪拌機、温度計、ガス導入管および還流冷却器を備えた反応容器を窒素置換し、該容器内に、比較製造例1で得た5員環環状カーボネート化合物、さらに液の固形分が35%になるようにN−メチルピロリドンを加え均一に溶解した。次に、ヘキサメチレンジアミンを所定当量加え、90℃の温度で10時間攪拌し、アミン化合物が確認できなくなるまで反応させた。得られたポリヒドロキシポリウレタン樹脂の性状は、表1に記載の通りであった。
<Comparative polymerization example 1> (Production of polyhydroxypolyurethane resin)
A reaction vessel equipped with a stirrer, a thermometer, a gas introduction pipe and a reflux condenser was replaced with nitrogen, and the 5-membered cyclic carbonate compound obtained in Comparative Production Example 1 and the solid content of the liquid were 35% in the vessel. N-methylpyrrolidone was added and dissolved uniformly. Next, a predetermined equivalent of hexamethylene diamine was added and stirred for 10 hours at a temperature of 90 ° C. until the amine compound could not be confirmed. The properties of the obtained polyhydroxypolyurethane resin were as shown in Table 1.
<比較重合例2>(ポリウレタン樹脂)
下記のようにして、比較例で用いるポリウレタン樹脂を合成した。まず、攪拌機、温度計、ガス導入管および還流冷却器を備えた反応容器を窒素置換し、該容器内に、平均分子量約2,000のポリブチレンアジペート150部と、1,4−ブタンジオール15部とを、200部のメチルエチルケトンと、50部のジメチルホルムアミドからなる混合有機溶剤中に溶解した。その後、60℃でよく攪拌しながら、62部の水添加MDIを、171部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後、80℃で6時間反応させた。
<Comparative polymerization example 2> (Polyurethane resin)
The polyurethane resin used in the comparative example was synthesized as follows. First, a reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser was replaced with nitrogen, and in this vessel, 150 parts of polybutylene adipate having an average molecular weight of about 2,000, 1,4-butanediol 15 Were dissolved in a mixed organic solvent consisting of 200 parts of methyl ethyl ketone and 50 parts of dimethylformamide. Thereafter, 62 parts of water-added MDI dissolved in 171 parts of dimethylformamide was gradually added dropwise while stirring well at 60 ° C., and the reaction was allowed to proceed at 80 ° C. for 6 hours.
この溶液は固形分35%で3.2MPa・s(25℃)の粘度を有していた。この溶液から得られたフィルムは、破断強度45MPaで、破断伸度480%を有し、熱軟化温度は110℃であった。更に、該樹脂溶液100部、シリコーンオイル(SH−200、東レダウコーニング(株)製)3部およびメチルエチルケトン300部からなる配合液を比較試験用の剥離性処理剤とした。 This solution had a viscosity of 3.2 MPa · s (25 ° C.) at a solid content of 35%. The film obtained from this solution had a breaking strength of 45 MPa, a breaking elongation of 480%, and a thermal softening temperature of 110 ° C. Further, a blending solution comprising 100 parts of the resin solution, 3 parts of silicone oil (SH-200, manufactured by Toray Dow Corning Co., Ltd.) and 300 parts of methyl ethyl ketone was used as a peelable treatment agent for comparative tests.
<比較重合例3>(ポリシロキサン変性ポリウレタン樹脂)
下記のようにして、比較例で用いるポリシロキサン変性ポリウレタン樹脂を合成した。上記式Eで表され、かつ、平均分子量が約3,200であるポリジメチルシロキサンジオール150部および1,4−ブタンジオール10部を、200部のメチルエチルケトンと50部のジメチルホルムアミドからなる混合有機溶媒を加え、また、40部の水添加MDIを120部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後、80℃で6時間反応させた。この溶液は、固形分35%で1.6MPa・s(25℃)の粘度を有し、この溶液から得られたフィルムは破断強度21MPaで、破断伸度250%を有し、熱軟化温度は135℃であった。
<Comparative Polymerization Example 3> (Polysiloxane-modified polyurethane resin)
The polysiloxane modified polyurethane resin used in the comparative example was synthesized as follows. 150 parts of polydimethylsiloxanediol represented by the above formula E and having an average molecular weight of about 3,200 and 10 parts of 1,4-butanediol are mixed organic solvents comprising 200 parts of methyl ethyl ketone and 50 parts of dimethylformamide. In addition, 40 parts of water-added MDI dissolved in 120 parts of dimethylformamide was gradually added dropwise, and after completion of the addition, the mixture was reacted at 80 ° C. for 6 hours. This solution has a solid content of 35% and a viscosity of 1.6 MPa · s (25 ° C.). A film obtained from this solution has a breaking strength of 21 MPa, a breaking elongation of 250%, and a thermal softening temperature of It was 135 ° C.
<実施例1〜3、比較例1〜3>
実施重合例1〜3、比較重合例1〜3で調製した各樹脂溶液(固形分35%)をそれぞれ用い、これにそれぞれ架橋剤を加えて表2に示した剥離性処理剤(塗工液)を調製した。得られた液状の剥離性処理剤を用い、グラビア印刷により、厚み30μmのポリエチレンテレフタレートフィルム(東レ製)の表面に、固形分0.5g/m2の塗布量となるように、更に溶剤で希釈後、塗布した。その後、これを90℃で、3分間加熱乾燥して、実施例および比較例の剥離性シートをそれぞれ作成した。
<Examples 1-3, Comparative Examples 1-3>
Using each of the resin solutions (solid content 35%) prepared in Example Polymerization Examples 1 to 3 and Comparative Polymerization Examples 1 to 3, a cross-linking agent was added thereto, and the releasable treatment agent (coating solution) shown in Table 2 was added. ) Was prepared. Using the obtained liquid releasable treatment agent, further diluting with a solvent so that the coating amount is 0.5 g / m 2 on the surface of a polyethylene terephthalate film (manufactured by Toray) with a thickness of 30 μm by gravure printing. After that, it was applied. Then, this was heat-dried at 90 degreeC for 3 minute (s), and the peelable sheet of an Example and a comparative example was created, respectively.
<比較例4>
シリコーン樹脂(信越化学製、KS−841)100部と触媒(信越化学製、PL−7)1部とをトルエン1,000部に溶解して、シリコーン樹脂の塗料組成物を作製した。これを用い、上記と同様にして、基材シート上に塗布し、剥離性処理層を形成して剥離性シートを得た。
<Comparative example 4>
A silicone resin coating composition was prepared by dissolving 100 parts of a silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KS-841) and 1 part of a catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., PL-7) in 1,000 parts of toluene. Using this, in the same manner as described above, it was applied onto a substrate sheet to form a peelable treatment layer to obtain a peelable sheet.
以上ようにして作成した各剥離性シート上に、幅20mmのアクリル系粘着テープ(積水化学工業(株)製)を、自重2kgのゴムローラにて圧着し、室温(23℃、湿度46%)で1日、および、高温(40℃、湿度90%以上)で3日、それぞれ放置した。その後、各試料の剥離力、残留接着率、脱落性、筆記性、環境対応性の評価を行った。その際の評価方法および評価基準は、以下の通りである。 On each peelable sheet prepared as described above, an acrylic adhesive tape (made by Sekisui Chemical Co., Ltd.) having a width of 20 mm was pressure-bonded with a rubber roller having its own weight of 2 kg, and at room temperature (23 ° C., humidity 46%). Each was left for 1 day and at high temperature (40 ° C., humidity 90% or more) for 3 days. Thereafter, the peel strength, residual adhesion rate, drop-off property, writing property, and environmental compatibility of each sample were evaluated. The evaluation method and evaluation criteria at that time are as follows.
<剥離力>
各剥離性シートの剥離性処理層に、幅20mmの粘着テープを貼り付け、40℃で20g/cm2で荷重の条件で24時間保存した。その後、引張試験機を用いて180°の角度、300mm/分の速度で粘着テープを剥がした時の力(g)を20℃で測定した。この力が少ないほど、その剥離性シートは剥離力に優れたものであるといえる。
<Peeling force>
An adhesive tape having a width of 20 mm was applied to the peelable treatment layer of each peelable sheet, and stored at 40 ° C. and 20 g / cm 2 under a load condition for 24 hours. Thereafter, the force (g) when the adhesive tape was peeled off at an angle of 180 ° and a speed of 300 mm / min was measured at 20 ° C. using a tensile tester. It can be said that the smaller this force, the better the peelable sheet.
<残留接着率>
前記剥離力を測定した後の粘着テープを、2kgのテープローラーに1往復かけステンレス板#280に貼着し、測定用試料とした。一方、剥離力試験に使用していない清浄な粘着テープをステンレス板#280に貼着したものをブランクとし、30分後に引張試験機を用いて、180°の角度、300mm/分の速度で粘着テープを剥がした時の力(g)を20℃で測定した。そして、ブランク(320g/20mm)に対しての百分比を算出した。この値が100%に近いほど残留接着率が良好であるといえる。
<Residual adhesion rate>
The pressure-sensitive adhesive tape after measuring the peeling force was applied to a stainless steel plate # 280 by reciprocating once on a 2 kg tape roller to obtain a measurement sample. On the other hand, a clean adhesive tape that was not used in the peel force test was affixed to stainless steel plate # 280, and a blank was used, and after 30 minutes, a tensile tester was used and an adhesive was applied at an angle of 180 ° and a speed of 300 mm / min. The force (g) when the tape was peeled was measured at 20 ° C. And the percentage with respect to a blank (320g / 20mm) was computed. The closer this value is to 100%, the better the residual adhesion rate.
<脱落性>
実施例および比較例の各剥離性処理剤を用いて得た各剥離性シートの剥離性処理層に、50g/cm2の荷重でガーゼを一往復させた後の試料に対し、剥離性処理層の脱落性を目視で観察し、以下の基準で評価した。
○;剥離性処理層の脱落なし。
×;剥離性処理層の脱落が見られる。
<Falling property>
For the sample after reciprocating the gauze with a load of 50 g / cm 2 to the peelable treatment layer of each peelable sheet obtained by using each peelable treatment agent of Examples and Comparative Examples, the peelable treatment layer The drop-off property was visually observed and evaluated according to the following criteria.
○: No peeling off of the peelable treatment layer.
X: Dropping of the peelable treatment layer is observed.
<筆記性>
実施例および比較例の各剥離性処理剤を用いて得た各剥離性シートの剥離性処理層に、市販の油性マジックインキで字を書き、筆記の際のインクのはじきの有無を目視で観察し、以下の基準で評価した。
○;インクのはじきなし。
×;インクのはじきが見られる。
<Writing>
Write letters with commercially available oil-based magic ink on the peelable treatment layer of each peelable sheet obtained using each of the peelable treatment agents of Examples and Comparative Examples, and visually observe the presence or absence of ink repelling during writing. And evaluated according to the following criteria.
○: No ink repellency.
X: Ink repelling is observed.
<環境対応性>
二酸化炭素の固定化の有無で○×判断した。
<Environmental compatibility>
A judgment was made as to whether or not carbon dioxide was immobilized.
以上の本発明によれば、特定のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を含有してなる剥離性処理剤は、低温焼付可能で、基材に対する選択性がなく適用性に優れ、これによって形成された剥離処理層は、ペンなどで筆記可能であり、かつ適度な剥離力を有するものになる。これは、本発明の剥離性処理剤によって剥離性処理層を形成すると、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂が、ポリシロキサンセグメントを表面にして配向することにより、ポリシロキサンセグメントの持つ非粘着性が付与されることで、優れた剥離性を示す剥離性処理層の形成が可能となる。これと共に、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂の水酸基が基材シートとの界面で強く相互作用することにより、基材に対する良好な接着性や可とう性等の優れた性能を得ることができる。また、地球温暖化ガス削減の観点からも、その構造中に二酸化炭素を取り入れた樹脂を用いることにより、本発明の剥離性処理剤によれば、従来品では到達できなかった環境対応の製品の提供が可能となる。 According to the present invention described above, the releasable treatment agent containing a specific polysiloxane-modified polyhydroxypolyurethane resin can be baked at a low temperature, has no selectivity to a substrate, has excellent applicability, and is formed thereby. The release treatment layer can be written with a pen or the like and has an appropriate release force. This is because when the peelable treatment layer is formed by the peelable treatment agent of the present invention, the polysiloxane-modified polyhydroxypolyurethane resin is oriented with the polysiloxane segment as the surface, thereby imparting the non-stickiness of the polysiloxane segment. By doing so, it becomes possible to form a peelable treatment layer exhibiting excellent peelability. At the same time, the hydroxyl group of the polysiloxane-modified polyhydroxypolyurethane resin interacts strongly at the interface with the substrate sheet, so that excellent performance such as good adhesion to the substrate and flexibility can be obtained. Also, from the viewpoint of reducing global warming gas, by using a resin incorporating carbon dioxide in its structure, according to the release treatment agent of the present invention, environmentally friendly products that could not be reached by conventional products Provision is possible.
Claims (6)
式中のR1は、炭素数1〜12のアルキレン基(該基中にO、S、又はNの各元素および/又は−(C2H4O)b−で連結されていてもよい)を表す。式(1)中のR2は、ないか、又は、炭素数2〜20のアルキレン基を表し、R2は、脂環族基又は芳香族基に連結していてもよい。式(1)中のbは1〜300の数を表わし、aは1〜300の数を表す。] In the releasable treating agent comprising a resin having a siloxane segment, the resin is a polysiloxane derived from a reaction between a 5-membered cyclic carbonate polysiloxane compound represented by the following general formula (1) and an amine compound: A peelable treating agent, which is a modified polyhydroxypolyurethane resin.
R 1 in the formula is an alkylene group having 1 to 12 carbon atoms (which may be linked to each element of O, S, or N and / or — (C 2 H 4 O) b —). Represents. R 2 in Formula (1) is not present or represents an alkylene group having 2 to 20 carbon atoms, and R 2 may be linked to an alicyclic group or an aromatic group. In formula (1), b represents a number from 1 to 300, and a represents a number from 1 to 300. ]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010218700A JP5558992B2 (en) | 2010-09-29 | 2010-09-29 | Release agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010218700A JP5558992B2 (en) | 2010-09-29 | 2010-09-29 | Release agent |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2012072292A true JP2012072292A (en) | 2012-04-12 |
JP5558992B2 JP5558992B2 (en) | 2014-07-23 |
Family
ID=46168817
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010218700A Active JP5558992B2 (en) | 2010-09-29 | 2010-09-29 | Release agent |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5558992B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012082369A (en) * | 2010-10-14 | 2012-04-26 | Dainichiseika Color & Chem Mfg Co Ltd | Releasable treating agent |
JP2013234246A (en) * | 2012-05-08 | 2013-11-21 | Dainichiseika Color & Chem Mfg Co Ltd | Reactive polysiloxane compound and method for producing the same |
CN105399948A (en) * | 2015-12-08 | 2016-03-16 | 王景泉 | Isocyanate-free polyurethane UV resin and preparation method thereof |
KR20170118157A (en) * | 2015-02-20 | 2017-10-24 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Silicon Carbonate Polymers as Release Layers for Pressure Sensitive Adhesive Containing Articles |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01126389A (en) * | 1987-11-11 | 1989-05-18 | Dainichiseika Color & Chem Mfg Co Ltd | Releasable treatment agent |
JPH08245791A (en) * | 1995-02-21 | 1996-09-24 | Th Goldschmidt Ag | Production of organopolysiloxane having carbonate group |
JP2005331772A (en) * | 2004-05-20 | 2005-12-02 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using same, resist pattern forming method, and method for manufacturing printed wiring board |
WO2009112418A1 (en) * | 2008-03-11 | 2009-09-17 | Momentive Performance Materials Gmbh | Novel polycarbonate polyorganosiloxane and/or polyurethane polyorganosiloxane compounds |
-
2010
- 2010-09-29 JP JP2010218700A patent/JP5558992B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01126389A (en) * | 1987-11-11 | 1989-05-18 | Dainichiseika Color & Chem Mfg Co Ltd | Releasable treatment agent |
JPH08245791A (en) * | 1995-02-21 | 1996-09-24 | Th Goldschmidt Ag | Production of organopolysiloxane having carbonate group |
JP2005331772A (en) * | 2004-05-20 | 2005-12-02 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using same, resist pattern forming method, and method for manufacturing printed wiring board |
WO2009112418A1 (en) * | 2008-03-11 | 2009-09-17 | Momentive Performance Materials Gmbh | Novel polycarbonate polyorganosiloxane and/or polyurethane polyorganosiloxane compounds |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012082369A (en) * | 2010-10-14 | 2012-04-26 | Dainichiseika Color & Chem Mfg Co Ltd | Releasable treating agent |
JP2013234246A (en) * | 2012-05-08 | 2013-11-21 | Dainichiseika Color & Chem Mfg Co Ltd | Reactive polysiloxane compound and method for producing the same |
KR20170118157A (en) * | 2015-02-20 | 2017-10-24 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Silicon Carbonate Polymers as Release Layers for Pressure Sensitive Adhesive Containing Articles |
US10611123B2 (en) | 2015-02-20 | 2020-04-07 | 3M Innovative Properties Company | Silicone carbonate polymers as release layers for pressure sensitive adhesive containing articles |
KR102515652B1 (en) * | 2015-02-20 | 2023-03-30 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Silicone Carbonate Polymers as Release Layers for Pressure Sensitive Adhesive Containing Articles |
CN105399948A (en) * | 2015-12-08 | 2016-03-16 | 王景泉 | Isocyanate-free polyurethane UV resin and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JP5558992B2 (en) | 2014-07-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5705511B2 (en) | Polysiloxane-modified polyhydroxypolyurethane resin, resin-containing composition and resin production method | |
US20220041787A1 (en) | Self-healing, self-cleaning omniphobic composition, related articles and related methods | |
KR101536848B1 (en) | Self-crosslinkable polysiloxane-modified polyhydroxy polyurethane resin, process for producing said resin, resin material comprising said resin, and artificial leather produced utilizing said resin | |
WO2011065129A1 (en) | Five-membered cyclocarbonate polysiloxane compound and process for preparation of same | |
JP5558992B2 (en) | Release agent | |
TWI603999B (en) | Organic polyxanthane compound containing isocyanate group, method for producing the same, adhesive agent, adhesive and coating agent | |
CN104073177A (en) | Double-sided adhesive sheet and roll thereof | |
CN103665315A (en) | Synthesis method of modified polyurethane resin for circuit board | |
JPWO2018174198A1 (en) | Adhesive composition, adhesive and laminate | |
CN108410373A (en) | Contact adhesive and pressure sensitive adhesion sheet | |
JP5501943B2 (en) | Thermal recording material | |
JP2007023117A (en) | Urethaneurea composition, urethaneurea resin, and adhesive using the same | |
JP2009096996A (en) | Main agent for adhesives and production method thereof, composition for preparing urethane resin-based adhesive, and method for production of urethane resin-based adhesives | |
CN105008478A (en) | Double-sided adhesive sheet | |
JP5574428B2 (en) | Polysiloxane-modified polyhydroxypolyurethane resin, method for producing the resin, and resin composition | |
JP5069737B2 (en) | imitation leather | |
JP5345599B2 (en) | Release agent | |
JP5367679B2 (en) | imitation leather | |
CN105524577A (en) | Adhesive composition and adhesive sheet | |
JP5367680B2 (en) | Thermoplastic polyolefin resin skin material | |
JP5501942B2 (en) | Thermal recording material | |
JP2011132653A (en) | Imitation leather | |
JP2012046631A (en) | Self-crosslinkablee polysiloxane-modified polyhydroxy polyurethane resin, and method for producing the same | |
JP5662867B2 (en) | Thermal transfer image receiving sheet | |
JP2011231300A (en) | Weather strip material and weather strip |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120920 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131004 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131022 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131216 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140603 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140605 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5558992 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |