JP2020063376A - Adhesive, adhesive sheet, and method for producing adhesive - Google Patents
Adhesive, adhesive sheet, and method for producing adhesive Download PDFInfo
- Publication number
- JP2020063376A JP2020063376A JP2018196291A JP2018196291A JP2020063376A JP 2020063376 A JP2020063376 A JP 2020063376A JP 2018196291 A JP2018196291 A JP 2018196291A JP 2018196291 A JP2018196291 A JP 2018196291A JP 2020063376 A JP2020063376 A JP 2020063376A
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene
- pressure
- sensitive adhesive
- meth
- parts
- 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
- 239000000853 adhesive Substances 0.000 title claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 145
- 239000004743 Polypropylene Substances 0.000 claims abstract description 104
- 229920001155 polypropylene Polymers 0.000 claims abstract description 104
- 239000002245 particle Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 239000003960 organic solvent Substances 0.000 claims abstract description 36
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 68
- 229920000058 polyacrylate Polymers 0.000 claims description 29
- 239000010410 layer Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 abstract description 11
- 229920006243 acrylic copolymer Polymers 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- 239000000243 solution Substances 0.000 description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 40
- 239000000178 monomer Substances 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 229920000098 polyolefin Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 10
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000005442 diisocyanate group Chemical group 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
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- 125000003700 epoxy group Chemical group 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 239000008096 xylene Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
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- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
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- JTINZFQXZLCHNS-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)butan-1-ol Chemical compound C1OC1COCC(CO)(CC)COCC1CO1 JTINZFQXZLCHNS-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-UHFFFAOYSA-N 0.000 description 1
- UECGJSXCVLTIMQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCCCC1C(=O)OCCOC(=O)C=C UECGJSXCVLTIMQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、粘着剤、粘着シート、および粘着剤の製造方法に関する。 The present invention relates to a pressure-sensitive adhesive, a pressure-sensitive adhesive sheet, and a method for manufacturing a pressure-sensitive adhesive.
近年、粘着剤の分野では、強固な粘着力を有し、より苛酷な状況においても剥がれ落ちない優れた粘着性を有する信頼性の高い粘着剤が求められている。
一般に、ポリエチレン、ポリプロピレンなどの非極性ポリオレフィン基材に、アクリル系重合体を主成分とする粘着剤を貼着する場合、強固な粘着力を発現させるためには、粘着剤中に適当な粘着付与樹脂を添加する必要がある。
しかしながら、従来の一般的なアクリル系重合体に単に粘着付与樹脂を添加しただけでは、非極性ポリオレフィン素材への貼り付けにおいて、高温環境下で充分な耐久性を有する粘着層が得られないことがある。
In recent years, in the field of pressure-sensitive adhesives, highly reliable pressure-sensitive adhesives having a strong pressure-sensitive adhesive force and excellent adhesiveness that does not peel off even under more severe conditions have been demanded.
Generally, when a pressure-sensitive adhesive containing an acrylic polymer as a main component is attached to a non-polar polyolefin substrate such as polyethylene or polypropylene, in order to exert a strong adhesive force, it is necessary to impart an appropriate tackiness to the pressure-sensitive adhesive. Resin needs to be added.
However, by simply adding a tackifying resin to a conventional general acrylic polymer, it may not be possible to obtain an adhesive layer having sufficient durability under a high temperature environment in sticking to a nonpolar polyolefin material. is there.
例えば、特許文献１では、アクリル系重合体、塩素化ポリオレフィン、硬化剤、非酸系硬化促進剤を含有する粘着剤が、温度２３℃の環境下で非極性ポリオレフィン系素材に対し、良好な粘着力を有する事が示されている。
また、特許文献２には、特定のアクリル系重合体、キレート型硬化剤、アルコール以外の有機溶剤、およびポリオレフィン等を含む粘着剤が記載されている（請求項１、３）。
For example, in Patent Document 1, a pressure-sensitive adhesive containing an acrylic polymer, a chlorinated polyolefin, a curing agent, and a non-acidic curing accelerator has good adhesion to a non-polar polyolefin-based material under a temperature of 23 ° C. It has been shown to have power.
Further, Patent Document 2 describes a pressure-sensitive adhesive containing a specific acrylic polymer, a chelate-type curing agent, an organic solvent other than alcohol, polyolefin, and the like (claims 1 and 3).
特許文献１では、高温下（例えば、６０℃）での粘着力については開示されていない。
特許文献２には、８０℃雰囲気下における保持力試験について記載されている。しかし、前記保持力試験は、粘着層を設けたポリエチレンテレフタレートをステンレス板に貼付した試料についての試験であり、ポリプロピレン板に貼付した試料についての試験ではない。ポリプロピレン板に貼付した試料については、２３℃における粘着力（１８０°剥離力）を測定しているに留まっている。
Patent Document 1 does not disclose the adhesive strength under high temperature (for example, 60 ° C.).
Patent Document 2 describes a holding power test under an atmosphere of 80 ° C. However, the holding power test is a test on a sample in which polyethylene terephthalate provided with an adhesive layer is attached to a stainless plate, and is not a test on a sample attached to a polypropylene plate. With respect to the sample attached to the polypropylene plate, the adhesive force at 180C (180 ° peel force) is only measured.
本発明の課題は、ポリプロピレンなどの非極性ポリオレフィン素材への貼り付けにおいても強固な粘着力（剥離力）を発揮し、高温環境下でも強固な粘着力（剥離力）を発現する粘着シートを提供することを目的とする。 An object of the present invention is to provide a pressure-sensitive adhesive sheet that exhibits a strong adhesive force (peeling force) even when attached to a non-polar polyolefin material such as polypropylene, and exhibits a strong adhesive force (peeling force) even in a high temperature environment. The purpose is to do.
本発明の粘着剤は、アクリル系重合体、粘着付与樹脂、ポリプロピレン、硬化剤および有機溶剤を含み、ポリプロピレンが粘着剤中に平均分散粒子径０．０２〜１００μｍの粒子として存在する。 The pressure-sensitive adhesive of the present invention contains an acrylic polymer, a tackifying resin, polypropylene, a curing agent and an organic solvent, and polypropylene is present in the pressure-sensitive adhesive as particles having an average dispersed particle diameter of 0.02 to 100 μm.
また、本発明は、基材、および本発明の粘着剤から有機溶剤を除いた成分の硬化物である粘着層を備える粘着シートに関する。 The present invention also relates to a pressure-sensitive adhesive sheet that includes a substrate and a pressure-sensitive adhesive layer that is a cured product of components obtained by removing the organic solvent from the pressure-sensitive adhesive of the present invention.
さらに、本発明は、アクリル系重合体、粘着付与樹脂、硬化剤、および前記三成分をそれぞれ溶解し得、ポリプロピレンは溶解しない有機溶剤ａを含む溶液Ａと、
前記溶剤ａには溶解しないポリプロピレン、およびポリプロピレン溶解し得る有機溶剤ｂを含む溶液Ｂとを混合し、
平均分散粒子径が０．０２〜１００μｍのポリプロピレン粒子を析出する、
粘着剤の製造方法に関する。
Furthermore, the present invention is a solution A containing an organic polymer a which can dissolve an acrylic polymer, a tackifying resin, a curing agent, and the above three components, respectively, and polypropylene cannot dissolve ,
The polypropylene which is not soluble in the solvent a and a solution B containing an organic solvent b capable of dissolving polypropylene are mixed,
Precipitating polypropylene particles having an average dispersed particle diameter of 0.02 to 100 μm,
The present invention relates to a method for producing an adhesive.
本発明により、ポリプロピレンなどの非極性ポリオレフィン素材への貼着おいても高い粘着力を発揮し、高温下でも強固な粘着力を発揮する粘着シートを提供する事ができる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet that exhibits high adhesive strength even when adhered to a non-polar polyolefin material such as polypropylene, and exhibits strong adhesive strength even at high temperatures.
本発明を詳細に説明する前に用語を定義する。
シート、フィルムおよびテープは同義語である。（メタ）アクリル酸は、アクリル酸およびメタクリル酸を含む。（メタ）アクリレートは、アクリレートおよびメタクリレートを含む。モノマーはエチレン性不飽和二重結合含有単量体である。被着体は、粘着シートを貼り付ける相手方をいう。
Before describing the present invention in detail, terms will be defined.
Sheet, film and tape are synonyms. (Meth) acrylic acid includes acrylic acid and methacrylic acid. (Meth) acrylate includes acrylate and methacrylate. The monomer is an ethylenically unsaturated double bond-containing monomer. The adherend refers to the other party to which the adhesive sheet is attached.
本発明の粘着剤は、塗工することで粘着層を形成して、基材を備えた粘着シートに加工して使用することが好ましい。なお、本発明の粘着剤は、粘着シートだけでなく、いわゆる「糊」のようにそのままの液体で使用することを妨げるものではない。また、基材を使用せずに粘着層のみから構成された、いわゆるキャスト粘着シートとしても使用できる。 The pressure-sensitive adhesive of the present invention is preferably used by forming a pressure-sensitive adhesive layer by coating and processing it into a pressure-sensitive adhesive sheet having a substrate. The pressure-sensitive adhesive of the present invention does not prevent not only the pressure-sensitive adhesive sheet but also so-called "glue" from being used as it is as a liquid. Further, it can be used as a so-called cast pressure-sensitive adhesive sheet which is composed of only the pressure-sensitive adhesive layer without using a substrate.
本発明においてアクリル系重合体とは、粘着力を発現させる（メタ）アクリレートモノマーと、硬化剤との架橋点となる官能基を有し、架橋により凝集力を付与するモノマーを混合し、溶液重合した重合物である。溶液重合は、公知の重合手法を使用できる。 In the present invention, the acrylic polymer is a solution-polymerized mixture of a (meth) acrylate monomer expressing adhesive force and a monomer having a functional group serving as a crosslinking point with a curing agent and imparting cohesive force by crosslinking. It is a polymerized product. For the solution polymerization, a known polymerization technique can be used.
（メタ）アクリレートモノマーは、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ−ドデシル（メタ）アクリレート、ｎ−トリデシル（メタ）アクリレート、ｎ−テトラデシル（メタ）アクリレート等が挙げられる。これら（メタ）アクリレートは１種または２種以上用いることができる。なお、（メタ）アクリル系モノマーは、（メタ）アクリル酸アルコキシエステルを含まない。 Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, and 2; -Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n -Dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. are mentioned. These (meth) acrylates may be used either individually or in combination of two or more. The (meth) acrylic monomer does not include (meth) acrylic acid alkoxy ester.
官能基を有するモノマーとしては、硬化剤と架橋する官能基を有するモノマーであれば限定されないが、硬化剤としてイソシアネートもしくはキレート型硬化剤を使用した場合、水酸基もしくはカルボキシル基を有しているモノマーが好ましい。 The monomer having a functional group is not limited as long as it is a monomer having a functional group that crosslinks with the curing agent, but when an isocyanate or a chelate type curing agent is used as the curing agent, a monomer having a hydroxyl group or a carboxyl group is used. preferable.
水酸基を有するモノマーとしては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、８−ヒドロキシオクチル（メタ）アクリレート、１０−ヒドロキシデシル（メタ）アクリレート、１２−ヒドロキシラウリル（メタ）アクリレート、（４−ヒドロキシメチルシクロヘキシル）メチルアクリレート、Ｎ−メチロール（メタ）アクリルアミド、ビニルアルコール、アリルアルコール、２−ヒドロキシエチルビニルエーテル、４−ヒドロキシブチルビニルエーテル等が挙げられる。 Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl Examples thereof include vinyl ether and 4-hydroxybutyl vinyl ether.
カルボキシル基を有するモノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリル酸２−カルボキシエチル、（メタ）アクリル酸ダイマー、クロトン酸、マレイン酸、無水マレイン酸、フマル酸、シトラコン酸、グルタコン酸、イタコン酸、アクリルアミドＮ−グリコール酸、ケイ皮酸、２−（メタ）アクリロイルオキシエチルヘキサヒドロフタレート、２−（メタ）アクリロイルオキシエチルフタレート、２−（メタ）アクリロイルオキシエチルサクシネート等が挙げられる。これらの中でも（メタ）アクリル酸が好ましい。 Examples of the monomer having a carboxyl group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, (meth) acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, and glutacon. Acid, itaconic acid, acrylamido N-glycolic acid, cinnamic acid, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl succinate and the like. To be Among these, (meth) acrylic acid is preferable.
本発明において、これらのモノマーの他に、アミド基を有するモノマー、アミノ基を有するモノマー、エポキシ基を有するモノマー、芳香環を有するモノマー、脂環式炭化水素基を有するモノマー、ビニルエステル、（メタ）アクリル酸アルコキシエステルを、任意に、単独または２種以上、混合重合時に用いてよい。 In the present invention, in addition to these monomers, a monomer having an amide group, a monomer having an amino group, a monomer having an epoxy group, a monomer having an aromatic ring, a monomer having an alicyclic hydrocarbon group, a vinyl ester, (meth) ) Acrylic acid alkoxy ester may be optionally used alone or in combination of two or more at the time of mixed polymerization.
アミド基を有するモノマーは、例えば、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ'−メチレンビスアクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−エチロール（メタ）アクリルアミド、Ｎ−メトキシエチル（メタ）アクリルアミド、Ｎ−ビニルピロリドン、ジアセトンアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン等が挙げられる。 Examples of the monomer having an amide group include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N'-methylenebisacrylamide. , N-methylol (meth) acrylamide, N-ethylol (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-vinylpyrrolidone, diacetone acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) Acryloyl morpholine etc. are mentioned.
アミノ基を有するモノマーは、例えば、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート等が挙げられる。 Examples of the monomer having an amino group include N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
エポキシ基を有するモノマーは、例えば、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート、アリルグリシジルエーテル等が挙げられる。 Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, and allylglycidyl ether.
芳香環を有するモノマーは、例えば、フェニルアクリレート、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、ビフェニル（メタ）アクリレート、スチレン、ビニルトルエン、α−メチルスチレン等が挙げられる。 Examples of the monomer having an aromatic ring include phenyl acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, biphenyl (meth) acrylate, styrene, vinyltoluene, and α-methylstyrene.
脂環式炭化水素基を有するモノマーとしては、例えば、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸イソボルニル等が挙げられる。 Examples of the monomer having an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and the like.
ビニルエステルは、例えば、酢酸ビニル、プロピオン酸ビニル、ラウリン酸ビニル等が挙げられる。 Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl laurate and the like.
（メタ）アクリル酸アルコキシエステルは、例えば、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸２−メトキシプロピル、（メタ）アクリル酸３−メトキシプロピル、（メタ）アクリル酸２−メトキシブチル、（メタ）アクリル酸４−メトキシブチル等が挙げられる。 The (meth) acrylic acid alkoxy ester is, for example, 2-methoxyethyl (meth) acrylic acid, 2-ethoxyethyl (meth) acrylic acid, 2-methoxypropyl (meth) acrylic acid, 3-methoxypropyl (meth) acrylic acid. , 2-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and the like.
溶液重合にはラジカル重合可能な重合開始剤を使用する。重合開始剤は、アゾ化合物、過酸化物等が好ましい。アゾ化合物は、例えば２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビスイソブチロニトリル等が挙げられる。過酸化物は、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ベンゾイルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン等が好ましい。
重合開始剤は、単独または２種類以上併用できる。
A radical-polymerizable polymerization initiator is used for the solution polymerization. The polymerization initiator is preferably an azo compound, a peroxide or the like. Examples of the azo compound include 2,2′-azobis (2-methylbutyronitrile) and 2,2′-azobisisobutyronitrile. Peroxides are t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl. Cyclohexane and the like are preferable.
The polymerization initiators can be used alone or in combination of two or more kinds.
重合開始剤は、モノマー混合物１００質量部に対して０．０３〜１．５質量部用いることが好ましく、０．１〜１質量部がより好ましい。重合開始剤を適量使用すると重合平均分子量を調整し易くなり、粘着物性を調整できる。
溶液重合の温度は、適宜調整できるが一般的に７０〜１００℃程度である。
The polymerization initiator is preferably used in an amount of 0.03 to 1.5 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the monomer mixture. When a proper amount of the polymerization initiator is used, the polymerization average molecular weight can be easily adjusted, and the adhesive physical properties can be adjusted.
The temperature of solution polymerization can be appropriately adjusted, but is generally about 70 to 100 ° C.
本発明で用いるアクリル系重合体の質量平均分子量は、前記課題を解決できる範囲であれば任意に設定できるが、４０万〜８０万が好しい。質量平均分子量を適切な範囲に設定すると耐熱性、および塗工性を両立し易くなる。なお、質量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて測定したポリスチレン換算の分子量である。 The mass average molecular weight of the acrylic polymer used in the present invention can be arbitrarily set within a range capable of solving the above problems, but is preferably 400,000 to 800,000. When the mass average molecular weight is set within an appropriate range, both heat resistance and coatability can be easily achieved. The mass average molecular weight is a polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC).
本発明で用いる粘着付与樹脂は、溶液重合の際に使用する方法、アクリル系重合体に配合する方法等、任意の方法で使用できる。アクリル系重合体に配合すると粘着力をより向上できる。 The tackifying resin used in the present invention can be used in any method such as a method used in solution polymerization or a method of blending with an acrylic polymer. When blended with an acrylic polymer, the adhesive strength can be further improved.
粘着付与樹脂の軟化点は、８０℃以上が好ましく、９０℃以上がより好ましく、１００℃以上がさらに好ましい。また、軟化点の上限は、１７０℃以下が好ましく、１６０℃以下がより好ましく、１５５℃以下がさらに好ましい。粘着付与樹脂の軟化点が８０〜１７０℃であることで粘着力と耐熱性を高いレベルで両立し易くなる。なお、軟化点は、ＪＩＳ Ｋ５９０２に規定されている環球法にしたがって測定した軟化温度である。 The softening point of the tackifying resin is preferably 80 ° C or higher, more preferably 90 ° C or higher, and even more preferably 100 ° C or higher. The upper limit of the softening point is preferably 170 ° C or lower, more preferably 160 ° C or lower, and even more preferably 155 ° C or lower. When the softening point of the tackifying resin is 80 to 170 ° C., it becomes easy to achieve both a high level of adhesion and heat resistance. The softening point is a softening temperature measured according to the ring and ball method specified in JIS K5902.
粘着付与樹脂は、例えば、ロジン系樹脂、重合ロジン系樹脂、ロジンエステル系樹脂、重合ロジンエステル系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロン系樹脂、クマロンインデン系樹脂、スチレン系樹脂、キシレン系樹脂、フェノール系樹脂、石油系樹脂等が挙げられる。これらの中でもアクリル系重合体との相溶性が良く粘着性能がより向上できる点から、ロジン系樹脂、重合ロジン系樹脂、ロジンエステル系樹脂および重合ロジンエステル系樹脂が好ましく、ロジンエステル系樹脂および重合ロジンエステル系樹脂がより好ましい。
粘着付与樹脂は、単独または２種類以上併用できる。
Tackifying resin, for example, rosin resin, polymerized rosin resin, rosin ester resin, polymerized rosin ester resin, terpene resin, terpene phenol resin, coumarone resin, coumarone indene resin, styrene resin, Examples include xylene-based resins, phenol-based resins, petroleum-based resins and the like. Of these, rosin-based resins, polymerized rosin-based resins, rosin ester-based resins and polymerized rosin ester-based resins are preferable, since they have good compatibility with acrylic polymers and can improve adhesive performance, and rosin ester-based resins and polymerized Rosin ester resins are more preferred.
The tackifier resins can be used alone or in combination of two or more.
粘着付与樹脂は、アクリル系重合体１００質量部に対して１０〜４０質量部用いることが好ましく、１５〜３５質量部がより好ましい。粘着付与樹脂を１０〜４０質量部用いると高い粘着力を得ることができる。 The tackifying resin is preferably used in an amount of 10 to 40 parts by mass, more preferably 15 to 35 parts by mass, based on 100 parts by mass of the acrylic polymer. High tackiness can be obtained by using 10 to 40 parts by mass of the tackifying resin.
本発明で用いるポリプロピレンは、未変性のポリプロピレン、塩素化されていないマレイン酸変性ポリプロピレン、アクリル酸変性ポリプロピレン、塩素化ポリプロピレン、酸変性塩素化ポリプロピレン、アクリル変性塩素化ポリプロピレンなど任意のものを単独もしくは２種以上用いてもいいが、状態としては２５℃の環境下で固体であることが好ましい。 As the polypropylene used in the present invention, unmodified polypropylene, unchlorinated maleic acid-modified polypropylene, acrylic acid-modified polypropylene, chlorinated polypropylene, acid-modified chlorinated polypropylene, acrylic-modified chlorinated polypropylene, etc. may be used alone or in combination with 2 More than one kind may be used, but it is preferably solid under the environment of 25 ° C.
本発明におけるポリプロピレンは、粘着剤中で粒子として存在し、その粒子径はレーザー回折式粒度分布計の測定で可能なものである。なお粒子径とはレーザー回折式粒度分布計の測定で得られる平均分散粒子径（Ｄ５０値）の事であり、その範囲は０．０２〜１００μｍであり、好ましくは１〜５０μｍである。 The polypropylene in the present invention exists as particles in the pressure-sensitive adhesive, and the particle diameter can be measured by a laser diffraction type particle size distribution meter. The particle diameter means an average dispersed particle diameter (D50 value) obtained by measurement with a laser diffraction type particle size distribution meter, and the range thereof is 0.02 to 100 μm, preferably 1 to 50 μm.
粘着剤中にポリプロピレンが粒子状に固体で存在することで、粘着シートにした際、粘着層の表面にポリオレフィン粒子が均一に分布し、非極性オレフィン被着体と親和し高い粘着力を発現させる。しかし、平均分散粒径が０．０２μｍよりも小さい場合、溶解に近い状態にあるので、粘着層の表面にあったポリプロピレンが高温下では粘着層の内部に移行し易くなり、高温下では粘着力低下すると考えられる。また平均分散粒径が１００μｍよりも大きい場合、粘着シート表面の凹凸が顕著になり、粘着力が低下する。 Since polypropylene is present as a solid in the form of particles in the pressure-sensitive adhesive, the polyolefin particles are evenly distributed on the surface of the pressure-sensitive adhesive layer when it is made into a pressure-sensitive adhesive sheet, and a high adhesive force is expressed in affinity with the non-polar olefin adherend. . However, when the average dispersed particle size is smaller than 0.02 μm, since it is in a state close to dissolution, polypropylene on the surface of the pressure-sensitive adhesive layer easily migrates into the pressure-sensitive adhesive layer at high temperature, and the adhesive strength at high temperature is high. It is expected to decrease. Further, when the average dispersed particle diameter is larger than 100 μm, the unevenness of the surface of the pressure-sensitive adhesive sheet becomes remarkable and the pressure-sensitive adhesive force decreases.
本発明の粘着剤は、例えば以下に示す（１）〜（３）のような方法で得ることができる。
（１） アクリル系重合体、粘着付与樹脂、硬化剤、および前記三成分をそれぞれ溶解し得る有機溶剤ａを含む溶液Ａと、
前記有機溶剤ａには溶解しないポリプロピレン、およびポリプロピレン溶解し得る有機溶剤ｂを含む溶液Ｂとを混合し、
平均分散粒子径が０．０２〜１００μｍのポリプロピレンを析出させる。
有機溶剤ａはポリプロピレンにとっての貧溶媒ということができる。
より具体的には、溶液Ａに溶液Ｂを滴下することが好ましい。滴下時の滴下速度や撹拌条件を変えることによって、分散粒子径を変えることができる。相溶化剤の利用により分散粒子径を変えることもできる。
なお、溶液Ａは、溶液Ｂを混合する際に、アクリル系重合体、粘着付与樹脂、および硬化剤のうちの少なくとも一つを含んでいればよい。
即ち、例えば、アクリル系重合体を有機溶剤ａに溶解した後、粘着付与樹脂、硬化剤を順次に溶解して溶液Ａを得た後、溶液Ｂを混合してもよいし、
前記三成分の溶液をそれぞれ用意しておき、各溶液を混合して溶液Ａを得た後、溶液Ｂを混合してもよいし、
アクリル系重合体を有機溶剤ａに溶解した後、前記溶液に粘着付与樹脂、硬化剤、および溶液Ｂを混合し、粘着付与樹脂および硬化剤の溶解と、ポリプロピレンの析出を同時に行ってもよい。
The pressure-sensitive adhesive of the present invention can be obtained by, for example, the following methods (1) to (3).
(1) A solution A containing an acrylic polymer, a tackifying resin, a curing agent, and an organic solvent a capable of dissolving each of the three components,
Polypropylene which is not soluble in the organic solvent a and a solution B containing an organic solvent b capable of dissolving polypropylene are mixed,
Polypropylene having an average dispersed particle diameter of 0.02 to 100 μm is deposited.
The organic solvent a can be said to be a poor solvent for polypropylene.
More specifically, it is preferable to add the solution B to the solution A dropwise. The dispersed particle size can be changed by changing the dropping speed and stirring conditions during dropping. The size of dispersed particles can be changed by using a compatibilizing agent.
The solution A may contain at least one of an acrylic polymer, a tackifying resin, and a curing agent when the solution B is mixed.
That is, for example, after dissolving the acrylic polymer in the organic solvent a, the tackifying resin and the curing agent are sequentially dissolved to obtain the solution A, and then the solution B may be mixed.
The solutions of the three components may be prepared respectively, and the solutions may be mixed to obtain the solution A, and then the solution B may be mixed.
After dissolving the acrylic polymer in the organic solvent a, the tackifying resin, the curing agent, and the solution B may be mixed with the solution, and the tackifying resin and the curing agent may be dissolved and the polypropylene may be simultaneously deposited.
（２） 前記有機溶剤ａには溶解しないポリプロピレン、およびポリプロピレン溶解し得る有機溶剤ｂを含む溶液Ｂを用意し、その中にポリプロピレンを溶解しない有機溶剤ａを滴下し、ポリプロピレンを析出させた後、分散機を用いて分散し分散粒子径０．０２〜１００μｍのポリプロピレンの分散液を用意する。
更に、これとは別にアクリル系重合体、粘着付与樹脂、および硬化剤のうちの少なくとも一つを、有機溶剤ａに溶かした溶液を用意し、この中に前記のポリプロピレンの分散液を加える。ポリプロピレンの分散液を加える際、または加えた後に、アクリル系重合体、粘着付与樹脂、および硬化剤のうちの残りの成分を加え、有機溶剤ａに溶解する。
(2) A solution B containing polypropylene that is insoluble in the organic solvent a and an organic solvent b that can dissolve polypropylene is prepared, and the organic solvent a that does not dissolve polypropylene is dropped therein to precipitate polypropylene. A polypropylene dispersion having dispersed particle diameters of 0.02 to 100 μm is prepared by dispersing using a disperser.
Separately from this, a solution is prepared in which at least one of an acrylic polymer, a tackifying resin, and a curing agent is dissolved in an organic solvent a, and the polypropylene dispersion liquid is added thereto. When or after adding the polypropylene dispersion, the remaining components of the acrylic polymer, the tackifying resin, and the curing agent are added and dissolved in the organic solvent a.
（３） アクリル系重合体、粘着付与樹脂、および硬化剤のうちの少なくとも一つを、有機溶剤ａに溶解し、溶液を用意する。
加熱し溶融状態にしたポリプロピレン溶融液を、前記溶液に添加し、平均分散粒子径が０．０２〜１００μｍのポリプロピレンを析出させる。ポリプロピレン溶融液を加える際、または加えた後に、アクリル系重合体、粘着付与樹脂、および硬化剤のうちの残りの成分を加え、有機溶剤ａに溶解する。
ポリプロピレン溶融液添加時のポリプロピレン溶融液の温度や溶液の温度、添加速度や撹拌条件を変えることによって、分散粒子径を変えることができる。
(3) At least one of an acrylic polymer, a tackifying resin, and a curing agent is dissolved in an organic solvent a to prepare a solution.
A polypropylene melt that has been heated to a molten state is added to the solution to precipitate polypropylene having an average dispersed particle size of 0.02 to 100 μm. When or after adding the polypropylene melt, the remaining components of the acrylic polymer, the tackifying resin, and the curing agent are added and dissolved in the organic solvent a.
The dispersed particle diameter can be changed by changing the temperature of the polypropylene melt at the time of adding the polypropylene melt, the temperature of the solution, the addition speed, and the stirring conditions.
有機溶剤ａ、ｂはそれぞれ単独の有機溶剤であってもよいし、複数の有機溶剤を併用するものであってもよい。
本発明で溶解とは、有機溶剤ａ：１００ｇに対し、対照（例えば、アクリル系重合体）１ｇを透明なガラス製の容器に入れ、４０℃に加温しながらマグネティックスターラー等を用いて１時間撹拌し、その後２５℃まで自然放冷し１時間放置後、白濁や沈殿のない状態の事をいう。
Each of the organic solvents a and b may be a single organic solvent or a combination of a plurality of organic solvents.
Dissolution in the present invention means that 1 g of a control (for example, an acrylic polymer) is placed in a transparent glass container with respect to 100 g of an organic solvent a and heated for 1 hour using a magnetic stirrer or the like while heating at 40 ° C. It is a state in which there is no turbidity or precipitation after stirring and then naturally cooling to 25 ° C. and leaving for 1 hour.
ポリプロピレンにとっての貧溶媒である有機溶剤ａは、アクリル系重合体、粘着付与樹脂、および硬化剤を溶解する。
有機溶剤ａとしては、例えば、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル、アセトン、メチルエチルケトン、シクロヘキサノン等のケトンが挙げられる。
The organic solvent a, which is a poor solvent for polypropylene, dissolves the acrylic polymer, the tackifying resin, and the curing agent.
Examples of the organic solvent a include esters such as ethyl acetate, propyl acetate and butyl acetate, and ketones such as acetone, methyl ethyl ketone and cyclohexanone.
一方、ポリプロピレンにとっての良溶媒である有機溶剤ｂとしては、例えばトルエン、キシレン、ベンゼン、ソルベントナフサ等の芳香族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、トリメチルシクロヘキサン、エチルシクロヘキサン、ジエチルシクロヘキサン、デカヒドロナフタレン、ビシクロヘプタン、トリシクロデカン、ヘキサヒドロインデンシクロヘキサン、シクロオクタン、α−ピネン、ターピノーレン、リモネン等の脂肪族炭化水素挙げられる。
なお、ポリプロピレンにとっての貧溶媒、良溶媒は、ポリプロピレンの種類によって変わる。例えば、塩素化ポリプロピレンは酢酸エチルに溶解するので、塩素化ポリプロピレンにとって酢酸エチルは有機溶媒ａに当たり、酢酸エチルに溶解しないポリプロピレンにとって酢酸エチルは有機溶媒ｂに当たる。
On the other hand, examples of the organic solvent b which is a good solvent for polypropylene include aromatic hydrocarbons such as toluene, xylene, benzene, and solvent naphtha, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane. And aliphatic hydrocarbons such as decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, cyclooctane, α-pinene, terpinolene and limonene.
The poor solvent and good solvent for polypropylene vary depending on the type of polypropylene. For example, since chlorinated polypropylene is dissolved in ethyl acetate, ethyl acetate corresponds to organic solvent a for chlorinated polypropylene, and ethyl acetate corresponds to organic solvent b for polypropylene not dissolved in ethyl acetate.
前述の（２）の方法において分散処理に用いる装置は、公知の混練機、分散機を使用できる。
混練機としては、例えばニーダー、加圧ニーダー、連続ニーダー、エクストルーダー、連続エクストルーダー、ヘンシェルミキサー、スーパーミキサー、プラネタリーミキサーなどが挙げられる。
分散機は、ボールミル、アトライター、サンドミル、コボールミル、アジテーターミル、スーパーミル、ショットミル、ピンミル、ジェットミル、ディスクミル、ホモジナイザー、バスケットミル、ペブルミル、ペイントコンディショナー、ペイントシェイカー、ディスパー、超音波分散機などが挙げられる。
混練機および分散機は、単独の装置または２種以上の装置を組み合わせて使用できる。
As the apparatus used for the dispersion treatment in the above method (2), known kneaders and dispersers can be used.
Examples of the kneader include a kneader, a pressure kneader, a continuous kneader, an extruder, a continuous extruder, a Henschel mixer, a super mixer, and a planetary mixer.
Dispersers include ball mills, attritors, sand mills, co-ball mills, agitator mills, super mills, shot mills, pin mills, jet mills, disc mills, homogenizers, basket mills, pebble mills, paint conditioners, paint shakers, dispersers, ultrasonic dispersers, etc. Is mentioned.
The kneader and the disperser may be used alone or in combination of two or more kinds.
分散機にメディアを使う場合には、例えばガラスビーズ、ジルコニアビーズ、アルミナビーズ、スチールビーズ、セラミックビーズ等を用いることができる。使用するメディアの大きさは１種類でもいいし、あるいは異なる２種類以上をそれぞれ段階的に用いてもよい。 When a medium is used in the dispersing machine, glass beads, zirconia beads, alumina beads, steel beads, ceramic beads, etc. can be used. The size of the medium used may be one type, or two or more different types may be used in stages.
本発明におけるポリプロピレンの含有量は、アクリル系重合体１００質量部に対し１〜１５質量部であることが好ましい。１〜１５質量部とする以下であることにより粘着層表面にポリオレフィン粒子を効果的に存在させることでき、非極性ポリオレフィン被着体に対する親和性が向上し、粘着力がより大きくなる。 The content of polypropylene in the present invention is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the acrylic polymer. When the content is 1 to 15 parts by mass or less, the polyolefin particles can be effectively present on the surface of the adhesive layer, the affinity for the non-polar polyolefin adherend is improved, and the adhesive force is further increased.
本発明における硬化剤は、キレート型硬化剤、イソシアネート硬化剤、エポキシ硬化剤またはアジリジン硬化剤等が使用できる。これらの硬化剤は単独または２種以上併用でき、アクリル系重合体１００質量部に対して０．０５〜５質量部配合することが好ましい。 As the curing agent in the present invention, a chelate type curing agent, an isocyanate curing agent, an epoxy curing agent, an aziridine curing agent, or the like can be used. These curing agents can be used alone or in combination of two or more, and it is preferable to add 0.05 to 5 parts by mass to 100 parts by mass of the acrylic polymer.
本発明においてキレート型硬化剤は、多価金属および配位子からなる化合物である。多価金属は、例えばニッケル、アルミニウム、クロム、鉄、チタン、亜鉛、コバルト、マンガン、ジルコニウム等が挙げられる。配位子は、例えばアセチルアセトン、アセト酢酸エステル等が挙げられる。
キレート型硬化剤は、多価金属および配位子をそれぞれ任意に組み合わせた化合部を使用できるところ、多価金属にアルミニウム、配位子にアセチルアセトン、またはアセト酢酸エステルを組み合わせた化合物が好ましい。
In the present invention, the chelate-type curing agent is a compound composed of a polyvalent metal and a ligand. Examples of the polyvalent metal include nickel, aluminum, chromium, iron, titanium, zinc, cobalt, manganese, and zirconium. Examples of the ligand include acetylacetone and acetoacetic acid ester.
As the chelate-type curing agent, a compound in which a polyvalent metal and a ligand are arbitrarily combined can be used, but a compound in which a polyvalent metal is aluminum and a ligand is acetylacetone or an acetoacetic acid ester is preferable.
本発明においてキレート型硬化剤を硬化剤として用いる際、反応遅延効果を目的にアルコールを配合する。アルコールの添加によって溶液中で硬化反応が起こらず、良好なポットライフを維持でき、さらに乾燥時に揮発することで、塗工・乾燥後の粘着剤では硬化反応が進み、良好な耐熱性を発現する。
アルコールは、例えばメタノール、エタノール、１−プロパノール、イソプロパノール、１−ブタノール、イソブタノール、ｔｅｒｔ−ブタノール、１−ペンタノール、イソペンタノール、１−ヘキサノール、４−メチル−２−ペンタノール、１−ヘプタノール、１−オクタノール、イソオクタノール、２−エチルヘキサノール、１−ノナノール、イソノナノール、１−デカノール、１−ドデカノール、１−ミリスチルアルコール、セチルアルコール、１−ステアリルアルコール、イソステアリルアルコール、２−オクチルデカノール、２−オクチルドデカノール、２−ヘキシルデカノール、ベヘニルアルコール、およびオレイルアルコール等が挙げられる。
When the chelate type curing agent is used as a curing agent in the present invention, alcohol is added for the purpose of a reaction retarding effect. The curing reaction does not occur in the solution by the addition of alcohol, a good pot life can be maintained, and further, by volatilizing during drying, the curing reaction progresses in the adhesive after coating and drying, and good heat resistance is expressed. .
Alcohol is, for example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol. , 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldecanol, Examples include 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, and oleyl alcohol.
イソシアネート硬化剤は、ジイソシアネート、およびジイソシアネートを変性した３官能以上のイソシアネート基を有するポリイソシアネートが好ましい。
ジイソシアネートは、芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネートが好ましい。
芳香族ジイソシアネートは、例えば１，５−ナフチレンジイソシアネート、４，４'−ジフェニルメタンジイソシアネート、４，４'−ジフェニルジメチルメタンジイソシアネート、４，４'−ジベンジルイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート、トリレンジイソシアネート等が挙げられる。
脂肪族ジイソシアネートは、例えばブタン−１，４−ジイソシアネート、ヘキサメチレンジイソシアネ−ト、イソプロピレンジイソシアネート、メチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、キシリレンジイソシアネート、ｍ−テトラメチルキシリレンジイソシアネート、ダイマー酸のカルボキシル基をイソシアネート基に転化したダイマージイソシアネート等が挙げられる。
脂環族ジイソシアネートは、例えばシクロヘキサン−１，４−ジイソシアネート、イソホロンジイソシアネート、リジンジイソシアネート、ジシクロヘキシルメタン−４、４'−ジイソシアネート、１，３ービス（イソシアネートメチル）シクロヘキサン、メチルシクロヘキサンジイソシアネート、ノルボルナンジイソシアネート等が挙げられる。
The isocyanate curing agent is preferably diisocyanate and polyisocyanate having a trifunctional or higher functional isocyanate group modified from diisocyanate.
The diisocyanate is preferably aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate.
Aromatic diisocyanates include, for example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, Examples thereof include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and tolylene diisocyanate.
Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate. Examples include isocyanate and dimerisocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group.
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate and the like. To be
ポリイソシアネートは、ジイソシアネートを３官能ポリオール成分で変性したいわゆるアダクト体、ジイソシアネートが水と反応したビュレット体、ジイソシアネートの３分子から形成されるイソシアヌレート環を有する３量体（イソシアヌレート体）が好ましい。
ポリイソシアネートは、例えば、トリレンジイソシアネートのトリメチロールプロパンアダクト体、ヘキサメチレンジイソシアネートのビュレット体、ヘキサメチレンジイソシアネートのアロファネート体、イソホロンジイソシアネートのイソシアヌレート体等が挙げられる。
The polyisocyanate is preferably a so-called adduct body obtained by modifying diisocyanate with a trifunctional polyol component, a buret body in which diisocyanate reacts with water, or a trimer having an isocyanurate ring formed from three molecules of diisocyanate (isocyanurate body).
Examples of the polyisocyanate include trimethylolpropane adduct of tolylene diisocyanate, buret of hexamethylene diisocyanate, allophanate of hexamethylene diisocyanate, and isocyanurate of isophorone diisocyanate.
エポキシ硬化剤は、例えば１，３−ビス（Ｎ，Ｎ'−ジグリシジジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ'，Ｎ'−テトラグリシジル−ｍ−キシリレンジアミン、エチレングリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン等が挙げられる。 The epoxy curing agent is, for example, 1,3-bis (N, N'-diglycididylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine, etc. are mentioned.
アジリジン硬化剤は、例えばジフェニルメタン−４，４'−ビス（１−アジリジンカーボキサミド）、トリメチロールプロパントリ−β−アジリジニルプロピオネート、テトラメチロールメタントリ−β−アジリジニルプロピオネート、トルエン−２，４−ビス（１−アジリジンカーボキサミド）、トリエチレンメラミン、ビスイソフタロイル−１−（２−メチルアジリジン）、トリス−１−（２−メチルアジリジン）フォスフィン、トリメチロールプロパントリ−β−（２−メチルアジリジン）プロピオネート等が挙げられる。 Examples of the aziridine curing agent include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane tri-β-aziridinyl propionate, and tetramethylolmethane tri-β-aziridinyl propionate. , Toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tris-1- (2-methylaziridine) phosphine, trimethylolpropane Examples thereof include tri-β- (2-methylaziridine) propionate.
本発明においてキレート型硬化剤を用いた場合、ケト−エノール互変異性体形成化合物を含んでもいい。ケト−エノール互変異性体形成化合物はケト−エノール互変異性体を形成できる化合物であり、アセチルアセトン、アセト酢酸エステル、マロン酸エステル等が好ましい。 When a chelate-type curing agent is used in the present invention, it may contain a keto-enol tautomer forming compound. The keto-enol tautomer forming compound is a compound capable of forming a keto-enol tautomer, and acetylacetone, acetoacetic acid ester, malonic acid ester and the like are preferable.
アセト酢酸エステルは、例えばアセト酢酸メチル、アセト酢酸エチル、アセト酢酸イソプロピル。アセト酢酸ブチル、アセト酢酸イソブチル、アセト酢酸ｔｅｒｔ−ブチル等が挙げられる。 Acetoacetic acid esters are, for example, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate. Examples include butyl acetoacetate, isobutyl acetoacetate, tert-butyl acetoacetate and the like.
マロン酸エステルは、例えばマロン酸ジメチル、マロン酸ジエチル、マロン酸ジブチル等が挙げられる。
これらの中でもケト−エノール互変異性体形成化合物は、乾燥時の揮発し易さからアセチルアセトンが好ましい。
Examples of the malonate ester include dimethyl malonate, diethyl malonate, and dibutyl malonate.
Among these, the keto-enol tautomer forming compound is preferably acetylacetone because of its volatility during drying.
本発明の粘着剤は、さらに任意成分として難燃助剤、耐熱安定剤、耐候安定剤、老化防止剤、紫外線吸収剤、レベリング剤、帯電防止剤、スリップ剤、アンチブロッキング剤、防曇剤、滑剤、染料、ワックス、乳剤、磁性体、誘電特性調整剤を含むことができる。 The pressure-sensitive adhesive of the present invention further comprises a flame retardant assistant, a heat stabilizer, a weather stabilizer, an antiaging agent, an ultraviolet absorber, a leveling agent, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, as an optional component. Lubricants, dyes, waxes, emulsions, magnetic materials, dielectric property adjusting agents can be included.
本発明の粘着シートは、基材、および粘着剤から有機溶剤を除いた成分の硬化物である粘着層を備えている。
粘着層は、基材上に粘着剤を塗工して形成する方法。または、剥離シート上に粘着剤を塗工し有機溶剤を除いた成分硬化物である粘着層を基材に転写する方法が一般的である。なお、粘着層の基材と接しない面には剥離シートを貼り合わせて保管するのが通常である。
The pressure-sensitive adhesive sheet of the present invention includes a base material and a pressure-sensitive adhesive layer that is a cured product of components obtained by removing an organic solvent from a pressure-sensitive adhesive.
The adhesive layer is formed by applying an adhesive on a base material. Alternatively, a method is generally used in which a pressure-sensitive adhesive is applied onto a release sheet and the pressure-sensitive adhesive layer, which is a cured product of components excluding the organic solvent, is transferred to a substrate. A release sheet is usually attached to the surface of the adhesive layer which is not in contact with the base material for storage.
基材は、紙、プラスチック、布が好ましい。また基材の形態は、シート状、板状、発泡体が好ましい。
基材の素材は、例えば、ポリエチレン、ポリプロピレン(ＰＰ)等のポリオレフィン、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステル、ポリスチレン、ポリ塩化ビニル、ポリカーボネート、セロファン等のプラスチック、上質紙、クラフト紙、クレープ紙、グラシン紙等の紙、織布、不織布等の布、エチレンプロピレンジエンゴム、クロロプレンゴム、イソプレンゴム等のエラストマー、表皮等が挙げられる。
基材の厚さは、通常２５〜１００００μｍ程度である。
The substrate is preferably paper, plastic or cloth. The form of the substrate is preferably a sheet, a plate, or a foam.
Examples of the material of the base material include polyolefin such as polyethylene and polypropylene (PP), polyester such as polyethylene terephthalate (PET), plastic such as polystyrene, polyvinyl chloride, polycarbonate and cellophane, fine paper, kraft paper, crepe paper, glassine. Examples thereof include paper such as paper, cloth such as woven cloth and non-woven cloth, elastomer such as ethylene propylene diene rubber, chloroprene rubber and isoprene rubber, and skin.
The thickness of the base material is usually about 25 to 10000 μm.
粘着剤の塗工方法は、例えばスピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ロールナイフコート法、ブレードコート法、ダイコート法、グラビアコート法等の公知の塗工方法を使用できる。また塗工に際して、乾燥工程を行うことも好ましい。乾燥工程は、熱風オーブン、電気オーブン、赤外線ヒーター等の公知の装置を使用できる。 The coating method of the pressure-sensitive adhesive is, for example, known coating methods such as spin coating method, spray coating method, bar coating method, knife coating method, roll coating method, roll knife coating method, blade coating method, die coating method and gravure coating method. Any method can be used. It is also preferable to carry out a drying step during coating. In the drying step, a known device such as a hot air oven, an electric oven or an infrared heater can be used.
粘着層の厚さは、コストと粘着性能のバランスを考慮すると通常２０〜３００μｍ程度であり、２０〜１００μｍ程度がより好ましい。 The thickness of the adhesive layer is usually about 20 to 300 μm, more preferably about 20 to 100 μm, in consideration of the balance between cost and adhesive performance.
本発明の粘着シートは、例えば車両の天板、床、内外装パネルの固定用、車両塗装や表面処理のマスキング用、出荷時の製品保護用、建築物の内外装部材固定用、コンクリートの養生保護用、家電製品の部材固定用、自動販売機の広告ステッカー用、ＬＣＤのスピーカーネット、ベゼル、化粧板の固定用、包装用、結束用、仮固定用等、様々な用途に使用できる。 The pressure-sensitive adhesive sheet of the present invention is, for example, for fixing a vehicle top plate, floor, interior / exterior panel, for masking vehicle coating or surface treatment, for protecting products at the time of shipment, for fixing interior / exterior members of a building, curing concrete. It can be used for various purposes such as protection, fixing home electric appliances, advertising stickers for vending machines, fixing LCD speaker nets, bezels, decorative plates, packaging, bundling, temporary fixing, etc.
以下に、実施例をもって本発明をより具体的に説明するが、本発明は実施例に限定されるものではない。なお、実施例で「部」とあるのは「質量部」を、「％ 」とあるのは「質量％ 」を意味する。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples. In the examples, "part" means "part by mass" and "%" means "mass%".
＜アクリル共重合体溶液の製造例＞
攪拌器、温度計、滴下管、還流冷却器を備えた重合装置を用い、ブチルアクリレート４１．８部、２−エチルヘキシルアクリレート４０部、エチルアクリレート７部、アクリル酸１０部、２−ヒドロキシエチルアクリレート１．２部、メチルエチルケトン４０部、酢酸エチル２５部、ベンゾイルパーオキシド０．１部を配合した原料混合物の半分を窒素雰囲気下、反応槽に仕込んだ。
別途、滴下層に原料混合物の残りの半分を仕込んだ。
次いで反応槽の加熱を開始した。重合反応開始を確認した後、滴下管から原料混合物を１時間かけて滴下した。滴下終了後、さらに還流下で７時間溶液重合を継続した。
反応終了後、冷却し、希釈溶剤として酢酸エチル１０部、メチルアルコール１０部、ケトーエノール互変異性体形成化合物としてアセチルアセトン０．５部を加え、充分攪拌後、質量平均分子量４９万、不揮発分５４％のアクリル共重合体溶液を得た。なお、２５℃まで自然冷却し、同温度で１時間経過しても、前記アクリル共重合体溶液には、沈殿物も白濁も認められなかった。
<Production Example of Acrylic Copolymer Solution>
Using a polymerization apparatus equipped with a stirrer, a thermometer, a dropping pipe, and a reflux condenser, 41.8 parts of butyl acrylate, 40 parts of 2-ethylhexyl acrylate, 7 parts of ethyl acrylate, 10 parts of acrylic acid, 1 part of 2-hydroxyethyl acrylate. Half of the raw material mixture containing 0.2 parts of methyl ethyl ketone, 40 parts of ethyl acetate, 25 parts of ethyl acetate and 0.1 part of benzoyl peroxide was charged into a reaction tank under a nitrogen atmosphere.
Separately, the other half of the raw material mixture was charged in the dropping layer.
Then heating of the reaction vessel was started. After confirming the start of the polymerization reaction, the raw material mixture was dropped from the dropping tube over 1 hour. After the dropping was completed, solution polymerization was further continued for 7 hours under reflux.
After completion of the reaction, the mixture was cooled, 10 parts of ethyl acetate as a diluting solvent, 10 parts of methyl alcohol, and 0.5 part of acetylacetone as a keto-enol tautomer forming compound were added, and after sufficient stirring, a mass average molecular weight of 490,000 and a nonvolatile content of 54%. To obtain an acrylic copolymer solution. Even when naturally cooled to 25 ° C. and 1 hour passed at the same temperature, neither precipitate nor cloudiness was observed in the acrylic copolymer solution.
＜ポリプロピレン溶解液１の製造例＞
攪拌器、温度計、還流冷却器を備えた装置を用い、質量平均分子量２万のリコセンＰＰ１３０２（ポリプロピレン、クラリアントケミカルズ(株)製）５０部、トルエン５０部をフラスコに仕込み６０℃に加温し１時間撹拌を行い、不揮発分５０％のポリプロピレン溶解液１を得た。なお、このポリプロピレン溶液１：２部とトルエン５０部を４０℃下で混合して希釈し、２５℃まで自然冷却し、同温度で１時間経過しても、このポリプロピレン溶解液１の希釈液には、沈殿物も白濁も認められなかった。
<Production example of polypropylene solution 1>
Using a device equipped with a stirrer, a thermometer, and a reflux condenser, 50 parts of Licocene PP1302 (polypropylene, manufactured by Clariant Chemicals Co., Ltd.) having a mass average molecular weight of 20,000 and 50 parts of toluene were charged into a flask and heated to 60 ° C. The mixture was stirred for 1 hour to obtain polypropylene solution 1 having a nonvolatile content of 50%. It should be noted that 1: 2 parts of this polypropylene solution and 50 parts of toluene were mixed and diluted at 40 ° C., diluted, and naturally cooled to 25 ° C. Even after 1 hour at the same temperature, the polypropylene solution 1 was diluted. No precipitate or white turbidity was observed.
＜ポリプロピレン溶解液２の製造例＞
ポリプロピレンをリコセンＰＰ１３０２から質量平均分子量５万７千のリコセンＰＰ１５０２（ポリプロピレン、クラリアントケミカルズ(株)製）に変更した以外はポリプロピレン溶解液１と同じ方法で、沈殿物も白濁も認められない不揮発分５０％のポリプロピレン溶解液２を得た。
<Production example of polypropylene solution 2>
Non-volatile content 50 in which neither precipitate nor white turbidity was observed by the same method as polypropylene solution 1 except that polypropylene was changed from lycocene PP1302 to lycocene PP1502 having a mass average molecular weight of 57,000 (polypropylene, manufactured by Clariant Chemicals Co., Ltd.). % Polypropylene solution 2 was obtained.
＜ポリプロピレン溶解液３の製造例＞
ポリプロピレンをリコセンＰＰ１３０２から質量平均分子量２万４千のリコセンＰＰＭＡ１３３２（マレイン酸変性ポリプロピレン、クラリアントケミカルズ(株)製）に変更した以外はポリプロピレン溶解液１と同じ方法で、沈殿物も白濁も認められない不揮発分５０％のポリプロピレン溶解液３を作成した。
<Production example of polypropylene solution 3>
Precipitate and cloudiness are not observed by the same method as polypropylene solution 1 except that polypropylene is changed from lycocene PP1302 to lycocene PPMA1332 (maleic acid modified polypropylene, manufactured by Clariant Chemicals Co., Ltd.) having a mass average molecular weight of 24,000. A polypropylene solution 3 having a nonvolatile content of 50% was prepared.
＜ポリプロピレン分散液の製造例＞
攪拌器、温度計、還流冷却器を備えた装置を用い、質量平均分子量２万のリコセンＰＰ１３０２（ポリプロピレン、クラリアントケミカルズ(株)製）５０部、トルエン５０部をフラスコに仕込み６０℃に加温し１時間撹拌を行って得た不揮発分５０％のポリプロピレン溶解液の中に、酢酸エチル１００部を滴下し、ポリプロピレンを析出させた後、３ｍｍ直径のガラスビーズと共に容器に入れペイントシェイカーで1時間分散し、不揮発分２５％、平均分散粒子径１μｍのポリプロピレン分散液を得た。
<Production example of polypropylene dispersion>
Using a device equipped with a stirrer, a thermometer, and a reflux condenser, 50 parts of Licocene PP1302 (polypropylene, manufactured by Clariant Chemicals Co., Ltd.) having a mass average molecular weight of 20,000 and 50 parts of toluene were charged into a flask and heated to 60 ° C. 100 parts of ethyl acetate was dropped into a polypropylene solution with a non-volatile content of 50% after stirring for 1 hour to precipitate polypropylene, which was then placed in a container with glass beads with a diameter of 3 mm and dispersed with a paint shaker for 1 hour. Then, a polypropylene dispersion liquid having a nonvolatile content of 25% and an average dispersed particle diameter of 1 μm was obtained.
＜実施例１＞
粘着付与樹脂（荒川化学工業社製ペンセルＤ−１２５、軟化温度：約１３０℃）２０部を酢酸エチル２０部で溶解し、そこにアクリル共重合体溶液１８５．２部（不揮発分としてアクリル共重合体を１００部含む）、硬化剤（アルミニウムトリスアセチルアセトナート）０．４部、酢酸エチル１４．４部を加え、ディスパーを用い毎分２０００回転で撹拌分散しながら、８０℃に加温されたポリプロピレン溶解液１：１０部（不揮発分としてポリプロピレンを５部含む）を徐々に加えた後、更に１０分間撹拌し、平均分散粒子径１５μｍのポリプロピレンを含有する、不揮発分５０％の粘着剤１を得た。
なお、粘着付与樹脂、硬化剤はそれぞれメチルエチルケトン、酢酸エチル、メチルアルコールに溶解し、リコセンＰＰ１３０２はこれらには溶解しない。
<Example 1>
20 parts of a tackifying resin (Pencel D-125 manufactured by Arakawa Chemical Industry Co., Ltd., softening temperature: about 130 ° C.) was dissolved in 20 parts of ethyl acetate, and 185.2 parts of an acrylic copolymer solution (acrylic copolymerization as a non-volatile component) was dissolved therein. 100 parts of the coalescence), a curing agent (aluminum tris acetylacetonate) 0.4 parts, and ethyl acetate 14.4 parts were added, and the mixture was heated to 80 ° C. while stirring and dispersing at 2000 rpm with a disper. Polypropylene solution 1: After gradually adding 10 parts (including 5 parts of polypropylene as a non-volatile component) and stirring for 10 minutes, a pressure-sensitive adhesive 1 having a non-volatile content of 50% containing polypropylene having an average dispersed particle diameter of 15 μm is added. Obtained.
The tackifying resin and the curing agent are dissolved in methyl ethyl ketone, ethyl acetate, and methyl alcohol, respectively, and lycocene PP1302 is not dissolved in these.
＜実施例２＞
実施例１と同様の配合で、ディスパーでの撹拌分散条件を毎分２０００回転で３分間撹拌とした以外は同じ方法で粘着剤を作成し、平均分散粒子径４０μｍのポリプロピレンを含有する、不揮発分５０％の粘着剤２を得た。
<Example 2>
A pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the stirring and dispersing conditions with the disperser were changed to 2000 rpm for 3 minutes, and a non-volatile component containing polypropylene having an average dispersed particle diameter of 40 μm was used. 50% adhesive 2 was obtained.
＜実施例３＞
ポリプロピレン溶解液１の代わりにポリプロピレン分散液を２０部（不揮発分としてポリプロピレンを５部含む）用い、酢酸エチルの配合量を１４．４部から４．４部に変更した以外は実施例１と同様の方法で、平均分散粒子径１μｍのポリプロピレンを含有する、不揮発分５０％の粘着剤３を得た。
<Example 3>
The same as Example 1 except that 20 parts of polypropylene dispersion liquid (including 5 parts of polypropylene as a non-volatile component) was used instead of the polypropylene solution 1, and the compounding amount of ethyl acetate was changed from 14.4 parts to 4.4 parts. By the method described above, a pressure-sensitive adhesive 3 containing polypropylene having an average dispersed particle diameter of 1 μm and a nonvolatile content of 50% was obtained.
＜実施例４＞
ポリプロピレン溶解液１の代わりにポリプロピレン溶解液２を用いた以外は実施例１と同様の方法で平均分散粒子径１５μｍのポリプロピレンを含有する、不揮発分５０％の粘着剤４を得た。
<Example 4>
A pressure-sensitive adhesive 4 containing a polypropylene having an average dispersed particle diameter of 15 μm and a nonvolatile content of 50% was obtained in the same manner as in Example 1 except that the polypropylene solution 2 was used instead of the polypropylene solution 1.
＜実施例５＞
ポリプロピレン溶解液１の代わりにポリプロピレン溶解液３を用いた以外は実施例１と同様の方法で平均分散粒子径１３μｍのポリプロピレンを含有する、不揮発分５０％の粘着剤５を得た。
<Example 5>
A pressure-sensitive adhesive 5 containing a polypropylene having an average dispersed particle diameter of 13 μm and a nonvolatile content of 50% was obtained in the same manner as in Example 1 except that the polypropylene solution 3 was used instead of the polypropylene solution 1.
＜実施例６＞
ポリプロピレン溶解液１の配合量を１０部から１部に変更した以外は実施例１と同じ方法で不揮発分５０％の粘着剤６を得た。
<Example 6>
A pressure-sensitive adhesive 6 having a nonvolatile content of 50% was obtained in the same manner as in Example 1 except that the compounding amount of the polypropylene solution 1 was changed from 10 parts to 1 part.
＜比較例１＞
ディスパーによる撹拌分散条件を毎分５００回転とし、ポリプロピレン溶解液１を徐々に加えた後、更に３分間撹拌した以外は実施例１と同様にして、平均分散粒子径２００μｍのポリプロピレンを含有する、不揮発分５０％の粘着剤７を得た。
<Comparative Example 1>
Non-volatile containing polypropylene having an average dispersed particle diameter of 200 μm in the same manner as in Example 1 except that the stirring and dispersing conditions with a disper were 500 rpm, and polypropylene solution 1 was gradually added, followed by stirring for 3 minutes. Adhesive 7 having a content of 50% was obtained.
＜比較例２＞
粘着付与樹脂（荒川化学社製ペンセルＤ−１２５、軟化温度：約１３０℃）２０部を酢酸エチル２０部で溶解し、そこにアクリル共重合体溶液１８５．２部（不揮発分としてアクリル共重合体を１００部含む）、硬化剤（アルミニウムトリスアセチルアセトナート）０．４部、スーパークロン９３０（日本製紙(株)製、塩素化ポリプロピレンの溶液、溶剤組成：トルエン／シクロヘキサン＝９／１（質量比）、不揮発分２０％）を２５部加え、全部配合後、ディスパー毎分２０００回転で１０分間撹拌分散し、不揮発分５０％の粘着剤８を得た。
なお、スーパークロン９３０は酢酸エチルやメチルエチルケトンに溶解しほとんど白濁しなかった。粘着剤８もほとんど白濁せず、レーザー散乱型粒度分布計で平均分散粒径の測定を試みたが、粒子を検出できなかった。
<Comparative example 2>
20 parts of a tackifying resin (Pencel D-125, manufactured by Arakawa Chemical Co., Ltd., softening temperature: about 130 ° C.) was dissolved in 20 parts of ethyl acetate, and 185.2 parts of an acrylic copolymer solution (acrylic copolymer as a non-volatile component was dissolved therein). 100 parts), a curing agent (aluminum trisacetylacetonate) 0.4 parts, Supercron 930 (manufactured by Nippon Paper Industries Co., Ltd., chlorinated polypropylene solution, solvent composition: toluene / cyclohexane = 9/1 (mass ratio) ), Non-volatile content 20%) was added, and the whole mixture was added, and the dispersion was stirred and dispersed at 2000 rpm for 10 minutes to obtain an adhesive 8 having a non-volatile content of 50%.
Super Clone 930 was dissolved in ethyl acetate or methyl ethyl ketone and was hardly clouded. The pressure-sensitive adhesive 8 was hardly clouded, and an attempt was made to measure the average dispersed particle diameter with a laser scattering type particle size distribution meter, but no particle could be detected.
＜比較例３＞
ポリプロピレン溶解液１の代わりに、ＰＢ６８０（ＤＡＥＬＩＭ社製 液状ポリブテン）５部をトルエン５部で希釈した液１０部を用いた以外は実施例１と同様の方法で粘着剤９を得た。
なお、ＰＢ６８０は酢酸エチルやメチルエチルケトンに溶解しほとんど白濁しなかった。粘着剤９もほとんど白濁せず、レーザー散乱型粒度分布計で平均分散粒径の測定を試みたが、粒子を検出できなかった。
<Comparative example 3>
An adhesive 9 was obtained in the same manner as in Example 1 except that 10 parts of a solution prepared by diluting 5 parts of PB680 (a liquid polybutene manufactured by DAELIM) with 5 parts of toluene was used instead of the polypropylene solution 1.
Note that PB680 was dissolved in ethyl acetate or methyl ethyl ketone and was hardly clouded. The pressure-sensitive adhesive 9 was also hardly clouded, and an attempt was made to measure the average dispersed particle diameter with a laser scattering type particle size distribution meter, but no particle could be detected.
＜比較例４＞
ポリプロピレン溶解液１を除いた以外は実施例１と同じ方法で不揮発分５０％の粘着剤１０を得た。
<Comparative example 4>
A pressure-sensitive adhesive 10 having a nonvolatile content of 50% was obtained in the same manner as in Example 1 except that the polypropylene solution 1 was omitted.
＜比較例５＞
アクリル共重合体溶液１８５．２部、硬化剤（アルミニウムトリスアセチルアセトナート）０．４部、酢酸エチル１４．４部を加え、全部配合後、ディスパー毎分２０００回転で１０分間撹拌し、不揮発分５０％の粘着剤１１を得た。
<Comparative Example 5>
Acrylic copolymer solution 185.2 parts, a curing agent (aluminum trisacetylacetonate) 0.4 parts, and ethyl acetate 14.4 parts were added, and after all the ingredients were mixed, the dispersion was stirred at 2000 rpm for 10 minutes to obtain a nonvolatile content. 50% of adhesive 11 was obtained.
評価項目と方法を以下に説明する。
＜質量平均分子量＞
質量平均分子量は、昭和電工社製ＳｈｏｄｅｘＧＰＣ−１０４／１０１システムを用いて測定した。
カラム：ＳｈｏｄｅｘＫＦ−８０５Ｌ＋ＫＦ−８０３Ｌ＋ＫＦ−８０２
検出器示差屈折率計（ＲＩ）
カラム温度：４０℃
溶離液：テトラヒドロフラン
流速：１．０ｍｌ/ｍｉｎ
試料濃度：０．１ｗｔ％
検量線用標準試料：ＴＳＫ標準ポリスチレン
The evaluation items and methods are described below.
<Mass average molecular weight>
The mass average molecular weight was measured using a Shodex GPC-104 / 101 system manufactured by Showa Denko KK.
Column: Shodex KF-805L + KF-803L + KF-802
Detector Differential Refractometer (RI)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 ml / min
Sample concentration: 0.1 wt%
Standard sample for calibration curve: TSK standard polystyrene
＜平均分散粒子径＞
粘着剤中のポリプロピレンの平均分散粒子径は、粒度分布計マイクロトラックＭＴ３０００II（マイクロトラック・ベル社製 測定範囲０．０２〜２０００μｍ）を使い、測定濃度は、濃度指標となるＴＲ値（試料無い場合は１．０で、試料濃度が高くなると小さくなる）が０．９０〜０．９５になるように調整し、希釈溶剤にメチルエチルケトン（溶剤屈折率１．３８）、粒子屈折率１．８０の値を用いて測定した。平均分散粒子径とはＤ５０値を意味する。
<Average dispersed particle size>
For the average dispersed particle size of polypropylene in the adhesive, a particle size distribution analyzer Microtrac MT3000II (manufactured by Microtrac Bell Co., measurement range 0.02 to 2000 μm) is used, and the measured concentration is a TR value (when there is no sample). Is 1.0, and decreases as the sample concentration increases) to 0.90 to 0.95, and the dilution solvent is methyl ethyl ketone (solvent refractive index 1.38) and particle refractive index 1.80. Was measured using. The average dispersed particle diameter means a D50 value.
［粘着シートの作成］
得られた粘着剤を剥離シートにコンマコーターを使用して、塗工し、電気オーブンで１００℃−２分間乾燥し、溶剤を除去し、乾燥厚みが５０μｍの粘着層に厚さ５０μｍのポリエスチレンテレフタレート（ＰＥＴ）フィルムを貼り合わせて粘着シートの前駆体を得た。これを２３℃−５０％ＲＨ雰囲気の恒温恒湿室にて、７日間養生し硬化を完了させ、粘着シートを得た。粘着シートについて以下の性能を評価した。
[Creation of adhesive sheet]
The obtained pressure-sensitive adhesive was applied to a release sheet using a comma coater, dried in an electric oven at 100 ° C. for 2 minutes to remove the solvent, and a dry thickness of 50 μm was applied to a pressure-sensitive adhesive layer of polyethylene styrene having a thickness of 50 μm. A terephthalate (PET) film was attached to obtain a precursor of a pressure-sensitive adhesive sheet. This was cured for 7 days in a constant temperature and constant humidity chamber in an atmosphere of 23 ° C. and 50% RH to complete curing to obtain an adhesive sheet. The following performances of the pressure-sensitive adhesive sheet were evaluated.
＜２３℃における粘着力（剥離力）＞
得られた粘着シートを幅２５ｍｍ・長さ１００ｍｍの大きさに切り取り試料とした。
次いで２３℃−５０％ＲＨ雰囲気下、ＪＩＳＺ０２３７に準拠して、試料から剥離シートを剥がし、露出した粘着層を研磨したステンレス（ＳＵＳ）板、またはポリプロピレン（ＰＰ）板に貼着し、２ｋｇロールで１往復圧着した後、引張試験機を使用して貼着２４時間後に剥離速度３００ｍｍ／ｍｉｎ、剥離角度１８０°の条件で粘着力（Ｎ／２５ｍｍ）を測定した。
<Adhesive strength (peel strength) at 23 ° C>
The obtained pressure-sensitive adhesive sheet was cut into a sample having a width of 25 mm and a length of 100 mm to obtain a sample.
Then, in a 23 ° C.-50% RH atmosphere, the release sheet was peeled off from the sample in accordance with JISZ0237, and the exposed adhesive layer was attached to a polished stainless steel (SUS) plate or polypropylene (PP) plate with a 2 kg roll. After one reciprocal pressure bonding, the adhesive force (N / 25 mm) was measured 24 hours after application using a tensile tester under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °.
＜６０℃における粘着力（剥離力）＞
試料を切り出した後、６０℃雰囲気下に２０分保持してから、６０℃に温めてあるＳＵＳ板、またはＰＰ板に、前記２３℃の場合と同様にして貼着および圧着し、６０℃雰囲気に２０分間静置した後、引張試験機を使用して前記２３℃の場合と同様にして６０℃雰囲気下での粘着力を測定した。
<Adhesive force at 60 ° C (peeling force)>
After cutting out the sample, hold it in an atmosphere of 60 ° C for 20 minutes, and then stick and press-bond it to a SUS plate or a PP plate that has been warmed to 60 ° C in the same manner as in the case of 23 ° C described above, in an atmosphere of 60 ° C. After standing still for 20 minutes, the adhesive strength in an atmosphere of 60 ° C. was measured using a tensile tester in the same manner as in the case of 23 ° C.
表１の結果から実施例１〜６の粘着剤およびそれを使用した粘着シートは、いずれも非極性ポリオレフィン被着体に対し高い粘着力を持ち、６０℃の環境下でも優れた粘着力を発現し耐熱性が優れている。 From the results of Table 1, the pressure-sensitive adhesives of Examples 1 to 6 and the pressure-sensitive adhesive sheets using the same all have high pressure-sensitive adhesive force to non-polar polyolefin adherends, and exhibit excellent pressure-sensitive adhesive force even in an environment of 60 ° C. Excellent heat resistance.
Claims (8)
前記有機溶剤ａには溶解しないポリプロピレン、およびポリプロピレンを溶解し得る有機溶剤ｂを含む溶液Ｂとを混合し、
平均分散粒子径が０．０２〜１００μｍのポリプロピレン粒子を析出する、
粘着剤の製造方法。 A solution A containing an acrylic polymer, a tackifying resin, a curing agent, and an organic solvent a in which the three components can be respectively dissolved and polypropylene is not dissolved,
A mixture of polypropylene not soluble in the organic solvent a and a solution B containing an organic solvent b capable of dissolving polypropylene,
Precipitating polypropylene particles having an average dispersed particle diameter of 0.02 to 100 μm,
Adhesive manufacturing method.
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