JP2015147833A - Pressure-sensitive adhesive and pressure-sensitive adhesive sheet - Google Patents
Pressure-sensitive adhesive and pressure-sensitive adhesive sheet Download PDFInfo
- Publication number
- JP2015147833A JP2015147833A JP2014020312A JP2014020312A JP2015147833A JP 2015147833 A JP2015147833 A JP 2015147833A JP 2014020312 A JP2014020312 A JP 2014020312A JP 2014020312 A JP2014020312 A JP 2014020312A JP 2015147833 A JP2015147833 A JP 2015147833A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- meth
- acrylate
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 66
- -1 isocyanate compound Chemical class 0.000 claims abstract description 52
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 25
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 230000001070 adhesive effect Effects 0.000 claims description 30
- 239000000853 adhesive Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 8
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 57
- 239000000178 monomer Substances 0.000 description 49
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000010410 layer Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 239000002390 adhesive tape Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 235000019645 odor Nutrition 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 239000002253 acid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 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 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
- 150000007513 acids Chemical class 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction 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
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
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Abstract
Description
本発明は、硬化触媒として樹脂酸塩を用いた粘着剤および粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet using a resin acid salt as a curing catalyst.
従来からイソシアネート化合物は、粘着剤の硬化剤として広く使用されている。かかる粘着剤に含まれるアクリル共重合体が水酸基を有する場合、水酸基とイソシアナト基との間の硬化速度が遅いため粘着剤の硬化反応は、完了まで時間が掛かっていた。そこで、硬化触媒としてジブチル錫ジラウレート等の有機錫化合物を使用することで粘着剤の熟成期間を短縮することが一般的に行われている。 Conventionally, isocyanate compounds have been widely used as curing agents for pressure-sensitive adhesives. When the acrylic copolymer contained in the pressure-sensitive adhesive has a hydroxyl group, the curing reaction of the pressure-sensitive adhesive takes time until completion because the curing rate between the hydroxyl group and the isocyanate group is slow. Therefore, it is a common practice to shorten the aging period of the pressure-sensitive adhesive by using an organic tin compound such as dibutyltin dilaurate as a curing catalyst.
しかし、単に粘着剤に硬化触媒を配合すると、硬化速度は速くなるが、同時に粘着剤のポットライフ（可使時間）も短くなるため、塗工性を低下させる。そこでポットライフ延長のため、特許文献１は、硬化遅延剤として酢酸等の揮発性酸を配合した粘着剤が開示されている。 However, simply adding a curing catalyst to the pressure-sensitive adhesive increases the curing speed, but at the same time shortens the pot life (usable time) of the pressure-sensitive adhesive, thereby reducing the coatability. In order to extend the pot life, Patent Document 1 discloses an adhesive containing a volatile acid such as acetic acid as a curing retarder.
しかし、従来の粘着剤は、揮発性酸を配合したことで、ある程度硬化速度とポットライフのバランスを取ることができたが、粘着剤を塗工する際に蒸発した揮発性酸は、塗工装置内の乾燥オーブンおよび排気管を腐食する原因になっていた。さらに蒸発した揮発性酸は、刺激臭が強く塗工作業者に不快感を与える原因となっており安全衛生面から改善が求められていた。また、粘着テープに残留した揮発性酸は、粘着テープを貼り付ける対象（以下、被着体）が金属である場合、金属に腐食が生じる問題があった。 However, conventional pressure-sensitive adhesives can balance the curing speed and pot life to some extent by blending volatile acids. However, volatile acids evaporated when applying pressure-sensitive adhesives are This caused corrosion of the drying oven and exhaust pipe in the apparatus. Further, the evaporated volatile acid has a strong irritating odor and causes discomfort to the painter, and improvement has been demanded from the viewpoint of safety and health. Further, the volatile acid remaining on the adhesive tape has a problem that the metal is corroded when the object (hereinafter referred to as an adherend) to which the adhesive tape is applied is a metal.
本発明は、塗工装置ないし被着体に腐食が生じ難く、塗工作業者に不快感を与え難く、硬化触媒を含む粘着剤および粘着シートの提供を目的とする。 An object of the present invention is to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet containing a curing catalyst that hardly cause corrosion in a coating apparatus or an adherend, hardly cause discomfort to a coating builder.
本発明の粘着剤は、水酸基を有するアクリル共重合体、樹脂酸塩、水およびイソシアネート化合物を含む。 The pressure-sensitive adhesive of the present invention contains an acrylic copolymer having a hydroxyl group, a resin acid salt, water and an isocyanate compound.
上記の本発明によれば、有機錫化合物に換えて樹脂酸塩を配合したところ、良好な硬化速度が得られたが、反面、ポットライフが短くなったため、硬化遅延剤として水を配合したことで適度な硬化速度と必要十分なポットライフを両立できた。かかる樹脂酸塩および水を含む本発明の粘着剤は、塗工装置内および金属被着体の腐食を抑制できた上、塗工作業者が不快感を感じ難くなった。さらに有機錫化合物と比較して樹脂酸塩は、毒性が低いため粘着剤の安全衛生性が大きく向上した。 According to the present invention, when a resin acid salt was blended instead of an organotin compound, a good curing rate was obtained, but on the other hand, because pot life was shortened, water was blended as a curing retarder. It was possible to achieve both an appropriate curing speed and a necessary and sufficient pot life. The pressure-sensitive adhesive of the present invention containing such a resin acid salt and water can suppress corrosion in the coating apparatus and the metal adherend, and makes it difficult for the coating builder to feel uncomfortable. Furthermore, since the resin acid salt is less toxic than the organotin compound, the safety and health of the adhesive is greatly improved.
本発明により塗工装置ないし被着体に腐食が生じ難く、塗工作業者に不快感を与え難く、硬化触媒を含む粘着剤および粘着シートを提供できた。 According to the present invention, it is possible to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet containing a curing catalyst, which hardly cause corrosion in the coating apparatus or adherend, hardly cause discomfort to the coating operator.
本発明の粘着剤は、アクリル共重合体、樹脂酸塩、水およびイソシアネート化合物を含む。前記粘着剤は、基材または剥離シートに塗工することで粘着剤層を形成し、粘着シートとして使用することが好ましい。また本発明の粘着剤は、粘着シートを被着体に貼着後に前記粘着シートを剥離しない用途（永久粘着タイプ）および粘着シートを被着体に貼着後に前記粘着シートを剥離する用途（再剥離タイプ）に使用できる。なお、本発明で粘着シートは、粘着テープ、粘着フィルム、粘着ラベルと同義語である。 The pressure-sensitive adhesive of the present invention contains an acrylic copolymer, a resin acid salt, water and an isocyanate compound. The pressure-sensitive adhesive is preferably used as a pressure-sensitive adhesive sheet by coating a base material or a release sheet to form a pressure-sensitive adhesive layer. In addition, the pressure-sensitive adhesive of the present invention can be used for applications in which the pressure-sensitive adhesive sheet is not peeled after being stuck to the adherend (permanent pressure-sensitive adhesive type) and for use in peeling the pressure-sensitive adhesive sheet after the pressure-sensitive adhesive sheet is stuck on the adherend (re-use). Can be used for peeling type). In the present invention, the adhesive sheet is synonymous with an adhesive tape, an adhesive film, and an adhesive label.
本発明においてアクリル共重合体は、粘着剤の主剤として機能し、反応性官能基を有する。前記反応性官能基は、イソシアネート化合物等の硬化剤と硬化可能な官能基であればよく限定されない。反応性官能基は、水酸基を必須とし、カルボキシル基、アミノ基、アミド基、グリシジル基、シアノ基等を併用できる。しかし前記併用により硬化速度およびポットライフの両立が難しくなる場合があるため、併用する官能基には注意が必要である。 In the present invention, the acrylic copolymer functions as a main component of the pressure-sensitive adhesive and has a reactive functional group. The reactive functional group is not limited as long as it is a functional group curable with a curing agent such as an isocyanate compound. The reactive functional group essentially requires a hydroxyl group, and a carboxyl group, amino group, amide group, glycidyl group, cyano group, or the like can be used in combination. However, since the combination of the curing rate and the pot life may be difficult due to the combined use, attention should be paid to the functional group used together.
前記アクリル共重合体は、（メタ）アクリル酸アルキルエステルおよび反応性官能基含有単量体を必須成分、その他単量体を任意成分とした単量体混合物を共重合して得た共重合体である。前記共重合は、溶液重合、乳化重合、懸濁重合および塊状重合等の公知の重合方法を利用できるが、本発明では分子量を調整しやすい溶液重合が好ましい。なお（メタ）アクリル酸アルキルエステルは、アクリル酸アルキルエステルおよびメタクリル酸アルキルエステルを含む。また単量体は、エチレン性不飽和二重結合を有するラジカル重合可能な化合物をいう。 The acrylic copolymer is a copolymer obtained by copolymerizing a monomer mixture containing a (meth) acrylic acid alkyl ester and a reactive functional group-containing monomer as essential components and other monomers as optional components. It is. For the copolymerization, known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization can be used. In the present invention, solution polymerization that allows easy adjustment of the molecular weight is preferred. The (meth) acrylic acid alkyl ester includes an acrylic acid alkyl ester and a methacrylic acid alkyl ester. The monomer refers to a radically polymerizable compound having an ethylenically unsaturated double bond.
前記アクリル共重合体は、重量平均分子量１０万〜２００万が好ましく、３０万〜１２０万がより好ましい。なお、重量平均分子量は、ＧＰＣ測定で求めたポリスチレン換算の重量平均分子量であり、ＧＰＣ測定条件は以下のとおりである。装置：ＳＨＩＭＡＤＺＵ Ｐｒｏｍｉｎｅｎｃｅ（（株）島津製作所製）カラム：ＴＯＳＯＨ ＴＳＫ−ＧＥＬ ＧＭＨＸＬ（東ソー（株）製）を使用。溶媒：テトラヒドロフラン、流速：０．５ｍｌ／ｍｉｎ、温度：４０℃、試料濃度：０．１ｗｔ％、試料注入量：１００μl。 The acrylic copolymer preferably has a weight average molecular weight of 100,000 to 2,000,000, more preferably 300,000 to 1,200,000. In addition, a weight average molecular weight is a weight average molecular weight of polystyrene conversion calculated | required by GPC measurement, and GPC measurement conditions are as follows. Apparatus: SHIMADZU Prominence (manufactured by Shimadzu Corporation) Column: TOSOH TSK-GEL GMHXL (manufactured by Tosoh Corporation) is used. Solvent: tetrahydrofuran, flow rate: 0.5 ml / min, temperature: 40 ° C., sample concentration: 0.1 wt%, sample injection amount: 100 μl.
また、前記アクリル共重合体のガラス転移温度（以下、Ｔｇともいう）は、−１００〜２０℃が好ましく、−８０〜０℃がより好ましい。 The glass transition temperature (hereinafter also referred to as Tg) of the acrylic copolymer is preferably -100 to 20 ° C, more preferably -80 to 0 ° C.
前記（メタ）アクリル酸アルキルエステルは、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、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｓ−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、ペンチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、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、およびｎ−テトラデシル（メタ）アクリレート等が挙げられる。これらに中でも粘着物性の点からｎ−ブチル（メタ）アクリレートおよび２−エチルヘキシル（メタ）アクリレートがより好ましい。（メタ）アクリル酸アルキルエステルは、単独または２種以上使用できる。なお、環状アルキル構造を含む単量体、アルキレンオキサイド構造を含む単量体、アルコキシ基を含む単量体およびアセトアセトキシ基を含む単量体は、（メタ）アクリル酸アルキルエステルには含まない。 Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl ( Examples include meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate. Among these, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable from the viewpoint of adhesive properties. The (meth) acrylic acid alkyl ester can be used alone or in combination of two or more. A monomer containing a cyclic alkyl structure, a monomer containing an alkylene oxide structure, a monomer containing an alkoxy group, and a monomer containing an acetoacetoxy group are not included in the (meth) acrylic acid alkyl ester.
（メタ）アクリル酸アルキルエステルは、単量体混合物１００重量％のうち５０〜９９．９重量％を配合することが好ましく、６５〜９９重量％がより好ましい。 The (meth) acrylic acid alkyl ester is preferably blended in an amount of 50 to 99.9% by weight out of 100% by weight of the monomer mixture, and more preferably 65 to 99% by weight.
前記反応性官能基含有単量体のうち水酸基含有単量体は、２−ヒドロキシエチル（メタ）アクリレート、３−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、（メタ）アクリル酸６−ヒドロキシヘキシル、（メタ）アクリル酸８−ヒドロキシオクチル、（メタ）アクリル酸１０−ヒドロキシデシル、（メタ）アクリル酸１２−ヒドロキシラウリル、（メタ）アクリル酸１８−ヒドロキシステアリル、（メタ）アクリル酸４−（ヒドロキシメチル）シクロヘキシルメチル等が挙げられる。これらの中でも２−ヒドロキシエチル（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、（メタ）アクリル酸６−ヒドロキシヘキシル、および（メタ）アクリル酸８−ヒドロキシオクチル等が好ましい。水酸基含有単量体は、単独または２種以上使用できる。 Among the reactive functional group-containing monomers, the hydroxyl group-containing monomers are 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid. 6-hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 18-hydroxystearyl (meth) acrylate, (meth) acrylic acid 4- (hydroxymethyl) cyclohexylmethyl and the like can be mentioned. Among these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and the like are preferable. The hydroxyl group-containing monomer can be used alone or in combination of two or more.
水酸基含有単量体は、単量体混合物１００重量％のうち０．１〜２０重量％を配合することが好ましい。前記配合量は、粘着剤の用途により適宜変更できる。例えば、再剥離用途の場合、２〜２０重量％が好ましい。また。再剥離以外の用途の場合、０．１〜１０重量％が好ましい。 The hydroxyl group-containing monomer is preferably blended in an amount of 0.1 to 20% by weight out of 100% by weight of the monomer mixture. The said compounding quantity can be suitably changed with the use of an adhesive. For example, in the case of a re-peeling application, 2 to 20% by weight is preferable. Also. In the case of uses other than re-peeling, 0.1 to 10% by weight is preferable.
前記反応性官能基含有単量体のうち水酸基含有単量体以外の単量体は、カルボキシル基含有単量体、アミノ基含有単量体、アミド基含有単量体、イミド基含有単量体、グリシジル基含有単量体、シアノ基含有単量体等が好ましい。 Among the reactive functional group-containing monomers, monomers other than the hydroxyl group-containing monomer are a carboxyl group-containing monomer, an amino group-containing monomer, an amide group-containing monomer, and an imide group-containing monomer. , Glycidyl group-containing monomers, cyano group-containing monomers, and the like are preferable.
カルボキシル基含有単量体は、例えば、アクリル酸、メタクリル酸、２−アクリロイロキシエチル−コハク酸、２−アクリロイロキシエチルヘキサヒドロフタル酸、および２−アクリロイロキシエチル−フタル酸等が挙げられる。 Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-acryloyloxyethyl-phthalic acid. It is done.
アミノ基含有単量体は、例えば、アミノエチル（メタ）アクリレート、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、および（メタ）アクリロイルモルホリン等が挙げられる。 Examples of the amino group-containing monomer include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and (meth) acryloylmorpholine. It is done.
アミド基含有単量体は、例えば、アクリルアミド、メタクリルアミド、ジエチルアクリルアミド、Ｎ−ビニルピロリドン、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ，Ｎ−ジエチルメタクリルアミド、Ｎ，Ｎ’−メチレンビスアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルメタクリルアミド、およびジアセトンアクリルアミド等が挙げられる。 Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, and N, N-diethyl. Examples include methacrylamide, N, N′-methylenebisacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, and diacetone acrylamide.
イミド基含有単量体は、例えば、シクロヘキシルマレイミド、イソプロピルマレイミド、Ｎ−シクロヘキシルマレイミド、およびイタコンイミド等が挙げられる。 Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
グリシジル基含有単量体は、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、およびアリルグリシジルエーテル等が挙げられる。 Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
シアノ基含有単量体は、例えば、アクリロニトリル、およびメタクリロニトリル等が挙げられる。 Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
前記反応性官能基含有単量体のうち水酸基含有単量体以外のその他単量体は、硬化反応とポットライフを両立できる範囲内で、水酸基含有単量体と併用できる。 Among the reactive functional group-containing monomers, other monomers other than the hydroxyl group-containing monomer can be used in combination with the hydroxyl group-containing monomer as long as both curing reaction and pot life can be achieved.
前記その他単量体は、必須成分の単量体と共に使用することで粘着物性を適宜調整できる。具体的には、（メタ）アクリル酸シクロアルキル、アルキレンオキサイド構造を有する（メタ）アクリル酸エステル、アルコキシル基含有単量体、およびビニル単量体等が好ましい。 By using the other monomers together with the essential component monomers, the adhesive physical properties can be appropriately adjusted. Specifically, (meth) acrylic acid cycloalkyl, (meth) acrylic acid ester having an alkylene oxide structure, an alkoxyl group-containing monomer, and a vinyl monomer are preferable.
前記（メタ）アクリル酸シクロアルキルは、例えば、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニルなどが挙げられる。芳香族アクリルモノマーとしては、および（メタ）アクリル酸ベンジル等が挙げられる。 Examples of the cycloalkyl (meth) acrylate include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and the like. Examples of the aromatic acrylic monomer include benzyl (meth) acrylate.
前記アルキレンオキサイド構造を有する（メタ）アクリル酸エステルは、例えば、メトキシ−ジエチレングリコール（メタ）アクリレート、メトキシ−トリエチレングリコール（メタ）アクリレートなどのメトキシ−ポリエチレングリコール（メタ）アクリレート型、エトキシ−ジエチレングリコール（メタ）アクリレート、エトキシ−トリエチレングリコール（メタ）アクリレートなどのエトキシ−ポリエチレングリコール（メタ）アクリレート型、ブトキシ−ジエチレングリコール（メタ）アクリレート、ブトキシ−トリエチレングリコール（メタ）アクリレートなどのブトキシ−ポリエチレングリコール（メタ）アクリレート型、フェノキシ−ジエチレングリコール（メタ）アクリレート、フェノキシ−トリエチレングリコール（メタ）アクリレートなどのフェノキシ−ポリエチレングリコール（メタ）アクリレート型、およびメトキシ−ジプロピレングリコール（メタ）アクリレートなどのメトキシ−ポリプロピレングリコール（メタ）アクリレート型等が挙げられる。 Examples of the (meth) acrylic acid ester having an alkylene oxide structure include methoxy-polyethylene glycol (meth) acrylate types such as methoxy-diethylene glycol (meth) acrylate and methoxy-triethylene glycol (meth) acrylate, ethoxy-diethylene glycol (meta ) Acrylate, ethoxy-polyethylene glycol (meth) acrylate type such as ethoxy-triethylene glycol (meth) acrylate, butoxy-polyethylene glycol (meth) such as butoxy-diethylene glycol (meth) acrylate, butoxy-triethylene glycol (meth) acrylate Acrylate type, phenoxy-diethylene glycol (meth) acrylate, phenoxy-triethylene glycol (meta Phenoxy, such as acrylate - polyethylene glycol (meth) acrylate type, and methoxy - methoxy, such as dipropylene glycol (meth) acrylate - polypropylene glycol (meth) acrylate type, and the like.
前記アルコキシル基含有単量体は、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、および（メタ）アクリル酸１−フェノキシエチル（メタ）アクリル酸２−フェノキシエチル等が挙げられる。 Examples of the alkoxyl group-containing monomer include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and 1-phenoxyethyl (meth) acrylate (2-phenoxyethyl) (meth) acrylate. Etc.
前記アセトアセトキシ基含有単量体は、例えば、２−アセトアセトキシエチル（メタ）アクリレート、および２−アセトアセトキシプロピル（メタ）アクリレート等が挙げられる。 Examples of the acetoacetoxy group-containing monomer include 2-acetoacetoxyethyl (meth) acrylate and 2-acetoacetoxypropyl (meth) acrylate.
前記ビニル単量体は、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、スチレン、クロロスチレン、クロロメチルスチレン、α−メチルスチレン、およびその他の置換スチレン等が挙げられる。 Examples of the vinyl monomer include vinyl acetate, vinyl propionate, vinyl laurate, styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and other substituted styrene.
その他単量体は、単量体混合物１００重量％のうち１〜４９．９重量％を配合することが好ましい。 The other monomers are preferably blended in an amount of 1 to 49.9% by weight out of 100% by weight of the monomer mixture.
ビニルエーテル類としては、例えば、メチルビニルエーテル、エチルビニルエーテル、およびイソブチルビニルエーテル等が挙げられる。 Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.
本発明におけるアクリル共重合体の合成方法について、溶液重合を例に挙げて説明する。
溶液重合は、上段で説明した単量体を有機溶媒および重合開始剤の存在下、共重合して得る。
The method for synthesizing the acrylic copolymer in the present invention will be described by taking solution polymerization as an example.
The solution polymerization is obtained by copolymerizing the monomers described above in the presence of an organic solvent and a polymerization initiator.
前記有機溶媒は、例えば、ベンゼン、トルエン、エチルベンゼン、ｎ−プロピルベンゼン、ｔ−ブチルベンゼン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、テトラリン、デカリン、芳香族ナフサなどの芳香族炭化水素類；例えば、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、ｉ−オクタン、ｎ−デカン、ジペンテン、石油スピリット、石油ナフサ、テレピン油などの脂肪系もしくは脂環族系炭化水素類；例えば、酢酸エチル、酢酸ｎ−ブチル、酢酸ｎ−アミル、酢酸２−ヒドロキシエチル、酢酸２−ブトキシエチル、酢酸３−メトキシブチル、安息香酸メチルなどのエステル類；例えば、アセトン、メチルエチルケトン、メチル−ｉ−ブチルケトン、イソホロン、シクロヘキサノン、メチルシクロヘキサノンなどのケトン類；例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテルなどのグリコールエーテル類；例えば、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、ｉ−プロピルアルコール、ｎ−ブチルアルコール、ｉ−ブチルアルコール、s-ブチルアルコール、およびｔ−ブチルアルコールのアルコール類；等が挙げられる。有機溶媒は単独または２種以上使用できる。 Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha; For example, aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, i-octane, n-decane, dipentene, petroleum spirit, petroleum naphtha, turpentine oil; Esters such as n-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, methyl benzoate; for example, acetone, methyl ethyl ketone, methyl-i-butyl ketone, isophorone, Ketones such as cyclohexanone and methylcyclohexanone; Glycol ethers such as tylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl And alcohols such as alcohol, n-butyl alcohol, i-butyl alcohol, s-butyl alcohol, and t-butyl alcohol; The organic solvent can be used alone or in combination of two or more.
前記重合開始剤は、過酸化物およびアゾ化合物から適宜選択して使用できる。前記過酸化物は、例えば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、および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挙げられる。前記アゾ化合物は、例えば、２，２’−アゾビス（２−メチルブチロニトリル）、および２，２’−アゾビスイソブチロニトリル等が挙げられる。重合開始剤は、単独または２種以上使用できる。
重合開始剤は、単量体混合物１００重量部に対して０．００１〜１０重量部使用できる。
The polymerization initiator can be appropriately selected from peroxides and azo compounds. Examples of the peroxide include t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, di-t-butyl peroxide, and 1,1-bis (t-butylperoxy) -3,3. Examples include 5-trimethylcyclohexane. Examples of the azo compound include 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, and the like. The polymerization initiators can be used alone or in combination of two or more.
The polymerization initiator can be used in an amount of 0.001 to 10 parts by weight with respect to 100 parts by weight of the monomer mixture.
前記共重合の際に分子量を調節する目的で、連鎖移動剤（重合調節剤ともいう）を使用できる。具体的には、例えば、ｎ−ブチルメルカプタン、ｎ−ヘキシルメルカプタン、ドデシルメルカプタン等のアルキルメルカプタン類；チオグリコール酸、メルカプトプロピオン酸、チオグリセロール、２−メルカプトエタノール等のその他メルカプタン類；ベンゾキノン、２，３，５，６−テトラメチル−ｐ−ベンゾキノンなどのベンゾキノン誘導体類；ビネン、ターピノレンなどのテルペン類；その他、α−メチルスチレンダイマー、ジスルフィド、イソプロピルアルコール、ジオキサン、四塩化炭素、およびクロロホルム等が挙げられる。連鎖移動剤は単独または２種以上を使用できる。
連鎖移動剤は、単量体混合物１００重量部に対して０．１〜３０重量部使用できる。
A chain transfer agent (also referred to as a polymerization regulator) can be used for the purpose of adjusting the molecular weight during the copolymerization. Specifically, for example, alkyl mercaptans such as n-butyl mercaptan, n-hexyl mercaptan and dodecyl mercaptan; other mercaptans such as thioglycolic acid, mercaptopropionic acid, thioglycerol and 2-mercaptoethanol; benzoquinone, 2, Benzoquinone derivatives such as 3,5,6-tetramethyl-p-benzoquinone; terpenes such as binene and terpinolene; and others, α-methylstyrene dimer, disulfide, isopropyl alcohol, dioxane, carbon tetrachloride, and chloroform It is done. The chain transfer agent can be used alone or in combination of two or more.
The chain transfer agent can be used in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the monomer mixture.
本発明において樹脂酸塩は、イソシアネート化合物とアクリル共重合体の反応性官能基との硬化反応を促進する硬化触媒である。ここで樹脂酸とは、松科の植物に多量に含まれる松脂の不揮発性の成分であり、アビエチン酸、ネオアビエチン酸、パラストリン酸、ピマール酸、イソピマール酸およびデヒドロアビエチン酸等のいずれかを含む混合物（以下ロジンともいい、カルボキシル基を有するロジンをロジン酸ともいう）である。前記樹脂酸塩は、前記樹脂酸のカルボキシル基と１価金属から構成される。前記１価金属は、Ａｇ，Ｂ，Ｂａ，Ｂｉ，Ｃｏ，Ｃｕ，Ｆｅ，Ｍｎ，Ｍｏ，Ｎｉ，Ｐｂ，Ｐｄ，Ｐｔ，Ｒｈ，Ｓｂ，Ｓｎ，Ｔａ，Ｔｉ，Ｖ，ＺｎおよびＺｒからなる群より選択するいずれかである。これらの中でもＢｉを使用した樹脂酸塩は、毒性が少ないため好ましい。
樹脂酸塩は、アクリル共重合体に対して０．００５〜３重量部配合することが好ましく、０．１〜１．５重量部がより好ましい。
In the present invention, the resin acid salt is a curing catalyst that accelerates the curing reaction between the isocyanate compound and the reactive functional group of the acrylic copolymer. Here, the resin acid is a non-volatile component of pine resin that is contained in a large amount in the plant of Pinaceae, and includes any one of abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, dehydroabietic acid and the like A mixture (hereinafter also referred to as rosin, and rosin having a carboxyl group is also referred to as rosin acid). The resin acid salt is composed of a carboxyl group of the resin acid and a monovalent metal. The monovalent metal is composed of Ag, B, Ba, Bi, Co, Cu, Fe, Mn, Mo, Ni, Pb, Pd, Pt, Rh, Sb, Sn, Ta, Ti, V, Zn, and Zr. Either one to choose from. Among these, a resin acid salt using Bi is preferable because of its low toxicity.
The resin acid salt is preferably added in an amount of 0.005 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight, based on the acrylic copolymer.
上記の通り粘着剤に硬化触媒として樹脂酸塩を使用すると硬化反応が速くなるが、反面ポットライフが短くなる。そこで本発明では、粘着剤に、さらに水を配合することで適度な硬化速度と必要十分なポットライフを両立できた。特にイソシアネート化合物の中でも後述する非芳香族イソシアネートは、反応速度が遅いため水を配合したことによるイソシアネート化合物とアクリル共重合体に水酸基との硬化反応が阻害される場合が少ない。水は、アクリル共重合体１００重量部に対して、０．０１〜１０重量部配合することが好ましく、０．１〜５重量部がより好ましく、０．５〜３重量部がさらに好ましい。０．０１〜１０重量部配合することで粘着剤層の透明性、およびポットライフをより高い水準で両立できる。なお水を配合する時期は、アクリル共重合体の合成の際、硬化剤等を配合する際等時期を選ばず、粘着剤を塗工する直前までに配合すれば良い。また、粘着剤の原料に混入した水が配合されていてもよい。 As described above, when a resin acid salt is used as a curing catalyst for the pressure-sensitive adhesive, the curing reaction is accelerated, but the pot life is shortened. Therefore, in the present invention, an appropriate curing speed and a necessary and sufficient pot life can be achieved by adding water to the pressure-sensitive adhesive. In particular, among the isocyanate compounds, non-aromatic isocyanates described later have a low reaction rate, so that the curing reaction between the isocyanate compound and the acrylic copolymer resulting from the incorporation of water with a hydroxyl group is rarely inhibited. The water is preferably blended in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the acrylic copolymer. By blending 0.01 to 10 parts by weight, the transparency of the pressure-sensitive adhesive layer and the pot life can be achieved at a higher level. In addition, the time to mix | blend water should just mix | blend by the time just before apply | coating an adhesive, without selecting time, such as the time of mix | blending a hardening | curing agent etc. at the time of the synthesis | combination of an acrylic copolymer. Moreover, the water mixed in the raw material of an adhesive may be mix | blended.
本発明においてイソシアネート化合物は、アクリル共重合体の水酸基と反応できる硬化剤である。前記イソシアネート化合物は、イソシアナト基を１分子中に３個以上有することが好ましい。
前記イソシアネート化合物は、ジイソシアネート化合物を水酸基を３個有する３官能ポリオールと反応させたアダクト体、ジイソシアネート化合物が水と反応したビュレット体、中心骨格にイソシアヌレート環を有しジイソシアネート化合物を３分子反応したイソシアヌレート体等が好ましい。
In the present invention, the isocyanate compound is a curing agent capable of reacting with the hydroxyl group of the acrylic copolymer. The isocyanate compound preferably has three or more isocyanato groups in one molecule.
The isocyanate compound includes an adduct obtained by reacting a diisocyanate compound with a trifunctional polyol having three hydroxyl groups, a burette obtained by reacting the diisocyanate compound with water, and an isocyanate obtained by reacting three molecules of a diisocyanate compound having an isocyanurate ring in the central skeleton. Nurates and the like are preferred.
前記ジイソシアネート化合物は、芳香族ジイソシアネート、脂肪族ジイソシアネート、芳香脂肪族ジイソシアネート、脂環族ジイソシアネート等が挙げられる。なお本発明で芳香族イソシアネートとは、イソシアナト基と芳香環が直接結合した化合物をいい、イソシアナト基がメチレン基を介して芳香環と結合した化合物は、芳香族イソシアネートとはいわない。 Examples of the diisocyanate compound include aromatic diisocyanate, aliphatic diisocyanate, araliphatic diisocyanate, and alicyclic diisocyanate. In the present invention, the aromatic isocyanate means a compound in which an isocyanato group and an aromatic ring are directly bonded, and a compound in which an isocyanato group is bonded to an aromatic ring through a methylene group is not called an aromatic isocyanate.
芳香族ジイソシアネートとしては、例えば１，３−フェニレンジイソシアネート、４，４’−ジフェニルジイソシアネート、１，４−フェニ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、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４’−トルイジンジイソシアネート、ジアニシジンジイソシアネート、４，４’−ジフェニルエーテルジイソシアネート等が挙げられる。 Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tridiisocyanate, and the like. Examples thereof include range isocyanate, 4,4′-toluidine diisocyanate, dianisidine diisocyanate, and 4,4′-diphenyl ether diisocyanate.
脂肪族ジイソシアネートは、例えばトリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１，２−プロピレンジイソシアネート、２，３−ブチレンジイソシアネート、１，３−ブチレンジイソシアネート、ドデカメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート等が挙げられる。 Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4. , 4-trimethylhexamethylene diisocyanate and the like.
芳香脂肪族ジイソシアネートは、例えばω，ω’−ジイソシアネート−１，３−ジメチルベンゼン、ω，ω’−ジイソシアネート−１，４−ジメチルベンゼン、ω，ω’−ジイソシアネート−１，４−ジエチルベンゼン、１，４−テトラメチルキシリレンジイソシアネート、１，３−テトラメチルキシリレンジイソシアネート等が挙げられる。 Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1, Examples include 4-tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.
脂環族ジイソシアネートは、例えば３−イソシアネートメチル−３，５，５−トリメチルシクロヘキシルイソシアネート、１，３−シクロペンタンジイソシアネート、１，３−シクロヘキサンジイソシアネート、１，４−シクロヘキサンジイソシアネート、メチル−２，４−シクロヘキサンジイソシアネート、メチル−２，６−シクロヘキサンジイソシアネート、４，４’−メチレンビス（シクロヘキシルイソシアネート）、１，４−ビス（イソシアネートメチル）シクロヘキサン、１，４−ビス（イソシアネートメチル）シクロヘキサン等が挙げられる。イソシアネート化合物は、単独または２種以上使用できる。 Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4- Examples include cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, and the like. The isocyanate compound can be used alone or in combination of two or more.
本発明の粘着剤は、さらに任意成分として他の樹脂、例えばアクリル樹脂、ポリエステル樹脂、アミノ樹脂、エポキシ樹脂、ポリウレタン樹脂を配合できる。また、必要に応じて、例えば、粘着付与剤、可塑剤、軟化剤、染料、顔料、無機充填剤、紫外線吸収剤、消泡剤、光安定剤、酸化防止剤等などを適宜配合できる。 The pressure-sensitive adhesive of the present invention can further contain other resins such as acrylic resins, polyester resins, amino resins, epoxy resins, and polyurethane resins as optional components. Further, for example, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, an ultraviolet absorber, an antifoaming agent, a light stabilizer, an antioxidant, and the like can be appropriately blended as necessary.
本発明の粘着シートは、基材および前記粘着剤から形成した粘着剤層を備えていることが好ましい。 The pressure-sensitive adhesive sheet of the present invention preferably includes a base material and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive.
本発明の粘着シートの製造は、例えば、粘着剤を基材上に塗工し、次いで乾燥することで粘着剤層を得る方法。または粘着剤を剥離シート上に塗工し、次いで乾燥することで粘着剤層を得て、さらに基材を貼り合わせる方法が好ましい。なお、粘着剤層は、ゴミ等の付着防止のため粘着テープが使用される直前まで剥離シートを貼り合わる必要があることはいうまでもない。また、粘着剤層の形成後、硬化反応完了まで数日間かかる場合がある。 The production of the pressure-sensitive adhesive sheet of the present invention is, for example, a method in which a pressure-sensitive adhesive layer is obtained by coating a pressure-sensitive adhesive on a substrate and then drying. Alternatively, a method in which a pressure-sensitive adhesive is coated on a release sheet and then dried to obtain a pressure-sensitive adhesive layer, and a substrate is further bonded is preferable. In addition, it cannot be overemphasized that it is necessary to stick a peeling sheet to an adhesive layer until just before an adhesive tape is used for adhesion prevention of refuse etc. In addition, it may take several days to complete the curing reaction after the pressure-sensitive adhesive layer is formed.
粘着剤層の厚みは、一般に０．１〜３００μｍ程度が好ましく、経済性の観点から０．１〜１００μｍ程度がより好ましい、 In general, the thickness of the pressure-sensitive adhesive layer is preferably about 0.1 to 300 μm, more preferably about 0.1 to 100 μm from the viewpoint of economy.
前記基材は、例えば紙、プラスチックス、合成紙、布および不織布等、ならびこれらの積層体を使用できる。前記プラスチックスは、ポリエステル樹脂、アセテート樹脂、ポリエーテルサルホン樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリオレフィン樹脂、アクリル樹脂等が挙げられる。 As the base material, for example, paper, plastics, synthetic paper, cloth, nonwoven fabric, and the like, and laminates thereof can be used. Examples of the plastics include polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, acrylic resin, and the like.
基材の厚みは、取り扱いの点から１〜５００μｍが好ましく、５〜３００μｍがより好ましい、また経済性の観点から５〜１００μｍがさらに好ましい。基材には粘着剤層との密着性を向上させるため公知の易接着処理が施されていてもよい。
これらの基材に片面又は両面には、剥離時の帯電防止を目的に、帯電防止層が設けられていてもよい。また該基材の、粘着剤層が設けられる側の表面には、粘着剤層との密着性を向上させるためにコロナ放電処理等が施されていてもよい。
The thickness of the substrate is preferably 1 to 500 μm from the viewpoint of handling, more preferably 5 to 300 μm, and further preferably 5 to 100 μm from the viewpoint of economy. The base material may be subjected to a known easy adhesion treatment in order to improve the adhesion with the pressure-sensitive adhesive layer.
An antistatic layer may be provided on one or both surfaces of these base materials for the purpose of preventing antistatic during peeling. The surface of the substrate on the side where the pressure-sensitive adhesive layer is provided may be subjected to a corona discharge treatment or the like in order to improve the adhesion with the pressure-sensitive adhesive layer.
前記剥離シートは、基材と剥離層を備えた構成が好ましい。前記基材は、紙およびプラスチックス等、ならびにこれらの積層体が好ましい。前記剥離層は、シリコーン樹脂、フッ素樹脂等の公知の剥離剤を塗工して形成できる。剥離シートの厚みは特に限定されず、一般に５μｍ〜５００μｍ程度である。 The release sheet preferably has a configuration including a base material and a release layer. The base material is preferably paper, plastics, or the like, and a laminate thereof. The release layer can be formed by applying a known release agent such as a silicone resin or a fluororesin. The thickness of the release sheet is not particularly limited, and is generally about 5 μm to 500 μm.
本発明の粘着シートの用途は、自動車や家電などの工業用途、偏光板やタッチパネルなどの光学用途などに適しており、そのなかでも、特に再剥離性を必要とする用途には最適である。 The application of the pressure-sensitive adhesive sheet of the present invention is suitable for industrial applications such as automobiles and home appliances, optical applications such as polarizing plates and touch panels, and among them, it is most suitable for applications requiring removability.
以下に実施例及び比較例を挙げ、本発明の効果を具体的に説明するが、本発明は実施例に限定されないことはいうまでもない。なお、以下「部」は「重量部」、「％」は「重量％」をそれぞれ示す。 EXAMPLES The effects of the present invention will be specifically described below with reference to examples and comparative examples, but it goes without saying that the present invention is not limited to the examples. Hereinafter, “part” means “part by weight”, and “%” means “% by weight”.
［実施例１］
＜アクリル共重合体の合成＞
撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコに窒素雰囲気下、２―エチルヘキシルアクリレート ４０部、２−ヒドロキシエチルアクリレート １部、ｎ−ブチルアクリレート １部、メチルアクリレート ０．５部、重合開始剤としてアゾビスイソブチロニトリルを適量、溶剤として酢酸エチル適量をフラスコに仕込んだ。次いで滴下ロートに２―エチルヘキシルアクリレート ５３部、２−ヒドロキシエチルアクリレート ３部、ｎ−ブチルアクリレート １部、メチルアクリレート ０．５部、開始剤としてアゾビスイソブチロニトリルを適量、溶剤として酢酸エチル適量を仕込んだ。前記４口フラスコを加熱し還流を確認後、モノマー混合物を滴下管から約２時間かけて滴下した。さらに還流温度で８時間反応を継続した。反応終了後、冷却し、酢酸エチルで希釈することで、不揮発分５０％・Ｍｗ（重量平均分子量）４５０，０００のアクリル共重合体溶液を得た。
[Example 1]
<Synthesis of acrylic copolymer>
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, under a nitrogen atmosphere, 40 parts of 2-ethylhexyl acrylate, 1 part of 2-hydroxyethyl acrylate, 1 part of n-butyl acrylate, methyl 0.5 parts of acrylate, an appropriate amount of azobisisobutyronitrile as a polymerization initiator, and an appropriate amount of ethyl acetate as a solvent were charged into a flask. Next, 53 parts of 2-ethylhexyl acrylate, 3 parts of 2-hydroxyethyl acrylate, 1 part of n-butyl acrylate, 0.5 parts of methyl acrylate, an appropriate amount of azobisisobutyronitrile as an initiator, and an appropriate amount of ethyl acetate as a solvent Was charged. The four-necked flask was heated to confirm reflux, and then the monomer mixture was dropped from the dropping tube over about 2 hours. Further, the reaction was continued for 8 hours at the reflux temperature. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate to obtain an acrylic copolymer solution having a nonvolatile content of 50% · Mw (weight average molecular weight) of 450,000.
＜粘着剤の配合＞
得られたアクリル共重合体溶液の不揮発分１００重量部に対して、樹脂酸ビスマス塩を０．３部、イオン交換水１．０部、ヘキサメチレンジイソシアネートイソシアヌレートアダクト体の７５％酢酸エチル溶液５.０部を配合し粘着剤を得た。
<Blend formulation>
0.3 parts of resin acid bismuth salt, 1.0 part of ion-exchange water, 75% ethyl acetate solution 5 of hexamethylene diisocyanate isocyanurate adduct is 5 parts by weight with respect to 100 parts by weight of the obtained acrylic copolymer solution. 0.0 part was mixed and the adhesive was obtained.
＜粘着テープの作成＞
得られた粘着剤を乾燥後の厚みが２０μｍになるように剥離シートに塗工し、熱風乾燥機で１００℃・１２０秒間乾燥した。次いで基材の厚さ３８μｍのポリエチレンテレフタレートフィルム（以下、ＰＥＴフィルム）を貼り合わせ、２３℃で７日間放置することで粘着シートを得た。
<Creation of adhesive tape>
The obtained pressure-sensitive adhesive was coated on a release sheet so that the thickness after drying was 20 μm, and dried with a hot air dryer at 100 ° C. for 120 seconds. Next, a 38 μm thick polyethylene terephthalate film (hereinafter referred to as “PET film”) was bonded together and left at 23 ° C. for 7 days to obtain an adhesive sheet.
得られた粘着剤・粘着シートを用いて下記物性評価を行った。 The following physical property evaluation was performed using the obtained adhesive and adhesive sheet.
＜粘着力＞
得られた粘着テープを幅２５ｍｍ・縦１００ｍｍの大きさに準備した。次いで２３℃−５０％ＲＨ雰囲気で剥離シートを剥がし、露出した粘着剤層を厚さ２ｍｍのガラス板に貼着した。そして２ｋｇロールを粘着テープ上から１往復を行い圧着した。前記圧着から２４時間経過後、引張試験機を使用して剥離角１８０°、剥離速度３００ｍｍ／ｍｉｎの条件で粘着力を測定した。なお粘着力はＪＩＳ Ｚ−０２３７に準拠した。
<Adhesive strength>
The obtained adhesive tape was prepared to have a width of 25 mm and a length of 100 mm. Next, the release sheet was peeled off in an atmosphere of 23 ° C.-50% RH, and the exposed pressure-sensitive adhesive layer was attached to a glass plate having a thickness of 2 mm. The 2 kg roll was reciprocated once on the pressure-sensitive adhesive tape. After 24 hours from the pressure bonding, the adhesive strength was measured using a tensile tester under the conditions of a peeling angle of 180 ° and a peeling speed of 300 mm / min. The adhesive strength conformed to JIS Z-0237.
＜高速剥離粘着力＞
剥離速度を３０ｍ／ｍｉｎに変更した以外は前記粘着力と同様に測定することで高速剥離粘着力を測定した。なお、実施例１２および１３の粘着剤は、永久粘着タイプであるため高速剥離粘着力は行っていない。
<High speed peel adhesion>
The high-speed peel adhesive strength was measured by measuring in the same manner as the adhesive strength except that the peel speed was changed to 30 m / min. In addition, since the adhesive of Examples 12 and 13 is a permanent adhesive type, high-speed peeling adhesive force is not performed.
＜再剥離性＞
得られた粘着テープを幅２５ｍｍ・縦１００ｍｍの大きさに準備した。次いで２３℃−５０％ＲＨ雰囲気で剥離シートを剥がし、露出した粘着剤層をガラス板に貼着した積層体を６０℃−９５％ＲＨ雰囲気に２４時間放置した。次いで前記積層体を２３℃−５０％ＲＨ雰囲気に１時間放置した後、粘着テープをガラス板から剥離した。剥離後のガラス板に付着した粘着剤層を下記基準で目視評価した。なお、実施例１２および１３の粘着剤は、永久粘着タイプであるため再剥離性の評価は行っていない。
○ 付着が全く無い （良好）
△ わずかに付着がある（実用上、問題なし）
× 全面的に付着した。（実用不可）
<Removability>
The obtained adhesive tape was prepared to have a width of 25 mm and a length of 100 mm. Next, the release sheet was peeled off in a 23 ° C.-50% RH atmosphere, and the laminate in which the exposed pressure-sensitive adhesive layer was adhered to a glass plate was left in a 60 ° C.-95% RH atmosphere for 24 hours. Next, the laminate was left in an atmosphere of 23 ° C.-50% RH for 1 hour, and then the adhesive tape was peeled from the glass plate. The pressure-sensitive adhesive layer attached to the peeled glass plate was visually evaluated according to the following criteria. In addition, since the adhesive of Examples 12 and 13 is a permanent adhesive type, evaluation of removability is not performed.
○ No adhesion (good)
△ Slight adhesion (no problem in practical use)
× Adhered entirely. (Not practical)
＜硬化性＞
得られた粘着剤を乾燥後の厚みが２０μｍになるように厚み３８μｍのＰＥＴフィルムに塗工し、熱風乾燥機で１００℃・１２０秒間乾燥し粘着剤層を形成した。次いで２３℃-５０％ＲＨで３日間養生し粘着シートを得た。得られた粘着シートを幅２５ｍｍ・縦１００ｍｍの大きさに準備し試料とした。前記試料からセパレーターを剥がして露出した粘着剤層をＳＵＳ２００メッシュに貼り付け、酢酸エチル溶液で満たした蓋つきガラス瓶に投入し、５０℃で２４時間抽出した。２４時間放置後、酢酸エチル溶液から取り出した試料を１００℃で２０分乾燥し、２３℃-５０％ＲＨで３０分放置した。その後、粘着シートをＳＵＳ２００メッシュから剥がし、剥がした試験片の重量を測定し、下記式（1）でゲル分率を算出した
式（１） ゲル分率（重量％）＝（M２／M１）×１００
M１：酢酸エチルで抽出する前の粘着層の重量
M２：酢酸エチルで抽出・乾燥した後の粘着層の重量
上記同様に７日間養生した粘着シートのゲル分率を作成し、７日間養生した粘着シートのゲル分率から３日間養生した粘着シートのゲル分率を差し引くことで硬化性を評価した。
○ ゲル分率の差が１０％未満（良好）
× ゲル分率の差が１０％以上（不良）
<Curing property>
The obtained pressure-sensitive adhesive was coated on a PET film having a thickness of 38 μm so that the thickness after drying was 20 μm, and dried with a hot air dryer at 100 ° C. for 120 seconds to form a pressure-sensitive adhesive layer. Subsequently, it was cured at 23 ° C.-50% RH for 3 days to obtain an adhesive sheet. The obtained pressure-sensitive adhesive sheet was prepared as a sample having a width of 25 mm and a length of 100 mm. The pressure-sensitive adhesive layer exposed by peeling the separator from the sample was attached to SUS200 mesh, put into a glass bottle with a lid filled with an ethyl acetate solution, and extracted at 50 ° C. for 24 hours. After leaving for 24 hours, the sample taken out from the ethyl acetate solution was dried at 100 ° C. for 20 minutes and then left at 23 ° C.-50% RH for 30 minutes. Thereafter, the pressure-sensitive adhesive sheet was peeled off from the SUS200 mesh, the weight of the peeled test piece was measured, and the gel fraction was calculated by the following formula (1). Formula (1) Gel fraction (% by weight) = (M2 / M1) × 100
M1: Weight of adhesive layer before extraction with ethyl acetate
M2: Weight of the pressure-sensitive adhesive layer after extraction and drying with ethyl acetate As described above, the gel fraction of the pressure-sensitive adhesive sheet cured for 7 days was prepared, and the pressure-sensitive adhesive sheet cured for 3 days from the gel fraction of the pressure-sensitive adhesive sheet cured for 7 days The curability was evaluated by subtracting the gel fraction.
○ Difference in gel fraction is less than 10% (good)
× 10% or more difference in gel fraction (defect)
＜ポットライフ＞
得られた粘着剤を直ぐに蓋つきガラス瓶に入れ、前記ガラス瓶を２５℃の恒温水槽で保温した。そしてガラス瓶を２５℃に投入した１時間後、および１２時間後の粘度を測定した。１時間後の粘度と１２時間後の粘度のその差を２段階で評価した。なお粘度は、Ｂ型粘度計、ローター＃３、回転数１２ｒｐｍで回転開始１分間後の数値を測定した。粘度と
○：１２時間後の粘度が配合直後の粘度の３未満（良好）
×：１２時間後の粘度が配合直後の粘度の３以上（不良）
<Pot life>
The obtained adhesive was immediately put in a glass bottle with a lid, and the glass bottle was kept warm in a constant temperature water bath at 25 ° C. And the viscosity after 1 hour and 12 hours after putting a glass bottle into 25 degreeC was measured. The difference between the viscosity after 1 hour and the viscosity after 12 hours was evaluated in two stages. The viscosity was measured by a B-type viscometer, rotor # 3, and a numerical value 1 minute after the start of rotation at a rotation speed of 12 rpm. Viscosity and ◯: The viscosity after 12 hours is less than 3 (good) immediately after blending
X: The viscosity after 12 hours is 3 or more of the viscosity immediately after blending (poor)
＜臭気＞
粘着剤を塗工した際、１００℃・１２０秒間乾燥し、粘着シートを熱風乾燥機から取り出した時の前記熱風乾燥機からの臭気をテスター５人がそれぞれ評価した。臭気は、アクリル共重合体の残留単量体、および酢酸エチル以外の臭気を評価した。なお、評価結果は、テスター５人の平均値である。
○：臭気を感じなかった。 （良好）
△：臭気をわずかに感じた。 （実用上、問題なし）
×：臭気を強く感じた。 （不良）
<Odor>
When the adhesive was applied, it was dried at 100 ° C. for 120 seconds, and five testers evaluated the odor from the hot air dryer when the adhesive sheet was taken out from the hot air dryer. The odor was evaluated by odors other than the residual monomer of the acrylic copolymer and ethyl acetate. The evaluation result is an average value of five testers.
○: No odor was felt. (Good)
Δ: A slight odor was felt. (No problem for practical use)
X: A strong odor was felt. (Bad)
＜腐食性＞
テストコーターの乾燥オーブン内の上面に幅２０ｃｍ・縦２０ｃｍ・厚さ１ｍｍの市販の鉄板を設置し、１ヶ月かけて粘着剤を、乾燥後の厚みが２０μｍになるように、温度９０℃、塗工速度１０ｍ／分で幅３０ｃｍで１万ｍの塗工を行った。次いで前記鉄板を取り出し、２３℃-５０％ＲＨ雰囲気で１ヶ月間放置し、前記鉄板表面の錆の発生の有無を目視で評価した。
○：錆が無かった。 （良好）
△：点状の錆が両面合計で５点以下発生した。 （実用上、問題なし）
×：点状の錆が両面に発生した。（実用不可）
<Corrosive>
Install a commercially available iron plate with a width of 20 cm, length of 20 cm, and thickness of 1 mm on the top surface of the drying oven of the test coater, and apply the adhesive over a month at a temperature of 90 ° C. so that the thickness after drying is 20 μm. Coating was performed at a work speed of 10 m / min and a width of 30 cm and 10,000 m. Next, the iron plate was taken out and allowed to stand in a 23 ° C.-50% RH atmosphere for one month, and the presence or absence of rust generation on the iron plate surface was visually evaluated.
○: There was no rust. (Good)
(Triangle | delta): The point-like rust generate | occur | produced 5 points or less in total on both surfaces. (No problem for practical use)
X: Spot-like rust occurred on both sides. (Not practical)
［実施例２〜１３、比較例１〜５］
アクリル共重合体に合成に使用した単量体、硬化触媒、水および硬化剤の種類、ならびに配合量を表１および表２の通りに変更した以外は、実施例１と同様に行うことで粘着剤および粘着テープを得た。次いで、実施例１と同様に上記の物性評価を行った。
[Examples 2 to 13, Comparative Examples 1 to 5]
Adhesion was carried out in the same manner as in Example 1 except that the monomers, curing catalysts, types of water and curing agents, and blending amounts used in the synthesis for the acrylic copolymer were changed as shown in Tables 1 and 2. An agent and an adhesive tape were obtained. Next, the physical properties were evaluated in the same manner as in Example 1.
Claims (4)
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| WO2018061730A1 (en) | 2016-09-29 | 2018-04-05 | 東洋紡株式会社 | Crystalline polyester resin and flame-resistant sealing resin composition |
| JP7299050B2 (en) | 2019-03-29 | 2023-06-27 | 菊水化学工業株式会社 | Method for coating paint containing granular coloring material |
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