JP2020142440A - Laminate and adhesive tape - Google Patents
Laminate and adhesive tape Download PDFInfo
- Publication number
- JP2020142440A JP2020142440A JP2019040784A JP2019040784A JP2020142440A JP 2020142440 A JP2020142440 A JP 2020142440A JP 2019040784 A JP2019040784 A JP 2019040784A JP 2019040784 A JP2019040784 A JP 2019040784A JP 2020142440 A JP2020142440 A JP 2020142440A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- adhesive tape
- weight
- molecular weight
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 92
- 239000002998 adhesive polymer Substances 0.000 claims abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 68
- 239000011521 glass Substances 0.000 claims abstract description 64
- 239000012790 adhesive layer Substances 0.000 claims abstract description 21
- 239000010410 layer Substances 0.000 claims description 64
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 49
- 239000006260 foam Substances 0.000 claims description 41
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 22
- 229920000058 polyacrylate Polymers 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 18
- 239000004840 adhesive resin Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- 239000000243 solution Substances 0.000 description 29
- 238000005259 measurement Methods 0.000 description 25
- 239000003431 cross linking reagent Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- -1 polytetrafluoroethylene Polymers 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- 238000010526 radical polymerization reaction Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000012948 isocyanate Substances 0.000 description 14
- 150000002513 isocyanates Chemical class 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- 238000006073 displacement reaction Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 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 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 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 6
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- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 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 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 5
- 241000040709 Boraras Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920013716 polyethylene resin Polymers 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012987 RAFT agent Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
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- 150000003498 tellurium compounds Chemical class 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、ガラスと樹脂部材とを粘着テープで接合した積層体及び該積層体を形成するための粘着テープに関する。 The present invention relates to a laminate in which glass and a resin member are bonded with an adhesive tape, and an adhesive tape for forming the laminate.
画像表示装置又は入力装置を搭載した携帯電子機器（例えば、携帯電話、携帯情報端末等）においては、組み立てのために両面粘着テープが用いられている。具体的には、例えば、携帯電子機器の表面を保護するためのカバーパネルをタッチパネルモジュール又はディスプレイパネルモジュールに接着したり、タッチパネルモジュールとディスプレイパネルモジュールとを接着したりするために両面粘着テープが用いられている。このような両面粘着テープは、例えば、額縁状等の形状に打ち抜かれ、表示画面の周辺に配置されるようにして用いられる（例えば、特許文献１、２）。また、車両部品（例えば、車載用パネル）を車両本体に固定する用途にも両面粘着テープが用いられている。 In portable electronic devices equipped with image display devices or input devices (for example, mobile phones, personal digital assistants, etc.), double-sided adhesive tapes are used for assembly. Specifically, for example, a double-sided adhesive tape is used to bond a cover panel for protecting the surface of a portable electronic device to a touch panel module or a display panel module, or to bond a touch panel module and a display panel module. Has been done. Such a double-sided adhesive tape is used, for example, by being punched into a shape such as a frame shape and arranged around a display screen (for example, Patent Documents 1 and 2). Double-sided adhesive tape is also used for fixing vehicle parts (for example, in-vehicle panels) to the vehicle body.
一方、車両の生産において、フロントガラスやサイドガラス等の車両用ガラスは接着剤によって車両のフレームに固定されている。この際、接着剤が完全に硬化するまでの間ガラスが接着位置からずれないようにするために、ガラスを樹脂部材と接着し、樹脂部材を介してガラスを車両のフレームに仮固定している。ここで、図１、２に仮固定の様子を表した模式図を示した。図１、２では例として自動車のフロントガラスを固定する様子を示している。図１、２に示すように、フロントガラス１を自動車のフレーム３に固定する際は、まず、フロントガラス１と樹脂部材２を接着する。樹脂部材２のフロントガラス１と対向する面とは反対側の面には突起が設けられており、この突起と対応する穴がフレーム３に開けられている。フロントガラス１と樹脂部材２の接着後、フロントガラス１の端部領域に接着剤４を塗り、樹脂部材２の突起をフレーム３に開けられた穴に差し込むことでフロントガラス１とフレーム３が仮固定される。その後接着剤が硬化すると、フロントガラス１とフレーム３は完全に固定される。
On the other hand, in the production of vehicles, vehicle glass such as windshields and side glasses is fixed to the frame of the vehicle by an adhesive. At this time, in order to prevent the glass from shifting from the bonding position until the adhesive is completely cured, the glass is adhered to the resin member, and the glass is temporarily fixed to the vehicle frame via the resin member. .. Here, FIGS. 1 and 2 show schematic views showing the state of temporary fixing. FIGS. 1 and 2 show how the windshield of an automobile is fixed as an example. As shown in FIGS. 1 and 2, when fixing the windshield 1 to the
従来の車両の製造では、ガラスと上記樹脂部材の接着にも接着剤を用いている。しかしながら、接着剤は乾燥までに時間を要することから生産効率が悪いという問題がある。そこで、ガラスと樹脂部材とを粘着テープで固定することが検討されたが、ガラスがフロントガラスのような大型で重いものである場合、粘着テープがガラスの重量に耐えきれず、粘着テープがずれてしまったり、剥がれたりしてしまうという問題がある。 In conventional vehicle manufacturing, an adhesive is also used to bond the glass and the resin member. However, the adhesive has a problem of poor production efficiency because it takes time to dry. Therefore, it was considered to fix the glass and the resin member with adhesive tape, but when the glass is large and heavy like a windshield, the adhesive tape cannot withstand the weight of the glass and the adhesive tape shifts. There is a problem that it will be peeled off or peeled off.
本発明は、上記現状に鑑み、ガラスと樹脂部材とを粘着テープで接合した積層体であって、大型のガラスを用いた場合であっても粘着テープの剥がれやずれが生じ難い積層体及び該積層体を形成するための粘着テープを提供することを目的とする。 In view of the above situation, the present invention is a laminate in which glass and a resin member are bonded with an adhesive tape, and the adhesive tape is unlikely to peel off or slip even when a large glass is used. It is an object of the present invention to provide an adhesive tape for forming a laminate.
本発明は、ガラス、粘着テープ及び樹脂部材がこの順番に積層した積層体であって、前記粘着テープは粘着ポリマーを含有する粘着剤層を有し、前記粘着ポリマーは、数平均分子量が３０万以上、重量平均分子量が５０万以上である、積層体である。
以下に本発明を詳述する。
The present invention is a laminate in which glass, an adhesive tape, and a resin member are laminated in this order. The adhesive tape has an adhesive layer containing an adhesive polymer, and the adhesive polymer has a number average molecular weight of 300,000. As described above, the laminated body has a weight average molecular weight of 500,000 or more.
The present invention will be described in detail below.
本発明の積層体は、ガラス、粘着テープ及び樹脂部材がこの順番に積層した積層体である。上記積層体としては、例えば、車両のガラス部材を車両のフレームに固定する際に用いる積層体や、はめ殺しの窓の取り付けにおいてガラス窓と窓枠とを固定する際に用いる積層体等が挙げられる。 The laminate of the present invention is a laminate in which glass, adhesive tape, and a resin member are laminated in this order. Examples of the laminate include a laminate used when fixing the glass member of the vehicle to the frame of the vehicle, a laminate used when fixing the glass window and the window frame in the installation of the fitting window, and the like. Be done.
上記粘着テープは粘着ポリマーを含有する粘着剤層を有し、上記粘着ポリマーは、数平均分子量が３０万以上、重量平均分子量が５０万以上である。本発明の積層体は、粘着剤層に上記範囲の数平均分子量及び重量平均分子量を有する粘着ポリマーを用いることで、ガラスが大型で重い場合であっても、粘着テープのずれや剥がれを起こり難くすることができる。
上記数平均分子量の好ましい下限は３５万、より好ましい下限は４０万、更に好ましい下限は４５万、特に好ましい下限は５０万である。上記数平均分子量の上限は特に限定されないが、被着体への濡れ性の観点から、１５０万以下であることが好ましい。
上記重量平均分子量の好ましい下限は５２万、より好ましい下限は５５万、更に好ましい下限は６０万、特に好ましい下限は７０万、とりわけ好ましい下限は８０万である。上記重量平均分子量の上限は特に限定されないが、被着体への濡れ性の観点から、２００万以下であることが好ましい。
なお、上記数平均分子量及び重量平均分子量は、ゲルパミエーションクロマトグラフィ（ＧＰＣ）法によりポリスチレン換算分子量として測定される。具体的には、以下の方法で測定することができる。
まず、粘着ポリマーをテトラヒドロフラン（ＴＨＦ）によって５０倍希釈して得られた希釈液を、ポア径０．２μｍのポリテトラフルオロエチレン製フィルターで濾過する。次いで、得られた濾液について、測定機としてｅ２６９５ Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｕｌｅ（Ｗａｔｅｒｓ社製）、検出器として示差屈折計（２４１４、Ｗａｔｅｒｓ社製）、カラムとしてＧＰＣ ＫＦ−８０６Ｌ（昭和電工社製）を用いて、サンプル流量：１ｍＬ／ｍｉｎ、カラム温度：４０℃の条件でＧＰＣ測定を行う。
The pressure-sensitive adhesive tape has a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive polymer, and the pressure-sensitive adhesive polymer has a number average molecular weight of 300,000 or more and a weight average molecular weight of 500,000 or more. In the laminate of the present invention, by using an adhesive polymer having a number average molecular weight and a weight average molecular weight in the above range for the adhesive layer, the adhesive tape is less likely to be displaced or peeled off even when the glass is large and heavy. can do.
The preferable lower limit of the number average molecular weight is 350,000, the more preferable lower limit is 400,000, the more preferable lower limit is 450,000, and the particularly preferable lower limit is 500,000. The upper limit of the number average molecular weight is not particularly limited, but is preferably 1.5 million or less from the viewpoint of wettability to the adherend.
The preferable lower limit of the weight average molecular weight is 520,000, the more preferable lower limit is 550,000, the further preferable lower limit is 600,000, the particularly preferable lower limit is 700,000, and the particularly preferable lower limit is 800,000. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 2 million or less from the viewpoint of wettability to the adherend.
The number average molecular weight and the weight average molecular weight are measured as polystyrene-equivalent molecular weights by a gel permeation chromatography (GPC) method. Specifically, it can be measured by the following method.
First, the diluted solution obtained by diluting the adhesive polymer 50 times with tetrahydrofuran (THF) is filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.2 μm. Next, with respect to the obtained filtrate, an e2695 Separations Module (manufactured by Waters) was used as a measuring machine, a differential refractometer (2414, manufactured by Waters) was used as a detector, and GPC KF-806L (manufactured by Showa Denko) was used as a column. GPC measurement is performed under the conditions of sample flow rate: 1 mL / min and column temperature: 40 ° C.
上記粘着ポリマーは、上記数平均分子量及び重量平均分子量の範囲を満たしていれば特に限定されず、例えば、アクリル系ポリマー、ゴム系ポリマー、ウレタン系ポリマー、シリコン系ポリマー、及びポリエステル系ポリマー等が挙げられる。中でも、上記数平均分子量及び重量平均分子量の範囲を満たしやすいことから、粘着ポリマーはアクリル系ポリマーを含有することが好ましく、アクリル系ポリマーであることがより好ましく、原料モノマーとしてブチルアクリレート用いたアクリル系ポリマーであることが更に好ましい。また上記粘着ポリマーの構造は特に限定されず、ランダム共重合体でも、ブロック共重合体でも良い。 The adhesive polymer is not particularly limited as long as it satisfies the range of the number average molecular weight and the weight average molecular weight, and examples thereof include acrylic polymers, rubber polymers, urethane polymers, silicon polymers, and polyester polymers. Be done. Among them, since it is easy to satisfy the ranges of the number average molecular weight and the weight average molecular weight, the adhesive polymer preferably contains an acrylic polymer, more preferably an acrylic polymer, and an acrylic polymer using butyl acrylate as a raw material monomer. It is more preferably a polymer. The structure of the adhesive polymer is not particularly limited, and may be a random copolymer or a block copolymer.
上記アクリル系ポリマーが原料モノマーとしてブチルアクリレートを用いたアクリル系ポリマーである場合、上記アクリル系ポリマーは、原料モノマー中にブチルアクリレートを２０重量％以上含有することが好ましい。
原料モノマー中にブチルアクリレートを２０重量％以上含有することで、より粘着力に優れ、ずれや剥がれが起き難い粘着テープとすることができる。粘着テープのずれや剥がれをさらに抑制できる観点から、上記原料モノマー中のブチルアクリレートの含有量は２５重量％以上であることがより好ましく、５０重量％以上であることが更に好ましい。上記原料モノマー中のブチルアクリレートの含有量の上限は特に限定されず、原料モノマーの全量がブチルアクリレートであってもよい。上記アクリル系ポリマーが原料モノマーとしてブチルアクリレートを用いたアクリル系ポリマーである場合、上記アクリル系ポリマーは、原料モノマー中にブチルアクリレートを、通常１００重量％以下、例えば９９重量％以下含有する。
When the acrylic polymer is an acrylic polymer using butyl acrylate as a raw material monomer, the acrylic polymer preferably contains 20% by weight or more of butyl acrylate in the raw material monomer.
By containing 20% by weight or more of butyl acrylate in the raw material monomer, it is possible to obtain an adhesive tape having more excellent adhesive strength and less likely to be displaced or peeled off. From the viewpoint of further suppressing the displacement and peeling of the adhesive tape, the content of the butyl acrylate in the raw material monomer is more preferably 25% by weight or more, and further preferably 50% by weight or more. The upper limit of the content of butyl acrylate in the raw material monomer is not particularly limited, and the total amount of the raw material monomer may be butyl acrylate. When the acrylic polymer is an acrylic polymer using butyl acrylate as a raw material monomer, the acrylic polymer usually contains butyl acrylate in the raw material monomer in an amount of 100% by weight or less, for example, 99% by weight or less.
上記アクリル系ポリマーが原料モノマーとしてブチルアクリレートを用いたアクリル系ポリマーである場合、上記アクリル系ポリマーは、原料モノマーとして必要に応じてブチルアクリレート以外の他の重合性モノマーを含んでいてもよい。
上他の重合性モノマーとして、例えば、２−エチルヘキシルアクリレート、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル等のアルキル基の炭素数が１〜３の（メタ）アクリル酸アルキルエステル、メタクリル酸トリデシル、（メタ）アクリル酸ステアリル等のアルキル基の炭素数が１３〜１８の（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸ヒドロキシアルキル、グリセリンジメタクリレート、（メタ）アクリル酸グリシジル、２−メタクリロイルオキシエチルイソシアネート、（メタ）アクリル酸、イタコン酸、無水マレイン酸、クロトン酸、マレイン酸、フマル酸、等の官能性モノマーが挙げられる。
When the acrylic polymer is an acrylic polymer using butyl acrylate as a raw material monomer, the acrylic polymer may contain a polymerizable monomer other than butyl acrylate as a raw material monomer, if necessary.
As other polymerizable monomers, carbons of alkyl groups such as 2-ethylhexyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Alkyl esters of (meth) acrylic acid having 13 to 18 carbon atoms, hydroxy (meth) acrylic acid, such as alkyl esters of (meth) acrylic acid having numbers 1 to 3, tridecyl methacrylate, and stearyl (meth) acrylate. Functional monomers such as alkyl, glycerin dimethacrylate, glycidyl (meth) acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, maleic acid, fumaric acid and the like can be mentioned. ..
上記粘着ポリマーを得るには、原料モノマーを、重合開始剤の存在下にてラジカル反応させればよい。上記モノマー混合物をラジカル反応させる方法、即ち、重合方法としては、従来公知の方法が用いられ、例えば、溶液重合（沸点重合又は定温重合）、乳化重合、懸濁重合、塊状重合等が挙げられる。
上記重合開始剤は特に限定されず、例えば、有機過酸化物、アゾ化合物等が挙げられる。上記有機過酸化物として、例えば、１，１−ビス（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、ｔ−ヘキシルパーオキシピバレート、ｔ−ブチルパーオキシピバレート、２，５−ジメチル−２，５−ビス（２−エチルヘキサノイルパーオキシ）ヘキサン、ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシラウレート等が挙げられる。上記アゾ化合物として、例えば、アゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル等が挙げられる。これらの重合開始剤は単独で用いてもよいし、２種以上を併用してもよい。
In order to obtain the above-mentioned adhesive polymer, the raw material monomer may be radically reacted in the presence of a polymerization initiator. As a method of radically reacting the monomer mixture, that is, a polymerization method, a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, and bulk polymerization.
The above-mentioned polymerization initiator is not particularly limited, and examples thereof include organic peroxides and azo compounds. Examples of the organic peroxide include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5. -Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Examples thereof include isobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate and t-butylperoxylaurate. Examples of the azo compound include azobisisobutyronitrile and azobiscyclohexanecarbonitrile. These polymerization initiators may be used alone or in combination of two or more.
上記粘着ポリマーはリビングラジカル重合によって得てもよい。
リビングラジカル重合は、重合反応が停止反応又は連鎖移動反応等の副反応で妨げられることなく分子鎖が生長していく重合である。リビングラジカル重合によれば、例えばフリーラジカル重合等と比較してより均一な分子量及び組成を有するポリマーが得られ、低分子量成分等の生成を抑えることができるため、高温下でも粘着剤組成物が剥がれにくくなる。また、均一かつ大きな分子量のポリマーが得られることから、得られる粘着ポリマーが上記数平均分子量及び重量平均分子量の範囲を満たしやすくなる。
The adhesive polymer may be obtained by living radical polymerization.
Living radical polymerization is a polymerization in which a molecular chain grows without being hindered by a side reaction such as a termination reaction or a chain transfer reaction. According to the living radical polymerization, a polymer having a more uniform molecular weight and composition as compared with, for example, free radical polymerization can be obtained, and the formation of low molecular weight components and the like can be suppressed, so that the pressure-sensitive adhesive composition can be obtained even at high temperatures. It becomes difficult to peel off. Further, since a polymer having a uniform and large molecular weight can be obtained, the obtained adhesive polymer can easily satisfy the ranges of the number average molecular weight and the weight average molecular weight.
リビングラジカル重合は一般的に用いられるものであれば特に限定されず、ＴＥＲＰ法、ＲＡＦＴ法、ＮＭＰ法等が挙げられる。ＴＥＲＰ法においては有機テルル化合物、ＲＡＦＴ法においてはＲＡＦＴ剤、ＮＭＰ法においてはニトロキシド化合物が用いられ、必要に応じてラジカル重合開始剤を組み合わせて使用する。 The living radical polymerization is not particularly limited as long as it is generally used, and examples thereof include a TERP method, a RAFT method, and an NMP method. An organic tellurium compound is used in the TERP method, a RAFT agent is used in the RAFT method, and a nitroxide compound is used in the NMP method, and a radical polymerization initiator is used in combination as necessary.
上記有機テルル化合物として、例えば、２−メチル−２−ｎ−ブチルテラニル−プロピオン酸、（メチルテラニル−メチル）ベンゼン、１−クロロ−４−（メチルテラニル−メチル）ベンゼン、１−ヒドロキシ−４−（メチルテラニル−メチル）ベンゼン、１−フェノキシカルボニル−４−（２−メチルテラニル−プロピル）ベンゼンが挙げられる。
ＲＡＦＴ剤として、例えば、Ｓ−シアノメチル−Ｓ−ドデシルトリチオ炭酸、ジチオ安息香酸２−シアノ−２−プロピル、Ｓ−（２−シアノ−２−プロピル）−Ｓ−ドデシルトリチオ炭酸、２−メチル−２−［（ドデシルスルファニルチオカルボニル）スルファニル］プロパン酸が挙げられる。
ニトロキシド化合物として、例えば、ジ−ｔｅｒｔ−ブチル−ニトロキシド、４−カルボキシ−２，２，６，６−テトラメチルピペリジン１−オキシル、テトラメチル−イソインドリン−１−オキシル、テトラエチル−イソインドリン−１−オキシル、Ｎ−ｔｅｒｔ−ブチル−Ｎ−［１−ジエチルフォスフォノ−（２，２−ジメチルプロピル）］ニトロキシド、２，２，５−トリメチル−４−フェニル−３−アザヘキサン−３−ニトロキシド等が挙げられる。
Examples of the organic tellurium compound include 2-methyl-2-n-butylteranyl-propionic acid, (methylteranyl-methyl) benzene, 1-chloro-4- (methylteranyl-methyl) benzene, and 1-hydroxy-4- (methylteranyl-). Examples thereof include methyl) benzene and 1-phenoxycarbonyl-4- (2-methylteranyl-propyl) benzene.
Examples of RAFT agents include S-cyanomethyl-S-dodecyltrithiocarbonate, 2-cyano-2-propyl dithiobenzoate, S- (2-cyano-2-propyl) -S-dodecyltrithiocarbonate, 2-methyl. -2-[(dodecylsulfanilthiocarbonyl) sulfanil] propanoic acid can be mentioned.
Examples of the nitroxide compound include di-tert-butyl-nitroxide, 4-carboxy-2,2,6,6-tetramethylpiperidin1-oxyl, tetramethyl-isoindoline-1-oxyl, and tetraethyl-isoindoline-1-. Oxyl, N-tert-butyl-N- [1-diethylphosphono- (2,2-dimethylpropyl)] nitroxide, 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide and the like. Be done.
上記リビングラジカル重合において、上記開始剤に加えて、重合速度の促進を目的としてアゾ化合物を用いてもよい。
上記アゾ化合物は、ラジカル重合に一般的に用いられるものであれば特に限定されず、例えば、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、１，１−アゾビス（シクロヘキサン−１−カルボニトリル）、１−［（１−シアノ−１−メチルエチル）アゾ］ホルムアミド、４，４’−アゾビス（４−シアノバレリアン酸）、ジメチル−２，２’−アゾビス（２−メチルプロピオネート）、ジメチル−１，１’−アゾビス（１−シクロヘキサンカルボキシレート）、２，２’−アゾビス｛２−メチル−Ｎ−［１，１’−ビス（ヒドロキシメチル）−２−ヒドロキシエチル］プロピオンアミド｝、２，２’−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］、２，２’−アゾビス［Ｎ−（２−プロペニル）−２−メチルプロピオンアミド］、２，２’−アゾビス（Ｎ−ブチル−２−メチルプロピオンアミド）、２，２’−アゾビス（Ｎ−シクロヘキシル−２−メチルプロピオンアミド）、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩、２，２’−アゾビス｛２−［１−（２−ヒドロキシエチル）−２−イミダゾリン−２−イル］プロパン｝二塩酸塩、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩、２，２’−アゾビス［Ｎ−（２−カルボキシエチル）−２−メチルプロピオンアミジン］四水和物、２，２’−アゾビス（１−イミノ−１−ピロリジノ−２−メチルプロパン）二塩酸塩、２，２’−アゾビス（２，４，４−トリメチルペンタン）等が挙げられる。これらのアゾ化合物は、単独で用いてもよく、２種以上を併用してもよい。
In the living radical polymerization, in addition to the initiator, an azo compound may be used for the purpose of promoting the polymerization rate.
The azo compound is not particularly limited as long as it is generally used for radical polymerization, and for example, 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-methylbutyronitrile). ), 2,2'-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile) ), 1-[(1-Cyano-1-methylethyl) azo] formamide, 4,4'-azobis (4-cyanovalerian acid), dimethyl-2,2'-azobis (2-methylpropionate), Dimethyl-1,1'-azobis (1-cyclohexanecarboxylate), 2,2'-azobis {2-methyl-N- [1,1'-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'- Azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (2- (2-) Imidazolin-2-yl) propane], 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine] tetrahydrate Examples thereof include 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2'-azobis (2,4,4-trimethylpentane) and the like. These azo compounds may be used alone or in combination of two or more.
上記リビングラジカル重合においては、分散安定剤を用いてもよい。上記分散安定剤として、例えば、ポリビニルピロリドン、ポリビニルアルコール、メチルセルロース、エチルセルロース、ポリ（メタ）アクリル酸、ポリ（メタ）アクリル酸エステル、ポリエチレングリコール等が挙げられる。 A dispersion stabilizer may be used in the above-mentioned living radical polymerization. Examples of the dispersion stabilizer include polyvinylpyrrolidone, polyvinyl alcohol, methyl cellulose, ethyl cellulose, poly (meth) acrylic acid, poly (meth) acrylic acid ester, polyethylene glycol and the like.
上記リビングラジカル重合の方法としては、従来公知の方法が用いられ、例えば、溶液重合（沸点重合又は定温重合）、乳化重合、懸濁重合、塊状重合等が挙げられる。
上記リビングラジカル重合において重合溶媒を用いる場合、該重合溶媒は特に限定されない。上記重合溶媒としては、例えば、ヘキサン、シクロヘキサン、オクタン、トルエン、キシレン等の非極性溶媒や、水、メタノール、エタノール、プロパノール、ブタノール、アセトン、メチルエチルケトン、メチルイソブチルケトン、テトラヒドロフラン、ジオキサン、Ｎ，Ｎ−ジメチルホルムアミド等の高極性溶媒を用いることができる。これらの重合溶媒は、単独で用いてもよく、２種以上を併用してもよい。
また、重合温度は、重合速度の観点から０〜１１０℃が好ましい。
As the method of the living radical polymerization, a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
When a polymerization solvent is used in the living radical polymerization, the polymerization solvent is not particularly limited. Examples of the polymerization solvent include non-polar solvents such as hexane, cyclohexane, octane, toluene and xylene, water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, N, N-. A highly polar solvent such as dimethylformamide can be used. These polymerization solvents may be used alone or in combination of two or more.
The polymerization temperature is preferably 0 to 110 ° C. from the viewpoint of the polymerization rate.
上記粘着剤層は、粘着付与樹脂を含有してもよい。
上記粘着付与樹脂として、例えば、ロジンエステル系樹脂、水添ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、脂環族飽和炭化水素系樹脂、Ｃ５系石油樹脂、Ｃ９系石油樹脂、Ｃ５−Ｃ９共重合系石油樹脂等が挙げられる。これらの粘着付与樹脂は単独で用いてもよいし、２種以上を併用してもよい。
The pressure-sensitive adhesive layer may contain a pressure-imparting resin.
Examples of the tackifier resin include rosin ester resin, hydrogenated rosin resin, terpen resin, terpenphenol resin, kumaron inden resin, alicyclic saturated hydrocarbon resin, C5 petroleum resin, and C9 resin. Examples thereof include petroleum resins and C5-C9 copolymerized petroleum resins. These tackifier resins may be used alone or in combination of two or more.
上記粘着付与樹脂の含有量は特に限定されないが、粘着力を向上させて粘着テープのずれや剥がれをより抑制する観点から、上記粘着ポリマー１００重量部に対する好ましい下限は１０重量部、好ましい上限は６０重量部である。 The content of the pressure-sensitive adhesive resin is not particularly limited, but from the viewpoint of improving the adhesive strength and further suppressing the displacement and peeling of the adhesive tape, the preferable lower limit is 10 parts by weight and the preferable upper limit is 60 parts by weight with respect to 100 parts by weight of the adhesive polymer. It is a part by weight.
上記粘着剤層は架橋剤を含有していてもよい。
上記架橋剤は特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、イソシアネート系架橋剤が好ましい。
The pressure-sensitive adhesive layer may contain a cross-linking agent.
The above-mentioned cross-linking agent is not particularly limited, and examples thereof include an isocyanate-based cross-linking agent, an aziridine-based cross-linking agent, an epoxy-based cross-linking agent, and a metal chelate-type cross-linking agent. Of these, isocyanate-based cross-linking agents are preferable.
上記架橋剤の含有量は特に限定されないが、上記粘着ポリマー１００重量部に対して０．０１〜１５重量部が好ましく、０．１〜１０重量部がより好ましい。 The content of the cross-linking agent is not particularly limited, but is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the adhesive polymer.
上記粘着剤層はゲル分率が１０％以上であることが好ましい。
上記粘着剤層のゲル分率が１０％以上であることで、粘着テープのずれや剥がれをより抑えることができる。粘着テープのずれや剥がれをさらに抑制できる観点から、上記粘着剤層のゲル分率のより好ましい下限は２０％、更に好ましい下限は３０％、更により好ましい下限は４０％、特に好ましい下限は５０％、とりわけ好ましい下限は６０％である。上記粘着剤層のゲル分率の上限は特に限定されないが、粘着力をより向上させる観点から９５％であることが好ましい。
The pressure-sensitive adhesive layer preferably has a gel fraction of 10% or more.
When the gel fraction of the pressure-sensitive adhesive layer is 10% or more, it is possible to further suppress the slippage and peeling of the pressure-sensitive adhesive tape. From the viewpoint of further suppressing the displacement and peeling of the adhesive tape, the more preferable lower limit of the gel fraction of the pressure-sensitive adhesive layer is 20%, the further preferable lower limit is 30%, the further preferable lower limit is 40%, and the particularly preferable lower limit is 50%. A particularly preferable lower limit is 60%. The upper limit of the gel fraction of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 95% from the viewpoint of further improving the adhesive strength.
上記粘着剤層の厚みは特に限定されないが、好ましい下限は５μｍ、好ましい上限は５００μｍである。上記粘着剤層の厚みをこの範囲内とすることにより、粘着テープのずれや剥がれをより抑えることができる。粘着テープのずれや剥がれをさらに抑制できる観点から、上記樹脂層の厚みのより好ましい下限は１０μｍ、より好ましい上限は４００μｍである。 The thickness of the pressure-sensitive adhesive layer is not particularly limited, but a preferable lower limit is 5 μm and a preferable upper limit is 500 μm. By setting the thickness of the adhesive layer within this range, it is possible to further suppress the displacement and peeling of the adhesive tape. From the viewpoint of further suppressing the displacement and peeling of the adhesive tape, the more preferable lower limit of the thickness of the resin layer is 10 μm, and the more preferable upper limit is 400 μm.
上記粘着剤層は、２３℃でのせん断貯蔵弾性率Ｇ’が好ましくは１×１０５Ｐａ以上、より好ましくは２×１０５Ｐａ以上、さらに好ましくは３×１０５Ｐａ以上であり、好ましくは１×１０７Ｐａ以下、より好ましくは５×１０６Ｐａ以下、さらに好ましくは１×１０６Ｐａ以下である。
粘着剤層の２３℃でのせん断貯蔵弾性率Ｇ’が上記範囲内であると、粘着テープのずれの抑制性と被着体への貼り付け性を両立することができる。なお、２３℃でのせん断貯蔵弾性率Ｇ’とは、アイティー計測制御社製のＤＶＡ−２００等の動的粘弾性測定装置を用いて、測定周波数１Ｈｚの条件で−５０℃から２００℃まで測定を行った際の、２３℃での値のことを指す。
The pressure-sensitive adhesive layer has a shear storage elastic modulus G'at 23 ° C. of preferably 1 × 10 5 Pa or more, more preferably 2 × 10 5 Pa or more, and further preferably 3 × 10 5 Pa or more, preferably 3 × 10 5 Pa or more. It is 1 × 10 7 Pa or less, more preferably 5 × 10 6 Pa or less, and further preferably 1 × 10 6 Pa or less.
When the shear storage elastic modulus G'at 23 ° C. of the pressure-sensitive adhesive layer is within the above range, it is possible to both suppress the displacement of the pressure-sensitive adhesive tape and attach it to the adherend. The shear storage elastic modulus G'at 23 ° C is defined as -50 ° C to 200 ° C under the condition of a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device such as DVA-200 manufactured by IT Measurement Control Co., Ltd. It refers to the value at 23 ° C when the measurement is performed.
上記粘着テープは、基材を有するサポートタイプであってもよく、基材を有さないノンサポートタイプであってもよい。上記粘着テープがサポートタイプの場合、基材は特に限定されないが、発泡体であることが好ましく、上記粘着テープは、粘着剤層、発泡体層、及び粘着剤層をこの順で有することが好ましい。
上記粘着テープが発泡体層を有することで、粘着テープに柔軟性を付与することができ、ガラス及び樹脂部材の凹凸に追従してより粘着力が向上することから、粘着テープのずれや剥がれをより抑えることができる。なお、上記発泡体層の両面に有する粘着剤層は、上記粘着ポリマーが上記数平均分子量及び重量平均分子量の範囲を満たしていれば同じ組成であってもよく異なる組成であってもよい。
The adhesive tape may be a support type having a base material or a non-support type having no base material. When the adhesive tape is a support type, the base material is not particularly limited, but it is preferably a foam, and the adhesive tape preferably has an adhesive layer, a foam layer, and an adhesive layer in this order. ..
Since the adhesive tape has a foam layer, flexibility can be imparted to the adhesive tape, and the adhesive strength is further improved by following the unevenness of the glass and the resin member, so that the adhesive tape can be displaced or peeled off. It can be suppressed more. The pressure-sensitive adhesive layers provided on both sides of the foam layer may have the same composition or different compositions as long as the pressure-sensitive adhesive polymer satisfies the range of the number average molecular weight and the weight average molecular weight.
上記発泡体は、連続気泡構造を有していても独立気泡構造を有していてもよいが、独立気泡構造を有することが好ましい。上記発泡体が独立気泡構造を有することで、より優れた基材強度を発揮することができる。上記発泡体は、単層構造であっても多層構造であってもよい。 The foam may have an open cell structure or a closed cell structure, but preferably has a closed cell structure. When the foam has a closed cell structure, more excellent base material strength can be exhibited. The foam may have a single-layer structure or a multi-layer structure.
上記発泡体層を構成する材料は特に限定されず、例えば、ポリオレフィン樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリウレタン樹脂、ゴム系樹脂、アクリル樹脂、ポリイミド樹脂等が挙げられる。また、例えば、エチレンプロピレンジエンゴム（ＥＰＤＭ）等のオレフィン系エラストマー、水添スチレン系熱可塑性エラストマー（ＳＥＢＳ）等のエラストマー樹脂等が挙げられる。なかでも、気泡構造を制御しやすく優れた強度と柔軟性とを発揮できることから、ポリウレタン樹脂又はポリオレフィン樹脂が好ましく、ポリオレフィン樹脂がより好ましい。これらの樹脂は単独で用いてもよいし、２種以上を併用してもよい。 The material constituting the foam layer is not particularly limited, and examples thereof include polyolefin resin, polyamide resin, polycarbonate resin, polyester resin, polyurethane resin, rubber resin, acrylic resin, and polyimide resin. Further, for example, an olefin-based elastomer such as ethylene propylene diene rubber (EPDM) and an elastomer resin such as a hydrogenated styrene-based thermoplastic elastomer (SEBS) can be mentioned. Of these, polyurethane resin or polyolefin resin is preferable, and polyolefin resin is more preferable, because the bubble structure can be easily controlled and excellent strength and flexibility can be exhibited. These resins may be used alone or in combination of two or more.
上記ポリオレフィン樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン−酢酸ビニル共重合体等が挙げられる。なかでも、ポリエチレン樹脂が好ましい。上記ポリエチレン樹脂としては、チーグラー・ナッタ化合物、メタロセン化合物、酸化クロム化合物等の重合触媒で重合されたポリエチレン樹脂が挙げられる。 Examples of the polyolefin resin include polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer and the like. Of these, polyethylene resin is preferable. Examples of the polyethylene resin include polyethylene resins polymerized with a polymerization catalyst such as a Ziegler-Natta compound, a metallocene compound, and a chromium oxide compound.
また、上記ポリエチレン樹脂としては、直鎖状低密度ポリエチレンが好ましい。直鎖状低密度ポリエチレンを用いることにより、上記発泡体層に高い柔軟性を付与できるとともに、上記発泡体層を薄くすることができる。
上記直鎖状低密度ポリエチレンは、エチレンと必要に応じて少量のα−オレフィンとを共重合することにより得られる直鎖状低密度ポリエチレンが好ましい。この場合、エチレンの含有量は特に限定されないが、全モノマー量に対して７５重量％以上が好ましく、９０重量％以上がより好ましい。
上記α−オレフィンとして、具体的には、プロピレン、１−ブテン、１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、１−ヘプテン及び１−オクテン等が挙げられる。なかでも、炭素数４〜１０のα−オレフィンが好ましい。
Further, as the polyethylene resin, linear low density polyethylene is preferable. By using the linear low-density polyethylene, high flexibility can be imparted to the foam layer, and the foam layer can be thinned.
The linear low-density polyethylene is preferably a linear low-density polyethylene obtained by copolymerizing ethylene with a small amount of α-olefin, if necessary. In this case, the ethylene content is not particularly limited, but is preferably 75% by weight or more, more preferably 90% by weight or more, based on the total amount of monomers.
Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene. Of these, α-olefins having 4 to 10 carbon atoms are preferable.
上記発泡体層は、２５％圧縮強度が２０ｋＰａ以上１０００ｋＰａ以下であることが好ましい。
上記発泡体層の２５％圧縮強度が上記範囲であることで、粘着テープの強度を維持しながら、優れた柔軟性を発揮させることができる。粘着テープの強度および柔軟性の更なる両立の観点から、上記発泡体層の２５％圧縮強度は５０ｋＰａ以上であることがより好ましく、７０ｋＰａ以上であることが更に好ましく、８００ｋＰａ以下であることがより好ましく、６００ｋＰａ以下であることが更に好ましい。
なお、上記２５％圧縮強度は、ＪＩＳ Ｋ ６２５４に準拠した方法で測定することによって求めることができる。
The foam layer preferably has a 25% compression strength of 20 kPa or more and 1000 kPa or less.
When the 25% compression strength of the foam layer is within the above range, excellent flexibility can be exhibited while maintaining the strength of the adhesive tape. From the viewpoint of further achieving both strength and flexibility of the adhesive tape, the 25% compression strength of the foam layer is more preferably 50 kPa or more, further preferably 70 kPa or more, and more preferably 800 kPa or less. It is preferably 600 kPa or less, and more preferably 600 kPa or less.
The 25% compression strength can be determined by measuring by a method conforming to JIS K 6254.
上記発泡体層は、見かけ密度が０．０５ｇ／ｃｍ３以上０．７ｇ／ｃｍ３以下であることが好ましい。
上記発泡体層の見かけ密度をこの範囲内とすることにより、粘着テープの強度を維持しながら、優れた柔軟性を発揮させることができる。粘着テープの強度および柔軟性の更なる両立の観点から、上記発泡体層の見かけ密度は０．１ｇ／ｃｍ３以上であることがより好ましく、０．１３ｇ／ｃｍ３以上であることが更に好ましく、０．６５ｇ／ｃｍ３以下であることがより好ましく、０．６ｇ／ｃｍ３以下であることが更に好ましい。なお上記見かけ密度はＪＩＳ Ｋ ６７６７に準拠した方法で測定することができる。
The foam layer is preferably the apparent density is less than 0.05 g / cm 3 or more 0.7 g / cm 3.
By setting the apparent density of the foam layer within this range, excellent flexibility can be exhibited while maintaining the strength of the adhesive tape. From the standpoint of adhesive tape strength and flexibility Naru further compatibility, more preferably an apparent density of the foam layer is 0.1 g / cm 3 or more, further preferably 0.13 g / cm 3 or more , 0.65 g / cm 3 or less, more preferably 0.6 g / cm 3 or less. The apparent density can be measured by a method conforming to JIS K 6767.
上記発泡体層の厚みは特に限定されないが、８０μｍ以上１５００μｍ以下であることが好ましい。発泡体層の厚みが上記範囲であることで、積層体を車両のガラス部材をフレームに固定する用途や窓ガラスを窓枠に固定する用途において、粘着テープの過度な変形を抑制しつつ、ガラスと樹脂部材との接触面に曲面や凹凸があっても、ガラスおよび樹脂部材との剥がれを生じ難くすることができる。粘着テープの過度な変形の更なる抑制及びガラスと樹脂部材との剥がれの更なる抑制の観点から、上記発泡体層の厚みのより好ましい下限は９０μｍ、更に好ましい下限は１００μｍ、更により好ましい下限は１１０μｍ、特に好ましい下限は１２０μｍである。また、より好ましい上限は１２００μｍ、更に好ましい上限は１０００μｍ、更により好ましい上限は８００μｍ、特に好ましい上限は６００μｍ、とりわけ好ましい上限は４００μｍである。 The thickness of the foam layer is not particularly limited, but is preferably 80 μm or more and 1500 μm or less. When the thickness of the foam layer is within the above range, the glass can be used to fix the glass member of the vehicle to the frame or the window glass to the window frame while suppressing excessive deformation of the adhesive tape. Even if the contact surface between the glass and the resin member has a curved surface or unevenness, it is possible to prevent the glass and the resin member from peeling off. From the viewpoint of further suppressing excessive deformation of the adhesive tape and further suppressing peeling of the glass and the resin member, a more preferable lower limit of the thickness of the foam layer is 90 μm, a further preferable lower limit is 100 μm, and a further preferable lower limit is 110 μm, and a particularly preferable lower limit is 120 μm. Further, a more preferable upper limit is 1200 μm, a further preferable upper limit is 1000 μm, a further preferable upper limit is 800 μm, a particularly preferable upper limit is 600 μm, and a particularly preferable upper limit is 400 μm.
上記粘着テープが粘着剤層、発泡体層、及び粘着剤層をこの順で有する場合、粘着剤層と発泡体層の間に樹脂フィルム層が存在してもよい。上記樹脂フィルム層は、粘着剤層と発泡体層との間に存在すると、粘着テープのリワーク性、加工性及びハンドリング性を向上させることができる。上記樹脂フィルム層は、発泡体層の一方の面上に存在してもよく、発泡体の両方の面上に存在してもよい。上記樹脂フィルムの厚みは、特に限定されないが、好ましくは１０μｍ以上、より好ましくは２０μｍ以上であり、好ましくは１００μｍ以下、より好ましくは５０μｍ以下である。 When the pressure-sensitive adhesive tape has a pressure-sensitive adhesive layer, a foam layer, and a pressure-sensitive adhesive layer in this order, a resin film layer may be present between the pressure-sensitive adhesive layer and the foam layer. When the resin film layer exists between the pressure-sensitive adhesive layer and the foam layer, the reworkability, processability, and handleability of the pressure-sensitive adhesive tape can be improved. The resin film layer may be present on one surface of the foam layer, or may be present on both surfaces of the foam. The thickness of the resin film is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, preferably 100 μm or less, and more preferably 50 μm or less.
上記粘着テープを製造する方法は特に限定されず、例えば、上記粘着テープが単層の粘着剤層からなる場合、上記粘着ポリマーと、必要に応じて架橋剤や粘着付与剤等の成分とを混合、攪拌して粘着剤溶液を調製し、この粘着剤溶液を離型処理したＰＥＴフィルムに塗工乾燥させることによって製造することができる。また、上記粘着テープが粘着剤層／発泡体層／粘着剤層の３層構造を有する場合は以下のような方法で製造することができる。
まず、発泡体層を射出発泡成形法や、発泡剤を混合した樹脂を押出機で押出す押出発泡成形法等によって形成する。次いで、上記粘着剤溶液を離型処理したＰＥＴフィルムに塗工乾燥させて粘着剤層を形成し、得られた粘着剤層を得られた発泡体層の両面に転着させることによって製造することができる。
The method for producing the adhesive tape is not particularly limited. For example, when the adhesive tape is composed of a single adhesive layer, the adhesive polymer is mixed with components such as a cross-linking agent and a pressure-sensitive adhesive, if necessary. , Stir to prepare a pressure-sensitive adhesive solution, and apply and dry the pressure-sensitive adhesive solution on a release-treated PET film. When the adhesive tape has a three-layer structure of an adhesive layer / a foam layer / an adhesive layer, it can be produced by the following method.
First, the foam layer is formed by an injection foam molding method, an extrusion foam molding method in which a resin mixed with a foaming agent is extruded with an extruder, or the like. Next, the pressure-sensitive adhesive solution is applied and dried on a release-treated PET film to form a pressure-sensitive adhesive layer, and the obtained pressure-sensitive adhesive layer is transferred to both sides of the obtained foam layer. Can be done.
上記ガラスは特に限定されず、一般に使用されているガラスを使用することができ、例えば、フロートガラス、磨きガラス、型板ガラス、網入りガラス、線入りガラス、着色ガラス等の無機ガラスが挙げられる。また、ポリエチレンテレフタレート、ポリカーボネート、ポリアクリレート等の有機プラスチックを用いることもできる。また、ガラスのサイズも特に限定されないが、大型で重量の大きなガラスを用いた時に本発明の効果が大きく発揮される。 The above glass is not particularly limited, and generally used glass can be used, and examples thereof include inorganic glass such as float glass, polished glass, template glass, wire-reinforced glass, wire-lined glass, and colored glass. In addition, organic plastics such as polyethylene terephthalate, polycarbonate, and polyacrylate can also be used. Further, the size of the glass is not particularly limited, but the effect of the present invention is greatly exhibited when a large and heavy glass is used.
上記樹脂部材の材料は特に限定されず、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、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル樹脂、ポリカーボネート樹脂、ＡＢＳ樹脂、ポリアミド樹脂等の一般的に用いられている樹脂を用いることができる。なかでも、剛性が高く、ガラスの重みによって変形しにくいことから、ポリエステル樹脂が好ましく、ポリエチレンテレフタレート、ポリブチレンテレフタレートがより好ましく、ポリブチレンテレフタレートが更に好ましい。 The material of the resin member is not particularly limited, and for example, a polyolefin resin such as polyethylene and polypropylene, a polyester resin such as polyethylene terephthalate and polybutylene terephthalate, a polycarbonate resin, an ABS resin, and a commonly used resin such as a polyamide resin. Can be used. Among them, polyester resin is preferable, polyethylene terephthalate and polybutylene terephthalate are more preferable, and polybutylene terephthalate is more preferable because of high rigidity and resistance to deformation due to the weight of glass.
上記樹脂部材の形状は特に限定されず、用途に応じて適宜決定される。例えば、上記樹脂部材の形状としては長方形、正方形、５角形、円形、楕円形等が挙げられる。 The shape of the resin member is not particularly limited, and is appropriately determined according to the intended use. For example, examples of the shape of the resin member include a rectangle, a square, a pentagon, a circle, and an ellipse.
上記樹脂部材のサイズは特に限定されず、用途に応じて適宜決定される。例えば、本発明の積層体が車両用ガラスを車両のフレームに取り付けるために用いられる場合、上記樹脂部材のサイズは１００ｍｍ２以上であることが好ましく２００ｍｍ２以上であることがより好ましい。上記樹脂部材が上記範囲のサイズであると、車両用ガラスの重みに耐えて接着剤が硬化するまでの間車両用ガラスをより確実に固定することができる。上記樹脂部材のサイズの上限は特に限定されず、コストやデザインの自由度の観点から粘着テープのずれや剥がれが起きない範囲でできるだけ小さいことが好ましいが、例えば、本発明の積層体が車両用ガラスを車両のフレームに取り付けるために用いられる場合、４０００ｍｍ２以下であることが好ましい。 The size of the resin member is not particularly limited, and is appropriately determined according to the application. For example, when the laminate of the present invention is used for attaching vehicle glass to a vehicle frame, the size of the resin member is preferably 100 mm 2 or more, and more preferably 200 mm 2 or more. When the resin member has a size in the above range, the vehicle glass can be more reliably fixed until the adhesive is cured by bearing the weight of the vehicle glass. The upper limit of the size of the resin member is not particularly limited, and from the viewpoint of cost and design freedom, it is preferable that the adhesive tape is as small as possible without slipping or peeling. For example, the laminate of the present invention is for vehicles. When used to attach glass to the frame of a vehicle, it is preferably 4000 mm 2 or less.
上記樹脂部材は、上記粘着剤層と接する接触面及び該接触面に対向する対向面を有し、前記対向面は長さ３ｍｍ以上の突起部を有することが好ましい。
上記樹脂部材の上記粘着剤層と接する面とは反対側の面に突起を有することで、フロントガラス等の車両用ガラスを車両のフレームに取り付ける際に積層体をフレームに固定することができる。より確実に固定を行う観点から、上記突起部の長さは５ｍｍ以上であることがより好ましい。なお、上記樹脂部材が有し得る突起部は、１個であってもよく、１個以上であってもよく、２個以上であってもよく、通常５個以下である。
The resin member preferably has a contact surface in contact with the pressure-sensitive adhesive layer and a facing surface facing the contact surface, and the facing surface has a protrusion having a length of 3 mm or more.
By having the protrusions on the surface of the resin member opposite to the surface in contact with the adhesive layer, the laminate can be fixed to the frame when the vehicle glass such as the windshield is attached to the vehicle frame. From the viewpoint of more reliable fixing, the length of the protrusion is more preferably 5 mm or more. The number of protrusions that the resin member can have may be one, one or more, two or more, and usually five or less.
本発明の積層体の用途は特に限定されないが、車両の生産において車両用ガラスを車両のフレームに接着する際に、接着剤が硬化するまでの間ガラスを固定する用途に好適に用いることができる。
このような、車両用ガラスとして用いられる本発明の積層体もまた、本発明の１つである。
ここで、車両用ガラスとして用いられる場合の本発明の積層体を表した模式図を図３に示した。図３ではガラスとしてフロントガラスを用いた例を示している。本発明の積層体は、ガラス（フロントガラス）１に樹脂部材２が粘着テープ５を介して接着されている。ガラス（フロントガラス）１と樹脂部材２とを粘着テープで接着することから、従来の接着剤を用いた場合と比べて乾燥が不要になり、格段に生産効率を向上させることができる。本発明の積層体は図１、２に示したような方法で車両のフレームに固定される。
また、車両用ガラスと樹脂部材を接着するために用いられる粘着テープであって、
粘着テープは粘着ポリマーを含有する粘着剤層を有し、前記粘着ポリマーは、数平均分子量が３０万以上、重量平均分子量が５０万以上である、粘着テープもまた、本発明の１つである。
The use of the laminate of the present invention is not particularly limited, but it can be suitably used for fixing the glass until the adhesive is cured when the vehicle glass is adhered to the vehicle frame in the production of a vehicle. ..
Such a laminate of the present invention used as vehicle glass is also one of the present inventions.
Here, FIG. 3 shows a schematic view showing the laminated body of the present invention when it is used as glass for vehicles. FIG. 3 shows an example in which a windshield is used as the glass. In the laminate of the present invention, the
In addition, it is an adhesive tape used for adhering vehicle glass and a resin member.
The adhesive tape has an adhesive layer containing an adhesive polymer, and the adhesive polymer has a number average molecular weight of 300,000 or more and a weight average molecular weight of 500,000 or more. The adhesive tape is also one of the present inventions. ..
また、本発明の積層体は、車両用ガラスの固定の用途以外にも、はめ殺しの窓を構築する際に窓ガラスと窓枠とを接着する用途にも好適に用いることができる。
このような、ガラス窓と窓枠を接着するために用いられる粘着テープであって、粘着テープは粘着ポリマーを含有する粘着剤層を有し、前記粘着ポリマーは、数平均分子量が３０万以上、重量平均分子量が５０万以上である、粘着テープもまた本発明の１つである。
Further, the laminate of the present invention can be suitably used not only for fixing the vehicle glass but also for adhering the window glass and the window frame when constructing a fitting window.
Such an adhesive tape used for adhering a glass window and a window frame, the adhesive tape has an adhesive layer containing an adhesive polymer, and the adhesive polymer has a number average molecular weight of 300,000 or more. Adhesive tapes with a weight average molecular weight of 500,000 or more are also one of the present inventions.
本発明によれば、ガラスと樹脂部材とを粘着テープで接合した積層体であって、大型のガラスを用いた場合であっても粘着テープの剥がれやずれが生じ難い積層体及び該積層体を形成するための粘着テープを提供することができる。 According to the present invention, a laminate obtained by joining glass and a resin member with an adhesive tape, and the adhesive tape is unlikely to peel off or shift even when a large glass is used, and the laminate. Adhesive tape for forming can be provided.
以下に実施例を挙げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例にのみ限定されるものではない。 Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
（粘着ポリマーの調製）
（１）粘着ポリマーＡの調製
重合開始剤６．３８ｇ（５０ｍｍｏｌ）をテトラヒドロフラン（ＴＨＦ）５０ｍＬに懸濁させ、これに１．６ｍｏｌ／Ｌのｎ−ブチルリチウム／ヘキサン溶液３４．４ｍＬ（５５ｍｍｏｌ）を、室温でゆっくり滴下した。この反応溶液を金属テルルが完全に消失するまで攪拌した。この反応溶液に、エチル−２−ブロモ−イソブチレート１０．７ｇ（５５ｍｍｏｌ）を室温で加え、２時間攪拌した。反応終了後、減圧下で溶媒を濃縮し、続いて減圧蒸留して、黄色油状物の２−メチル−２−ｎ−ブチルテラニル−プロピオン酸エチルを得た。
アルゴン置換したグローブボックス内で、反応容器中に、製造した２−メチル−２−ｎ−ブチルテラニル−プロピオン酸エチル４５．７μＬ、２，２’−アゾビス（２，４−ジメチルバレロニトリル）１０ｍｇ、酢酸エチル０．５ｍＬを投入した後、反応容器を密閉し、反応容器をグローブボックスから取り出した。続いて、反応容器にアルゴンガスを流入しながら、反応容器内に、原料モノマー混合物を加えた。原料モノマー混合物の組成は、ブチルアクリレート（ＢＡ）１００重量部、アクリル酸（Ａａｃ）３重量部、及び、アクリル酸２−ヒドロキシエチル（ＨＥＡ）０．１重量部とした。更に、重合溶媒として酢酸エチル６８．７ｇを投入し、６０℃で２０時間重合反応を行い、リビングラジカル重合アクリル系ポリマー（粘着ポリマーＡ）含有溶液を得た。なお、原料は以下のものを用いた。
重合開始剤：Ｔｅｌｌｕｒｉｕｍ、金属テルル、４０メッシュ、アルドリッチ社製
ｎ−ブチルリチウム／ヘキサン溶液：アルドリッチ社製
２，２’−アゾビス（２，４−ジメチルバレロニトリル）：和光純薬工業社製
(Preparation of adhesive polymer)
(1) Preparation of Adhesive Polymer A 6.38 g (50 mmol) of the polymerization initiator is suspended in 50 mL of tetrahydrofuran (THF), and 34.4 mL (55 mmol) of a 1.6 mol / L n-butyllithium / hexane solution is added thereto. , Dropped slowly at room temperature. The reaction solution was stirred until the metallic tellurium disappeared completely. To this reaction solution, 10.7 g (55 mmol) of ethyl-2-bromo-isobutyrate was added at room temperature, and the mixture was stirred for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure and then distilled under reduced pressure to obtain ethyl 2-methyl-2-n-butylteranyl-propionate as a yellow oil.
45.7 μL of ethyl 2-methyl-2-n-butylteranyl-propionate produced, 10 mg of 2,2'-azobis (2,4-dimethylvaleronitrile), acetate in an argon-substituted glove box in a reaction vessel. After adding 0.5 mL of ethyl, the reaction vessel was sealed and the reaction vessel was taken out from the glove box. Subsequently, the raw material monomer mixture was added into the reaction vessel while flowing argon gas into the reaction vessel. The composition of the raw material monomer mixture was 100 parts by weight of butyl acrylate (BA), 3 parts by weight of acrylic acid (Aac), and 0.1 parts by weight of 2-hydroxyethyl acrylate (HEA). Further, 68.7 g of ethyl acetate was added as a polymerization solvent, and the polymerization reaction was carried out at 60 ° C. for 20 hours to obtain a living radical polymerization acrylic polymer (adhesive polymer A) -containing solution. The following raw materials were used.
Polymerization initiator: Tellurium, metal tellurium, 40 mesh, Aldrich n-butyllithium / hexane solution:
次いで、得られた粘着ポリマーＡ含有溶液をテトラヒドロフラン（ＴＨＦ）によって５０倍に希釈して得られた希釈液を、ポア径０．２μｍのポリテトラフルオロエチレン製フィルターで濾過した。その後、得られた濾液をゲルパミエーションクロマトグラフに供給してＧＰＣ測定を行った。粘着ポリマーＡのポリスチレン換算分子量を測定して、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）を求めた。なお、測定機器と測定条件は以下の通りとした。
ゲルパミエーションクロマトグラフ：ｅ２６９５ Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｕｌｅ（Ｗａｔｅｒｓ社製）
検出器：示差屈折計（２４１４、Ｗａｔｅｒｓ社製）
カラム：ＧＰＣ ＫＦ−８０６Ｌ（昭和電工社製）
標準試料：ＳＴＡＮＤＲＡＤ ＳＭ−１０５、昭和電工社製
サンプル流量：１ｍＬ／ｍｉｎ
カラム温度：４０℃
Then, the obtained adhesive polymer A-containing solution was diluted 50-fold with tetrahydrofuran (THF), and the obtained diluted solution was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.2 μm. Then, the obtained filtrate was supplied to a gel permeation chromatograph and GPC measurement was performed. The polystyrene-equivalent molecular weight of the adhesive polymer A was measured to determine the weight average molecular weight (Mw) and the number average molecular weight (Mn). The measuring equipment and measuring conditions are as follows.
Gel permeation chromatograph: e2695 Separations Module (manufactured by Waters)
Detector: Differential refractometer (2414, manufactured by Waters)
Column: GPC KF-806L (manufactured by Showa Denko KK)
Standard sample: STANDRAD SM-105, manufactured by Showa Denko Co., Ltd. Sample flow rate: 1 mL / min
Column temperature: 40 ° C
（２）粘着ポリマーＢの調製
２−メチル−２−ｎ−ブチルテラニル−プロピオン酸エチルの投入量を３３．０μＬとし、２，２’−アゾビス（２，４−ジメチルバレロニトリル）の投入量を７．２ｍｇとした以外は粘着ポリマーＡの調製と同様にしてリビングラジカル重合アクリル系ポリマー（粘着ポリマーＢ）含有溶液を得た。また、得られた粘着ポリマーＢ含有溶液について、粘着ポリマーＡの調製と同様にして重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。
(2) Preparation of Adhesive Polymer B The amount of ethyl 2-methyl-2-n-butylteranyl-propionate added was 33.0 μL, and the amount of 2,2'-azobis (2,4-dimethylvaleronitrile) added was 7. A living radical polymerization acrylic polymer (adhesive polymer B) -containing solution was obtained in the same manner as in the preparation of the adhesive polymer A except that the amount was adjusted to 2 mg. Further, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) of the obtained pressure-sensitive adhesive polymer B-containing solution were determined in the same manner as in the preparation of the pressure-sensitive adhesive polymer A.
（３）粘着ポリマーＣの調製
粘着ポリマーＡの調製において２−メチル−２−ｎ−ブチルテラニル−プロピオン酸エチルの投入量を３３．０μＬに、２，２’−アゾビス（２，４−ジメチルバレロニトリル）の投入量を７．２ｍｇに変更した。また、原料モノマー混合物の組成を、ブチルアクリレート（ＢＡ）２５重量部、２−エチルヘキシルアクリレート（２ＥＨＡ）７５重量部、アクリル酸（Ａａｃ）３重量部、及び、アクリル酸２−ヒドロキシエチル（ＨＥＡ）０．１重量部とし、重量溶媒を酢酸エチル４３．０ｇに変更した。上記の点以外は粘着ポリマーＡの調製と同様にしてリビングラジカル重合アクリル系ポリマー（粘着ポリマーＣ）含有溶液を得て、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。
(3) Preparation of Adhesive Polymer C In the preparation of the adhesive polymer A, the amount of ethyl 2-methyl-2-n-butylteranyl-propionate added was adjusted to 33.0 μL, and 2,2'-azobis (2,4-dimethylvaleronitrile) was added. ) Was changed to 7.2 mg. The composition of the raw material monomer mixture is 25 parts by weight of butyl acrylate (BA), 75 parts by weight of 2-ethylhexyl acrylate (2EHA), 3 parts by weight of acrylic acid (Aac), and 0 of 2-hydroxyethyl acrylate (HEA). The weight was adjusted to 1 part by weight, and the weight solvent was changed to 43.0 g of ethyl acetate. Except for the above points, a living radical polymerization acrylic polymer (adhesive polymer C) -containing solution was obtained in the same manner as in the preparation of the adhesive polymer A, and the weight average molecular weight (Mw), the number average molecular weight (Mn) and the molecular weight distribution (Mw /) were obtained. Mn) was calculated.
（４）粘着ポリマーＤの調製
粘着ポリマーＡの調製において２−メチル−２−ｎ−ブチルテラニル−プロピオン酸エチルの投入量を３３．０μＬに、２，２’−アゾビス（２，４−ジメチルバレロニトリル）の投入量を７．２ｍｇに変更した。また、原料モノマー混合物の組成を、２−エチルヘキシルアクリレート（２ＥＨＡ）１００重量部、アクリル酸（Ａａｃ）３重量部、及び、アクリル酸２−ヒドロキシエチル（ＨＥＡ）０．１重量部とし、重量溶媒を酢酸エチル４３．０ｇとした。上記点以外は粘着ポリマーＡの調製と同様にしてリビングラジカル重合アクリル系ポリマー（粘着ポリマーＤ）含有溶液を得て、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。
(4) Preparation of Adhesive Polymer D In the preparation of the adhesive polymer A, the amount of ethyl 2-methyl-2-n-butylteranyl-propionate added was adjusted to 33.0 μL, and 2,2'-azobis (2,4-dimethylvaleronitrile) was added. ) Was changed to 7.2 mg. The composition of the raw material monomer mixture was 100 parts by weight of 2-ethylhexyl acrylate (2EHA), 3 parts by weight of acrylic acid (Aac), and 0.1 parts by weight of 2-hydroxyethyl acrylate (HEA), and the weight solvent was used. The amount was 43.0 g of ethyl acetate. Except for the above points, a living radical polymerization acrylic polymer (adhesive polymer D) -containing solution was obtained in the same manner as in the preparation of the adhesive polymer A, and the weight average molecular weight (Mw), the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were obtained. ) Was asked.
（５）粘着ポリマーＥの調製
２−メチル−２−ｎ−ブチルテラニル−プロピオン酸エチルの投入量を２６．０μＬとし、２，２’−アゾビス（２，４−ジメチルバレロニトリル）の投入量を７．０ｍｇとした以外は粘着ポリマーＡの調製と同様にしてリビングラジカル重合アクリル系ポリマー（粘着ポリマーＥ）含有溶液を得た。また、得られた粘着ポリマーＥ含有溶液について、粘着ポリマーＡの調製と同様にして重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。
(5) Preparation of Adhesive Polymer E The amount of ethyl 2-methyl-2-n-butylteranyl-propionate added was 26.0 μL, and the amount of 2,2'-azobis (2,4-dimethylvaleronitrile) added was 7. A living radical polymerization acrylic polymer (adhesive polymer E) -containing solution was obtained in the same manner as in the preparation of the adhesive polymer A except that the amount was 0.0 mg. Further, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) of the obtained pressure-sensitive adhesive polymer E-containing solution were determined in the same manner as in the preparation of the pressure-sensitive adhesive polymer A.
（６）粘着ポリマーＦの調製
温度計、攪拌機、冷却管を備えた反応器にブチルアクリレート（ＢＡ）１００重量部、アクリル酸（Ａａｃ）３重量部、アクリル酸２−ヒドロキシエチル（ＨＥＡ）０．１重量部、酢酸エチル８７重量部及びトルエン３８重量部を加え、窒素置換した後、反応器を６０℃に加熱して還流を開始した。続いて、上記反応器内に、重合開始剤としてアゾビスイソブチロニトリル０．１５重量部を添加し、３時間還流させることで、粘着ポリマーＦの酢酸エチル溶液を得た。得られた粘着ポリマーＦ含有溶液について、粘着ポリマーＡと同様の方法で重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。
(6) Preparation of Adhesive Polymer F In a reactor equipped with a thermometer, a stirrer, and a cooling tube, 100 parts by weight of butyl acrylate (BA), 3 parts by weight of acrylic acid (Aac), and 2-hydroxyethyl acrylate (HEA) 0. After adding 1 part by weight, 87 parts by weight of ethyl acetate and 38 parts by weight of toluene and replacing with nitrogen, the reactor was heated to 60 ° C. to start reflux. Subsequently, 0.15 parts by weight of azobisisobutyronitrile as a polymerization initiator was added into the reactor and refluxed for 3 hours to obtain an ethyl acetate solution of the adhesive polymer F. The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the obtained adhesive polymer F-containing solution were determined by the same method as for adhesive polymer A.
（７）粘着ポリマーＧの調製
温度計、攪拌機、冷却管を備えた反応器にブチルアクリレート（ＢＡ）１００重量部、アクリル酸（Ａａｃ）３重量部、アクリル酸２−ヒドロキシエチル（ＨＥＡ）０．１重量部、及び、酢酸エチル１０５重量部、トルエン２０重量部を加え、窒素置換した後、反応器を６０℃に加熱して還流を開始した。続いて、上記反応器内に、重合開始剤としてアゾビスイソブチロニトリル０．１５重量部を添加し、３時間還流させることで、粘着ポリマーＧの酢酸エチル溶液を得た。得られた粘着ポリマーＧ含有溶液について、粘着ポリマーＡと同様の方法で重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。
(7) Preparation of Adhesive Polymer G In a reactor equipped with a thermometer, a stirrer, and a cooling tube, 100 parts by weight of butyl acrylate (BA), 3 parts by weight of acrylic acid (Aac), and 2-hydroxyethyl acrylate (HEA) 0. After adding 1 part by weight, 105 parts by weight of ethyl acetate and 20 parts by weight of toluene and replacing with nitrogen, the reactor was heated to 60 ° C. to start reflux. Subsequently, 0.15 parts by weight of azobisisobutyronitrile as a polymerization initiator was added into the reactor and refluxed for 3 hours to obtain an ethyl acetate solution of the adhesive polymer G. The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the obtained adhesive polymer G-containing solution were determined by the same method as for adhesive polymer A.
（８）粘着ポリマーＨの調製
温度計、攪拌機、冷却管を備えた反応器にブチルアクリレート（ＢＡ）１００重量部、アクリル酸（Ａａｃ）３重量部、アクリル酸２−ヒドロキシエチル（ＨＥＡ）０．１重量部、及び、酢酸エチル９５重量部、トルエン３０重量部を加え、窒素置換した後、反応器を加熱して還流を開始した。続いて、上記反応器内に、重合開始剤としてアゾビスイソブチロニトリル０．１５重量部を添加し、６時間還流させることで、粘着ポリマーＨの酢酸エチル溶液を得た。得られた粘着ポリマーＨ含有溶液について、粘着ポリマーＡと同様の方法で重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。
(8) Preparation of Adhesive Polymer H In a reactor equipped with a thermometer, a stirrer, and a cooling tube, 100 parts by weight of butyl acrylate (BA), 3 parts by weight of acrylic acid (Aac), and 2-hydroxyethyl acrylate (HEA) 0. After adding 1 part by weight, 95 parts by weight of ethyl acetate and 30 parts by weight of toluene and replacing with nitrogen, the reactor was heated to start reflux. Subsequently, 0.15 parts by weight of azobisisobutyronitrile as a polymerization initiator was added into the reactor and refluxed for 6 hours to obtain an ethyl acetate solution of the adhesive polymer H. The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the obtained adhesive polymer H-containing solution were determined by the same method as for adhesive polymer A.
（９）粘着ポリマーＩの調製
温度計、攪拌機、冷却管を備えた反応器にブチルアクリレート（ＢＡ）１００重量部、アクリル酸（Ａａｃ）３重量部、アクリル酸２−ヒドロキシエチル（ＨＥＡ）０．１重量部、及び、酢酸エチル６１重量部、トルエン６０重量部を加え、窒素置換した後、反応器を６０℃に加熱して還流を開始した。続いて、上記反応器内に、重合開始剤としてアゾビスイソブチロニトリル０．１５重量部を添加し、３時間還流させることで、粘着ポリマーＩの酢酸エチル溶液を得た。得られた粘着ポリマーＩ含有溶液について、粘着ポリマーＡと同様の方法で重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。
(9) Preparation of Adhesive Polymer I In a reactor equipped with a thermometer, a stirrer, and a cooling tube, 100 parts by weight of butyl acrylate (BA), 3 parts by weight of acrylic acid (Aac), and 2-hydroxyethyl acrylate (HEA) 0. After adding 1 part by weight, 61 parts by weight of ethyl acetate and 60 parts by weight of toluene and replacing with nitrogen, the reactor was heated to 60 ° C. and reflux was started. Subsequently, 0.15 parts by weight of azobisisobutyronitrile as a polymerization initiator was added into the reactor and refluxed for 3 hours to obtain an ethyl acetate solution of the adhesive polymer I. The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the obtained adhesive polymer I-containing solution were determined by the same method as for adhesive polymer A.
（１０）粘着ポリマーＪの調製
２−メチル−２−ｎ−ブチルテラニル−プロピオン酸エチル５１．０μＬ、２，２’−アゾビス（２，４−ジメチルバレロニトリル）１１．０ｍｇに変えた以外は粘着ポリマーＡの調製と同様にしてリビングラジカル重合アクリル系ポリマーＪ含有溶液を得て、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。
(10) Preparation of Adhesive Polymer J Adhesive polymer except that it was changed to 51.0 μL of ethyl 2-methyl-2-n-butylteranyl-propionate and 11.0 mg of 2,2′-azobis (2,4-dimethylvaleronitrile). A living radical polymerization acrylic polymer J-containing solution was obtained in the same manner as in the preparation of A, and the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) were determined.
（実施例１）
（粘着剤溶液の調製）
得られた粘着ポリマーＡ含有液の固形成分１００重量部に対して、粘着付与剤として水添ロジンエステル樹脂１０重量部、テルペンフェノール樹脂１０重量部、重合ロジンエステル樹脂１０重量部を加えた。更に、酢酸エチル１２５重量部、イソシアネート系架橋剤６．４重量部（固形分換算）を添加し、攪拌して、粘着剤の酢酸エチル溶液を得た。なお、粘着付与剤及び架橋剤は以下のものを用いた。
水添ロジンエステル樹脂：ＫＥ３５９、荒川化学工業社製、軟化点１００℃
テルペンフェノール樹脂：Ｇ１５０、ヤスハラケミカル社製、軟化点１５０℃
重合ロジンエステル樹脂：Ｄ−１６０、荒川化学工業社製、軟化点１６０℃
イソシアネート系架橋剤：コロネートＬ４５、東ソー社製
(Example 1)
(Preparation of adhesive solution)
To 100 parts by weight of the solid component of the obtained adhesive polymer A-containing liquid, 10 parts by weight of hydrogenated rosin ester resin, 10 parts by weight of terpene phenol resin, and 10 parts by weight of polymerized rosin ester resin were added as tackifiers. Further, 125 parts by weight of ethyl acetate and 6.4 parts by weight of the isocyanate-based cross-linking agent (in terms of solid content) were added and stirred to obtain an ethyl acetate solution of the pressure-sensitive adhesive. The following tackifiers and cross-linking agents were used.
Hydrogenated rosin ester resin: KE359, manufactured by Arakawa Chemical Industry Co., Ltd., softening point 100 ° C.
Terpene phenolic resin: G150, manufactured by Yasuhara Chemical Co., Ltd., softening point 150 ° C
Polymerized rosin ester resin: D-160, manufactured by Arakawa Chemical Industries, Ltd., softening point 160 ° C.
Isocyanate cross-linking agent: Coronate L45, manufactured by Tosoh Corporation
（発泡体層の調製）
発泡体層に使用する発泡体として以下のものを使用した。
ボラーラＸＬＨ−０５００３黒、積水化学工業社製、厚み：３００μｍ、見かけ密度：０．１８ｇ／ｃｍ３、２５％圧縮強度：７５ｋＰａ
(Preparation of foam layer)
The following foams were used as the foams used for the foam layer.
Borara XLH-05003 Black, manufactured by Sekisui Chemical Co., Ltd., thickness: 300 μm, apparent density: 0.18 g / cm 3 , 25% compression strength: 75 kPa
（粘着テープの製造）
厚み１５０μｍの離型紙を用意し、この離型紙の離型処理面に得られた粘着剤の酢酸エチル溶液を塗布し、１１０℃で３分間乾燥させることにより、厚み５０μｍの粘着剤層を形成した。この粘着剤層を、発泡体層の表面と貼り合わせた。次いで、同様の要領で、発泡体層の反対の表面にも上記と同じ粘着剤層を貼り合わせた。これにより、厚み４００μｍの離型紙で覆われた粘着テープを得た。
(Manufacturing of adhesive tape)
A release paper having a thickness of 150 μm was prepared, an ethyl acetate solution of the obtained adhesive was applied to the release-treated surface of the release paper, and the mixture was dried at 110 ° C. for 3 minutes to form an adhesive layer having a thickness of 50 μm. .. This pressure-sensitive adhesive layer was bonded to the surface of the foam layer. Then, in the same manner, the same adhesive layer as above was attached to the opposite surface of the foam layer. As a result, an adhesive tape covered with a paper pattern having a thickness of 400 μm was obtained.
（せん断貯蔵弾性率Ｇ’の測定）
上記方法で粘着剤層のみからなる測定用サンプルを作製した。得られた測定用サンプルについて、動的粘弾性測定装置（アイティー計測制御社製、ＤＶＡ−２００）を用いて、周波数１Ｈｚ、昇温速度５℃／ｍｉｎで−５０℃から２００℃まで測定を行い、２３℃におけるせん断貯蔵弾性率Ｇ’を測定した。
(Measurement of shear storage elastic modulus G')
A measurement sample consisting of only the pressure-sensitive adhesive layer was prepared by the above method. The obtained measurement sample was measured from -50 ° C to 200 ° C at a frequency of 1 Hz and a heating rate of 5 ° C / min using a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Measurement Control Co., Ltd.). The shear storage elastic modulus G'at 23 ° C. was measured.
（ゲル分率の測定）
得られた粘着テープの粘着剤層のみを０．１ｇこそぎ取って酢酸エチル５０ｍｌ中に浸漬し、振とう機で温度２３度、２００ｒｐｍの条件で２４時間振とうした（以下、こそぎ取った粘着剤層のことを粘着剤組成物という）。振とう後、金属メッシュ（目開き＃２００メッシュ）を用いて、酢酸エチルと酢酸エチルを吸収し膨潤した粘着剤組成物を分離した。分離後の粘着剤組成物を１１０℃の条件下で１時間乾燥させた。乾燥後の金属メッシュを含む粘着剤組成物の重量を測定し、下記式を用いて粘着剤層のゲル分率を算出した。
ゲル分率（重量％）＝１００×（Ｗ１−Ｗ２）／Ｗ０
（Ｗ０：初期粘着剤組成物重量、Ｗ１：乾燥後の金属メッシュを含む粘着剤組成物重量、Ｗ２：金属メッシュの初期重量）
(Measurement of gel fraction)
Only 0.1 g of the adhesive layer of the obtained adhesive tape was scraped off, immersed in 50 ml of ethyl acetate, and shaken with a shaker at a temperature of 23 ° C. and 200 rpm for 24 hours (hereinafter, scraped off). The pressure-sensitive adhesive layer is called a pressure-sensitive adhesive composition). After shaking, a metal mesh (opening # 200 mesh) was used to separate the swelling pressure-sensitive adhesive composition by absorbing ethyl acetate and ethyl acetate. The separated pressure-sensitive adhesive composition was dried under the condition of 110 ° C. for 1 hour. The weight of the pressure-sensitive adhesive composition containing the metal mesh after drying was measured, and the gel fraction of the pressure-sensitive adhesive layer was calculated using the following formula.
Gel fraction (% by weight) = 100 x (W 1- W 2 ) / W 0
(W 0 : Weight of initial pressure-sensitive adhesive composition, W 1 : Weight of pressure-sensitive adhesive composition including dried metal mesh, W 2 : Initial weight of metal mesh)
（実施例２）
粘着ポリマーＢを使用した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Example 2)
An adhesive tape was obtained in the same manner as in Example 1 except that the adhesive polymer B was used, and each measurement was performed.
（実施例３）
粘着ポリマーＢを使用しイソシアネート系架橋剤４．５重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Example 3)
Adhesive tapes were obtained in the same manner as in Example 1 except that the adhesive polymer B was used and 4.5 parts by weight (solid content equivalent) of the isocyanate-based cross-linking agent was added, and each measurement was carried out.
（実施例４）
粘着ポリマーＢを使用しイソシアネート系架橋剤３．５重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Example 4)
An adhesive tape was obtained in the same manner as in Example 1 except that the adhesive polymer B was used and 3.5 parts by weight (in terms of solid content) of an isocyanate-based cross-linking agent was added, and each measurement was carried out.
（実施例５）
粘着ポリマーＣを使用しイソシアネート系架橋剤６．４重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Example 5)
Adhesive tapes were obtained in the same manner as in Example 1 except that the adhesive polymer C was used and 6.4 parts by weight (in terms of solid content) of the isocyanate-based cross-linking agent was added, and each measurement was carried out.
（実施例６）
粘着ポリマーＤを使用しイソシアネート系架橋剤８．０重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Example 6)
An adhesive tape was obtained in the same manner as in Example 1 except that 8.0 parts by weight (in terms of solid content) of an isocyanate-based cross-linking agent was added using the adhesive polymer D, and each measurement was carried out.
（実施例７）
粘着ポリマーＥを使用しイソシアネート系架橋剤６．４重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Example 7)
Adhesive tapes were obtained in the same manner as in Example 1 except that the adhesive polymer E was used and 6.4 parts by weight (in terms of solid content) of the isocyanate-based cross-linking agent was added, and each measurement was carried out.
（実施例８）
粘着ポリマーＦを使用しイソシアネート系架橋剤６．０重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Example 8)
An adhesive tape was obtained in the same manner as in Example 1 except that 6.0 parts by weight (in terms of solid content) of an isocyanate-based cross-linking agent was added using the adhesive polymer F, and each measurement was carried out.
（実施例９）
粘着ポリマーＧを使用しイソシアネート系架橋剤６．０重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Example 9)
An adhesive tape was obtained in the same manner as in Example 1 except that 6.0 parts by weight (in terms of solid content) of an isocyanate-based cross-linking agent was added using the adhesive polymer G, and each measurement was carried out.
（実施例１０）
発泡体層として以下のものを使用した以外は実施例２と同様にして粘着テープを得て、各測定を行った。
ボラーラＸＬＨ−０１８００１黒、積水化学工業社製、厚み：１００μｍ、見かけ密度：０．５６ｇ／ｃｍ３、２５％圧縮強度：６００ｋＰａ
(Example 10)
An adhesive tape was obtained in the same manner as in Example 2 except that the following was used as the foam layer, and each measurement was performed.
Borara XLH-018001 Black, manufactured by Sekisui Chemical Co., Ltd., thickness: 100 μm, apparent density: 0.56 g / cm 3 , 25% compression strength: 600 kPa
（実施例１１）
発泡体層として以下のものを使用した以外は実施例２と同様にして粘着テープを得て、各測定を行った。
ボラーラＸＬＨ−０１６００１黒、積水化学工業社製、厚み：１００μｍ、見かけ密度０．６４ｇ／ｃｍ３、２５％圧縮強度：８００ｋＰａ
(Example 11)
An adhesive tape was obtained in the same manner as in Example 2 except that the following was used as the foam layer, and each measurement was performed.
Borara XLH-016001 Black, manufactured by Sekisui Chemical Co., Ltd., thickness: 100 μm, apparent density 0.64 g / cm 3 , 25% compression strength: 800 kPa
（実施例１２）
発泡体層として以下のものを使用した以外は実施例２と同様にして粘着テープを得て、各測定を行った。
ボラーラＸＬＨ−１００１黒、積水化学工業社製、厚み：１０００μｍ、見かけ密度：０．１ｇ／ｃｍ３、２５％圧縮強度：４０ｋＰａ
(Example 12)
An adhesive tape was obtained in the same manner as in Example 2 except that the following was used as the foam layer, and each measurement was performed.
Borara XLH-1001 Black, manufactured by Sekisui Chemical Co., Ltd., thickness: 1000 μm, apparent density: 0.1 g / cm 3 , 25% compression strength: 40 kPa
（実施例１３）
発泡体層として以下のものを使用した以外は実施例２と同様にして粘着テープを得て、各測定を行った。
ボラーラＸＬＨ−０２５０００８黒、積水化学工業社製、厚み：８０μｍ、見かけ密度：０．４ｇ／ｃｍ３、２５％圧縮強度：１２０ｋＰａ
(Example 13)
An adhesive tape was obtained in the same manner as in Example 2 except that the following was used as the foam layer, and each measurement was performed.
Borara XLH-0250008 Black, manufactured by Sekisui Chemical Co., Ltd., thickness: 80 μm, apparent density: 0.4 g / cm 3 , 25% compression strength: 120 kPa
（比較例１）
粘着ポリマーＨを使用しイソシアネート系架橋剤５．０重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Comparative Example 1)
An adhesive tape was obtained in the same manner as in Example 1 except that 5.0 parts by weight (in terms of solid content) of an isocyanate-based cross-linking agent was added using the adhesive polymer H, and each measurement was carried out.
（比較例２）
粘着ポリマーＩを使用しイソシアネート系架橋剤６．０重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Comparative Example 2)
Adhesive tape was obtained in the same manner as in Example 1 except that 6.0 parts by weight (in terms of solid content) of an isocyanate-based cross-linking agent was added using the adhesive polymer I, and each measurement was carried out.
（比較例３）
粘着ポリマーＪを使用しイソシアネート系架橋剤８．０重量部（固形分換算）を添加した以外は実施例１と同様にして粘着テープを得て、各測定を行った。
(Comparative Example 3)
An adhesive tape was obtained in the same manner as in Example 1 except that 8.0 parts by weight (in terms of solid content) of an isocyanate-based cross-linking agent was added using the adhesive polymer J, and each measurement was carried out.
＜評価＞
実施例、比較例で得られた粘着テープについて以下の評価を行った。結果を表２、３に示した。
<Evaluation>
The following evaluations were made on the adhesive tapes obtained in Examples and Comparative Examples. The results are shown in Tables 2 and 3.
（粘着テープのずれの評価）
７０ｍｍ×１１ｍｍ、厚み１ｍｍのポリブチレンテレフタレート製の樹脂板の片面中央に直径６ｍｍ高さ１４ｍｍの突起を有する樹脂部材を用意した。樹脂部材の突起を有している面とは反対側の面に７０ｍｍ×１１ｍｍに切り出した粘着テープを貼り付けた。次いで、粘着テープの樹脂部材が貼り付けられた面とは反対側の面を黒色セラミック印刷を施したガラス（２００ｍｍ×２００ｍｍ×５ｍｍ）の印刷面に貼り付けた。樹脂部材の突起に３ｋｇの重りを結んだ紐を引っ掛け、外気温２３℃、湿度５０％ＲＨの条件で５日間放置した。５日後、粘着テープのずれを測定した。なお、粘着テープのずれは、ずれの大きさが最大のものを用いた。比較例１〜３については樹脂部材が落下してしまい、粘着テープのずれを測定することができなかった。
(Evaluation of adhesive tape misalignment)
A resin member having a protrusion 6 mm in diameter and 14 mm in height was prepared in the center of one side of a resin plate made of polybutylene terephthalate having a thickness of 70 mm × 11 mm and a thickness of 1 mm. An adhesive tape cut out to a size of 70 mm × 11 mm was attached to the surface of the resin member opposite to the surface having the protrusions. Next, the surface of the adhesive tape opposite to the surface to which the resin member was attached was attached to the printed surface of glass (200 mm × 200 mm × 5 mm) subjected to black ceramic printing. A string with a weight of 3 kg was hooked on the protrusion of the resin member, and the mixture was left for 5 days under the conditions of an outside air temperature of 23 ° C. and a humidity of 50% RH. After 5 days, the displacement of the adhesive tape was measured. As for the displacement of the adhesive tape, the one having the maximum displacement was used. In Comparative Examples 1 to 3, the resin member fell off, and the deviation of the adhesive tape could not be measured.
本発明によれば、ガラスと樹脂部材とを粘着テープで接合した積層体であって、大型のガラスを用いた場合であっても粘着テープの剥がれやずれが生じ難い積層体及び該積層体を形成するための粘着テープを提供することができる。 According to the present invention, a laminate obtained by joining glass and a resin member with an adhesive tape, and the adhesive tape is unlikely to peel off or shift even when a large glass is used, and the laminate. Adhesive tape for forming can be provided.
１ フロントガラス
２ 樹脂部材
３ フレーム
４ 接着剤
５ 粘着テープ
1
Claims (12)
前記粘着テープは粘着ポリマーを含有する粘着剤層を有し、
前記粘着ポリマーは、数平均分子量が３０万以上、重量平均分子量が５０万以上である、積層体。 A laminate in which glass, adhesive tape, and resin members are laminated in this order.
The adhesive tape has an adhesive layer containing an adhesive polymer and has an adhesive layer.
The adhesive polymer is a laminate having a number average molecular weight of 300,000 or more and a weight average molecular weight of 500,000 or more.
粘着テープは粘着ポリマーを含有する粘着剤層を有し、前記粘着ポリマーは、数平均分子量が３０万以上、重量平均分子量が５０万以上である、粘着テープ。 Adhesive tape used to bond vehicle glass and resin members.
The adhesive tape has an adhesive layer containing an adhesive polymer, and the adhesive polymer has a number average molecular weight of 300,000 or more and a weight average molecular weight of 500,000 or more.
粘着テープは粘着ポリマーを含有する粘着剤層を有し、前記粘着ポリマーは、数平均分子量が３０万以上、重量平均分子量が５０万以上である、粘着テープ。 Adhesive tape used to bond glass windows and window frames.
The adhesive tape has an adhesive layer containing an adhesive polymer, and the adhesive polymer has a number average molecular weight of 300,000 or more and a weight average molecular weight of 500,000 or more.
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| JP2007261521A (en) * | 2006-03-29 | 2007-10-11 | Asahi Glass Co Ltd | Temporary fixing member for window glass and window glass with temporary fixing member |
| JP2008176173A (en) * | 2007-01-22 | 2008-07-31 | Sumitomo Chemical Co Ltd | Optical film with pressure-sensitive adhesive and optical laminate |
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