JPH02115291A - Pressure-sensitive adhesive - Google Patents
Pressure-sensitive adhesiveInfo
- Publication number
- JPH02115291A JPH02115291A JP26721688A JP26721688A JPH02115291A JP H02115291 A JPH02115291 A JP H02115291A JP 26721688 A JP26721688 A JP 26721688A JP 26721688 A JP26721688 A JP 26721688A JP H02115291 A JPH02115291 A JP H02115291A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- meth
- acrylate
- polymer
- pressure
- 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.)
- Pending
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 61
- 230000001070 adhesive effect Effects 0.000 claims abstract description 31
- 239000000853 adhesive Substances 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 19
- 229920001577 copolymer Polymers 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- -1 alkyl glycidyl ether Chemical compound 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 2
- CKQAOGOZKZJUGA-UHFFFAOYSA-N 1-nonyl-4-(4-nonylphenoxy)benzene Chemical compound C1=CC(CCCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCCC)C=C1 CKQAOGOZKZJUGA-UHFFFAOYSA-N 0.000 description 2
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical class CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- MVWPVABZQQJTPL-UHFFFAOYSA-N 2,3-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MVWPVABZQQJTPL-UHFFFAOYSA-N 0.000 description 1
- MYVRXWMSQGSJDD-UHFFFAOYSA-N 2-(2-methylpentoxymethyl)oxirane Chemical compound CCCC(C)COCC1CO1 MYVRXWMSQGSJDD-UHFFFAOYSA-N 0.000 description 1
- ATERKBCSRXXVEY-UHFFFAOYSA-N 2-(4-methylpentan-2-yloxymethyl)oxirane Chemical compound CC(C)CC(C)OCC1CO1 ATERKBCSRXXVEY-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- QCPOKPFKMYZWBC-UHFFFAOYSA-N 2-octoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCCCCCC)C(=O)C1=CC=CC=C1 QCPOKPFKMYZWBC-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- HYDWALOBQJFOMS-UHFFFAOYSA-N 3,6,9,12,15-pentaoxaheptadecane Chemical compound CCOCCOCCOCCOCCOCC HYDWALOBQJFOMS-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical class CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000001797 benzyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AZFQCTBZOPUVOW-UHFFFAOYSA-N methyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 AZFQCTBZOPUVOW-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- IZUPJOYPPLEPGM-UHFFFAOYSA-N sodium phthalic acid Chemical compound [Na+].OC(=O)C1=CC=CC=C1C(O)=O IZUPJOYPPLEPGM-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
- DSROZUMNVRXZNO-UHFFFAOYSA-K tris[(1-naphthalen-1-yl-3-phenylnaphthalen-2-yl)oxy]alumane Chemical compound C=1C=CC=CC=1C=1C=C2C=CC=CC2=C(C=2C3=CC=CC=C3C=CC=2)C=1O[Al](OC=1C(=C2C=CC=CC2=CC=1C=1C=CC=CC=1)C=1C2=CC=CC=C2C=CC=1)OC(C(=C1C=CC=CC1=C1)C=2C3=CC=CC=C3C=CC=2)=C1C1=CC=CC=C1 DSROZUMNVRXZNO-UHFFFAOYSA-K 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
(イ)発明の目的
[産業上の利用分野]
本発明は、高沸点を有する特殊なアクリル系単量体を構
成単量体単位とする重合体からなり、臭気が少なく毒性
も低い無公害な粘着剤に関するものである。Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention consists of a polymer whose constitutional monomer unit is a special acrylic monomer having a high boiling point, and which has no odor. It relates to a non-polluting adhesive with low toxicity.
[従来の技術]
従来の粘着剤はゴム系又はアクリル系重合体からなり、
アクリル系重合体としては、ブチルアクリレートや2−
エチルへキシルアクリレート等の単量体を主成分とした
重合体が用いられている。[Prior art] Conventional adhesives are made of rubber or acrylic polymers,
Examples of acrylic polymers include butyl acrylate and 2-
A polymer whose main component is a monomer such as ethylhexyl acrylate is used.
粘着剤には、粘着性の他、凝集力及び接着力の基本特性
がバランス良く満足されていることが要求されるが、上
記の単量体のみを使用する場合には、粘着性は良好であ
るが、凝集力及び接着力という基本特性を満足する重合
体は得られない。そこで、上記アクリル系重合体を得る
際、(メタ)アクリル酸(アクリル酸及び/又はメタク
リル酸を表す。以下同じ)等のカルボキシル基を有する
単量体及び/又はヒドロキシエチル(メタ)アクリレー
ト(アクリレート及び/又はメタクリレートを表す、以
下同じ)等の水酸基を有する単量体を共重合させること
によって、基本特性のバランスを調整しなければならな
いという問題がある。Adhesives are required to satisfy the basic characteristics of cohesive force and adhesive strength in addition to tackiness in a well-balanced manner, but when only the above monomers are used, the tackiness is not good. However, it is not possible to obtain a polymer that satisfies the basic properties of cohesive force and adhesive force. Therefore, when obtaining the above acrylic polymer, monomers having a carboxyl group such as (meth)acrylic acid (representing acrylic acid and/or methacrylic acid; the same applies hereinafter) and/or hydroxyethyl (meth)acrylate (acrylate There is a problem in that the balance of basic properties must be adjusted by copolymerizing a monomer having a hydroxyl group such as and/or methacrylate (the same shall apply hereinafter).
又、これらの粘着剤はトルエン、キシレン及び酢酸エチ
ル等の有機溶削に溶解した状態で使用されており、溶剤
を使用することによって種々の問題が生じていた。即ち
、作業者に対する有害性、火災の危険性、環境汚染、乾
燥速度、資源(78剤)の浪費等の問題である。Furthermore, these adhesives are used in a state dissolved in organic solvents such as toluene, xylene, and ethyl acetate, and the use of solvents has caused various problems. That is, there are problems such as toxicity to workers, risk of fire, environmental pollution, drying speed, and waste of resources (78 agents).
これらの問題を改良するため、近年重合手段として活性
エネルギー線を利用した粘着剤の検討がなされている。In order to improve these problems, studies have recently been made on adhesives that utilize active energy rays as a polymerization means.
この種の活性エネルギー線硬化型粘着剤は、有機溶剤を
本質的に必要としていないが、アクリル系重合体をアク
リル酸ブチル、アクリル酸−2−エチルヘキシル等の低
沸点のアクリル系単量体に溶解し、これに活性エネルギ
ー線を照射することによって硬化したものであるため、
その硬化時に又は場合により得られる製品が特有の臭気
を存しており、臭気公害を回避するための陸奥装置等を
備えなければならず、さらに粘着剤として要求される種
々の特性を具備させるために、多種類の単量体を併用し
共重合させる必要があるという問題がある。This type of active energy ray-curable adhesive does not essentially require an organic solvent, but the acrylic polymer is dissolved in a low boiling point acrylic monomer such as butyl acrylate or 2-ethylhexyl acrylate. However, since it is cured by irradiating it with active energy rays,
The product obtained during curing or in some cases has a unique odor, and must be equipped with a Mutsu device, etc. to avoid odor pollution, and in order to have various properties required as an adhesive. Another problem is that it is necessary to use and copolymerize many types of monomers.
[本発明が解決しようとする課題]
本発明は、種々の単量体を共重合することによって、粘
着剤が備えるべき粘着性、凝集力及び接着力の基本特性
を調整する必要がなく、又低沸点のアクリル系単量体を
本質的に含ませる必要もない粘着剤を提供することによ
り、従来技術における種々の問題点、即ち粘着剤の製造
工程における煩雑性、臭気対策等を改善することを課題
とする。[Problems to be solved by the present invention] By copolymerizing various monomers, the present invention eliminates the need to adjust the basic properties of tackiness, cohesive force, and adhesive force that should be provided by the pressure-sensitive adhesive. By providing an adhesive that does not essentially require the inclusion of a low-boiling point acrylic monomer, various problems in the prior art, such as complexity in the adhesive manufacturing process and odor countermeasures, can be improved. The task is to
(ロ)発明の構成
[課題を解決するための手段]
本発明者等は、鋭意検討した結果、以下に示す単量体[
A]を構成単量体単位とする重合体が、接着力、凝集力
及び粘着性の全てを満足する粘着剤となり得ることを見
いだし、本発明を完成するに到った。(b) Structure of the invention [Means for solving the problem] As a result of intensive study, the present inventors have discovered the following monomer [
It was discovered that a polymer having A] as a constituent monomer unit can be used as a pressure-sensitive adhesive that satisfies all of adhesive force, cohesive force, and tackiness, and the present invention was completed.
即ち、本発明は、下記単量体[A]の少なくとも1種又
はこれとその他の共重合性単量体との重合体を含有する
粘着剤である。That is, the present invention is an adhesive containing at least one of the following monomers [A] or a polymer of this and other copolymerizable monomers.
OOH
(上式中のRは炭素数が4〜18個のアルキル基を表す
。)
以下本発明の粘着剤における重合体に関し、その構成単
量体及び重合方法について説明する。OOH (R in the above formula represents an alkyl group having 4 to 18 carbon atoms) Regarding the polymer in the adhesive of the present invention, its constituent monomers and polymerization method will be explained below.
く単量体[A1〉
単量体[A]は次式で示される単官能アクリレートであ
る。Monomer [A1] Monomer [A] is a monofunctional acrylate represented by the following formula.
OOH
上式においてRは、炭素数が4〜18のアルキル基を表
す。OOH In the above formula, R represents an alkyl group having 4 to 18 carbon atoms.
この単量体[A]は種々の反応記より得られるが、例え
ばアルキルグリシジルエーテルとアクリル酸との付加反
応によって容易に得ることができる。This monomer [A] can be obtained through various reaction methods, and can be easily obtained, for example, by an addition reaction between an alkyl glycidyl ether and acrylic acid.
アルキルグリシジルエーテルとしては、アルキル基の炭
素数が4〜18のものであれば、いずれでも良く、例え
ば2−エチルブチルグリシジルエテル、2−エチルへキ
シルグリシジルエーテル(市販品として例えば、ウィル
ミントン・ケミカル社製のrMK−11’6Jがある)
、2−メチルペンチルグリシジルエーテル、4−メチル
−2−ペンチルグリシジルエーテル
エーテル、3−へブチルグリシジルエーテル、ドデカン
グリシジルエーテル、テトラデカングリシジルエーテル
(この化合物とドデカングリシジルエーテルとの混合物
の市販品として例えば、ウィルミントン・ケミカル社製
のrWc−Ellがある)、ブチルグリシジルエーテル
(市販品として例えば、四日市合成株式会社製のrDY
−BP Jがある)、ヘキサデカングリシジルエーテル
、オクタデカングリシジルエーテル等の、直鎖状又は分
枝状のアルキル基を存するものがある。Any alkyl glycidyl ether may be used as long as the alkyl group has 4 to 18 carbon atoms, such as 2-ethyl butyl glycidyl ether, 2-ethylhexyl glycidyl ether (commercially available products such as Wilmington Chemical Co., Ltd. There is rMK-11'6J made by the company)
, 2-methylpentyl glycidyl ether, 4-methyl-2-pentyl glycidyl ether, 3-hebutyl glycidyl ether, dodecane glycidyl ether, tetradecane glycidyl ether (commercially available mixtures of this compound and dodecane glycidyl ether include Will rWc-Ell manufactured by Minton Chemical Co.), butyl glycidyl ether (commercially available products include rDY manufactured by Yokkaichi Gosei Co., Ltd.)
-BPJ), hexadecane glycidyl ether, octadecane glycidyl ether, etc., which have a linear or branched alkyl group.
アクリル酸とグリシジルエーテルとを反応させるときの
仕込み割合としては、従来の技術に従えば良く、例えば
グリシジルエーテル1モルに対し、アクリル酸0.9〜
1.0モルの割合とするのが好ましい。The charging ratio when reacting acrylic acid and glycidyl ether may be according to conventional techniques, for example, 0.9 to 1 mol of acrylic acid to 1 mole of glycidyl ether.
Preferably, the proportion is 1.0 mol.
アクリル酸とグリシジルエーテルとの付加反応は、触媒
を添加しないで加熱することによっても進行するが、一
般に公知の触媒を添加した反応溶媒中で反応させる方が
、反応速度が速く好ましい。The addition reaction between acrylic acid and glycidyl ether can also proceed by heating without adding a catalyst, but it is generally preferable to carry out the reaction in a reaction solvent containing a known catalyst because the reaction rate is faster.
好ましい触媒としては、三弗化ホウ素又はスルホン酸等
のルイス酸型化合物;パラトルエンスルホン酸又はトリ
フェニルスルホニウムクロライド等のスルホニウム塩類
;苛性ソーダ、苛性カリ又は水酸化リチウム等の金属水
酸化物類;トリエチルアミン、ベンジルジメチルアミン
又はジメチルアミン塩酸塩等のアミン頻;テトラブチル
アンモニウムブロマイド等の第4級アンモニウム塩類;
塩化錫等の金属ハロゲン化物類:ベンゼンホスホン酸、
トリフェニルメチルホスホニウムヨータイド等のホスホ
ニウム塩類;フタル酸のナトリウム塩等の有機酸塩類等
がある。Preferred catalysts include Lewis acid type compounds such as boron trifluoride or sulfonic acid; sulfonium salts such as para-toluenesulfonic acid or triphenylsulfonium chloride; metal hydroxides such as caustic soda, caustic potash or lithium hydroxide; triethylamine, Amine salts such as benzyldimethylamine or dimethylamine hydrochloride; Quaternary ammonium salts such as tetrabutylammonium bromide;
Metal halides such as tin chloride: benzenephosphonic acid,
Examples include phosphonium salts such as triphenylmethylphosphonium iotide; and organic acid salts such as sodium phthalic acid.
触媒の使用量は、アクリル酸とグリシジルエーテルの合
計1100重量部(以下部とあるのは重量部を表す)に
対して0.0001〜20部、より好ましく子よo、o
os〜5部の範囲とするのがよい。The amount of the catalyst used is 0.0001 to 20 parts, more preferably 0.0001 to 20 parts, based on a total of 1100 parts by weight of acrylic acid and glycidyl ether.
The range is preferably from os to 5 parts.
溶媒としては、例えばジプロピルケトン等のケトン類、
ヘンゼン、トルエン、石油等の芳香族炭化水素類;酢酸
エチル、酢酸ブチル、乳酸ブチル等のエステル類;エチ
ルアルコール、ジアセトンアルコール等のアルコール類
;イソプロピルセロソルブ、酢酸セロソルブ等のセロソ
ルブ頚;アセチルエチルエーテル、テトラエチレングリ
コールジエチルエーテル等のエーテル頚;アセト酢酸等
の中から選ばれた1種又は2種以上を用いることができ
る。Examples of solvents include ketones such as dipropyl ketone,
Aromatic hydrocarbons such as henzene, toluene, and petroleum; Esters such as ethyl acetate, butyl acetate, and butyl lactate; Alcohols such as ethyl alcohol and diacetone alcohol; Cellosolve necks such as isopropyl cellosolve and celloacetate; acetyl ethyl ether , tetraethylene glycol diethyl ether, and acetoacetic acid. One or more of them can be used.
溶媒の使用量としては、全反応物中に占める割合を30
〜80重量%(以下%とあるのは重量%を表す)の範囲
とするのがよい。The amount of solvent used is 30% of the total reactants.
It is preferable that the content be in the range of ~80% by weight (hereinafter, % represents weight%).
又、必要に応じて、反応中のゲル化を防止するために、
フェノール類及びキノン類等の化合物を重合防止剤とし
て使用することができる。又、これらの重合防止剤は反
応後に添加した場合、重合体が貯蔵中にゲル化するのを
防止する効果もある。Also, if necessary, to prevent gelation during the reaction,
Compounds such as phenols and quinones can be used as polymerization inhibitors. Furthermore, when these polymerization inhibitors are added after the reaction, they also have the effect of preventing the polymer from gelling during storage.
好ましい重合防止剤の具体例としては、例えばハイドロ
キノン、ハイドロキノンモノメチルニーテノン、ナフト
キノン、ジフェニルベンゾキノン等のキノン類、フェノ
チアジン及び銅塩類等がある。Specific examples of preferred polymerization inhibitors include quinones such as hydroquinone, hydroquinone monomethyl nitenone, naphthoquinone, and diphenylbenzoquinone, phenothiazine, and copper salts.
これらの重合防止剤の使用量は単量体[AIに対して0
.0001〜0.3%の範囲とするのがよい。The amount of these polymerization inhibitors used is 0 for the monomer [AI].
.. It is preferable to set it in the range of 0001 to 0.3%.
く共重合性単量体〉
単量体成分として単量体[A]のみを用いることにより
、粘着剤としての特性が充分に優れた重合体を得ること
ができるが、単量体[A]をこれと共重合性の単量体と
共重合することもできる。Copolymerizable monomer> By using only monomer [A] as a monomer component, a polymer with sufficiently excellent properties as an adhesive can be obtained, but monomer [A] It is also possible to copolymerize with a monomer copolymerizable with this.
共重合性単量体の中で、以下に示す単量体が特に好まし
い。Among the copolymerizable monomers, the following monomers are particularly preferred.
■単量体[B]
単量体[B]は次式で示される単官能アクリレートであ
り、金属及びガラス等との接着性及び凝集力を向上させ
ることができる効果がある。(2) Monomer [B] Monomer [B] is a monofunctional acrylate represented by the following formula, and has the effect of improving adhesiveness and cohesive force with metals, glass, etc.
CH2=CHC0士(CH,)、CO叶7H(m=2〜
7、f=1〜7)
この単官能アクリレートは1種類又は2種類以上併用し
てもよい。これに該当する単官能アクリレートの具体例
は、アクリル酸に例えばラクトン類を開環付加重合させ
た化合物で、特開昭6067446号公報にその例が示
され、市販品の一例として「アロニックスト5300J
(東亜合成化学工業株式会社製商品名、m=5、N
=1〜5、lの平均値−1,8)が挙げられる。CH2=CHC0ushi (CH,), CO Kano7H (m=2~
7, f=1-7) These monofunctional acrylates may be used alone or in combination of two or more. A specific example of a monofunctional acrylate corresponding to this is a compound obtained by ring-opening addition polymerization of, for example, a lactone to acrylic acid.
(Product name manufactured by Toagosei Chemical Industry Co., Ltd., m = 5, N
=1 to 5, average value of l -1.8).
上記単官能アクリレートの他の例は、アクリル酸の付加
重合体で、市販品として[アロニソクスM−5600J
(東亜合成化学工業株式会社製商品名、m=2、l
=1〜7、lの平均値−1,4)が挙げられる。Another example of the above-mentioned monofunctional acrylate is an addition polymer of acrylic acid, which is commercially available as [Alonisox M-5600J].
(Product name manufactured by Toagosei Chemical Industry Co., Ltd., m = 2, l
=1 to 7, average value of l -1,4).
■単量体[B]基以外共重合性単量体
単量体[B]基以外共重合性単量体として、以下に示し
た単官能(メタ)アクリレートを用いることもできる。(2) Copolymerizable monomer other than the monomer [B] group As the copolymerizable monomer other than the monomer [B] group, the following monofunctional (meth)acrylates can also be used.
■)フェノール又はアルキルフェノールのエチレンオキ
シド、プロピレンオキシド等のアルキレンオキシド重付
加物の(メタ)アクリレート例えば
・ポリエチレングリコールモノフェニルエーテル千ノ
(メタ)アクリレート、
・ポリエチレングリコールモノノニルフェニルエーテル
モノ(メタ)アクリレート、
・ポリプロピレングリコールモノノニルフェニルエーテ
ルモノ (メタ)アクリレート。■) (Meth)acrylates of alkylene oxide polyadducts of phenol or alkylphenols such as ethylene oxide and propylene oxide.For example, polyethylene glycol monophenyl ether.
(meth)acrylate, ・Polyethylene glycol monononylphenyl ether mono(meth)acrylate, ・Polypropylene glycol monononylphenyl ether mono(meth)acrylate.
2)モノエポキシドと(メタ)アクリル酸との反応より
得られる(メタ)アクリレート例えば
・2−ヒドロキシ−3−へキシルオキシプロピル(メタ
)アクリレート、
・2−ヒドロキシ−3−フェノキンプロピル(メタ)ア
クリレート、
・2−ヒドロキシ−3−ブトキシプロピル(メタ)アク
リレート。2) (Meth)acrylate obtained from the reaction of monoepoxide and (meth)acrylic acid, such as 2-hydroxy-3-hexyloxypropyl (meth)acrylate, 2-hydroxy-3-phenoquinepropyl (meth) Acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate.
3)水酸基含有(メタ)アクリレートにラクトン類を開
環重付加させた(メタ)アクリレート例えば
・2−ヒドロキシエチル(メタ)アクリレートの6−ヘ
キサノリド重付加物。3) A (meth)acrylate obtained by ring-opening polyaddition of a lactone to a hydroxyl group-containing (meth)acrylate, such as a 6-hexanolide polyadduct of 2-hydroxyethyl (meth)acrylate.
4)その他の単官能アルコールの(メタ)アクフレート
例えば
・ジシクロペンテニルオキシエチル(メタ)アクリレー
ト、
テトラヒドロフルフリルオキシエチル(メタ)アクリレ
ート(テトラヒドロフルフリルアコールのエチレンオキ
シド付加物の(メタ)アクレート)、
・テトラヒドロフルフリルアルコールの6−ヘキサノリ
ド重付加物の(メタ)アクリレート。4) (Meth)acflates of other monofunctional alcohols, such as dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryloxyethyl (meth)acrylate ((meth)acrylate of ethylene oxide adduct of tetrahydrofurfuryl alcohol), (Meth)acrylate of 6-hexanolide polyadduct of tetrahydrofurfuryl alcohol.
単量体(A)および単量体CB)以外の上記単官能(メ
タ)アクリレートの分子量は、200〜1000の範囲
であることが望ましい。分子量が200未満であると、
単官能(メタ)アクリレートの蒸気圧が高いため臭気に
よる問題を発生し、一方分子量が1000を越えると、
粘着剤の粘度が高くなると共に、一分子当たりの(メタ
)アクリロイル基の濃度が低下するため、重合性が不充
分となることがある。The molecular weight of the monofunctional (meth)acrylates other than monomer (A) and monomer CB) is preferably in the range of 200 to 1000. When the molecular weight is less than 200,
The high vapor pressure of monofunctional (meth)acrylates causes odor problems, while when the molecular weight exceeds 1000,
As the viscosity of the adhesive increases, the concentration of (meth)acryloyl groups per molecule decreases, which may result in insufficient polymerizability.
共重合性単量体の共重合量は、全単量体における割合が
好ましくは0〜50%、より好ましくは0〜40%の範
囲であり、その量が増加するにつれて単量体[A]に固
有の優れた特性が重合体におい単量体[A]又はこれと
共重合性の単量体の重合は、通常のラジカル重合法、即
ち溶液重合、乳化重合及び懸濁重合等による方法又は紫
外線(以下Uvという)及び電子線(以下EBという)
で代表される活性エネルギー線を照射する方法によって
行えばよい。The copolymerized amount of the copolymerizable monomer is preferably in the range of 0 to 50%, more preferably 0 to 40% of the total monomers, and as the amount increases, the proportion of the monomer [A] Polymerization of monomer [A] or monomers copolymerizable with it can be carried out by ordinary radical polymerization methods, such as solution polymerization, emulsion polymerization, suspension polymerization, etc. Ultraviolet rays (hereinafter referred to as Uv) and electron beams (hereinafter referred to as EB)
This may be carried out by a method of irradiating active energy rays as typified by:
/8液重合、乳化重合及び懸濁重合等を重合手段とする
場合は、熱重合開始剤を用いることが望ましく、その具
体例としては例えば、アゾビスイソブチロニトリル(以
下AIBNと略称する)等のアゾ化合物類;ケトンパー
オキサイド、ハイドロパーオキサイド、アルキルパーオ
キサイド、アシルパーオキサイド、パーオキシエステル
の名称で総称される各種有機過酸化物類;過硫酸アンモ
ニウム、過硫酸カリウム、過酸化水素等の無機パーオキ
サイド類等がある。/8 When using liquid polymerization, emulsion polymerization, suspension polymerization, etc. as a polymerization method, it is desirable to use a thermal polymerization initiator, and specific examples thereof include azobisisobutyronitrile (hereinafter abbreviated as AIBN). Azo compounds such as ketone peroxide, hydroperoxide, alkyl peroxide, acyl peroxide, peroxy ester; various organic peroxides such as ammonium persulfate, potassium persulfate, hydrogen peroxide, etc. There are inorganic peroxides, etc.
体側としては、ベンゾイン、ベンゾインメチルエーテル
、ベンゾインエチルエーテル、ベンゾインイソプロピル
エーテル、ベンゾインイソブチルエーテル、ベンゾイン
オクチルエーテル等のベンゾイン化合物:ベンジル、ジ
アセチル、メチルアントラキノン、アセトフェノン、ペ
ンゾフヱノン、2−ヒドロキシ−2−メチルプロピオフ
ェノン等のカルボニル化合物;ジフェニルジスルフイッ
ド、ジチオカーバメート等の硫黄化合物;α−クロルメ
チルナフタリン等のナフクレン系化合物;アントラセン
、塩化鉄等の金属塩等がある。一方、EBやγ線のよう
な電離性放射線の照射を重合手段とする場合は、光開始
剤を用いなくても速やかに硬化するので、特に光開始剤
を用いる必要はない。On the body side, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, etc.: benzyl, diacetyl, methylanthraquinone, acetophenone, penzophenone, 2-hydroxy-2-methylpropio Carbonyl compounds such as phenone; sulfur compounds such as diphenyl disulfide and dithiocarbamate; naphcrene compounds such as α-chloromethylnaphthalene; and metal salts such as anthracene and iron chloride. On the other hand, when irradiation with ionizing radiation such as EB or gamma rays is used as a polymerization means, there is no need to use a photoinitiator because the polymer is quickly cured without the use of a photoinitiator.
活性エネルギー線の照射は常法に従って行えば良い。Irradiation with active energy rays may be performed according to a conventional method.
好ましくは0.1〜lO%の範囲であるのがよい。It is preferably in the range of 0.1 to 10%.
〈その他の成分〉
本発明の粘着剤は本質的に溶剤を必要としないものであ
るが、例えば、メチルエチルケトン、メチルイソブチト
ルケトン等のケトン類;酢酸エチル、酢酸ブチル等の酢
酸エステル類;ベンゼン、トルエン、キシレン等の芳香
族炭化水素等その他の一般によく用いられる有機溶剤に
よって、本発明の粘着剤を希釈して使用することも可能
である。<Other components> The adhesive of the present invention essentially does not require a solvent, but includes, for example, ketones such as methyl ethyl ketone and methyl isobutytorketone; acetic acid esters such as ethyl acetate and butyl acetate; benzene. It is also possible to use the adhesive of the present invention diluted with other commonly used organic solvents such as aromatic hydrocarbons such as toluene and xylene.
又、本発明の粘着剤に可溶なその他の重合体を、それら
が溶解可能な範囲で添加することも可能であるが、粘着
特性をtUなわないようにするため、その使用量は全重
合体に占める割合を好ましくは0〜50%、より好まし
くは0〜40%の範囲とするのがよい。It is also possible to add other polymers that are soluble in the adhesive of the present invention, but in order to keep the adhesive properties from exceeding tU, the amount used should be limited to the total weight. The proportion in the coalescence is preferably in the range of 0 to 50%, more preferably in the range of 0 to 40%.
さらに、従来から粘着剤の分野で使用されている各種の
添加剤、例えばレベリング剤、消泡剤、タッキファイヤ
−及び流動抑制剤等を、本発明の粘着剤に配合すること
も可能である。これらの添加剤の配合量については、従
来の技術に従って定めれば良い。Furthermore, various additives conventionally used in the field of adhesives, such as leveling agents, antifoaming agents, tackifiers, flow inhibitors, etc., can also be incorporated into the adhesive of the present invention. The amounts of these additives may be determined according to conventional techniques.
[実施例] 以下に実施例により本発明を更に具体的に説明〜。[Example] The present invention will be explained in more detail with reference to Examples below.
まず、単量体[A]を以下の様にして製造した。First, monomer [A] was produced as follows.
製造例1
2−エチルへキシルグリシジルエーテル(ウイルミント
ン・ケミカル社製のrMK−116]) 112 gと
アクリル酸253gを酢酸ブチル1026 gに溶解し
、この’G?&に重合防止剤としてハイドロキノンモノ
メチルエーテル0.51 g及び触媒としてテトラブチ
ルアンモニウムブロマイド10.3gを加え、反応温度
120°Cにおいて、還流させながら7時間反応させ
た後、水洗、脱溶剤し、前記−綴代におけるRが炭素数
8のアルキル基である単量体CA]を得た。Production Example 1 112 g of 2-ethylhexyl glycidyl ether (rMK-116 manufactured by Wilmington Chemical Co.) and 253 g of acrylic acid were dissolved in 1026 g of butyl acetate, and this 'G? 0.51 g of hydroquinone monomethyl ether as a polymerization inhibitor and 10.3 g of tetrabutylammonium bromide as a catalyst were added to &, and the mixture was reacted for 7 hours under reflux at a reaction temperature of 120°C. - Monomer CA in which R in the binding margin is an alkyl group having 8 carbon atoms] was obtained.
リシジルエーテルとの混合物(ウイルミントンケミカル
社製のrhc−8J ) 822 gとアクリル酸20
4gを酢酸ブチル1026 gに溶かし、この溶液に製
造例1と同一種で同量の重合防止剤、触媒を加え、反応
温度120°Cにおいて還流させながら8時間反応させ
た後、水洗、脱溶剤し、前記−綴代におけるRが炭素数
IO及び14のアルキル基である単量体[A]の混合物
を得た。822 g of a mixture with lysidyl ether (rhc-8J manufactured by Wilmington Chemical Co.) and 20 g of acrylic acid.
4 g was dissolved in 1026 g of butyl acetate, and the same type and amount of polymerization inhibitor and catalyst as in Production Example 1 were added to this solution. After reacting for 8 hours under reflux at a reaction temperature of 120°C, the solution was washed with water and desolventized. Then, a mixture of monomer [A] in which R in the above-mentioned binding margin was an alkyl group having IO and 14 carbon atoms was obtained.
製造例3
プチルグリンジルエーテル(四日市合成■製のrDY−
BP J ) 655 gとアクリル酸363gを酢酸
ブチル1034 gに溶かし、この1容ン夜に製造例1
と同一種で同量の重合防止剤、触媒を加え、反応温度1
20°Cにおいて還流させながら10時間反応させた後
、水洗、脱溶剤し、前記−綴代におけるRが炭素数4の
アルキル基である単量体[A]を得た。Production Example 3 Butylgrindyl ether (rDY- manufactured by Yokkaichi Gosei ■)
Dissolve 655 g of BPJ) and 363 g of acrylic acid in 1034 g of butyl acetate, and add 1 volume of this to 363 g of acrylic acid.
Add the same type and the same amount of polymerization inhibitor and catalyst, and raise the reaction temperature to 1.
After reacting for 10 hours while refluxing at 20°C, the mixture was washed with water and the solvent was removed to obtain a monomer [A] in which R in the above-mentioned binding margin is an alkyl group having 4 carbon atoms.
以下の各実施例で作成した感圧性粘着剤シートの各種物
性は、温度23°C5湿度65%の室内において下記の
方法により測定した。Various physical properties of the pressure-sensitive adhesive sheets prepared in the following examples were measured in a room at a temperature of 23° C. and a humidity of 65% by the following method.
接着カニ
感圧性粘着剤シートをステンレス板に圧着し、JIS−
に6854に従って、180°剥離試験を行った。Adhesive crab pressure sensitive adhesive sheet is crimped onto a stainless steel plate and JIS-
A 180° peel test was conducted in accordance with 6854.
保持カニ
感圧性粘着剤シートをアルミ板に圧着し、40°Cのオ
ーブン中で感圧性粘着剤シートの圧着面を下方に向けて
水平に保持し、感圧性粘着剤シート1平方インチ当り1
kgの荷重が掛かるようにおもりを付け、感圧性粘着剤
シートがアルミ板から剥離脱落するまでの時間を測定し
た。180分後においても脱落しないものはNCと表示
した。Press the pressure-sensitive adhesive sheet onto an aluminum plate, hold it horizontally in an oven at 40°C with the pressure-sensitive adhesive sheet facing downward, and apply 1.5% per square inch of the pressure-sensitive adhesive sheet.
A weight was attached so that a load of kg was applied, and the time until the pressure-sensitive adhesive sheet peeled off from the aluminum plate was measured. Those that did not fall off even after 180 minutes were labeled as NC.
ボールタック:
感圧性粘着剤シートをその粘着剤塗布側を表にして角度
30″の斜面に貼付し、JIS20237に従って測定
した。Ball tack: A pressure sensitive adhesive sheet was attached to an inclined surface at an angle of 30'' with the adhesive coated side facing up, and measurements were taken according to JIS20237.
実施例1
製造例1で得た単量体[A115g、酢酸エチル50g
及びトルエン70gを窒素気流中で加熱撹拌して、70
°Cまで温度を上昇させた。そこへAIBNを0.09
g添加してから10分後、同じ単量体[A]65gとA
IBNの0.41 gとの混合物を3時間かけて滴下し
た0滴下1時間後にA I B No、05gをさらに
添加し、1時間撹拌した。最後に温度90°Cにおいて
1時間撹拌して反応を終了した。Example 1 Monomer obtained in Production Example 1 [A115g, ethyl acetate 50g
and 70 g of toluene were heated and stirred in a nitrogen stream to give 70 g.
The temperature was increased to °C. AIBN 0.09 there
10 minutes after adding g, 65 g of the same monomer [A] and A
A mixture with 0.41 g of IBN was added dropwise over 3 hours. One hour after the dropwise addition, 05 g of AI B No. 05 was further added and stirred for 1 hour. Finally, the reaction was completed by stirring for 1 hour at a temperature of 90°C.
上記の様にして得た重合体溶液をポリエチレンテレフタ
レートのフィルム上に塗布して加熱乾燥によって溶剤を
揮発させ、粘着剤の厚さが約25μmの感圧性粘着剤シ
ートを作成した。その各種物性値は第2表に示すとおり
であった。The polymer solution obtained as described above was applied onto a polyethylene terephthalate film and the solvent was evaporated by heating and drying to prepare a pressure-sensitive adhesive sheet with an adhesive thickness of about 25 μm. The various physical property values are as shown in Table 2.
なお、ゲルパーミュエーション(cpc)により分析し
た結果、上記の重合体は標準ポリスチレンで換算された
分子量が約4万であった。In addition, as a result of analysis by gel permeation (CPC), the molecular weight of the above polymer was approximately 40,000 in terms of standard polystyrene.
実施例2
製造例2で得た単量体[A]15g、酢酸エチル50g
及びトルエン70gを窒素気流中で加熱撹拌して、70
°Cまで温度を上昇させた。そこへATBNを0.09
g添加してから10分後、同じ単量体[A365gとA
IBHの0.41gとの混合物を3時間かけて滴下した
。a下1時間後にA I B No、05gをさらに添
加し、1時間撹拌した。最後に温度90’Cにおいて1
時間撹拌して反応を終了した。上記の様にして得た重合
体溶液を用いて、実施例1と同様にして感圧性粘着剤シ
ートを作成した。その各物性値は第2表に示すとおりで
あった。Example 2 15 g of monomer [A] obtained in Production Example 2, 50 g of ethyl acetate
and 70 g of toluene were heated and stirred in a nitrogen stream to give 70 g.
The temperature was increased to °C. There, ATBN is 0.09
10 minutes after adding g of the same monomers [365 g of A and A
A mixture with 0.41 g of IBH was added dropwise over 3 hours. After 1 hour under a, 05 g of AI B No. was further added and stirred for 1 hour. Finally, at a temperature of 90'C, 1
The reaction was completed by stirring for an hour. A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 using the polymer solution obtained as described above. The physical property values were as shown in Table 2.
なお、ゲルバーミュエーション(cpc)により分析し
た結果、上記の重合体は標準ポリスチレンで換算された
分子量が約4万であった。In addition, as a result of gel permutation (CPC) analysis, the molecular weight of the above polymer was approximately 40,000 in terms of standard polystyrene.
実施例3
製造例3で得た単量体[A]15g、酢酸エチル50g
及びトルエン70gを窒素気流中で加熱撹拌して、70
″Cまで温度を上昇させた。そこへAIBNO,09g
を添加してから10分後、同じ単量体[A365gとA
IBNの0.41 gとの混合物を3時間かけて滴下し
た0滴下1時間後にA I B No、05 gをさら
に添加し、1時間撹拌した。最後に温度90°C11時
間撹拌して反応を終了した。Example 3 15 g of monomer [A] obtained in Production Example 3, 50 g of ethyl acetate
and 70 g of toluene were heated and stirred in a nitrogen stream to give 70 g.
The temperature was raised to ``C. AIBNO, 09g
10 minutes after the addition of the same monomers [A365g and A
A mixture with 0.41 g of IBN was added dropwise over 3 hours. 1 hour after the dropwise addition, 05 g of AI B No. 05 was further added and stirred for 1 hour. Finally, the reaction was completed by stirring at a temperature of 90° C. for 11 hours.
上記の様にして得た重合体溶液を用いて、実施例1と同
様にして感圧性粘着剤シートを作成した。A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 using the polymer solution obtained as described above.
その各物性は第2表に示すとおりであった。Its physical properties were as shown in Table 2.
なお、ゲルパーミュエーション(GPC)により分析し
た結果、上記の重合体は標準ポリスチレンで換算された
分子量が約5万であった。As a result of analysis by gel permeation (GPC), the molecular weight of the above polymer was approximately 50,000 in terms of standard polystyrene.
実施例4〜13
第1表に示した組成を有する単量体混合物を調製し、各
単量体混合物をポリエチレンテレフタレ−1−のフィル
ム上に約25μmの厚さに塗布して、下記条件によりE
B又はUVを照射して重合させ、感圧性粘着剤シートを
作成した。それらの各物性値は第3表に示すとおりであ
った。Examples 4 to 13 A monomer mixture having the composition shown in Table 1 was prepared, and each monomer mixture was coated on a polyethylene terephthalate film to a thickness of about 25 μm, and the following conditions were applied. By E
B or UV rays were irradiated to polymerize, and a pressure-sensitive adhesive sheet was prepared. Their respective physical property values are as shown in Table 3.
EB照射
KF : E S 1社製[エレクトロカーテン」加速
電圧:170KV
照射線量: 5Mr a d
雰囲気中の酸素濃度:100〜200ppmUV照射
U■照射装置:ウシオ電機@製「ユニキュア000J
ランプ:80W/cm、オゾンタイプ高圧水銀灯
反射板:集光タイプ(コンヘア上で集光)コンベア・ス
ピード:10m/閤
照射回数:5回
光開始剤:2−ヒドロキシ−2−メチルプロピオフェノ
ンを5%配合
(ハ)発明の効果
本発明の粘着剤は、特殊なアクリル系単量体を構成単量
体単位とする重合体からなり、接着力、凝集力、粘着性
の基本特性を全て満足させるために、種々の単量体を共
重合する必要がなく、粘着剤の製造工程における煩雑性
を軽減することができる。EB irradiation KF: [Electrocurtain] manufactured by ES 1 Acceleration voltage: 170 KV Irradiation dose: 5 Mr ad Oxygen concentration in atmosphere: 100-200 ppm UV irradiation U Irradiation device: Unicure 000J manufactured by Ushio Inc. Lamp: 80 W/cm , Ozone type High pressure mercury lamp reflector: Light condensing type (light condensed on con hair) Conveyor speed: 10 m/Number of irradiations: 5 times Photoinitiator: Contains 5% of 2-hydroxy-2-methylpropiophenone (Ha ) Effects of the Invention The adhesive of the present invention is made of a polymer containing a special acrylic monomer as a constituent monomer unit, and has been modified in various ways to satisfy all the basic properties of adhesive strength, cohesive strength, and tackiness. There is no need to copolymerize these monomers, and the complexity of the pressure-sensitive adhesive manufacturing process can be reduced.
又、本発明の粘着剤は、本質的に低沸点のアクリル系単
量体を含まないため、これらの成分に起因する臭気対策
等の問題を改善することができる。Further, since the adhesive of the present invention does not essentially contain a low-boiling point acrylic monomer, problems such as odor control caused by these components can be improved.
Claims (1)
他の共重合性単量体との重合体を含有する粘着剤。 [A]:▲数式、化学式、表等があります▼ (上式中のRは炭素数が4〜18個のアルキル基を表す
。)[Claims] 1. An adhesive containing at least one of the following monomers [A] or a polymer of this and other copolymerizable monomers. [A]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R in the above formula represents an alkyl group with 4 to 18 carbon atoms.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26721688A JPH02115291A (en) | 1988-10-25 | 1988-10-25 | Pressure-sensitive adhesive |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26721688A JPH02115291A (en) | 1988-10-25 | 1988-10-25 | Pressure-sensitive adhesive |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02115291A true JPH02115291A (en) | 1990-04-27 |
Family
ID=17441753
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP26721688A Pending JPH02115291A (en) | 1988-10-25 | 1988-10-25 | Pressure-sensitive adhesive |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02115291A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7258919B2 (en) | 2002-04-04 | 2007-08-21 | Sekisui Chemical Co., Ltd. | Acrylic pressure sensitive adhesive and pressure sensitive adhesive tape |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5179132A (en) * | 1974-12-28 | 1976-07-09 | Kuramoto Sangyo Kk |
-
1988
- 1988-10-25 JP JP26721688A patent/JPH02115291A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5179132A (en) * | 1974-12-28 | 1976-07-09 | Kuramoto Sangyo Kk |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7258919B2 (en) | 2002-04-04 | 2007-08-21 | Sekisui Chemical Co., Ltd. | Acrylic pressure sensitive adhesive and pressure sensitive adhesive tape |
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