JP2008195753A - Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet - Google Patents
Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet Download PDFInfo
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- JP2008195753A JP2008195753A JP2007029517A JP2007029517A JP2008195753A JP 2008195753 A JP2008195753 A JP 2008195753A JP 2007029517 A JP2007029517 A JP 2007029517A JP 2007029517 A JP2007029517 A JP 2007029517A JP 2008195753 A JP2008195753 A JP 2008195753A
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- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 64
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 45
- 239000000853 adhesive Substances 0.000 claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003827 glycol group Chemical group 0.000 claims description 4
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 55
- 239000000945 filler Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- 229920002799 BoPET Polymers 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
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- 230000003449 preventive effect Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- -1 isocyanate compound Chemical class 0.000 description 4
- 230000000873 masking effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
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- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OBNIRVVPHSLTEP-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(O)COCCO OBNIRVVPHSLTEP-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
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 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
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GRSGFPUWHKVFJW-UHFFFAOYSA-N 1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]-3-methoxypropan-2-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.COCC(O)COC(C)COC(C)CO GRSGFPUWHKVFJW-UHFFFAOYSA-N 0.000 description 1
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 1
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- COORVRSSRBIIFJ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]-1-methoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(O)COCCOCCO COORVRSSRBIIFJ-UHFFFAOYSA-N 0.000 description 1
- SMBRHGJEDJVDOB-UHFFFAOYSA-N 2-methylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.CC(C)C(N)=N SMBRHGJEDJVDOB-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 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 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- IFBMOBFQBJZBMV-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphanyl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C IFBMOBFQBJZBMV-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012462 polypropylene substrate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 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 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、粘着剤組成物ならびにそれを用いた粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet using the same.
アクリルポリマーはそれ自体に接着性があり、様々な分野で使用されているが、防錆油が塗布された鋼板やポリプロピレン基材などの低表面エネルギーの表面への接着性は劣っている。この欠点を解消するためには、ロジン系樹脂、テルペン系樹脂などの天然樹脂系粘着付与樹脂を添加するのが一般的ではあるが、耐候性低下などの問題がある。 The acrylic polymer itself has adhesiveness and is used in various fields, but its adhesiveness to a surface with a low surface energy such as a steel plate or a polypropylene substrate coated with a rust preventive oil is poor. In order to eliminate this drawback, natural resin-based tackifying resins such as rosin-based resins and terpene-based resins are generally added, but there are problems such as deterioration in weather resistance.
特許文献１および特許文献２では、低分子量のアクリルポリマーを粘着付与樹脂として、母材となる高分子量アクリルポリマーに添加することにより、耐候性の低下を招くことなく低エネルギー表面への接着性を上げている。また、特許文献３、特許文献４では、前述の課題に対して、アクリルポリマーを構成する配合の中に、極性の極めて低い成分を加える手法を開示している。しかしながら、これら先行技術は、低エネルギー表面への接着性の向上にのみ着目しており、再剥離性は考慮されていない。 In Patent Document 1 and Patent Document 2, by adding a low molecular weight acrylic polymer as a tackifying resin to a high molecular weight acrylic polymer as a base material, adhesion to a low energy surface without causing a decrease in weather resistance is achieved. Raised. Further, Patent Document 3 and Patent Document 4 disclose a method of adding an extremely low-polarity component to the composition constituting the acrylic polymer in response to the above-described problems. However, these prior arts focus only on improving adhesion to low energy surfaces and do not consider removability.
一方、特許文献５では、油面接着性を有すると共に再剥離性に優れた感圧接着シートを教示しているが、その粘着剤には架橋剤として多官能イソシアネート化合物が必要なため、耐水性に問題があり、また、イソシアネートの反応性から、有機溶媒を用いずに製造することは困難である。
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、表面エネルギーの低い被着体に対しても充分な接着力を有し、かつ、再剥離性、耐候性に優れ、更に有機溶媒を使用せずに作製できる環境に配慮したアクリル系粘着組成物及びそれを用いた粘着シートを提供することにある。 The present invention has been made in view of such problems of the prior art, and the problem is that it has a sufficient adhesive force even on an adherend having a low surface energy, and An object of the present invention is to provide an acrylic pressure-sensitive adhesive composition that is excellent in removability and weather resistance and can be prepared without using an organic solvent, and a pressure-sensitive adhesive sheet using the same.
本発明者らは上記課題を達成すべく鋭意検討した結果、以下に示す粘着剤組成物によって、上記課題を達成することが可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by the pressure-sensitive adhesive composition shown below, and have completed the present invention.
即ち、本発明によれば、以下に示す粘着剤組成物が提供される。 That is, according to the present invention, the following pressure-sensitive adhesive composition is provided.
［１］ （Ａ）炭素数が８から１３までのアルキル基を有するアクリレート１００質量部と、（Ｂ）飽和脂環族を側鎖に持つアクリレート１０〜９０質量部と、（Ｃ）エチレングリコール鎖またはプロピレングリコール鎖を持ち、その繰り返し数が２から２３であるアクリレート１〜４０質量部と、重合開始剤と、架橋剤とを含む粘着剤組成物。 [1] (A) 100 parts by mass of an acrylate having an alkyl group having 8 to 13 carbon atoms, (B) 10 to 90 parts by mass of an acrylate having a saturated alicyclic group in the side chain, and (C) an ethylene glycol chain Alternatively, a pressure-sensitive adhesive composition comprising 1 to 40 parts by mass of an acrylate having a propylene glycol chain and a repetition number of 2 to 23, a polymerization initiator, and a crosslinking agent.
［２］ 前記（Ｃ）がグリコール鎖の繰り返し単位が９であるメトキシポリエチレングリコールアクリレートである上記［１］に記載の粘着剤組成物。 [2] The pressure-sensitive adhesive composition according to [1], wherein (C) is methoxypolyethylene glycol acrylate having a glycol chain repeating unit of 9.
［３］ 前記飽和脂環族を側鎖にもつアクリレート（Ｂ）が、イソボルニルアクリレート、シクロヘキシルアクリレートおよびジジクロペンタニルアクリレートからなる群から選択される１種または複数のアクリレートである上記［１］または［２］に記載の粘着剤組成物。 [3] The above [1], wherein the acrylate (B) having the saturated alicyclic group in the side chain is one or a plurality of acrylates selected from the group consisting of isobornyl acrylate, cyclohexyl acrylate, and didiclopentanyl acrylate. ] Or the pressure-sensitive adhesive composition according to [2].
［４］ 上記［１］〜［３］のいずれかに記載の粘着剤組成物を、剥離処理された２枚の透明なフィルムの間に挟んで光を照射して得られる粘着シート。 [4] A pressure-sensitive adhesive sheet obtained by irradiating light with the pressure-sensitive adhesive composition according to any one of the above [1] to [3] sandwiched between two transparent films subjected to a release treatment.
［５］ 上記［４］に記載の粘着シートを基材にラミネートして得られる基材付き粘着シート。 [5] A pressure-sensitive adhesive sheet with a substrate obtained by laminating the pressure-sensitive adhesive sheet according to the above [4] on a substrate.
本発明による粘着剤組成物は、低エネルギー表面の被着体に対しても、比較的良好な接着力を有する。また、接着後の接着力の上昇が抑制されるため、特に、加熱後の再剥離性に優れる。更に、アクリルポリマーを用いているので耐候性も良好であり、有機溶媒を用いずに作製できるので、環境にも配慮した組成物および粘着シートを提供できる。 The pressure-sensitive adhesive composition according to the present invention has a relatively good adhesion even to an adherend having a low energy surface. Moreover, since the raise of the adhesive force after adhesion | attachment is suppressed, it is excellent in the removability especially after a heating. Furthermore, since the acrylic polymer is used, the weather resistance is also good, and it can be produced without using an organic solvent, so that it is possible to provide an environment-friendly composition and pressure-sensitive adhesive sheet.
以下、本発明の実施の最良の形態について説明するが、本発明は以下の実施の形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施の形態に対し適宜変更、改良等が加えられたものも本発明の範囲に入ることが理解されるべきである。 BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.
［成分（Ａ）］
（Ａ）は粘着剤の基本成分となり、接着性に大きく寄与する。（Ａ）としては、アルキル基の炭素数が８から１３までのアクリレートを用いることができ、具体的には、２−エチルヘキシルアクリレート、イソオクチルアクリレート、イソデシルアクリレートなどが代表的に挙げられる。中でも、炭素数が８の２−エチルヘキシルアクリレート、または、イソオクチルアクリレートが好ましい。それらのうち、１種、または２種以上を組み合わせて用いることもできる。アルキル基鎖が短すぎると、その極性が強く現れてくるため、低エネルギー表面との親和性が低下し、接着性を失う（比較例１１参照）。また逆に長すぎると、一般の粘着剤と同様に結晶性が現れるため、接着性を失う。
[Component (A)]
(A) is a basic component of the pressure-sensitive adhesive and greatly contributes to adhesiveness. As (A), an acrylate having an alkyl group having 8 to 13 carbon atoms can be used, and specific examples thereof include 2-ethylhexyl acrylate, isooctyl acrylate, and isodecyl acrylate. Among them, 2-ethylhexyl acrylate having 8 carbon atoms or isooctyl acrylate is preferable. Among these, it can also be used combining 1 type or 2 types or more. If the alkyl group chain is too short, its polarity appears strongly, so the affinity with the low energy surface is lowered and the adhesiveness is lost (see Comparative Example 11). On the other hand, if the length is too long, crystallinity appears as in the case of a general pressure-sensitive adhesive, so that the adhesiveness is lost.
［成分（Ｂ）］
（Ｂ）の特徴は、飽和脂環族を側鎖に持っているという点である。一般に、環状の炭化水素基を持つと極性が低くなるため、（Ｂ）のもう一つの特徴としては極性が低いということが言える。極性は、一般には溶解パラメータ（ＳＰ値）という指標で表されるが、この（Ｂ）に関しては、Ｆｅｄｏｒｓの方法に従って（Ｆｅｄｏｒｓ, Ｐｏｌｙｍ． Ｅｎｇ． ａｎｄ Ｓｃｉ．， １４， １４７ （１９７４））計算した値で、１０．５０以下が目安となる。具体的に好適なモノマーとしては、イソボルニルアクリレート、シクロヘキシルアクリレート、ジシクロペンタニルアクリレートなどが代表的に挙げられ、これらの二種類以上の混合も可能である。参考として、上記好適なアクリレート、比較例として用いたアクリレート、および一般的なアクリレートの各値を表１に示す。この成分は、低エネルギー表面との親和性向上に寄与する。そのため、多すぎると（Ａ）の比率が低下して接着力が低下し、少なすぎると低エネルギー表面への親和性がなく、接着性を失う。
[Component (B)]
The feature of (B) is that it has a saturated alicyclic group in the side chain. In general, when a cyclic hydrocarbon group is included, the polarity becomes low. Therefore, it can be said that the polarity is low as another feature of (B). The polarity is generally expressed by an index called a solubility parameter (SP value), and (B) was calculated according to the method of Fedors (Fedors, Polym. Eng. And Sci., 14, 147 (1974)). The value is 10.50 or less as a guide. Specific examples of suitable monomers include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, and the like, and a mixture of two or more of these is also possible. For reference, Table 1 shows values of the above preferred acrylates, acrylates used as comparative examples, and general acrylates. This component contributes to improved affinity with low energy surfaces. Therefore, if it is too much, the ratio of (A) is reduced and the adhesive strength is lowered, and if it is too little, there is no affinity for the low energy surface and the adhesiveness is lost.
［成分（Ｃ）］
（Ｃ）は、本発明における最も特徴的な成分であり、接着力を制御する効果があり、特に、経時や加熱後の接着力の上昇を抑制する役割を持つ。エチレングリコール（実施例９など）、または、プロピレングリコール（実施例１０など）の繰り返し単位を持つアクリルモノマーを用いることができる。また、それらの二種類以上の混合物、あるいは、一つの分子鎖にエチレングリコール鎖、プロピレングリコール鎖、両方を含んだモノマーを用いることもできる。エチレングリコールまたはプロピレングリコールの鎖長は限定の必要はないが、以降の実施例で示す通り、繰り返し単位は２から２３の間がよく、特に９程度がよい。長すぎると、配合の比率によっては他の成分との混合が困難になる。また、短すぎると（ヒドロキシエチルアクリレートが相当、比較例１２参照）、接着力を制御する効果がなくなる。また、これらグリコール鎖の末端は、ヒドロキシル基（実施例９，１０）、メチル基（実施例１など）、エチル基（実施例７）のいずれでも良い。代表的なモノマーとしては、メトキシポリエチレングリコールアクリレート、エトキシジエチレングリコールアクリレート、ポリプロピレングリコールアクリレートなどが挙げられる。なかでも上記繰り返し単位が９であるメトキシポリエチレングリコールアクリレートが作業性などを考慮すると、好適である。
[Component (C)]
(C) is the most characteristic component in the present invention, has an effect of controlling the adhesive force, and particularly has a role of suppressing an increase in the adhesive force with time or after heating. An acrylic monomer having a repeating unit of ethylene glycol (such as Example 9) or propylene glycol (such as Example 10) can be used. Further, a mixture of two or more kinds thereof, or a monomer containing both an ethylene glycol chain and a propylene glycol chain in one molecular chain can be used. The chain length of ethylene glycol or propylene glycol need not be limited, but as shown in the following examples, the repeating unit is preferably between 2 and 23, particularly about 9. If it is too long, mixing with other components becomes difficult depending on the blending ratio. On the other hand, if it is too short (corresponding to hydroxyethyl acrylate, see Comparative Example 12), the effect of controlling the adhesive force is lost. The ends of these glycol chains may be any of a hydroxyl group (Examples 9 and 10), a methyl group (Example 1 and the like), and an ethyl group (Example 7). Representative monomers include methoxypolyethylene glycol acrylate, ethoxydiethylene glycol acrylate, polypropylene glycol acrylate and the like. Of these, methoxypolyethylene glycol acrylate having 9 repeating units is preferable in view of workability.
一般に、粘着剤は被着体に接着した後、経時的な表面の変形や、湿度や光、熱などの外部環境による濡れ性の変化などによって、接着力の上昇が起こる。この現象はアドヒージョンビルドアップ（Ａｄｈｅｓｉｏｎ Ｂｕｉｌｄ−ｕｐ）と呼ばれる（以下、ビルドアップと呼ぶ）。再剥離性を考慮する際には、初期の接着力と合わせて、使用環境によるビルドアップ後の接着力も重要となる。（Ｃ）は、ガラス転移点が低く、また、自身の接着力は非常に低いという特徴がある。この成分の添加により、粘着剤全体も軟らかくなり、また、最終的に到達する接着力も低くなる。すなわち、接着直後と、ビルドアップ後の接着力の変化が小さくなり、再剥離性の面からは非常に好ましい特性を持つことができる。 In general, after the adhesive is bonded to the adherend, the adhesive force increases due to surface deformation over time and changes in wettability due to external environments such as humidity, light, and heat. This phenomenon is referred to as adhesion build-up (hereinafter referred to as build-up). When considering removability, the adhesive strength after build-up depending on the use environment is also important in addition to the initial adhesive strength. (C) is characterized by a low glass transition point and very low adhesive strength. By adding this component, the entire pressure-sensitive adhesive is softened, and the finally reached adhesive force is also reduced. That is, the change in the adhesive force immediately after bonding and after build-up becomes small, and it can have very favorable characteristics from the viewpoint of removability.
（Ａ）（Ｂ）（Ｃ）各成分の配合割合は、（Ａ）成分１００質量部に対して（Ｂ）成分１０〜９０質量部、（Ｃ）成分１〜４０質量部である。好適なモノマーをそれぞれ選択して、組み合わせた例を挙げると、（Ａ）として、２−エチルヘキシルアクリレートを選択し、その１００質量部に対して、（Ｂ）としてイソボルニルアクリレートを選択した場合、好ましくは１０〜９０質量部、さらに好ましくは、２０〜７０質量部、（Ｃ）として、グリコール鎖の繰り返し単位がおよそ９のメトキシポリエチレングリコールアクリレートを選択した場合、１〜４０、好ましくは５〜４０質量部、さらに好ましくは、５〜３０質量部の範囲に含まれる組成が所望の特性の粘着物を得ることができる。 (A) (B) (C) The mixture ratio of each component is 10-90 mass parts of (B) component with respect to 100 mass parts of (A) component, and 1-40 mass parts of (C) component. When a suitable monomer is selected and combined examples are given, when 2-ethylhexyl acrylate is selected as (A), and isobornyl acrylate is selected as (B) with respect to 100 parts by mass, Preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, and (C), when methoxypolyethylene glycol acrylate having approximately 9 repeating units of glycol chain is selected, 1 to 40, preferably 5 to 40 A pressure-sensitive adhesive having a desired characteristic can be obtained in which the composition contained in the range of 5 parts by mass, more preferably in the range of 5 to 30 parts by mass.
各アクリレートの混合物に、重合開始剤、架橋剤を所定量加えて重合を行い、粘着剤組成物を得る。重合開始剤の種類を選択することにより、任意の方法での重合が可能である。熱重合を選択する場合、例えば、２，２’−アゾビズ（２−メチルプロピオナミダイン）ジハイドロクロライド、２，２’−アゾビズ（２，４−ジメチルバレロニトリル）、ベンゾイルパーオキサイドなどが、代表的な開始剤として挙げられ、光重合を選択する場合は、例えば、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、１−[４−（２−ヒドロキシエトキシ）フェニル]−２−ヒドロキシ−２−メチル−１−プロパン−１−オンなどが代表的な開始剤として挙げられる。また架橋剤は特に限定はしないが、１，６−ヘキサンジオールジアクリレート、１，９−ノナンジオールジアクリレートや、ジエチレングリコールジアクリレートなどの多官能アクリレートが好ましい。本発明では、紫外線による光重合についての場合のみ以下説明する。その際の光重合開始剤量は、特に限定はしないが、（Ａ）（Ｂ）（Ｃ）合わせて１００質量部とした時、おおよそ０．１〜０．５質量部が好ましい。また、架橋剤の量も、特に限定はしないが、おおよそ０．１〜０．３質量部が好ましい。また、シリカ、チタニアなどの粉体やガラスビーズなどの、各種フィラーや、水酸化アルミニウムや臭化物などの難燃剤など他の機能性成分を添加しても良い。 A predetermined amount of a polymerization initiator and a crosslinking agent is added to each acrylate mixture to conduct polymerization, thereby obtaining a pressure-sensitive adhesive composition. By selecting the type of the polymerization initiator, polymerization can be performed by any method. When selecting thermal polymerization, for example, 2,2′-azobiz (2-methylpropionamidine) dihydrochloride, 2,2′-azobiz (2,4-dimethylvaleronitrile), benzoyl peroxide, etc. As typical initiators, when photopolymerization is selected, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Finoxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and the like are listed as typical initiators. The crosslinking agent is not particularly limited, but polyfunctional acrylates such as 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and diethylene glycol diacrylate are preferable. In the present invention, only the case of photopolymerization with ultraviolet rays will be described below. The amount of the photopolymerization initiator at that time is not particularly limited, but is preferably about 0.1 to 0.5 parts by mass when the total of (A), (B) and (C) is 100 parts by mass. The amount of the crosslinking agent is not particularly limited, but is preferably about 0.1 to 0.3 parts by mass. In addition, various functional components such as various fillers such as powders such as silica and titania and glass beads, and flame retardants such as aluminum hydroxide and bromide may be added.
重合による硬化の場合、窒素置換や真空脱泡などでモノマー中から酸素を除き、剥離処理された２枚の透明なフィルムの間に所望の厚さになるように挟んで光を照射すると、シート状の粘着剤を得ることができる。このシートは、両面のフィルムを剥がして、低エネルギー表面被着体同士の接着に使うことができる。また、片面に別の適当な基材をラミネートすれば片面粘着シートとなり、防錆油が塗布された鋼板（以下油面塗板と記述する）用のマスキングテープやラベルシールとして使うことができる。再剥離性に優れるため、マスキングテープやラベルシールが不要になったときに糊残りや基材の破壊がなく、きれいに剥がすことができる。 In the case of curing by polymerization, the oxygen is removed from the monomer by nitrogen substitution or vacuum defoaming, etc., and the sheet is irradiated with light by sandwiching it between two transparent films that have been peeled off so as to obtain a desired thickness. Can be obtained. This sheet can be used for bonding low-energy surface adherends by peeling the films on both sides. Moreover, if another suitable base material is laminated on one side, it becomes a single-sided adhesive sheet and can be used as a masking tape or a label seal for a steel plate (hereinafter referred to as an oil-side coated plate) coated with rust preventive oil. Since it has excellent re-peelability, it can be peeled cleanly without any adhesive residue or substrate damage when masking tape or label seals are no longer required.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
［粘着剤組成物の作製手順］
後述する各実施例および比較例の配合の通りに、各アクリルモノマー、光重合開始剤の一部（全量のうち２０質量％相当量）を、透明なガラス容器に入れて混合した。容器内および混合物に溶け込んだ気体を窒素に置換した後（例えば、モノマーの合計重量を１００ｇとした場合、２５０ｍｌの容積の容器に、毎分１リットル程度の流量で５分以上のバブリングを行う）、攪拌しながら紫外線を照射（約２０〜２５ｍＪ／ｃｍ２）して粘度が２０００〜３０００ｃｐｓになるまで部分的に重合させた。重合による発熱が収まるまで放置し（前述の量では約１０分程度）、さらに、残りの光重合開始剤（８０質量％相当量）、架橋剤、フィラーを加え、攪拌混合（Ｈｙｂｒｉｄ ＭｉｘｅｒＨＭ−５００、ＫＥＹＥＮＣＥ社製、を使用）した後、減圧脱泡（前述の量・粘度で、約０．０２ＭＰａ下で約３０分静置）することで、粘着剤組成物を得た。
[Procedure for producing pressure-sensitive adhesive composition]
Each acrylic monomer and a part of the photopolymerization initiator (equivalent to 20% by mass of the total amount) were put in a transparent glass container and mixed as described in the examples and comparative examples described later. After replacing the gas dissolved in the container and in the mixture with nitrogen (for example, when the total weight of the monomer is 100 g, bubbling for 5 minutes or more at a flow rate of about 1 liter per minute in a container with a volume of 250 ml) The mixture was partially polymerized by irradiation with ultraviolet rays (about 20 to 25 mJ / cm 2 ) while stirring until the viscosity reached 2000 to 3000 cps. Leave until the exotherm due to polymerization has subsided (about 10 minutes in the above-mentioned amount), add the remaining photopolymerization initiator (equivalent to 80% by mass), crosslinking agent, filler, and stir and mix (Hybrid Mixer HM-500, After using KEYENCE, the pressure-sensitive adhesive composition was obtained by defoaming under reduced pressure (the amount and viscosity described above were allowed to stand for about 30 minutes under about 0.02 MPa).
［粘着シートの作製手順］
次に、シリコーン離型処理されたＰＥＴフィルム（ピューレックス Ａ５０、テイジン社製、および、セラピール ＭＩＢ（Ｔ）、東レフィルム加工社製）の間に、粘着剤組成物を、重合後に所望の厚さになるように塗布して挟み、両面から紫外線を照射（１ｍＷ／ｃｍ２にて３分、その後 ７ｍＷ／ｃｍ２にて３分)して光重合を完了させた。後述する全ての実施例、比較例の試料は、厚さが約１００μｍになるように塗布量を調整した。重合後得られたシートのうち、外周部から約１５ｍｍの部分は酸素阻害による未重合部分が含まれる可能性があるため廃棄した。
[Procedure for producing adhesive sheet]
Next, between the PET films (Purex A50, manufactured by Teijin Co., Ltd., and Therapy MIB (T), manufactured by Toray Film Processing Co., Ltd.) subjected to silicone release treatment, the pressure-sensitive adhesive composition has a desired thickness after polymerization. Then, ultraviolet light was irradiated from both sides (1 mW / cm 2 for 3 minutes, then 7 mW / cm 2 for 3 minutes) to complete photopolymerization. The coating amount was adjusted so that the thickness of all the examples and comparative examples described later was about 100 μm. Of the sheet obtained after the polymerization, a portion of about 15 mm from the outer peripheral portion was discarded because an unpolymerized portion due to oxygen inhibition may be included.
以上の手順で、シリコーン離型処理ＰＥＴフィルムに挟まれたシート状粘着剤を得た。なお、今回用いた架橋剤、光重合開始剤、フィラーは以下の通りである。
架橋剤：１，６−ヘキサンジオールジアクリレート（Ｌａｒｏｍｅｒ ＨＤＤＡ、ＢＡＳＦ社製）
光重合開始剤：２，２−ジメトキシ−１，２−ジフェニルエタン−1−オン（Ｉｒｇａｃｕｒｅ６５１、Ｃｈｉｂａ社製）
フィラー：ヒュームドシリカ（ＡＥＲＯＳＩＬ Ａ−２００、日本エアロジル社製）
With the above procedure, a sheet-like pressure-sensitive adhesive sandwiched between silicone release-treated PET films was obtained. In addition, the crosslinking agent, photoinitiator, and filler which were used this time are as follows.
Cross-linking agent: 1,6-hexanediol diacrylate (Laromer HDDA, manufactured by BASF)
Photopolymerization initiator: 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, manufactured by Chiba)
Filler: Fumed silica (AEROSIL A-200, manufactured by Nippon Aerosil Co., Ltd.)
［評価準備］
被着体は、低エネルギー表面を持つものとして、防錆油を塗布した鋼板（以下、油面塗板と呼ぶ）、ポリプロピレン板（５ｍｍ厚、３０×７５ｍｍ、ＰＰ Ｊ７０４ＬＢ、山三商事社、以下ＰＰ板と呼ぶ）およびポリエチレン板（２ｍｍ厚、５３×１００ｍｍ、日本タクト社、以下ＰＥ板と呼ぶ）を用意した。
[Preparation for evaluation]
The adherend has a low energy surface and is coated with a steel plate coated with rust preventive oil (hereinafter referred to as an oil surface coated plate), a polypropylene plate (5 mm thickness, 30 × 75 mm, PP J704LB, Yamasan Shoji Co., Ltd., hereinafter referred to as PP). And a polyethylene plate (2 mm thickness, 53 × 100 mm, Nippon Tact Co., Ltd., hereinafter referred to as PE plate).
油面塗板はＳＰＣＣ−ＳＤ鋼板（０．８ｍｍ厚、６５×１５０ｍｍ、テストピース）をイソプロピルアルコールで洗浄・脱脂を行った後、防錆油（プレトン Ｒ−３０３ＰＸ２、スギムラ化学工業社製）を塗布し（約５．５ｇ／ｍ２）、垂直に立てて１日静置しておいた。ＰＰ板、ＰＥ板は、表面をイソプロピルアルコールで清拭し、アルコールの乾燥後、速やかに使用した。 The oil-surface coated plate is washed and degreased with SPCC-SD steel plate (0.8 mm thickness, 65 x 150 mm, test piece) with isopropyl alcohol, and then coated with anti-rust oil (Preton R-303PX2, manufactured by Sugimura Chemical Co., Ltd.). (About 5.5 g / m 2 ) and left standing for one day in a vertical position. The PP plate and PE plate were wiped with isopropyl alcohol and used immediately after the alcohol was dried.
フィルム間に作製したシート状粘着剤から、２５ｍｍ幅８０ｍｍ長の試料片を切り出し、一方の面のシリコーン離型処理されたＰＥＴフィルムを剥がした後、その面を、２５ｍｍ幅、約２５ｃｍ長に切ったＰＥＴフィルム（マット加工品・タイプＳＭ、２５μｍ厚、開成工業社製）のマット加工面側に貼り付けた。約２５ｃｍ長のＰＥＴフィルムのうち、シート状粘着剤の貼り付けられていない部分を評価測定用の持ち手とし、試料片とした。 After cutting out a 25 mm wide and 80 mm long sample piece from the sheet-like adhesive produced between the films and peeling off the PET film that had been subjected to the silicone release treatment on one side, the side was cut into a 25 mm wide and about 25 cm long. It was affixed on the matte surface side of a PET film (matte processed product, type SM, 25 μm thick, manufactured by Kaisei Kogyo Co., Ltd.). Of the PET film having a length of about 25 cm, a portion where the sheet-like adhesive was not attached was used as a handle for evaluation measurement, and a sample piece was obtained.
［油面塗板に対する加熱後再剥離性の評価］
本評価は、本発明の粘着剤組成物を、油面塗板の洗浄・塗装・乾燥工程時のマスキングテープとして用いることを想定して行った。
[Evaluation of re-peelability after heating on oil-coated plate]
This evaluation was performed on the assumption that the pressure-sensitive adhesive composition of the present invention was used as a masking tape during the cleaning, painting and drying steps of the oil-coated plate.
試料片の、残っている側のシリコーン離型処理されたＰＥＴフィルムを剥がし、剥き出しになった粘着剤面が被着体に接するように試料片を油面塗板被着体に載せ、２ｋｇのロールを一往復させて貼り付けた。これを２０分静置後、蒸留水に１時間浸漬した。その後すぐに、オーブン（ＫＭ−６００、ＡＤＶＡＮＴＥＣ社製）にて１７０℃２０分の熱処理を行った。オーブンから取り出した後、１時間ほど放置して常温に戻るまで待ってから、引張試験機（Ａｕｔｏｇｒａｐｈ ＡＧ−５００Ｂ、島津製作所製）にて引き剥がし速度３００ｍｍ／ｍｉｎの１８０°ピール力を測定した。 Peel off the remaining silicone release PET film of the sample piece and place the sample piece on the oil-coated plate adherend so that the exposed adhesive surface is in contact with the adherend. Pasted once and pasted. This was allowed to stand for 20 minutes and then immersed in distilled water for 1 hour. Immediately thereafter, heat treatment was performed at 170 ° C. for 20 minutes in an oven (KM-600, manufactured by ADVANTEC). After taking out from the oven, it was allowed to stand for about 1 hour until it returned to room temperature, and then a 180 ° peel force at a peeling speed of 300 mm / min was measured with a tensile tester (Autograph AG-500B, manufactured by Shimadzu Corporation).
［常温保存時油面塗板に対する剥離力の評価］
本評価は、本発明の粘着剤組成物の、油面塗板同士の仮固定や、油面塗板用ラベルシートなどの用途を想定して行った。
[Evaluation of peel strength for oil-coated sheet when stored at room temperature]
This evaluation was performed on the assumption that the pressure-sensitive adhesive composition of the present invention was used for temporary fixing between oil-coated plates or a label sheet for oil-coated plates.
油面塗板被着体に、試料片の残っている側のシリコーン離型処理されたＰＥＴフィルムを剥がし、剥き出しになった粘着剤面が被着体に接するように試料片を油面塗板被着体に載せ、２ｋｇのロールを一往復させて貼り付け、常温で静置し、２時間後、１日後に、それぞれ、引張試験機（Ａｕｔｏｇｒａｐｈ ＡＧ−５００Ｂ、島津製作所製）にて引き剥がし速度３００ｍｍ／ｍｉｎの１８０°ピール力を測定し、比較した。 Peel the silicone release PET film on the side where the sample piece remains on the oil-coated plate adherend, and apply the sample piece to the oil-coated plate so that the exposed adhesive surface is in contact with the adherend. Place it on the body, paste it back and forth with a 2 kg roll, leave it at room temperature, and after 2 hours and 1 day, peel off with a tensile tester (Autograph AG-500B, manufactured by Shimadzu Corporation) at a speed of 300 mm. A 180 ° peel force of / min was measured and compared.
［常温保存時オレフィン板に対する剥離力の評価］
本評価は、本発明の粘着剤組成物が、ＰＰ板、ＰＥ板同士の仮固定や、ラベルシートなどの用途を想定して行った。
[Evaluation of peel strength for olefin plates during normal temperature storage]
This evaluation was performed assuming that the pressure-sensitive adhesive composition of the present invention was used for temporary fixing between PP plates and PE plates, label sheets, and the like.
ＰＰ板、ＰＥ板被着体に、試料片の残っている側のシリコーン離型処理されたＰＥＴフィルムを剥がし、剥き出しになった粘着剤面が被着体に接するように試料片を被着体に載せ、２ｋｇのロールを一往復させて貼り付け、常温で静置し、２時間後に、引張試験機（Ａｕｔｏｇｒａｐｈ ＡＧ−５００Ｂ、島津製作所製）にて引き剥がし速度３００ｍｍ／ｍｉｎの１８０°ピール力を測定し、比較した。 Peel off the PET film that has been subjected to the silicone release treatment on the PP plate and PE plate adherent side, and attach the sample piece so that the exposed adhesive surface is in contact with the adherend. A 2 kg roll was reciprocated once and pasted, left at room temperature, and after 2 hours, a 180 ° peel force with a tensile tester (Autograph AG-500B, manufactured by Shimadzu Corporation) at a peeling speed of 300 mm / min. Were measured and compared.
［評価時の基準］
低エネルギー表面を持つ被着体（油面塗板等）に対する接着性とビルドアップの変化幅を評価対象とした。被着体への接着２時間後の１８０°ピール力において、２．０Ｎを接着性の有無の境界とし、また、１日後のピール力を２時間後の値と比較しその変化量が２．０Ｎ以内に収まっていることをビルドアップ抑制効果の有無の境界とした。なお、いずれの場合においても、１８０°ピール力が１０Ｎを超えないことも条件とした。１０Ｎを超えると、糊残りが発生する傾向にあるからである。
[Evaluation criteria]
The adhesiveness to an adherend having a low energy surface (such as an oil-coated plate) and the range of change in build-up were evaluated. At 180 ° peel force after 2 hours of adhesion to the adherend, 2.0N is used as the boundary for the presence or absence of adhesion, and the peel force after 1 day is compared with the value after 2 hours, and the amount of change is 2. It was set as the boundary of the presence or absence of the buildup suppression effect that it was settled within 0N. In any case, the condition is that the 180 ° peel force does not exceed 10N. This is because if it exceeds 10 N, adhesive residue tends to occur.
（実施例１）
（Ａ）成分として、２−エチルヘキシルアクリレート（日本触媒社製、以下、２ＥＨＡと呼ぶ）１００質量部、（Ｂ）成分として、イソボルニルアクリレート（ＩＢＸＡ、大阪有機化学社製、以下、ＩＢＸＡと呼ぶ）４６質量部、（Ｃ）成分として、メトキシポリエチレングリコールアクリレート（ＮＫエステルＡＭ−９０Ｇ、新中村化学社製、以下ＡＭＧと呼ぶ）８質量部、以上３種の混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。ＰＰ板に対するピール力は６．０Ｎ、ＰＥ板に対するピール力は３．４Ｎであった。油面塗板に対する２時間後のピール力は３．３Ｎ、１日後のピール力は４．２Ｎであった。また、１７０℃で２０分加熱後のピール力は、６．０Ｎであった。
(Example 1)
As component (A), 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd., hereinafter referred to as 2EHA) 100 parts by mass, and as component (B), isobornyl acrylate (IBXA, manufactured by Osaka Organic Chemical Co., Ltd., hereinafter referred to as IBXA). ) 46 parts by mass, as component (C), 8 parts by mass of methoxypolyethyleneglycol acrylate (NK ester AM-90G, manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as AMG) A pressure-sensitive adhesive composition was prepared by adding parts by weight, 0.38 parts by weight of a crosslinking agent, and 1.5 parts by weight of a filler. The peel force against the PP plate was 6.0 N, and the peel force against the PE plate was 3.4 N. The peel force after 2 hours on the oil surface coated plate was 3.3 N, and the peel force after 1 day was 4.2 N. The peel force after heating at 170 ° C. for 20 minutes was 6.0 N.
（実施例２）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として５８質量部のＩＢＸＡ、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．４０質量部、架橋剤０．４２質量部、フィラー１．７質量部を加えて、粘着剤組成物を作製した。ＰＰ板に対するピール力は８．２Ｎ、ＰＥ板に対するピール力は４．６Ｎであった。油面塗板に対する２時間後のピール力は４．０Ｎ、１日後のピール力は４．３Ｎであった。また、１７０℃で２０分加熱後のピール力は、７．８Ｎであった。
(Example 2)
(0) 0.40 parts by mass of photoinitiator to a mixture of 100 parts by mass of 2EHA as component (A), 58 parts by mass of IBXA as component (B), and 8 parts by mass of AMG as component (C) Then, 0.42 parts by mass of a cross-linking agent and 1.7 parts by mass of a filler were added to prepare an adhesive composition. The peel force against the PP plate was 8.2N, and the peel force against the PE plate was 4.6N. The peel force after 2 hours on the oil surface coated plate was 4.0 N, and the peel force after 1 day was 4.3 N. The peel force after heating at 170 ° C. for 20 minutes was 7.8 N.
（実施例３）
（Ａ）成分としてイソオクチルアクリレート（３Ｍ社製、以下ＩＯＡと呼ぶ）１００質量部に対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。ＰＰ板に対するピール力は６．４Ｎ、ＰＥ板に対するピール力は３．６Ｎであった。油面塗板に対する２時間後のピール力は３．２Ｎ、１日後のピール力は３．６Ｎであった。
(Example 3)
(A) 46 parts by mass of IBXA as component (B) and 8 parts by mass of AMG as component (C) were added to 100 parts by mass of isooctyl acrylate (manufactured by 3M, hereinafter referred to as IOA) as component (A). A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the mixture. The peel force against the PP plate was 6.4 N, and the peel force against the PE plate was 3.6 N. The peel force after 2 hours on the oil surface coated plate was 3.2 N, and the peel force after 1 day was 3.6 N.
（実施例４）
（Ａ）成分として５０質量部の２ＥＨＡ、５０質量部のＩＯＡを混合したものに対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．４４質量部、架橋剤０．４５質量部、フィラー１．８質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は３．６Ｎ、１日後のピール力は３．７Ｎであった。
Example 4
(A) A mixture of 50 parts by mass of 2EHA and 50 parts by mass of IOA mixed with 46 parts by mass of IBXA as component (B) and 8 parts by mass of AMG as component (C) A pressure-sensitive adhesive composition was prepared by adding 0.44 parts by mass of a photoinitiator, 0.45 parts by mass of a crosslinking agent, and 1.8 parts by mass of a filler. The peel force after 2 hours against the oil surface coated plate was 3.6 N, and the peel force after 1 day was 3.7 N.
（実施例５）
（Ａ）成分としてイソデシルアクリレート（ＳＲ３９５、化薬サートマー社製）１００質量部に対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は３．０Ｎ、１日後のピール力は５．０Ｎであった。
(Example 5)
(A) A mixture obtained by adding 46 parts by mass of IBXA as a component (B) and 8 parts by mass of AMG as a component (C) to 100 parts by mass of isodecyl acrylate (SR395, manufactured by Kayaku Sartomer) as a component A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler. The peel force after 2 hours against the oil surface coated plate was 3.0 N, and the peel force after 1 day was 5.0 N.
（実施例６）
（Ａ）成分としてトリデシルアクリレート（ＳＲ４８９、化薬サートマー社製）１００質量部に対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．０Ｎ、１日後のピール力は３．４Ｎであった。
(Example 6)
(A) Mixture obtained by adding 46 parts by mass of IBXA as component (B) and 8 parts by mass of AMG as component (C) to 100 parts by mass of tridecyl acrylate (SR489, manufactured by Kayaku Sartomer) as component (A) A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler. The peel force after 2 hours against the oil surface coated plate was 2.0 N, and the peel force after 1 day was 3.4 N.
（実施例７）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分としてエトキシジエチレングリコールアクリレート（ビスコート＃１９０、大阪有機化学社製）８質量部をそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．６Ｎ、１日後のピール力は４．１Ｎであった。また、１７０℃で２０分加熱後のピール力は、７．１Ｎであった。
(Example 7)
Add 100 parts by mass of 2EHA as component (A), 46 parts by mass of IBXA as component (B), and 8 parts by mass of ethoxydiethylene glycol acrylate (Biscoat # 190, manufactured by Osaka Organic Chemical Co., Ltd.) as component (C). A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the mixture. The peel force after 2 hours on the oil surface coated plate was 2.6 N, and the peel force after 1 day was 4.1 N. The peel strength after heating at 170 ° C. for 20 minutes was 7.1 N.
（実施例８）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分としてメトキシトリプロピレングリコールアクリレート（ビスコート＃３２０、大阪有機化学社製）８質量部をそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．３Ｎ、１日後のピール力は３．６Ｎであった。また、１７０℃で２０分加熱後のピール力は、６．６Ｎであった。
(Example 8)
(A) 100 parts by mass of 2EHA as component, 46 parts by mass of IBXA as component (B), 8 parts by mass of methoxytripropylene glycol acrylate (Biscoat # 320, manufactured by Osaka Organic Chemical Co., Ltd.) as component (C) Photoinitiator 0.37 mass part, crosslinking agent 0.38 mass part, and filler 1.5 mass part were added to each added mixture, and the adhesive composition was produced. The peel force after 2 hours against the oil surface coated plate was 2.3 N, and the peel force after 1 day was 3.6 N. Moreover, the peeling force after heating for 20 minutes at 170 degreeC was 6.6N.
（実施例９）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分としてポリエチレングリコールアクリレート（ブレンマーＡＥ−２００、日本油脂社製）８質量部をそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．０Ｎ、１日後のピール力は２．６Ｎであった。また、１７０℃で２０分加熱後のピール力は、２．７Ｎであった。
Example 9
Add 100 parts by mass of 2EHA as component (A), 46 parts by mass of IBXA as component (B), and 8 parts by mass of polyethylene glycol acrylate (Blemmer AE-200, manufactured by NOF Corporation) as component (C). A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the mixture. The peel force after 2 hours on the oil surface coated plate was 2.0 N, and the peel force after 1 day was 2.6 N. The peel force after heating at 170 ° C. for 20 minutes was 2.7N.
（実施例１０）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分としてポリプロピレングリコールアクリレート（ブレンマーＡＰ−１５０、日本油脂社製）８質量部をそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．１Ｎ、１日後のピール力は３．７Ｎであった。
(Example 10)
Add 100 parts by mass of 2EHA as component (A), 46 parts by mass of IBXA as component (B), and 8 parts by mass of polypropylene glycol acrylate (Blenmer AP-150, manufactured by NOF Corporation) as component (C). A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the mixture. The peel force after 2 hours on the oil surface coated plate was 2.1 N, and the peel force after 1 day was 3.7 N.
（実施例１１）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分としてメトキシポリエチレングリコールアクリレート（ＮＫエステルＡＭ−２３０Ｇ、新中村化学社製）８質量部をそれぞれ加えた混合物に、光開始剤０．３５質量部、架橋剤０．３６質量部、フィラー１．４質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は３．４Ｎ、１日後のピール力は５．２Ｎであった。
(Example 11)
(A) 100 parts by mass of 2EHA as component, (B) 46 parts by mass of IBXA, (C) component as methoxypolyethylene glycol acrylate (NK ester AM-230G, Shin-Nakamura Chemical Co., Ltd.) 8 parts by mass Were added to each of the mixture, 0.35 parts by weight of a photoinitiator, 0.36 parts by weight of a crosslinking agent, and 1.4 parts by weight of a filler to prepare a pressure-sensitive adhesive composition. The peel force after 2 hours on the oil surface coated plate was 3.4 N, and the peel force after 1 day was 5.2 N.
（実施例１２）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４３質量部のＩＢＸＡ、（Ｃ）成分としてメトキシポリエチレングリコールアクリレート（ＮＫエステルＡＭ−２３０Ｇ、新中村化学社製）１質量部をそれぞれ加えた混合物に、光開始剤０．３５質量部、架橋剤０．３６質量部、フィラー１．４質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は４．５Ｎ、１日後のピール力は５．３Ｎであった。
(Example 12)
(A) 100 parts by mass of 2EHA as component, (B) 43 parts by mass of IBXA, (C) component as methoxypolyethylene glycol acrylate (NK ester AM-230G, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1 part by mass Were added to each of the mixture, 0.35 parts by weight of a photoinitiator, 0.36 parts by weight of a crosslinking agent, and 1.4 parts by weight of a filler to prepare a pressure-sensitive adhesive composition. The peel force after 2 hours on the oil surface coated plate was 4.5 N, and the peel force after 1 day was 5.3 N.
（実施例１３）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分としてメトキシトリエチレングリコールアクリレート（ビスコートＭＴＧ、大阪有機化学社製）８質量部をそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は３．３Ｎ、１日後のピール力は４．６Ｎであった。
(Example 13)
(A) 100 parts by mass of 2EHA as component, (B) 46 parts by mass of IBXA, (C) component as 8 parts by mass of methoxytriethylene glycol acrylate (Biscoat MTG, Osaka Organic Chemical Co., Ltd.) A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the added mixture. The peel force after 2 hours on the oil surface coated plate was 3.3 N, and the peel force after 1 day was 4.6 N.
（実施例１４）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として５０質量部のＩＢＸＡ、（Ｃ）成分として１７質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．４０質量部、架橋剤０．４２質量部、フィラー１．７質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．８Ｎ、１日後のピール力は３．８Ｎであった。
(Example 14)
(A) 0.40 parts by mass of photoinitiator to a mixture obtained by adding 50 parts by mass of IBXA as component (B) and 17 parts by mass of AMG as component (C) to 100 parts by mass of 2EHA as component Then, 0.42 parts by mass of a cross-linking agent and 1.7 parts by mass of a filler were added to prepare an adhesive composition. The peel force after 2 hours on the oil surface coated plate was 2.8 N, and the peel force after 1 day was 3.8 N.
（実施例１５）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として６４質量部のＩＢＸＡ、（Ｃ）成分として１８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．４４質量部、架橋剤０．４５質量部、フィラー１．８質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．７Ｎ、１日後のピール力は３．８Ｎであった。
(Example 15)
(A) 0.44 parts by mass of photoinitiator to a mixture obtained by adding 64 parts by mass of IBXA as component (B) and 18 parts by mass of AMG as component (C) to 100 parts by mass of 2EHA as component Then, 0.45 parts by mass of a crosslinking agent and 1.8 parts by mass of a filler were added to prepare an adhesive composition. The peel force after 2 hours on the oil surface coated plate was 2.7 N, and the peel force after 1 day was 3.8 N.
（実施例１６）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として２９質量部のＩＢＸＡ、（Ｃ）成分として１４質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３４質量部、架橋剤０．３６質量部、フィラー１．４質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．４Ｎ、１日後のピール力は３．１Ｎであった。
(Example 16)
(A) 100 parts by mass of 2EHA as component, 29 parts by mass of IBXA as component (B), 14 parts by mass of AMG as component (C), and 0.34 parts by mass of photoinitiator A pressure-sensitive adhesive composition was prepared by adding 0.36 parts by mass of a crosslinking agent and 1.4 parts by mass of a filler. The peel force after 2 hours on the oil surface coated plate was 2.4 N, and the peel force after 1 day was 3.1 N.
（実施例１７）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として８９質量部のＩＢＸＡ、（Ｃ）成分として３３質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．５３質量部、架橋剤０．５６質量部、フィラー２．２質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．１Ｎ、１日後のピール力は３．７Ｎであった。
(Example 17)
(A) 100 parts by mass of 2EHA as component, 89 parts by mass of IBXA as component (B), 33 parts by mass of AMG as component (C), and 0.53 parts by mass of photoinitiator A pressure-sensitive adhesive composition was prepared by adding 0.56 parts by mass of a crosslinking agent and 2.2 parts by mass of a filler. The peel force after 2 hours on the oil surface coated plate was 2.1 N, and the peel force after 1 day was 3.7 N.
（実施例１８）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として、ジシクロペンタニルアクリレート（ファンクリルＦＡ−５１３Ａ、日立化成社製）４６重両部、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は２．９Ｎ、１日後のピール力は３．４Ｎであった。
(Example 18)
(A) 100 parts by mass of 2EHA as the component, (B) as the component, dicyclopentanyl acrylate (funcryl FA-513A, manufactured by Hitachi Chemical Co., Ltd.) 46 double parts, (C) as the component 8 parts by mass To the mixture in which AMG was added, 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler were added to prepare an adhesive composition. The peel force after 2 hours on the oil surface coated plate was 2.9 N, and the peel force after 1 day was 3.4 N.
（実施例１９）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として、ジシクロペンタニルアクリレート（ファンクリルＦＡ−５１３Ａ、日立化成社製）２３質量部および２３質量部のＩＢＸＡ、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は３．２Ｎ、１日後のピール力は４．０Ｎであった。
(Example 19)
(A) 100 parts by mass of 2EHA as component, (B) as component (B), 23 parts by mass of dicyclopentanyl acrylate (Fancryl FA-513A, manufactured by Hitachi Chemical Co., Ltd.) and 23 parts by mass of IBXA, (C) A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to a mixture obtained by adding 8 parts by mass of AMG as a component. The peel force after 2 hours on the oil surface coated plate was 3.2 N, and the peel force after 1 day was 4.0 N.
（比較例１）
一般的に用いられる粘着剤として、１００質量部の２ＥＨＡに対して、アクリル酸１１質量部を加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。ＰＰ板に対するピール力は２．２Ｎ、ＰＥ板に対するピール力は２．５Ｎであった。油面塗板に対する２時間後のピール力は０．２Ｎ、１日後のピール力は０．７Ｎであった。
(Comparative Example 1)
As a commonly used pressure-sensitive adhesive, a mixture obtained by adding 11 parts by mass of acrylic acid to 100 parts by mass of 2EHA, 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts of filler A pressure-sensitive adhesive composition was prepared by adding parts by mass. The peel force against the PP plate was 2.2 N, and the peel force against the PE plate was 2.5 N. The peel force after 2 hours on the oil surface coated plate was 0.2 N, and the peel force after 1 day was 0.7 N.
（比較例２）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として６７質量部のＩＢＸＡの混合物に、光開始剤０．４０質量部、架橋剤０．４２質量部、フィラー１．７質量部を加えて、粘着剤組成物を作製した。（Ｃ）成分は添加しなかった。ＰＰ板に対するピール力は１３．６Ｎ、ＰＥ板に対するピール力は９．８Ｎであった。油面塗板に対する2時間後のピール力は５．１Ｎ、１日後のピール力は１３．０Ｎであった。また、１７０℃で２０分加熱後のピール力は、１４．９Ｎであった。
(Comparative Example 2)
(A) 100 parts by mass of 2EHA as a component, and (B) a mixture of 67 parts by mass of IBXA as a component, 0.40 parts by mass of a photoinitiator, 0.42 parts by mass of a crosslinking agent, and 1.7 parts by mass of a filler Part was added and the adhesive composition was produced. Component (C) was not added. The peel force against the PP plate was 13.6 N, and the peel force against the PE plate was 9.8 N. The peel force after 2 hours on the oil surface coated plate was 5.1 N, and the peel force after 1 day was 13.0 N. The peel force after heating at 170 ° C. for 20 minutes was 14.9 N.
（比較例３）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４３質量部のＩＢＸＡの混合物に、光開始剤０．３４質量部、架橋剤０．３６質量部、フィラー１．４質量部を加えて、粘着剤組成物を作製した。（Ｃ）成分は添加しなかった。油面塗板に対する２時間後のピール力は５．５Ｎ、１日後のピール力は９．３Ｎであった。
(Comparative Example 3)
(A) 100 parts by mass of 2EHA as component, 43 parts by mass of IBXA as component (B), 0.34 parts by mass of photoinitiator, 0.36 parts by mass of crosslinking agent, 1.4 masses of filler Part was added and the adhesive composition was produced. Component (C) was not added. The peel force after 2 hours on the oil surface coated plate was 5.5 N, and the peel force after 1 day was 9.3 N.
（比較例４）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として２００質量部のＩＢＸＡ、（Ｃ）成分として３３質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．８０質量部、架橋剤０．８３質量部、フィラー３．３質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は０．３Ｎ、１日後のピール力は１．６Ｎであった。
(Comparative Example 4)
(A) 100 parts by mass of 2EHA as component, 200 parts by mass of IBXA as component (B), 33 parts by mass of AMG as component (C), and 0.80 parts by mass of photoinitiator Then, 0.83 parts by mass of a crosslinking agent and 3.3 parts by mass of a filler were added to prepare an adhesive composition. The peel force after 2 hours on the oil surface coated plate was 0.3 N, and the peel force after 1 day was 1.6 N.
（比較例５）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として１２５質量部のＩＢＸＡ、（Ｃ）成分として２５質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．６０質量部、架橋剤０．６３質量部、フィラー２．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は３．３Ｎ、１日後のピール力は６．０Ｎであった。
(Comparative Example 5)
(0) 0.60 parts by mass of photoinitiator to a mixture obtained by adding 125 parts by mass of IBXA as component (B) and 25 parts by mass of AMG as component (C) to 100 parts by mass of 2EHA as component (A) Then, 0.63 parts by mass of a crosslinking agent and 2.5 parts by mass of a filler were added to prepare an adhesive composition. The peel force after 2 hours against the oil-coated plate was 3.3 N, and the peel force after 1 day was 6.0 N.
（比較例６）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として１７質量部のＩＢＸＡ、（Ｃ）成分として５０質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．４０質量部、架橋剤０．４２質量部、フィラー１．７質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は０．３Ｎ、１日後のピール力は０．９Ｎであった。
(Comparative Example 6)
(A) 0.40 parts by mass of photoinitiator to a mixture obtained by adding 17 parts by mass of IBXA as component (B) and 50 parts by mass of AMG as component (C) to 100 parts by mass of 2EHA as component Then, 0.42 parts by mass of a cross-linking agent and 1.7 parts by mass of a filler were added to prepare an adhesive composition. The peel force after 2 hours against the oil-coated plate was 0.3 N, and the peel force after 1 day was 0.9 N.
（比較例７）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として１３３質量部のＩＢＸＡ、（Ｃ）成分として１００質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．８０質量部、架橋剤０．８３質量部、フィラー３．３質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は０．１Ｎ、１日後のピール力は１．６Ｎであった。
(Comparative Example 7)
(A) 0.80 parts by mass of photoinitiator to a mixture obtained by adding 133 parts by mass of IBXA as component (B) and 100 parts by mass of AMG as component (C) to 100 parts by mass of 2EHA as component (A) Then, 0.83 parts by mass of a crosslinking agent and 3.3 parts by mass of a filler were added to prepare an adhesive composition. The peel force after 2 hours on the oil surface coated plate was 0.1 N, and the peel force after 1 day was 1.6 N.
（比較例８）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｃ）成分として２５質量部のＡＭＧを加えた混合物に、光開始剤０．３０質量部、架橋剤０．３１質量部、フィラー１．３質量部を加えて、粘着剤組成物を作製した。なお、（Ｂ）成分は添加しなかった。その結果、油面塗板には接着性を示さず、ピール力の測定はできなかった。
(Comparative Example 8)
To a mixture obtained by adding 25 parts by mass of AMG as component (C) to 100 parts by mass of 2EHA as component (A), 0.30 parts by mass of photoinitiator, 0.31 parts by mass of crosslinking agent, 3 parts by mass was added to prepare an adhesive composition. In addition, (B) component was not added. As a result, the oil-coated plate did not show adhesiveness, and the peel force could not be measured.
（比較例９）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として１４質量部のＩＢＸＡ、（Ｃ）成分として２９質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３４質量部、架橋剤０．３６質量部、フィラー１．４質量部を加えて、粘着剤組成物を作製した。その結果、油面塗板には接着性を示さず、ピール力の測定はできなかった。
(Comparative Example 9)
(A) 0.34 parts by mass of photoinitiator to a mixture obtained by adding 14 parts by mass of IBXA as component (B) and 29 parts by mass of AMG as component (C) to 100 parts by mass of 2EHA as component A pressure-sensitive adhesive composition was prepared by adding 0.36 parts by mass of a crosslinking agent and 1.4 parts by mass of a filler. As a result, the oil-coated plate did not show adhesiveness, and the peel force could not be measured.
（比較例１０）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分に相当するものは入れずに、代わりにアクリル酸（東亞合成社製）８質量部をそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は０．３Ｎ、１日後のピール力は１．２Ｎであった。
(Comparative Example 10)
(A) 100 parts by mass of 2EHA as the component, 46 parts by mass of IBXA as the component (B), and no equivalent to the component (C), instead of acrylic acid (manufactured by Toagosei Co., Ltd.) 8 mass A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the mixture obtained by adding each part. The peel force after 2 hours on the oil surface coated plate was 0.3 N, and the peel force after 1 day was 1.2 N.
（比較例１１）
（Ａ）成分としてブチルアクリレート（ＢＡＳＦ社製）１００質量部に対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は０．１Ｎ、１日後のピール力は１．５Ｎであった。
(Comparative Example 11)
(A) Photoinitiator to a mixture obtained by adding 46 parts by mass of IBXA as component (B) and 8 parts by mass of AMG as component (C) to 100 parts by mass of butyl acrylate (manufactured by BASF) as component (A) 0.37 parts by mass, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler were added to prepare an adhesive composition. The peel force after 2 hours on the oil surface coated plate was 0.1 N, and the peel force after 1 day was 1.5 N.
（比較例１２）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分として４６質量部のＩＢＸＡ、（Ｃ）成分として２−ヒドロキシエチルアクリレート（ＨＥＡ、大阪有機化学社製）８質量部をそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は１．２Ｎ、１日後のピール力は６．１Ｎであった。また、１７０℃で２０分加熱後のピール力は、３．８Ｎであった。
(Comparative Example 12)
Add 100 parts by mass of 2EHA as component (A), 46 parts by mass of IBXA as component (B), and 8 parts by mass of 2-hydroxyethyl acrylate (HEA, manufactured by Osaka Organic Chemical Co., Ltd.) as component (C). A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the mixture. The peel force after 2 hours on the oil surface coated plate was 1.2 N, and the peel force after 1 day was 6.1 N. The peel force after heating at 170 ° C. for 20 minutes was 3.8 N.
（比較例１３）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分としてフェノキシエチルアクリレート（ビスコート＃１９２、大阪有機化学社製）４６質量部、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は０．９Ｎ、１日後のピール力は１．４Ｎであった。
(Comparative Example 13)
Add 100 parts by mass of 2EHA as component (A), 46 parts by mass of phenoxyethyl acrylate (Biscoat # 192, manufactured by Osaka Organic Chemical Co., Ltd.) as component (B), and 8 parts by mass of AMG as component (C). A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the mixture. The peel force after 2 hours against the oil-coated plate was 0.9 N, and the peel force after 1 day was 1.4 N.
（比較例１４）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分としてイソステアリルアクリレート（ＮＫエステルＩＳＡ、新中村化学社製）４６質量部、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は１．２Ｎ、１日後のピール力は１．２Ｎであった。
(Comparative Example 14)
Add 100 parts by mass of 2EHA as component (A), 46 parts by mass of isostearyl acrylate (NK ester ISA, Shin-Nakamura Chemical Co., Ltd.) as component (B), and 8 parts by mass of AMG as component (C). A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the mixture. The peel force after 2 hours on the oil surface coated plate was 1.2 N, and the peel force after 1 day was 1.2 N.
（比較例１５）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分としてジシクロペンテニルアクリレート（ファンクリルＦＡ−５１１Ａ、日立化成社製）４６質量部、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は０．２Ｎ、１日後のピール力は０．５Ｎであった。
(Comparative Example 15)
(A) 100 parts by mass of 2EHA as a component, (B) 46 parts by mass of dicyclopentenyl acrylate (Fancryl FA-511A, manufactured by Hitachi Chemical Co., Ltd.), (C) 8 parts by mass of AMG as a component Photoinitiator 0.37 mass part, crosslinking agent 0.38 mass part, and filler 1.5 mass part were added to each added mixture, and the adhesive composition was produced. The peel force after 2 hours on the oil surface coated plate was 0.2 N, and the peel force after 1 day was 0.5 N.
（比較例１６）
（Ａ）成分として１００質量部の２ＥＨＡに対して、（Ｂ）成分としてジシクロペンテニルオキシエチルアクリレート（ファンクリルＦＡ−５１２Ａ、日立化成社製）４６質量部、（Ｃ）成分として８質量部のＡＭＧをそれぞれ加えた混合物に、光開始剤０．３７質量部、架橋剤０．３８質量部、フィラー１．５質量部を加えて、粘着剤組成物を作製した。油面塗板に対する２時間後のピール力は０．１Ｎ、１日後のピール力は０．３Ｎであった。
(Comparative Example 16)
(A) 100 parts by mass of 2EHA as a component, (B) 46 parts by mass of dicyclopentenyloxyethyl acrylate (Fancryl FA-512A, manufactured by Hitachi Chemical Co., Ltd.), and (C) 8 parts by mass of a component A pressure-sensitive adhesive composition was prepared by adding 0.37 parts by mass of a photoinitiator, 0.38 parts by mass of a crosslinking agent, and 1.5 parts by mass of a filler to the mixture to which AMG was added. The peel force after 2 hours on the oil-coated plate was 0.1 N, and the peel force after 1 day was 0.3 N.
比較例１３は（Ｂ）成分に芳香族側鎖、比較例１４は、非環状炭化水素側鎖、比較例１５、１６では、不飽和脂環族側鎖を持つものをそれぞれ用いたが、結果で示した通り、油面塗板に対しての接着性は低い。飽和脂環族側鎖が良い理由は明らかではないが、それら比較例と合わせると、（ＳＰ値による）極性による親和性だけではなく、被着体表面の防錆油を良く吸収するため、接着力が発現するものと推察される。 Comparative Example 13 used an aromatic side chain as the component (B), Comparative Example 14 used an acyclic hydrocarbon side chain, and Comparative Examples 15 and 16 used unsaturated alicyclic side chains. As shown by, the adhesion to the oil-coated plate is low. The reason why the saturated alicyclic side chain is good is not clear, but when combined with these comparative examples, not only the affinity due to the polarity (depending on the SP value) but also the rust preventive oil on the adherend surface is well absorbed. It is inferred that force is developed.
実施例１、２、７、８、９、および、比較例２、１２の、１７０℃加熱後のピール力を比較した図を図１に示す。水への浸漬、熱処理の外的環境の変化によりビルドアップが現れているが、実施例の試料は、その変化幅が小さい。一方、比較例２は、ビルドアップが著しく、再剥離に非常に大きな力が必要で、実作業者の負担が大きく、また、基材の破壊の恐れが出てくる。また、比較例１２は１日後のピール力と比較すると接着力が低下しており、この環境での使用は好ましくないことが分かる。 The figure which compared the peeling force after 170 degreeC heating of Examples 1, 2, 7, 8, 9, and Comparative Examples 2 and 12 is shown in FIG. Although build-up appears due to changes in the external environment of immersion in water and heat treatment, the sample of the example has a small change width. On the other hand, Comparative Example 2 has a significant build-up, requires a very large force for re-peeling, places a heavy burden on the actual operator, and causes the possibility of destruction of the base material. Moreover, it turns out that the adhesive force is falling compared with the peeling force of the comparative example 12 one day later, and use in this environment is not preferable.
全ての実施例および比較例の、油面塗板に対する２時間後、１日後、それぞれの１８０°ピール力を図２に示す。各実施例は２時間後と１日後のピール力を比較するとその変化幅は小さく、安定した接着力を示す。それに対して、比較例は、接着力の変化幅が大きく、再剥離時に大きな力が必要になったり、防錆油面に対して接着力が発現しなかったりなどの問題がある。 FIG. 2 shows the respective 180 ° peel forces after 2 hours and 1 day for the oil-coated plate in all examples and comparative examples. In each example, when the peel force after 2 hours and after 1 day are compared, the change width is small and a stable adhesive force is exhibited. On the other hand, the comparative example has a problem that the range of change in the adhesive force is large, a large force is required at the time of re-peeling, and the adhesive force does not appear on the antirust oil surface.
以上、（Ａ）（Ｂ）および（Ｃ）各成分を好ましい配合で作製した粘着剤組成物は、低表面エネルギー表面に対して、良好な接着性および再剥離性を有することが分かる。 As described above, it can be seen that the pressure-sensitive adhesive composition prepared by blending the components (A), (B), and (C) has favorable adhesiveness and removability with respect to the low surface energy surface.
本発明は、具体的な用途としては、防錆油や潤滑油などが塗布された鋼板の、仮固定用粘着剤や塗装時のマスキングテープ用の粘着剤などが挙げられる。また、低表面エネルギーであるＰＰ板、ＰＥ板に対しても良好な接着性および再剥離性あるので、粘着ラベル、シール、等として有用である。 Specific applications of the present invention include temporary fixing pressure sensitive adhesives and masking tape pressure sensitive adhesives for steel sheets coated with rust preventive oil or lubricating oil. Moreover, since it has good adhesiveness and removability to PP and PE plates having low surface energy, it is useful as an adhesive label, a seal, and the like.
Claims (5)
（Ｂ）飽和脂環族を側鎖に持つアクリレート１０〜９０質量部と、
（Ｃ）エチレングリコール鎖またはプロピレングリコール鎖を持ち、その繰り返し数が２から２３であるアクリレート１〜４０質量部と、
重合開始剤と、架橋剤とを含む粘着剤組成物。 (A) 100 parts by mass of an acrylate having an alkyl group having 8 to 13 carbon atoms;
(B) 10 to 90 parts by mass of an acrylate having a saturated alicyclic group in the side chain;
(C) 1-40 parts by mass of an acrylate having an ethylene glycol chain or a propylene glycol chain, the number of repetitions of which is 2 to 23;
A pressure-sensitive adhesive composition comprising a polymerization initiator and a crosslinking agent.
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| JP2010144046A (en) * | 2008-12-18 | 2010-07-01 | Lintec Corp | Release agent and release sheet |
| WO2012150682A1 (en) * | 2011-05-02 | 2012-11-08 | 日東電工株式会社 | Adhesive, adhesive layer, and adhesive sheet |
| JP2013032500A (en) * | 2011-06-30 | 2013-02-14 | Nitto Denko Corp | Adhesive agent composition, adhesive agent layer, and adhesive sheet |
| JP2013091713A (en) * | 2011-10-25 | 2013-05-16 | Sekisui Chem Co Ltd | Adhesive tape |
| JP2013133440A (en) * | 2011-12-27 | 2013-07-08 | Nitto Denko Corp | Pressure-sensitive adhesive, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet |
| JP2013173912A (en) * | 2011-11-10 | 2013-09-05 | Nitto Denko Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JP2014531501A (en) * | 2011-09-26 | 2014-11-27 | スリーエム イノベイティブ プロパティズ カンパニー | Multilayer pressure sensitive adhesive film having a pressure sensitive adhesive comprising a (meth) acrylate ester of 2-alkylalkanol |
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| JP2016053180A (en) * | 2010-08-27 | 2016-04-14 | 日東電工株式会社 | Acrylic pressure-sensitive adhesive composition, acrylic pressure-sensitive adhesive layer, and acrylic pressure-sensitive adhesive tape |
| US9890304B2 (en) | 2012-12-10 | 2018-02-13 | 3M Innovative Properties | Liquid optical adhesive compositions |
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| JP2010144046A (en) * | 2008-12-18 | 2010-07-01 | Lintec Corp | Release agent and release sheet |
| JP2016053180A (en) * | 2010-08-27 | 2016-04-14 | 日東電工株式会社 | Acrylic pressure-sensitive adhesive composition, acrylic pressure-sensitive adhesive layer, and acrylic pressure-sensitive adhesive tape |
| US10308844B2 (en) | 2011-05-02 | 2019-06-04 | Nitto Denko Corporation | Pressure-sensitive adhesive, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet |
| WO2012150682A1 (en) * | 2011-05-02 | 2012-11-08 | 日東電工株式会社 | Adhesive, adhesive layer, and adhesive sheet |
| JP2012246477A (en) * | 2011-05-02 | 2012-12-13 | Nitto Denko Corp | Adhesive, adhesive layer, and adhesive sheet |
| JP2013032500A (en) * | 2011-06-30 | 2013-02-14 | Nitto Denko Corp | Adhesive agent composition, adhesive agent layer, and adhesive sheet |
| JP2014531501A (en) * | 2011-09-26 | 2014-11-27 | スリーエム イノベイティブ プロパティズ カンパニー | Multilayer pressure sensitive adhesive film having a pressure sensitive adhesive comprising a (meth) acrylate ester of 2-alkylalkanol |
| JP2013091713A (en) * | 2011-10-25 | 2013-05-16 | Sekisui Chem Co Ltd | Adhesive tape |
| JP2013173912A (en) * | 2011-11-10 | 2013-09-05 | Nitto Denko Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JP2013133440A (en) * | 2011-12-27 | 2013-07-08 | Nitto Denko Corp | Pressure-sensitive adhesive, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet |
| US9309443B2 (en) | 2012-05-29 | 2016-04-12 | 3M Innovative Properties Company | Liquid optical adhesive compositions |
| US9890304B2 (en) | 2012-12-10 | 2018-02-13 | 3M Innovative Properties | Liquid optical adhesive compositions |
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| JP2020045418A (en) * | 2018-09-19 | 2020-03-26 | リンテック株式会社 | Adhesive sheet for oil surface |
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