JP4555427B2 - Surface protection adhesive sheet - Google Patents
Surface protection adhesive sheet Download PDFInfo
- Publication number
- JP4555427B2 JP4555427B2 JP2000082495A JP2000082495A JP4555427B2 JP 4555427 B2 JP4555427 B2 JP 4555427B2 JP 2000082495 A JP2000082495 A JP 2000082495A JP 2000082495 A JP2000082495 A JP 2000082495A JP 4555427 B2 JP4555427 B2 JP 4555427B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- acrylic
- pressure
- adhesive sheet
- group
- 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.)
- Expired - Fee Related
Links
- 239000000853 adhesive Substances 0.000 title description 28
- 230000001070 adhesive effect Effects 0.000 title description 28
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 43
- 229920000098 polyolefin Polymers 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 27
- 239000012943 hotmelt Substances 0.000 claims description 24
- 229920002545 silicone oil Polymers 0.000 claims description 23
- 229920006243 acrylic copolymer Polymers 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- -1 ethylene-butylene Chemical group 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004831 Hot glue Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229940048053 acrylate Drugs 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical class CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical class CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- PYGXUPRQBBNETH-UHFFFAOYSA-N acetic acid;2-hydroxypropyl prop-2-enoate Chemical compound CC(O)=O.CC(O)COC(=O)C=C PYGXUPRQBBNETH-UHFFFAOYSA-N 0.000 description 1
- 229940114077 acrylic acid Drugs 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Adhesive Tapes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、金属板、塗装鋼板、合成樹脂板、化粧合板、熱反射ガラス等の表面に仮着し、塵の付着や傷つきがないように、その表面を保護するために使用される表面保護用粘着シートに関する。
【０００２】
【従来の技術】
金属板、塗装鋼板、合成樹脂板、化粧合板、熱反射ガラス等の表面を加工時や搬送時の傷つきや汚れ等から防止するために表面保護用粘着シートが用いられている。これら表面保護用粘着シートは、適度の粘着力（仮着性）を有するとともに、使用後に各種被着体の表面を粘着剤で汚染することなく容易に剥がすことができなければならない。
【０００３】
表面保護用粘着シートとしては、例えば、特公昭５８−３０９１１号公報、特開昭６１−１０３９７５号公報等に、ポリオレフィン樹脂等の熱可塑性樹脂からなる基材層の片面に、一般式Ａ−Ｂ−Ａ（Ａはスチレン系重合体ブロック、Ｂはブタジエン重合体ブロック、イソプレン重合体ブロック又はエチレン−ブチレン重合体ブロック）で表されるブロック共重合体エラストマー単独又はこれと粘着付与樹脂とを混和してなる粘着剤層が形成された表面保護用粘着シートが開示されている。しかしながら、この先行技術記載の表面保護用粘着シートは、粘着剤層の基材に対する投錨性は優れているものの、屋外用製品の用途に対して耐候性が満足するものではなかった。
【０００４】
そこで、屋外用途等の特に耐候性が必要とされる用途では、塩化ビニル樹脂やポリオレフィン樹脂等の基材に、アクリル系粘着剤溶液を塗布してなる表面保護用粘着シートが用いられている。しかしながら、これらの粘着剤は、高温下に曝された際、接着力が増加し容易に剥がすこと（再剥離性）が困難となるという問題点があった。これを解決する方法として、特公昭５８−１３１１７号公報には、シリコーンオイルを粘着剤に含有させる技術が開示されているが、再剥離した後の被着体表面にシリコーンオイルが残り、その後の印刷性等に問題があった。
【０００５】
【発明が解決しようとする課題】
本発明は、上記に鑑み、良好な仮着性、適度な再剥離性を有し、更に再剥離後も被着体表面が印刷性に優れ、耐候性が要求される用途にも好適に用いることのできる表面保護用粘着シートを提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明は、アクリル系ホットメルト粘着剤からなる粘着剤層をポリオレフィン基材の片面に積層してなる表面保護用粘着シートであって、上記アクリル系ホットメルト粘着剤は、末端に反応性基を有するオレフィン重合体（ａ）とアクリルモノマーとを共重合させてなるアクリル系共重合体（ｂ）に、下記一般式（１）で表されるシリコーンオイル及び／又は下記一般式（２）で表されるシリコーンオイルが添加されてなる表面保護用粘着シートである。
【０００７】
【化３】
式中、Ｒは炭素数１〜６のアルキル基を表し、Ｘはエポキシ基又はアミノ基を有する官能基を表し、Ｙはポリエーテル基を表し、ｍは０〜２０の整数を表し、ｎ及びｐは１〜２０の整数を表す。
【０００９】
【化４】
式中、ｑは１０〜４０の整数を表す。
以下に、本発明を詳述する。
【００１１】
本発明の表面保護用粘着シートに用いられるアクリル系ホットメルト粘着剤は、末端に反応性基を有するオレフィン重合体（ａ）とアクリルモノマーとを共重合させてなるアクリル系共重合体（ｂ）に、上記一般式（１）で表されるシリコーンオイル及び／又は上記一般式（２）で表されるシリコーンオイルが添加されてなる。
【００１２】
本発明の表面保護用粘着シートにおいて、上記末端に反応性基を有するオレフィン重合体（ａ）（以下、オレフィン重量体（ａ）という）としては特に限定されず、例えば、ポリエチレン、ポリプロピレン、エチレン−ブチレン共重合物等のオレフィン骨格を有し、その末端に反応性基を有するもの等が挙げられる。また、上記オレフィン重量体（ａ）は、反応性基を両末端に有するものであってもよく、一方の末端のみに有するものであってもよい。
上記の末端の反応性基としては特に限定されず、例えば、ラジカル重合性の不飽和二重結合、カルボキシル基、エポキシ基、水酸基等が挙げられる。
上記オレフィン重合体（ａ）としては、例えば、商品名「ＫＲＡＴＯＮ ＬＩＱＵＩＤ Ｐｏｌｙｍｅｒ Ｌ−１２５３」（Ｓｈｅｌｌ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ社製）、特開平５−１９４６３１号公報や特開平６−３２９７２０号公報等に開示されている末端にラジカル重合性の不飽和二重結合を有するオレフィン重合体、特開平７−２９２８号公報に開示されている末端にカルボキシル基を有するオレフィン重合体、特開平５−２４７１１９号公報に開示されている末端にエポキシ基を有するオレフィン重合体等が挙げられる。これらは単独で用いられてもよく、２種以上併用されてもよい。
【００１３】
本発明の表面保護用粘着シートに用いられる上記アクリルモノマーとしては特に限定されないが、例えば、炭素数１〜１４のアルキル基を有する（メタ）アクリル酸アルキルエステル等が好適に用いられる。上記炭素数１〜１４のアルキル基を有する（メタ）アクリル酸アルキルエステルとしては特に限定されず、例えば（メタ）アクリル酸メチルエステル、アクリル酸エチルエステル、（メタ）アクリル酸ｎ−プロピルエステル、（メタ）アクリル酸イソプロピルエステル、（メタ）アクリル酸ｎ−ブチルエステル、（メタ）アクリル酸ｓｅｃ−ブチルエステル、（メタ）アクリル酸ｔ−ブチルエステル、メタクリル酸シクロヘキシルエステル、（メタ）アクリル酸ｎ−オクチルエステル、アクリル酸イソオクチルエステル、（メタ）アクリル酸２−エチルヘキシルエステル、アクリル酸イソノニルエステル、（メタ）アクリル酸ラウリルエステル等が挙げられる。これらは単独で用いられてもよく、２種以上併用されてもよい。
【００１４】
本発明の表面保護用粘着シートに用いられるアクリル系共重合体（ｂ）は、上記オレフィン重合体（ａ）とアクリルモノマーとを共重合させてなるものである。上記オレフィン重合体（ａ）とアクリルモノマーとを反応させる方法としては特に限定されず、オレフィン重合体（ａ）の末端の反応性基の種類により適宜選択されればよく、例えば、オレフィン重合体（ａ）の末端の反応性基が不飽和二重結合の場合は、オレフィン重合体（ａ）とアクリルモノマーとを反応させればよい。オレフィン重合体（ａ）の末端の反応性基がその他の反応性基の場合には、その反応性基と反応する官能基を有するアクリルモノマーとオレフィン重合体（ａ）とを反応させた後に、他のアクリルモノマーを反応させてもよく、又は、その他の反応性基と反応する官能基を有するモノマーを含むアクリルポリマーを重合した後に、このアクリルポリマーとオレフィン重合体（ａ）とを反応させてもよい。
また、得られるアクリル系共重合体（ｂ）のガラス転移温度や極性の調整のため、又は、官能基を導入するために、上記アクリルモノマーと共重合可能な他の重合性単量体を共重合させてもよい。
【００１５】
上記アクリルモノマーと共重合可能な重合性単量体としては特に限定されず、例えば、α−メチルスチレン、ビニルトルエン、スチレン等のスチレン系単量体；メチルビニルエーテル、エチルビニルエーテル、イソブチルビニルエーテル等のビニルエーテル系単量体；フマル酸のモノアルキルエステル、フマル酸のジアルキルエステル、マレイン酸のモノアルキルエステル、マレイン酸のジアルキルエステル、イタコン酸のモノアルキルエステル、イタコン酸のジアルキルエステル、（メタ）アクリロニトリル、ブタジエン、イソプレン、塩化ビニル、塩化ビニリデン、酢酸ビニル、ビニルケトン、ビニルピロリドン、ビニルピリジン、（メタ）アクリルアミド、ビニルカルバゾール等が挙げられる。これらは単独で用いられてもよく、２種以上併用されてもよい。
【００１６】
また、官能基を導入する重合性単量体としては特に限定されず、例えば、（メタ）アクリル酸、イタコン酸、クロトン酸、（無水）マレイン酸、（無水）フマル酸、カルボキシエチルアクリレート等のカルボキシル基を有する単量体；（メタ）アクリル酸２−ヒドロキシエチルエステル、アクリル酸ヒドロキシプロピルエステル、アクリル酸４−ヒドロキシブチルエステル、カプロラクトン変成（メタ）アクリレート、ポリオキシエチレンオキシド変成（メタ）アクリレート等の水酸基を有する単量体；メタクリル酸グリシジルエステル等のエポキシ基を有する単量体；メタクリロイルイソシアネート等のイソシアネート基を有する単量体；ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等の３級アミノ基を有する単量体等が挙げられる。これらは単独で用いられてもよく、２種以上併用されてもよい。
【００１７】
上記オレフィン重合体（ａ）の添加量としては、上記アクリルモノマー１００重量部に対して、３〜１００重量部が好ましい。３重量部未満の場合には、得られるアクリル系ホットメルト粘着剤がポリオレフィン基材への所望の接着力を有さず、金属板、塗装鋼板等に対して糊残りしてしまうことがある。１００重量部を超えると、得られるアクリル系ホットメルト粘着剤の凝集力が低下し、凝集破壊が発生することがある。
【００１８】
上記オレフィン重合体（ａ）とアクリルモノマーとを用いてアクリル系共重合体（ｂ）を重合する方法としては特に限定されず、例えば、溶液重合法、塊状重合法、懸濁重合法、エマルジョン重合法等が挙げられるが、通常、例えば、酢酸エチル等の適当な溶剤に溶解させ、重合開始剤を用いた溶液重合法により容易に得ることができる。
【００１９】
上記のようにして得られるアクリル系共重合体（ｂ）の重量平均分子量は、１万〜３００万であることが好ましい。１万未満であると、重合体としての特性を発揮できないことがある。３００万を超えると、製造時の粘度が高くなり、生産性の点で好ましくない。より好ましくは、２０万〜２００万である。
【００２０】
また、上記アクリル系共重合体（ｂ）は、オレフィン重合体（ａ）がグラフト結合してなる側鎖を有するグラフト共重合体であることが好ましい。上記アクリル系共重合体（ｂ）が、オレフィン重合体（ａ）がグラフト結合してなる側鎖を有するグラフト共重合体であることにより、得られるアクリル系ホットメルト粘着剤は、より良好な仮着性、適度な再剥離性を有し、再剥離後も被着体表面の印刷性を損なわないものとなる。更に、耐候性も向上する。
【００２１】
上記アクリル系共重合体（ｂ）は、数平均分子量が２０００〜３万でありガラス転移温度が３０℃以上である重合体（ｃ）がグラフト結合してなる側鎖を有するグラフト共重合体であることが好ましい。上記重合体（ｃ）を側鎖として有することにより、得られるアクリル系ホットメルト粘着剤は、より良好な仮着性、適度な再剥離性を有し、再剥離後も被着体表面の印刷性を損なわないものとなる。
更に、耐候性も向上する。
上記重合体（ｃ）のガラス転移温度が３０℃未満であると、得られるアクリル系ホットメルト粘着剤の再剥離性が低下することがある。上記重合体（ｃ）の分子量が２０００未満であると、得られるアクリル系ホットメルト粘着剤は充分な凝集力を有さないことがあり、３万を超えると、得られるアクリル系ホットメルト粘着剤の凝集力が低下することがある。
【００２２】
上記重合体（ｃ）としては、ラジカル重合性の不飽和二重結合で末端を修飾され、数平均分子量が２０００〜３万であり、かつ、ガラス転移温度が３０℃以上である特性を有する重量体であれば特に限定されるものではない。上記ラジカル重合性不飽和二重結合としては特に限定されず、例えば、ビニル基、（メタ）アクリロイル基、アリル基等が挙げられる。また、このような重合体としては、例えば、末端にメタクリロイル基を有するポリメチルメタクリレート（商品名：ＡＡ−６、数平均分子量６０００、ガラス転移温度１０２℃、東亜合成社製）等が挙げられる。
【００２３】
本発明の表面保護用粘着シートに用いられるアクリル系ホットメルト粘着剤は、上記アクリル系共重合体（ｂ）に、上記一般式（１）で表されるシリコーンオイル及び／又は上記一般式（２）で表されるシリコーンオイルが添加されてなる。上記一般式（１）で表されるシリコーンオイルとしては特に限定されず、例えば、エポキシ基を有するものとしては、商品名「Ｘ−２２−３６６７」（信越化学社製）、アミノ基を有するものとしては、商品名「Ｘ−２２−３９３９Ａ」（信越化学社製）等が挙げられる。上記一般式（２）で表されるシリコーンオイルとしては特に限定されず、例えば、商品名「Ｘ−２２−１７３Ｂ」（信越化学社製）等が挙げられる。
【００２４】
上記シリコーンオイルの添加量としては、上記アクリル系共重合体（ｂ）１００重量部に対して、０．１〜７重量部が好ましい。０．１重量部未満であると、得られるアクリル系ホットメルト粘着剤は、所望の再剥離性を得難く、７重量部を超えると、得られるアクリル系ホットメルト粘着剤により被着体表面が汚染されやすく、再剥離後の被着体表面の印刷性を著しく低下させることがある。
【００２５】
なお、上記アクリル系ホットメルト粘着剤には、本発明の目的を阻害しない範囲で必要に応じて従来既知の各種添加剤、例えば、粘着付与樹脂、可塑剤、軟化剤、充填剤、安定剤、酸化防止剤、顔料、染料等が加えられてもよい。
【００２６】
本発明の表面保護用粘着シートにおいて、上記アクリル系ホットメルト粘着剤を製造する方法としては特に限定されず、例えば、上記アクリル系共重合体（ｂ）、上記一般式（１）で表されるシリコーンオイル及び／又は上記一般式（２）で表されるシリコーンオイル並びに必要に応じて添加される各種添加剤の所定量を配合し、ニーダー、ミキサー等により混練する方法等が挙げられる。また、上記の工程は、脱溶剤を行う工程を含んでいてもよい。
【００２７】
本発明の表面保護用粘着シートは、上記アクリル系ホットメルト粘着剤からなる粘着剤層をポリオレフィン基材の片面に積層してなる。
上記ポリオレフィン基材としては特に限定されず、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂からなるプラスチックフィルム等が挙げられる。
また、上記ポリオレフィン基材には、必要な耐候性を付与するために、酸化防止剤、紫外線吸収剤、紫外線安定剤等を含有させてもよい。
【００２８】
本発明の表面保護用粘着シートにおいて、上記ポリオレフィン基材にアクリル系ホットメルト粘着剤からなる粘着剤層を積層する方法としては特に限定されず、通常押出法が用いられ、ポリオレフィン基材上にアクリル系ホットメルト粘着剤を押し出しコーティングする方法、アクリル系ホットメルト粘着剤とポリオレフィン基材とを共押出する方法（共押出法）等が挙げられる。なかでも、本発明の表面保護用粘着シートは、アクリル系ホットメルト粘着剤とポリオレフィン基材とを共押出してなることが好ましい。共押出による方法は、製造装置及び製造工程が簡便であり、また、製造効率もよい。更に、共押出による方法で得られる表面保護用粘着シートは、積層強度が高い。
【００２９】
本発明の表面保護用粘着シートは、粘着剤層にオレフィン骨格を含有し、粘着性を発揮するアクリル成分とオレフィン骨格とが化学的に結合しているので、粘着剤層とポリオレフィン基材との接着性がよい。また、上記一般式（１）で表されるシリコーンオイル及び／又は上記一般式（２）で表されるシリコーンオイルを含むことにより、粘着剤が被着体表面に残存することがなく、被着体に対する粘着性を調整することができ剥離性が良好となる。更に、粘着剤層がアクリル系であるので、耐候性が優れている。
【００３０】
【実施例】
以下に実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。
【００３１】
実施例１
撹拌器、冷却器、温度計及び窒素ガス導入口を備えた２Ｌセパラブルフラスコに、アクリル酸ブチルエステル（ＢＡ）４９２ｇ、アクリル酸２０ｇ、片末端にエポキシ基を有するオレフィン重合体（ＫＲＡＴＯＮ ＬＩＱＵＩＤ Ｐｏｌｙｍｅｒ Ｌ−１２５３、Ｓｈｅｌｌ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ社製）の５０％トルエン溶液を１２０ｇ、ラジカル重合性の不飽和二重結合を末端に有する重合体（商品名：ＡＡ−６、分子量６０００、ガラス転移温度１０２℃、東亞合成社製）９０ｇ及び重合溶剤としてトルエン４５０．９１ｇを仕込み、撹拌混合することによりモノマー混合溶液を得た。
【００３２】
上記モノマー混合溶液を窒素ガスを用いて２０分間バブリングすることによって溶存酸素を除去した後、セパラブルフラスコ系内を窒素ガスで置換、１００ｒｐｍの撹拌回転数で撹拌しながら、ウォーターバスを用いてモノマー混合溶液を昇温させた。冷却管に還流液が確認された時点で、重合開始剤として１，１−ジ（ｔ−ヘキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン（パーヘキサＴＭＨ、日本油脂社製）０．３０ｇを約１ｇの酢酸エチルに溶解し、投入することによって重合を開始させた。１時間後に再びパーヘキサＴＭＨ０．６０ｇを約１ｇの酢酸エチルに溶解し、投入した。また、重合開始２、３及び４時間後にそれぞれジ（３，５，５−トリメチルヘキサノイル）パーオキシド（パーロイル３５５、日本油脂社製）０．６０ｇ、１．２０ｇ及び１．８０ｇを約１ｇの酢酸エチルに溶解して添加した。８時間重合を行いアクリル系共重合体溶液を得た。
【００３３】
次いで、上記より得られたアクリル系共重合体溶液に、エポキシ基含有シリコーンオイル（商品名：Ｘ−２２−３６６７、信越化学社製）をアクリル系共重合体１００重量部に対し０．３重量部になるように配合し、２００℃にて脱溶剤を行いアクリル系ホットメルト粘着剤を得た。
【００３４】
実施例２〜３
上記エポキシ基含有シリコーンオイル（商品名：Ｘ−２２−３６６７、信越化学社製）の配合量を表１に示すようにしたこと以外は、実施例１と同様にしてアクリル系ホットメルト粘着剤を得た。
【００３５】
実施例４
エポキシ基含有シリコーンオイルとして、商品名「Ｘ−２２−１７３Ｂ」（信越化学社製）を用い、その配合量を表１に示すようにしたこと以外は、実施例１と同様にしてアクリル系ホットメルト粘着剤を得た。
【００３６】
比較例１
実施例１で得たアクリル系共重合体溶液をそのまま使用した。
【００３７】
比較例２〜３
シリコーンオイルとして、商品名「ＫＦ−４１２」（信越化学社製）を用い、その配合量を表１に示すようにした以外は、実施例１と同様にしてアクリル系ホットメルト粘着剤を得た。
【００３８】
（表面保護用粘着シートの作製）
実施例１〜４及び比較例１〜３で得られたアクリル系ホットメルト粘着剤を線状低密度ポリエチレン（三菱化成社製、商品名：ＨＹ５４０）と２層共押出法により押出して、厚み５０μｍの線状低密度ポリエチレンに１０μｍの粘着剤層が積層されてなる表面保護用粘着シートを得た。
【００３９】
（評価）
得られた表面保護用粘着シートについて、下記項目について評価を行った。結果を表１に示す。
（初期粘着力）
上記表面保護用粘着シートを、ＪＩＳ Ｚ ０２３７に準じて、ＳＵＳ３０４板に２５ｍｍ幅で貼り合わせ、２３℃、２０分間放置した後、１８０゜方向、引っ張り速度３００ｍｍ／ｍｉｎの条件で剥離し、その剥離強度を測定した。
【００４０】
（耐熱粘着力）
上記表面保護用粘着シートを、ＪＩＳ Ｚ ０２３７に準じて、ＳＵＳ３０４板に２５ｍｍ幅で貼り合わせ、８０℃、７日間放置した後、１８０゜方向、引っ張り速度３００ｍｍ／ｍｉｎの条件で剥離し、その剥離強度を測定した。
【００４１】
（耐候性）
上記表面保護用粘着シートを、ＪＩＳ Ｚ ０２３７に準じて、ＳＵＳ３０４板に２５ｍｍ幅で貼り合わせ、サンシャインウェザーメーター（ＷＯＭ）による促進耐候試験（ブラックパネル温度：６３℃）を３００時間行った後、剥離し、その剥離形態を観察した。
【００４２】
（印刷性）
耐熱粘着力測定後のＳＵＳ板に水性のボールペンで線を描き、水性インクのはじきを観察した。
○：はじかない
△：ややはじく
×：描けない
【００４３】
【表１】
表１より、実施例１〜４で作製した表面保護用粘着シートは、初期粘着力及び耐熱粘着力が適正であり、かつ、被着体から剥離した場合に糊残りがなかった。更に、剥離した後の被着体の印刷性が良好であった。上記一般式（１）や上記一般式（２）で表されるシリコーンオイルを添加しなかった比較例１〜３の表面保護用粘着シートは、初期粘着力及び耐熱粘着力が適正でなかった。また、耐候性及び剥離した後の被着体の印刷性が共に優れるものではなかった。
【００４５】
【発明の効果】
本発明の表面保護用粘着シートは、上述の構成よりなるので、金属板、塗装鋼板等の被着体に貼り付け、長期に保管しておいた後も糊残りなく再剥離が可能であり、高耐候性である。また、再剥離後も被着体の表面の印刷性を低下させることがない。[0001]
BACKGROUND OF THE INVENTION
The present invention is a surface protection that is used to protect a surface of a metal plate, a coated steel plate, a synthetic resin plate, a decorative plywood, a heat reflecting glass, etc. so that the surface is protected from dust adhesion and damage. The present invention relates to a pressure-sensitive adhesive sheet.
[0002]
[Prior art]
In order to prevent the surface of a metal plate, a coated steel plate, a synthetic resin plate, a decorative plywood, a heat reflecting glass, or the like from being damaged or soiled during processing or transportation, a surface protecting adhesive sheet is used. These surface-protective pressure-sensitive adhesive sheets must have an appropriate pressure-sensitive adhesive force (temporary adhesion) and can be easily peeled off after use without contaminating the surfaces of various adherends with pressure-sensitive adhesives.
[0003]
Examples of the surface protective pressure-sensitive adhesive sheet include, for example, Japanese Patent Publication No. 58-30911, Japanese Patent Application Laid-Open No. 61-103975, and the like, on one side of a base material layer made of a thermoplastic resin such as polyolefin resin, a general formula AB A block copolymer elastomer represented by -A (A is a styrenic polymer block, B is a butadiene polymer block, isoprene polymer block or ethylene-butylene polymer block) alone or a tackifying resin is mixed. A surface-protective pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed thereon is disclosed. However, although the adhesive sheet for surface protection described in the prior art is excellent in anchoring property to the base material of the pressure-sensitive adhesive layer, the weather resistance is not satisfactory for the use of outdoor products.
[0004]
Therefore, in applications that require particularly weather resistance, such as outdoor applications, surface-protective pressure-sensitive adhesive sheets obtained by applying an acrylic pressure-sensitive adhesive solution to a substrate such as a vinyl chloride resin or a polyolefin resin are used. However, these pressure-sensitive adhesives have a problem that, when exposed to a high temperature, the adhesive force increases and it is difficult to easily remove (removability). As a method for solving this, Japanese Patent Publication No. 58-13117 discloses a technique for containing silicone oil in an adhesive, but the silicone oil remains on the surface of the adherend after re-peeling. There was a problem with printability.
[0005]
[Problems to be solved by the invention]
In view of the above, the present invention has good temporary attachment properties and moderate re-peelability, and is suitable for applications where the adherend surface is excellent in printability even after re-peeling and weather resistance is required. An object of the present invention is to provide an adhesive sheet for surface protection that can be used.
[0006]
[Means for Solving the Problems]
The present invention is a pressure-sensitive adhesive sheet for surface protection obtained by laminating a pressure-sensitive adhesive layer comprising an acrylic hot-melt pressure-sensitive adhesive on one side of a polyolefin substrate, and the acrylic hot-melt pressure-sensitive adhesive has a reactive group at its end. An acrylic copolymer (b) obtained by copolymerizing an olefin polymer (a) having an acrylic monomer with a silicone oil represented by the following general formula (1) and / or the following general formula (2) It is the adhesive sheet for surface protection formed by adding the silicone oil.
[0007]
[Chemical 3]
In the formula, R represents an alkyl group having 1 to 6 carbon atoms, X represents a functional group having an epoxy group or an amino group, Y represents a polyether group, m represents an integer of 0 to 20, n and p represents an integer of 1 to 20.
[0009]
[Formula 4]
In the formula, q represents an integer of 10 to 40.
The present invention is described in detail below.
[0011]
The acrylic hot-melt pressure-sensitive adhesive used for the surface-protective pressure-sensitive adhesive sheet of the present invention is an acrylic copolymer (b) obtained by copolymerizing an olefin polymer (a) having a reactive group at the terminal and an acrylic monomer. In addition, the silicone oil represented by the general formula (1) and / or the silicone oil represented by the general formula (2) is added.
[0012]
In the surface-protective pressure-sensitive adhesive sheet of the present invention, the olefin polymer (a) having a reactive group at the terminal (hereinafter referred to as olefin weight body (a)) is not particularly limited. For example, polyethylene, polypropylene, ethylene- Examples thereof include those having an olefin skeleton such as a butylene copolymer and having a reactive group at the terminal. Moreover, the said olefin weight body (a) may have a reactive group in both ends, and may have only in one terminal.
The terminal reactive group is not particularly limited, and examples thereof include a radical polymerizable unsaturated double bond, a carboxyl group, an epoxy group, and a hydroxyl group.
Examples of the olefin polymer (a) are disclosed in the trade name “KRATON LIQUID Polymer L-1253” (manufactured by Shell Chemical Company), Japanese Patent Laid-Open No. 5-194631, Japanese Patent Laid-Open No. 6-329720, and the like. An olefin polymer having a radical polymerizable unsaturated double bond at the terminal, an olefin polymer having a carboxyl group at the terminal disclosed in JP-A-7-2928, and disclosed in JP-A-5-247119. Examples thereof include an olefin polymer having an epoxy group at the terminal. These may be used alone or in combination of two or more.
[0013]
Although it does not specifically limit as said acrylic monomer used for the adhesive sheet for surface protection of this invention, For example, the (meth) acrylic-acid alkylester etc. which have a C1-C14 alkyl group are used suitably. The (meth) acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms is not particularly limited. For example, (meth) acrylic acid methyl ester, acrylic acid ethyl ester, (meth) acrylic acid n-propyl ester, ( (Meth) acrylic acid isopropyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid sec-butyl ester, (meth) acrylic acid t-butyl ester, methacrylic acid cyclohexyl ester, (meth) acrylic acid n-octyl ester Examples thereof include esters, isooctyl acrylate esters, (meth) acrylic acid 2-ethylhexyl esters, isononyl acrylate esters, (meth) acrylic acid lauryl esters, and the like. These may be used alone or in combination of two or more.
[0014]
The acrylic copolymer (b) used for the surface protecting pressure-sensitive adhesive sheet of the present invention is obtained by copolymerizing the olefin polymer (a) and an acrylic monomer. The method for reacting the olefin polymer (a) with the acrylic monomer is not particularly limited, and may be appropriately selected depending on the type of the reactive group at the end of the olefin polymer (a). When the reactive group at the terminal of a) is an unsaturated double bond, the olefin polymer (a) may be reacted with an acrylic monomer. When the reactive group at the terminal of the olefin polymer (a) is other reactive group, after the acrylic monomer having a functional group that reacts with the reactive group and the olefin polymer (a) are reacted, Another acrylic monomer may be reacted, or after polymerizing an acrylic polymer containing a monomer having a functional group that reacts with another reactive group, the acrylic polymer and the olefin polymer (a) are reacted. Also good.
In addition, in order to adjust the glass transition temperature and polarity of the acrylic copolymer (b) to be obtained, or to introduce a functional group, another polymerizable monomer copolymerizable with the above acrylic monomer is copolymerized. It may be polymerized.
[0015]
The polymerizable monomer copolymerizable with the acrylic monomer is not particularly limited, and examples thereof include styrene monomers such as α-methylstyrene, vinyl toluene, and styrene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether. Monomers: fumaric acid monoalkyl ester, fumaric acid dialkyl ester, maleic acid monoalkyl ester, maleic acid dialkyl ester, itaconic acid monoalkyl ester, itaconic acid dialkyl ester, (meth) acrylonitrile, butadiene , Isoprene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ketone, vinyl pyrrolidone, vinyl pyridine, (meth) acrylamide, vinyl carbazole and the like. These may be used alone or in combination of two or more.
[0016]
Moreover, it does not specifically limit as a polymerizable monomer which introduce | transduces a functional group, For example, (meth) acrylic acid, itaconic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) fumaric acid, carboxyethyl acrylate etc. Monomers having a carboxyl group; (meth) acrylic acid 2-hydroxyethyl ester, acrylic acid hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, caprolactone-modified (meth) acrylate, polyoxyethylene oxide-modified (meth) acrylate, etc. Monomers having a hydroxyl group; monomers having an epoxy group such as glycidyl methacrylate; monomers having an isocyanate group such as methacryloyl isocyanate; 3 such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate Class Monomers having a amino group. These may be used alone or in combination of two or more.
[0017]
The amount of the olefin polymer (a) added is preferably 3 to 100 parts by weight with respect to 100 parts by weight of the acrylic monomer. When the amount is less than 3 parts by weight, the resulting acrylic hot-melt pressure-sensitive adhesive does not have a desired adhesive force to the polyolefin substrate, and may remain glued to a metal plate, a coated steel plate or the like. If it exceeds 100 parts by weight, the cohesive force of the resulting acrylic hot melt pressure-sensitive adhesive may be reduced, and cohesive failure may occur.
[0018]
The method for polymerizing the acrylic copolymer (b) using the olefin polymer (a) and the acrylic monomer is not particularly limited, and examples thereof include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion weight. Examples thereof include a synthesis method, but it can usually be easily obtained by a solution polymerization method using a polymerization initiator after dissolving in an appropriate solvent such as ethyl acetate.
[0019]
The weight average molecular weight of the acrylic copolymer (b) obtained as described above is preferably 10,000 to 3,000,000. If it is less than 10,000, the polymer properties may not be exhibited. When it exceeds 3 million, the viscosity at the time of production increases, which is not preferable in terms of productivity. More preferably, it is 200,000 to 2,000,000.
[0020]
The acrylic copolymer (b) is preferably a graft copolymer having a side chain formed by grafting the olefin polymer (a). When the acrylic copolymer (b) is a graft copolymer having a side chain formed by graft-bonding the olefin polymer (a), the resulting acrylic hot-melt pressure-sensitive adhesive has a better temporary It has adhesion and moderate removability, and does not impair the printability of the adherend surface even after removability. Furthermore, weather resistance is also improved.
[0021]
The acrylic copolymer (b) is a graft copolymer having a side chain formed by grafting a polymer (c) having a number average molecular weight of 2000 to 30,000 and a glass transition temperature of 30 ° C. or higher. Preferably there is. By having the polymer (c) as a side chain, the resulting acrylic hot-melt pressure-sensitive adhesive has better temporary attachment properties and appropriate removability, and can be printed on the adherend surface even after re-removal. It will not impair the sex.
Furthermore, weather resistance is also improved.
When the glass transition temperature of the polymer (c) is less than 30 ° C., the removability of the resulting acrylic hot melt pressure-sensitive adhesive may be lowered. When the molecular weight of the polymer (c) is less than 2000, the resulting acrylic hot melt pressure-sensitive adhesive may not have sufficient cohesive force. When it exceeds 30,000, the resulting acrylic hot melt pressure-sensitive adhesive The cohesive strength of may decrease.
[0022]
The polymer (c) has a characteristic that the terminal is modified with a radically polymerizable unsaturated double bond, the number average molecular weight is 2000 to 30,000, and the glass transition temperature is 30 ° C. or higher. If it is a body, it will not specifically limit. The radically polymerizable unsaturated double bond is not particularly limited, and examples thereof include a vinyl group, a (meth) acryloyl group, and an allyl group. Examples of such a polymer include polymethyl methacrylate having a methacryloyl group at the terminal (trade name: AA-6, number average molecular weight 6000, glass transition temperature 102 ° C., manufactured by Toagosei Co., Ltd.).
[0023]
The acrylic hot-melt pressure-sensitive adhesive used for the surface-protective pressure-sensitive adhesive sheet of the present invention is obtained by adding the silicone oil represented by the general formula (1) and / or the general formula (2) to the acrylic copolymer (b). ) Is added. The silicone oil represented by the general formula (1) is not particularly limited. For example, those having an epoxy group include trade names “X-22-3667” (manufactured by Shin-Etsu Chemical Co., Ltd.), those having an amino group. Examples of such a product include “X-22-3939A” (manufactured by Shin-Etsu Chemical Co., Ltd.). It does not specifically limit as a silicone oil represented by the said General formula (2), For example, brand name "X-22-173B" (made by Shin-Etsu Chemical Co., Ltd.) etc. are mentioned.
[0024]
The addition amount of the silicone oil is preferably 0.1 to 7 parts by weight with respect to 100 parts by weight of the acrylic copolymer (b). If the amount is less than 0.1 parts by weight, the resulting acrylic hot melt pressure-sensitive adhesive is difficult to obtain the desired removability. If the amount exceeds 7 parts by weight, the surface of the adherend is removed by the resulting acrylic hot melt pressure-sensitive adhesive. It is easily contaminated, and the printability of the adherend surface after re-peeling may be significantly reduced.
[0025]
In addition, the acrylic hot-melt pressure-sensitive adhesive has various conventionally known additives as required within a range not impairing the object of the present invention, such as a tackifier resin, a plasticizer, a softener, a filler, a stabilizer, Antioxidants, pigments, dyes and the like may be added.
[0026]
In the pressure-sensitive adhesive sheet for surface protection of the present invention, the method for producing the acrylic hot-melt pressure-sensitive adhesive is not particularly limited, and is represented by, for example, the acrylic copolymer (b) or the general formula (1). Examples include a method of blending a predetermined amount of silicone oil and / or silicone oil represented by the general formula (2) and various additives added as necessary, and kneading with a kneader, a mixer, or the like. Moreover, said process may include the process of removing a solvent.
[0027]
The pressure-sensitive adhesive sheet for surface protection of the present invention is formed by laminating a pressure-sensitive adhesive layer made of the acrylic hot-melt pressure-sensitive adhesive on one side of a polyolefin substrate.
It does not specifically limit as said polyolefin base material, For example, the plastic film etc. which consist of polyolefin resins, such as polyethylene and a polypropylene, are mentioned.
The polyolefin base material may contain an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, etc., in order to impart necessary weather resistance.
[0028]
In the surface protective pressure-sensitive adhesive sheet of the present invention, the method for laminating the pressure-sensitive adhesive layer made of an acrylic hot melt pressure-sensitive adhesive on the polyolefin base material is not particularly limited, and an ordinary extrusion method is used. Examples thereof include a method of extrusion-coating a hot melt adhesive and a method of coextruding an acrylic hot melt adhesive and a polyolefin substrate (coextrusion method). Especially, it is preferable that the adhesive sheet for surface protection of this invention coextrudes an acrylic hot-melt adhesive and a polyolefin base material. In the method by coextrusion, the production apparatus and the production process are simple, and the production efficiency is good. Furthermore, the pressure-sensitive adhesive sheet for surface protection obtained by the method by coextrusion has high lamination strength.
[0029]
Since the pressure-sensitive adhesive sheet for surface protection of the present invention contains an olefin skeleton in the pressure-sensitive adhesive layer and the acrylic component and the olefin skeleton exhibiting adhesiveness are chemically bonded, the pressure-sensitive adhesive layer and the polyolefin base material Good adhesion. In addition, since the silicone oil represented by the general formula (1) and / or the silicone oil represented by the general formula (2) is included, the adhesive does not remain on the surface of the adherend, The adhesiveness to the body can be adjusted, and the peelability becomes good. Furthermore, since the pressure-sensitive adhesive layer is acrylic, weather resistance is excellent.
[0030]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
[0031]
Example 1
In a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, 492 g of butyl acrylate (BA), 20 g of acrylic acid, and an olefin polymer having an epoxy group at one end (KRATON LIQUID Polymer L) -1253, 120 g of 50% toluene solution of Shell Chemical Company, a polymer having a radical polymerizable unsaturated double bond at the end (trade name: AA-6, molecular weight 6000, glass transition temperature 102 ° C., Tojo 90 g of Synthesizer Co., Ltd. and 450.91 g of toluene as a polymerization solvent were charged and mixed with stirring to obtain a monomer mixed solution.
[0032]
After the dissolved oxygen was removed by bubbling the monomer mixture solution with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas, and the monomer was stirred using a water bath while stirring at 100 rpm. The mixed solution was heated. When the reflux liquid is confirmed in the cooling pipe, 0.30 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation) is used as a polymerization initiator. Polymerization was initiated by dissolving in about 1 g of ethyl acetate and charging. After 1 hour, 0.60 g of Perhexa TMH was again dissolved in about 1 g of ethyl acetate and charged. In addition, 0.60 g, 1.20 g and 1.80 g of di (3,5,5-trimethylhexanoyl) peroxide (Perroyl 355, manufactured by NOF Corporation) were added to about 1 g of acetic acid after 2, 3 and 4 hours from the start of polymerization. Dissolved in ethyl and added. Polymerization was performed for 8 hours to obtain an acrylic copolymer solution.
[0033]
Next, an epoxy group-containing silicone oil (trade name: X-22-3667, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the acrylic copolymer solution obtained above by 0.3 weight with respect to 100 parts by weight of the acrylic copolymer. The acrylic hot melt pressure-sensitive adhesive was obtained by removing the solvent at 200 ° C.
[0034]
Examples 2-3
An acrylic hot melt pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the amount of the epoxy group-containing silicone oil (trade name: X-22-3667, manufactured by Shin-Etsu Chemical Co., Ltd.) was as shown in Table 1. Obtained.
[0035]
Example 4
As an epoxy group-containing silicone oil, the product name “X-22-173B” (manufactured by Shin-Etsu Chemical Co., Ltd.) was used, and the amount of blending was as shown in Table 1. A melt adhesive was obtained.
[0036]
Comparative Example 1
The acrylic copolymer solution obtained in Example 1 was used as it was.
[0037]
Comparative Examples 2-3
An acrylic hot melt pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the trade name “KF-412” (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silicone oil and the blending amount thereof was as shown in Table 1. .
[0038]
(Preparation of adhesive sheet for surface protection)
The acrylic hot melt pressure-sensitive adhesives obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were extruded with a linear low density polyethylene (manufactured by Mitsubishi Kasei Co., Ltd., trade name: HY540) by a two-layer coextrusion method, and the thickness was 50 μm. A pressure-sensitive adhesive sheet for surface protection obtained by laminating a 10 μm pressure-sensitive adhesive layer on the linear low-density polyethylene was obtained.
[0039]
(Evaluation)
About the obtained adhesive sheet for surface protection, the following item was evaluated. The results are shown in Table 1.
(Initial adhesive strength)
In accordance with JIS Z 0237, the surface protective adhesive sheet was bonded to a SUS304 plate with a width of 25 mm, left at 23 ° C. for 20 minutes, and then peeled off at 180 ° direction and at a pulling speed of 300 mm / min. The strength was measured.
[0040]
(Heat resistant adhesive strength)
In accordance with JIS Z 0237, the surface protective adhesive sheet was bonded to a SUS304 plate with a width of 25 mm, left at 80 ° C. for 7 days, then peeled off at 180 ° direction and at a pulling speed of 300 mm / min. The strength was measured.
[0041]
(Weatherability)
The surface-protective pressure-sensitive adhesive sheet was bonded to a SUS304 plate with a width of 25 mm according to JIS Z 0237, and subjected to an accelerated weathering test (black panel temperature: 63 ° C.) with a sunshine weather meter (WOM) for 300 hours, followed by peeling. And the peeling form was observed.
[0042]
(Printability)
A line was drawn with a water-based ballpoint pen on the SUS plate after the measurement of heat-resistant adhesive force, and the repelling of the water-based ink was observed.
○: Not repelling △: Slightly repelling ×: Unable to draw [0043]
[Table 1]
From Table 1, the adhesive sheet for surface protection produced in Examples 1 to 4 had appropriate initial adhesive force and heat-resistant adhesive force, and had no adhesive residue when peeled from the adherend. Furthermore, the printability of the adherend after peeling was good. The adhesive sheet for surface protection of Comparative Examples 1 to 3 in which the silicone oil represented by the general formula (1) or the general formula (2) was not added did not have appropriate initial adhesive strength and heat-resistant adhesive strength. Moreover, neither the weather resistance nor the printability of the adherend after peeling was excellent.
[0045]
【The invention's effect】
Since the adhesive sheet for surface protection of the present invention has the above-mentioned configuration, it can be re-peeled without any adhesive residue even after being attached to an adherend such as a metal plate or a coated steel plate and stored for a long period of time. High weather resistance. Moreover, the printability of the surface of the adherend is not lowered even after re-peeling.
Claims (3)
前記アクリル系ホットメルト粘着剤は、末端に反応性基を有するオレフィン重合体（ａ）とアクリルモノマーとを共重合させてなるアクリル系共重合体（ｂ）に、下記一般式（１）で表されるシリコーンオイル及び／又は下記一般式（２）で表されるシリコーンオイルが添加されてなり、
前記アクリル系共重合体（ｂ）は、前記末端に反応性基を有するオレフィン重合体（ａ）がグラフト結合してなる側鎖を有するグラフト共重合体であり、
下記一般式（１）で表されるシリコーンオイル及び／又は下記一般式（２）で表されるシリコーンオイルの添加量は、前記アクリル系共重合体（ｂ）１００重量部に対して、０．１〜７重量部である
ことを特徴とする表面保護用粘着シート。
The acrylic hot melt pressure-sensitive adhesive is represented by the following general formula (1) to an acrylic copolymer (b) obtained by copolymerizing an olefin polymer (a) having a reactive group at a terminal and an acrylic monomer. Ri Na is added silicone oils and / or silicone oil represented by the following general formula (2) is found
The acrylic copolymer (b) is a graft copolymer having a side chain formed by grafting the olefin polymer (a) having a reactive group at the terminal,
The addition amount of the silicone oil represented by the following general formula (1) and / or the silicone oil represented by the following general formula (2) is 0. 1-7 the pressure-sensitive adhesive sheet for surface protection, characterized in parts der Rukoto.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000082495A JP4555427B2 (en) | 1999-09-29 | 2000-03-23 | Surface protection adhesive sheet |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-276727 | 1999-09-29 | ||
| JP27672799 | 1999-09-29 | ||
| JP2000082495A JP4555427B2 (en) | 1999-09-29 | 2000-03-23 | Surface protection adhesive sheet |
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| Publication Number | Publication Date |
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| JP2001164211A JP2001164211A (en) | 2001-06-19 |
| JP4555427B2 true JP4555427B2 (en) | 2010-09-29 |
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| JP2000082495A Expired - Fee Related JP4555427B2 (en) | 1999-09-29 | 2000-03-23 | Surface protection adhesive sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003014247A1 (en) * | 2001-08-10 | 2003-02-20 | Cosmed. Co., Ltd. | Pressure-sensitive adhesive for the skin and tapes or sheets for the skin made by using the same |
| JP2005297546A (en) * | 2004-03-17 | 2005-10-27 | Osaka Gas Co Ltd | Hot melt adhesive handling member |
| JP5399312B2 (en) * | 2010-04-26 | 2014-01-29 | 日東電工株式会社 | Adhesive sheet |
| WO2024095971A1 (en) * | 2022-10-31 | 2024-05-10 | 積水化学工業株式会社 | Pressure-sensitive adhesive agent composition and pressure-sensitive adhesive tape |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5813117A (en) * | 1981-07-15 | 1983-01-25 | Honda Motor Co Ltd | Control device for secondary air supply in exhaust gas purifier device of internal combustion engine |
| JPH02167380A (en) * | 1988-08-01 | 1990-06-27 | E I Du Pont De Nemours & Co | Hot-melt, pressure-sensitive acrylic |
| JPH03243679A (en) * | 1990-02-19 | 1991-10-30 | Sekisui Chem Co Ltd | Acrylic adhesive composition and adhesive tape, lavel, sheet |
| JPH05306380A (en) * | 1991-11-20 | 1993-11-19 | Sekisui Chem Co Ltd | Hotmelt tacky agent composition and tacky tape, label or sheet coated therewith |
| JPH10140075A (en) * | 1996-11-12 | 1998-05-26 | Toagosei Co Ltd | Composition for coating |
-
2000
- 2000-03-23 JP JP2000082495A patent/JP4555427B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5813117A (en) * | 1981-07-15 | 1983-01-25 | Honda Motor Co Ltd | Control device for secondary air supply in exhaust gas purifier device of internal combustion engine |
| JPH02167380A (en) * | 1988-08-01 | 1990-06-27 | E I Du Pont De Nemours & Co | Hot-melt, pressure-sensitive acrylic |
| JPH03243679A (en) * | 1990-02-19 | 1991-10-30 | Sekisui Chem Co Ltd | Acrylic adhesive composition and adhesive tape, lavel, sheet |
| JPH05306380A (en) * | 1991-11-20 | 1993-11-19 | Sekisui Chem Co Ltd | Hotmelt tacky agent composition and tacky tape, label or sheet coated therewith |
| JPH10140075A (en) * | 1996-11-12 | 1998-05-26 | Toagosei Co Ltd | Composition for coating |
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| JP2001164211A (en) | 2001-06-19 |
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