JP4362564B2 - UV curable adhesive composition - Google Patents
UV curable adhesive composition Download PDFInfo
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- JP4362564B2 JP4362564B2 JP28636898A JP28636898A JP4362564B2 JP 4362564 B2 JP4362564 B2 JP 4362564B2 JP 28636898 A JP28636898 A JP 28636898A JP 28636898 A JP28636898 A JP 28636898A JP 4362564 B2 JP4362564 B2 JP 4362564B2
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- sensitive adhesive
- ultraviolet curable
- ultraviolet
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- 239000000203 mixture Substances 0.000 title claims description 41
- 230000001070 adhesive effect Effects 0.000 title description 37
- 239000000853 adhesive Substances 0.000 title description 36
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 20
- 239000012965 benzophenone Substances 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 9
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000008366 benzophenones Chemical class 0.000 claims description 4
- 238000012662 bulk polymerization Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 28
- 229920001577 copolymer Polymers 0.000 description 23
- 239000002313 adhesive film Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000000155 melt Substances 0.000 description 17
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- -1 methacryloyl group Chemical group 0.000 description 15
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 5
- 239000004831 Hot glue Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
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- 238000001723 curing Methods 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BEUGBYXJXMVRFO-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-phenylmethanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=CC=C1 BEUGBYXJXMVRFO-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
- 239000003522 acrylic cement Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 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
- 229960002130 benzoin Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、紫外線硬化型粘着剤組成物に関し、更に詳細には、組成物としての塗工性が優れ、しかも紫外線照射により硬化して、せん断力、凝集力の優れた粘着剤となり、両面テープ、包梱テープ、ラベル等へ使用することのできる紫外線硬化型粘着剤組成物に関する。
【０００２】
【従来の技術】
近年、可視光や紫外線等の光を照射することにより、組成物を硬化させ、粘着性を得るタイプの粘着剤が開発されつつある。
このような光硬化型の粘着剤組成物の従来技術としては、次のもの等が知られている。
▲１▼バインダーポリマーに１分子中に少なくとも１個のアクリロイル基を有する光重合性化合物と開裂型光重合開始剤および水素引き抜き型光重合開始剤を併用して添加してなる光硬化型感圧接着剤（特開昭６１−０６４７７３号）
▲２▼特定の（メタ）アクリル酸アルキルエステルを重合して得られるアクリル系重合体と水素引き抜き型光重合開始剤を含有することを特徴とする紫外線硬化型粘着剤組成物（特開平９−４０９２８号）
▲３▼アクリル系重合体にアクリロイル基、メタクリロイル基、アクリロキシ基又はメタクリロキシ基を２個以上もつ化合物、次の式
ＣＨ２＝ＣＲ１ＣＯ−Ｘ−Ｒ２−ＮＲ３Ｒ４
で表される化合物および酸化防止剤を添加してなる活性エネルギー線硬化型ホットメルト組成物（特許第２７４３２８８号）
【０００３】
しかしながら、上記した光硬化型粘着剤組成物には、いずれも問題があり、未だ十分なものとは言い難かった。 例えば、▲１▼ の光硬化型感圧接着剤は、開裂型光重合開始剤を使用していることにより、酸素の影響を受けやすく、性能バラツキの原因となり、大きな凝集力・せん断強度の向上は見れないといった問題がある。 また、▲２▼ の紫外線硬化型粘着剤組成物では、水素引き抜き型光開始剤を多く入れる必要があるため、性能を安定化させるには、紫外線量を多くする必要があり、また、光開始剤の水素引き抜きのみによる性能コントロールのため、粘着力・凝集力・せん断強度等の性能のバランスをとることは難しいという問題があった。 更に ▲３▼ の活性エネルギー線硬化型ホットメルト組成物に関しては、特性バランスはとれるものの活性エネルギーの照射量を多くする必要があり生産性が悪いという問題があった。
【０００４】
一方、粘着剤組成物としては、環境問題、作業性、コスト性等の観点から、最近、溶剤を含まないホットメルト型接着剤が着目されつつある。 このホットメルト型接着剤としては、ＳＩＳ（スチレン−イソプレン−スチレンブロックポリマー）、ＳＢＲ（スチレン−ブタジェン−ランダムポリマー）等のゴム系が主流である。 しかしながら、上記のホットメルト型接着剤には、透明性、耐光性などの問題点もあり、粘着性、高温凝集力、透明性、耐光性に優れ、性能コントロールがし易い等の点から、アクリル系ホットメルト型粘着剤が注目されつつある。
【０００５】
しかし、アクリル系無溶剤型粘着剤では、加熱流動性と粘着性との特性バランスをとることが難しいとか、耐熱性が悪く、高温時の粘着性・凝集力・せん断が低下してしまうなどというものも多く、改良が求められている。
【０００６】
【発明が解決しようとする課題】
本発明者らは、アクリル系粘着剤に関し、長年研究を行っていたが、ホットメルト型として利用できるアクリル系粘着剤としては、紫外線硬化型の粘着剤組成物が最適であるとの確信を得るに至った。そこで、公知の光硬化型の粘着剤組成物をホットメルト型として利用すべく検討したが、いずれも前記したような欠点があり、十分なものとは言い難かった。
従って本発明は、前記したような問題を有さず、せん断強度、粘着性、高温凝集力、透明性、耐光性等に優れたアクリル系粘着剤を提供することを課題とするものである。
【０００７】
【課題を解決するための手段】
本発明者は、ホットメルト型粘着剤として利用できる紫外線硬化型アクリル系粘着剤、すなわち、実質的に溶剤を含まず、紫外線を照射する前は加熱流動性が優れ、良好な塗工性を有しながら、紫外線を照射した場合には適切な粘着物性を有するアクリル系化合物を求めて鋭意検討した結果、紫外線照射前後において、ゲル分率およびせん断強度が一定の範囲で変化するアクリル系粘着剤組成物が当該性質を有するものであることを見出した。
【０００８】
また、このような粘着剤組成物の一例としては、特定のアクリル共重合体と重合性モノマー、及び光開始剤を配合したものがあることを見出し、本発明を完成した。
【０００９】
すなわち本発明は、アクリル系化合物を中心として構成される実質的に溶剤を含まない粘着剤組成物であって、紫外線を照射する前のゲル分率が５％以下、せん断強度が０.５ｋｇ／ｃｍ２以下であり、１００〜２０００ｍＪ／ｃｍ２の紫外線を照射した後は、ゲル分率が３０〜７５％、せん断強度が５ｋｇ／ｃｍ２以上となる紫外線硬化型粘着剤組成物を提供するものである。
【００１０】
また本発明は、次の三成分（ａ）〜（ｃ）
（ａ）アクリル酸及びアルキル（メタ）アクリレートからなる重量平均分子量
５〜１８万のポリマー １００重量部
（ｂ）分子内に３個以上のアクリロイル基を有する単量体 ０.１〜２重量部
（ｃ）光開始剤としてのベンゾフェノン類 ０.５〜５重量部
を含有し、上記の性質を有する紫外線硬化型粘着剤組成物を提供するものである。
【００１１】
【発明の実施の形態】
本発明の粘着剤組成物は、実質的に溶剤を含まずアクリル系化合物を中心として構成される紫外線硬化型のものであり、紫外線照射前はゲル分率が５％以下、せん断強度は、０.５ｋｇ／ｃｍ２以下のものである。 このものに１００〜２０００ｍＪ／ｃｍ２の紫外線を照射することにより、ゲル分率が３０〜７５％になり、せん断強度が５ｋｇ／ｃｍ２以上となるものである。
【００１２】
本発明の粘着剤組成物に対する紫外線照射は系の反応の完結と紫外線のあてすぎによるポリマー劣化を考えると、１００〜２０００ｍＪ／ｃｍ２程度、好ましくは１００〜１０００ｍＪ／ｃｍ２である。 また、紫外線照射後のゲル分率が３０％未満である場合は凝集力が落ち、せん断破壊において糊面で凝集破壊し、せん断強度が低下する。 また、紫外線照射後のゲル分率が７５％を越えると、せん断破壊において、糊面と被着体との界面での、接着性が弱まり、せん断強度が落ちる傾向が見られる。 従って、せん断強度が５ｋｇ／ｃｍ２以上となるにはゲル分率が３０〜７５％、さらに４０〜６５％であることが好ましい。
【００１３】
上記の性質を有する紫外線硬化型粘着剤組成物の一例としては、次の三成分（ａ）、（ｂ）および（ｃ）より構成されるものが挙げられる。
（ａ）アクリル酸及びアルキル（メタ）アクリレートからなる重量平均分子量
５〜１８万のポリマー １００重量部
（ｂ）分子内に３個以上のアクリロイル基を有する単量体 ０.１〜２重量部
（ｃ）光開始剤としてのベンゾフェノン類 ０.５〜５重量部
【００１４】
このうち、成分（ａ）であるアクリル酸及びアルキル（メタ）アクリレートからなる重量平均分子量５〜１８万のポリマーの主成分としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ベキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。 中でもｎ−ブチルアクリレート、２−エチルヘキシルアクリレートが特に好ましい。 また、必要に応じて（メタ）アクリル酸、酢酸ビニル、スチレン、アクリロニトリル、アクリルアマイド、ジエチルアミノエチル（メタ）アクリレート等を共重合しても良い。 これらは必要に応じて単独であるいは２種以上を併用して使用することができ、重合体のガラス転移点温度（Ｔｇ）は塗工性、粘着性等の問題より−２０℃以下であることが好ましい。 なお、ポリマーの重量平均分子量は５〜１８万であるが、塗工性、せん断強度を考慮すると、８〜１５万であることがより好ましい。
【００１５】
また、成分（ｂ）である分子内に３個以上のアクリロイル基を有する単量体の具体例としては、トリメチロールプロパントリアクリレート、エトキシ化トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールヘキサアクリレート等が挙げられる。 これらはそれぞれ単独、または２種類以上を併用して使用することが出来る。
【００１６】
更に成分（ｃ）である光開始剤としてのベンゾフェノン類の例としては、ベンゾフェノン及びその誘導体、ｐ−クロロベンゾフェノン、ｐ−ジメチルアミノベンゾフェノン等が挙げられる。 特に、物性等からベンゾフェノンを使用するのが好ましい。
【００１７】
上記三成分のうち、成分（ａ）は、ラジカル重合法により製造され、溶液重合法、塊状重合法、懸濁重合法等により製造することができる。 しかしながら、作業環境の点から無溶剤型とする必要があり、溶剤重合では、溶剤を除去する工程が必要となり、また懸濁重合では分離・洗浄工程が必要となる等、いずれもコストがかかるので塊状重合とすることが望ましい。
【００１８】
前記三成分（ａ）〜（ｃ）を用いて紫外線硬化型粘着剤組成物を調製するための配合割合は、成分（ａ）１００重量部に対し、成分（ｂ）が０.１〜２重量部、成分（ｃ）が０.５〜５重量部であるが、このうち成分（ｂ）が２重量部を越えると紫外線照射後のゲル分率が７５％を越え、被着体界面の接着力が低下し、せん断強度が低くなる。 また、成分（ｃ）を５重量部を越えるとポリマー劣化が起こり、ゲル分率の低下、せん断強度の低下が見られる。このことから好ましくは成分（ｂ）は０.５〜１.５重量部、成分（ｃ）は０.５〜３重量部であることが好ましい。
【００１９】
本発明の紫外線硬化型粘着剤組成物、例えば上記した成分（ａ）〜成分（ｃ）で調製される粘着剤組成物が紫外線照射により高せん断、高凝集力となる理由は次のように考えられる。
【００２０】
すなわち、紫外線が照射されると、成分（ｂ）が成分（ｃ）の光開始剤により、高分子化される。 この成分（ｂ）は多官能化合物であるため、高密度架橋型ポリマーとなり、さらにこれが成分（ａ）と絡み合って凝架橋構造となる。 そして成分（ａ）と成分（ｂ）より得られたポリマー間で水素引き抜きによるゲル化が発生し、ゲル分率が高まって、高せん断、高凝集力となるものと考えられる。
【００２１】
本発明の紫外線硬化型粘着剤組成物は、紫外線照射の前後において前記したゲル分率およびせん断強度の条件を満たせばよいが、更に１２０℃以下で塗布することを前提に塗工性、作業性を考慮すれば、１００〜１２０℃の温度範囲で３０〜３００ｐｓ、特に３０〜２００ｐｓの粘度を有することがより好ましい。
【００２２】
【発明の効果】
以上説明した本発明の紫外線硬化型粘着剤組成物は、紫外線照射前には加熱流動性が優れ、良好な塗工性を有し、かつ、紫外線を照射した後には粘着性・凝集性・せん断力等が向上するものであるため、加工性の極めて優れた粘着剤組成物ということができる。
従って、両面テープ、包梱テープ、ラベル等の粘着剤として広く使用することが可能なものである。
【００２３】
【実施例】
次に、実施例、比較例および試験例を挙げ、本発明を更に詳しく説明するが、本発明はこれら実施例等に何等制約されるものではない。 なお、実施例中の「部」は「重量部」を意味する。
【００２４】
実 施 例 １
攪拌機、還流冷却器、温度計、窒素導入管および紫外線照射装置を備えた装置に、２−エチルヘキシルアクリレート ９８部、アクリル酸 ２部、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１を０.００５部を仕込み、１３０℃に保ちながら３０分間窒素パージした。 次いで、光源から最も近い重合系内におけるＵＶ強度を５.６ｍＷ／ｃｍ２に設定して、１０秒間ＵＶ照射と冷却操作とを交互に繰り返し行い、光重合装置内の温度を１３０±２℃に保ちながら総ＵＶ照射量が６０００ｍＪ／ｃｍ２になるまでＵＶを照射して重合を行い、重量平均分子量１０万の無溶剤共重合体を得た。 得られた共重合体に、ペンタエリスリトールトリアクリレート（共栄社化学（株）製）０.５部とベンゾフェノン １部を添加して、１２０℃における溶融粘度が１０２ｐｓである紫外線硬化型粘着剤を得た。
【００２５】
得られた紫外線硬化型粘着剤を１２０℃にて溶融して５０μｍ厚のポリエチレンテレフタレートフィルムに粘着剤層の厚さが２５μとなるように塗布し、塗工直後に１０００ｍＪ／ｃｍ２の紫外線を照射し、更に３８μｍ厚シリコン処理ポリエチレンテレフタレートフィルムをあてて粘着フィルムとした。
【００２６】
実 施 例 ２
実施例１と同処方で得られた重量平均分子量１０万の無溶剤共重合体にペンタエリスリトールトリアクリレート １.５部とベンゾフェノン １部を添加して１２０℃における溶融粘度が９５ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００２７】
実 施 例 ３
実施例１と同処方で得られた重量平均分子量１０万の無溶剤共重合体にペンタエリスリトールテトラアクリレート １部とベンゾフェノン １部を添加して１２０℃における溶融粘度が１０１ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００２８】
実 施 例 ４
実施例１と同処方で得られた重量平均分子量１０万の無溶剤共重合体にペンタエリスリトールヘキサアクリレート １部とベンゾフェノン １部を添加して１２０℃における溶融粘度が１０５ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００２９】
実 施 例 ５
実施例１と同じ装置に、２−エチルヘキシルアクリレート ９８部、アクリル酸 ２部、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１ ０.００７部を仕込んだ。実施例１と同様に窒素パージを行い、実施例１と同様なＵＶ照射条件下で重合反応を行い、重量平均分子量６万の無溶剤共重合体を得た。 得られた共重合体にペンタエリスリトールトリアクリレート １部とベンゾフェノン １部を添加して、１２０℃における溶融粘度が５８ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００３０】
実 施 例 ６
実施例１と同じ装置に、２−エチルヘキシルアクリレート ９８部、アクリル酸 ２部、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１ ０.００４部を仕込んだ。実施例１と同様に窒素パージを行い、実施例１と同様なＵＶ照射条件下で重合反応を行い、重量平均分子量１７万の無溶剤共重合体を得た。 得られた共重合体にペンタエリスリトールトリアクリレート １部とベンゾフェノン １部を添加して、１２０℃における溶融粘度が２５６ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００３１】
実 施 例 ７
実施例１と同じ装置に、ブチルアクリレート ９８部、アクリル酸 ２部、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１ ０.００５部を仕込んだ。実施例１と同様に窒素パージを行い、実施例１と同様なＵＶ照射条件下で重合反応を行い、重量平均分子量１１万の無溶剤共重合体を得た。 得られた共重合体にぺンタエリスリトールトリアクリレート １部とベンゾフェノン １部を添加して、１２０℃における溶融粘度が１２８ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００３２】
実 施 例 ８
攪拌機、還流冷却管、温度計及び窒素導入管を備えた装置に、２−エチルヘキシルアクリレート ９６重量部、アクリル酸 ４重量部、酢酸エチル １００部、メチルエチルケトン １４０部を仕込み、アゾビスイソニトリル ０.５部を加えた。 窒素ガス気流中、７２℃にて６時間重合反応を行い、重量平均分子量１４万の共重合体溶液を得た。
【００３３】
得られた重合体溶液の溶剤を全て揮散させ、これにペンタエリスリトールトリアクリレート １重量部、ベンジフェノン １重量部添加して、１２０℃における溶融粘度が１４８ｐｓの紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤について、実施例１と同様にして粘着フィルムを得た。
【００３４】
実 施 例 ９
実施例８と同じ装置に、２−エチルヘキシルアクリレート ４８重量部、ブチルアクリレート ４８重量部、アクリル酸 ４重量部、酢酸エチル １００重量部、メチルエチルケトン ３０重量部を仕込み、アゾビスイソニトリル ０.５部を加えた以外は実施例９と同様に重合を行い、重量平均分子量１７万の共重合体溶液を得た。
得られた重合体溶液の溶剤を全て揮散させた後、これにペンタエリスリトールトリアクリレート １重量部、ベンゾフェノン １重量部を添加し、１２０℃における溶融粘度が２６８ｐｓの紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤について、実施例１と同様にして粘着フィルムを得た。
【００３５】
比 較 例 １
実施例１と同じ装置に、２−エチルヘキシルアクリレート ９８部、アクリル酸 ２部、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１ ０.００２部を仕込んだ。実施例１と同様に窒素パージを行い、実施例１と同様なＵＶ照射条件下で重合反応を行い、重量平均分子量２０万の無溶剤共重合体溶液を得た。 得られた共重合体にペンタエリスリトールトリアクリレート １部とベンゾフェノン １部を添加して、１２０℃における溶融粘度が３３０ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００３６】
比 較 例 ２
実施例１と同じ装置に、２−エチルヘキシルアクリレート ９８部、アクリル酸 ２部、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１ ０.００８部を仕込んだ。実施例１と同様に窒素パージを行い、実施例１と同様なＵＶ照射条件下で重合反応を行い、重量平均分子量４万の無溶剤共重合体を得た。 得られた共重合体にペンタエリスリトールトリアクリレート １部とベンゾフェノン １部を添加して、１２０℃における溶融粘度が３５ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００３７】
比 較 例 ３
実施例１と同処方で得られた重量平均分子量１０万の無溶剤共重合体に、ジエチレングリコールジアクリレート １部とベンゾフェノン １部を添加して１２０℃における溶融粘度が９８ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００３８】
比 較 例 ４
実施例１で得られた重量平均分子量１０万の無溶剤共重合体に、１２０℃における溶融粘度が１１２ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００３９】
比 較 例 ５
実施例１と同処方で得られた重量平均分子量１０万の無溶剤共重合体に、ペンタエリスリトールトリアクリレート １部を添加して１２０℃における溶融粘度が１０１ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００４０】
比 較 例 ６
実施例１と同処方で得られた重量平均分子量１０万の無溶剤共重合体に、ペンタエリスリトールトリアクリレート ３部とベンゾフェノン １部を添加して１２０℃における溶融粘度が９０ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００４１】
比 較 例 ７
実施例１と同処方で得られた重量平均分子量１０万の無溶剤共重合体に、ペンタエリスリトールトリアクリレート １部とベンゾフェノン ６部を添加して１２０℃における溶融粘度が１０２ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００４２】
比 較 例 ８
実施例１と同処方で得られた重量平均分子量１０万の無溶剤共重合体に、ペンタエリスリトールトリアクリレート １部とベンゾイン １部を添加して１２０℃における溶融粘度が１０２ｐｓである紫外線硬化型粘着剤を得た。 得られた紫外線硬化型粘着剤を実施例１と同様にして粘着フィルムとした。
【００４３】
比 較 例 ９
実施例１で得られた紫外線硬化接着剤を１２０℃にて溶融させ、５０μｍ厚のポリエチレンテトラフタレートフィルムに粘着剤層の厚さが２５μｍとなるように塗布し、塗工直後に５０ｍＪ／ｃｍ２の紫外線を照射し、粘着フィルムとした。
【００４４】
比 較 例 １０
ＵＶ照射量を２３００ｍＪ／ｃｍ２とする以外は比較例９と同様にして粘着フィルムを得た。
【００４５】
試 験 例
実施例１〜９および比較例１〜１０で調製した粘着フィルムについて、下記方法で保持力、せん断強度およびゲル分率を測定した。 この結果を表１に示す。
【００４６】
（１）保持力の測定
（ａ）試験サンプル
試験サンプルとしては、実施例１〜９および比較例１〜１０で調製した粘着フィルムを２０ｍｍ幅に切断した試験片を用いた。
【００４７】
（ｂ）試験装置、器具等
保持力試験機としては、４０±１℃に保つことができる送風循環式乾燥機で、試験板の試験面が鉛直に設置でき、試料の下端に１ｋｇの荷重がかかるものを用いた。また、圧着装置としては、表面がゴムで被覆された２ｋｇの綱製ローラを用いた。更に、試験板としては、ＪＩＳ−Ｇ−４３０５（冷間圧延ステンレス鋼鈑）に規定する厚さ２.０ｍｍのＳＵＳ３０４のステンレス鋼板を幅５０ｍｍ、長さ１００ｍｍ（フック用の穴のあるもの）に切断し、その表面をＪＩＳ−Ｒ−６２５３に規定する＃２８０耐水研磨紙で長手方向によく磨き、酢酸エチルで清浄化してから使用した。
【００４８】
（ｃ）測定操作
試験片を試験板の下端に２０×２０ｍｍの面積で貼り付け、圧着装置で速度３００ｍｍ／分で１往復圧着させた。４０±１℃に保たれた試験機内に試験板を取付け、２０分間放置した後、１ｋｇの荷重をかけて測定を始める。
保持力は試験片が試験板からずり落ちるまでの時間とし、１時間経過しても落ちない場合には、ずれた距離を０.１ｍｍの単位で測定し、その値とした。測定は２枚の試験片について行い、１時間以内に落ちた場合は落下時間の平均値を１分単位に丸めて求め、１時間保持した場合はずれた距離の平均値を０.１ｍｍ単位に丸めて示した。
【００４９】
（２）せん断強度
（ａ）試験サンプル
試験サンプルとしては、実施例１〜９および比較例１〜１０で調製した粘着フィルムを２０ｍｍ幅に切断した試験片を用いた。
【００５０】
（ｂ）試験装置、器具等
試験機として、ＪＩＳ−Ｂ−７７２１に規定する定速伸長形引張り試験機を用いた。また、圧着装置および試験板は、保持力試験に用いたものと同じものを使用した。
【００５１】
（ｃ）測定操作
試験片を試験板の下端に２０×２０ｍｍの面積で貼り付け、圧着装置で速度３００ｍｍ／分で１往復圧着させた。図１に示すように、試験板および試験片を引張り試験機の上部チャックおよび下部チャックに固定し、圧着から２０分後に５０ｍｍ／分の速さで引剥がし、破壊した強さを記録した。この強さを１ｃｍ２当たりに換算し、せん断強度とした。
【００５２】
（３）ゲル分率
１０×１０ｃｍ２の試料を１００ｇの酢酸エチルに２３℃で２４時間浸し、２００メッシュ金網にて濾過し、金網上の残留物を１００℃で２時間乾燥させ計量した。 また、粘着剤を塗布していない１０×１０ｃｍ２の基材の重量も測定し、次の計算式からゲル分率を算出した。
【式１】
（ 結 果 ）
【表１】
上記結果から明らかなように、本発明の紫外線硬化型粘着剤組成物は、紫外線照射前はせん断強度、ゲル分率は共に低いが、紫外線照射を受けた後はせん断強度、ゲル分率とも著しく高くなり、また優れた保持力を示すようになるものである。
【図面の簡単な説明】
【図１】 せん断強度を測定するための試験板および試験片の取り付け方を模式的に示した図面
【符号の説明】
１ … … 試験板
２ … … 試験片
３ … … 接着部
４ … … 上部チャック
５ … … 下部チャック
以 上[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ultraviolet curable pressure-sensitive adhesive composition. More specifically, the present invention provides a pressure-sensitive adhesive having excellent coating properties as a composition, cured by irradiation with ultraviolet rays, and having excellent shearing force and cohesive force. The present invention relates to an ultraviolet curable pressure-sensitive adhesive composition that can be used for packaging tapes, labels, and the like.
[0002]
[Prior art]
In recent years, pressure-sensitive adhesives are being developed that are cured by irradiating light such as visible light or ultraviolet light, thereby curing the composition.
The following are known as conventional techniques of such a photocurable pressure-sensitive adhesive composition.
(1) A photocurable pressure-sensitive pressure obtained by adding a photopolymerizable compound having at least one acryloyl group per molecule, a cleavage photopolymerization initiator, and a hydrogen abstraction photopolymerization initiator to a binder polymer. Adhesive (Japanese Patent Laid-Open No. 61-064773)
(2) An ultraviolet curable pressure-sensitive adhesive composition comprising an acrylic polymer obtained by polymerizing a specific (meth) acrylic acid alkyl ester and a hydrogen abstraction type photopolymerization initiator 40928)
(3) A compound having two or more acryloyl group, methacryloyl group, acryloxy group or methacryloxy group in an acrylic polymer, the following formula CH 2 = CR 1 CO—X—R 2 —NR 3 R 4
Active energy ray-curable hot melt composition comprising a compound represented by formula (II) and an antioxidant (Japanese Patent No. 2743288)
[0003]
However, all of the above-described photocurable pressure-sensitive adhesive compositions have problems, and it is still difficult to say that they are sufficient. For example, the photo-curing pressure sensitive adhesive (1) is easily affected by oxygen due to the use of a cleavage type photopolymerization initiator, causing variation in performance and improving large cohesive force and shear strength. There is a problem that can not be seen. In addition, in the ultraviolet curable pressure-sensitive adhesive composition (2), since it is necessary to add a large amount of hydrogen abstraction type photoinitiator, it is necessary to increase the amount of ultraviolet rays in order to stabilize the performance. There is a problem that it is difficult to balance the performance such as adhesive strength, cohesive strength, and shear strength because the performance is controlled only by hydrogen extraction of the agent. Furthermore, the active energy ray-curable hot melt composition (3) has a problem that productivity is poor because it is necessary to increase the irradiation amount of the active energy although the property balance is obtained.
[0004]
On the other hand, as a pressure-sensitive adhesive composition, hot-melt adhesives that do not contain a solvent have recently been attracting attention from the viewpoints of environmental problems, workability, cost, and the like. As the hot melt adhesive, rubber systems such as SIS (styrene-isoprene-styrene block polymer) and SBR (styrene-butadiene-random polymer) are mainly used. However, the above hot-melt adhesives also have problems such as transparency and light resistance, and are excellent in tackiness, high-temperature cohesion, transparency and light resistance, and easy to control performance. Hot melt adhesives are attracting attention.
[0005]
However, with acrylic solventless adhesives, it is difficult to balance the characteristics of heat fluidity and adhesiveness, heat resistance is poor, and adhesiveness, cohesive force and shear at high temperatures are reduced. There are many things and improvements are required.
[0006]
[Problems to be solved by the invention]
The present inventors have been studying acrylic adhesives for many years, but as acrylic adhesives that can be used as hot-melt adhesives, it is convinced that UV-curable adhesive compositions are optimal. It came to. Then, although it examined so that a well-known photocurable adhesive composition might be utilized as a hot-melt type, all had the fault as mentioned above and it was hard to say that it was sufficient.
Accordingly, an object of the present invention is to provide an acrylic pressure-sensitive adhesive that does not have the above-described problems and is excellent in shear strength, adhesiveness, high-temperature cohesive force, transparency, light resistance, and the like.
[0007]
[Means for Solving the Problems]
The inventor of the present invention is an ultraviolet curable acrylic pressure-sensitive adhesive that can be used as a hot-melt pressure-sensitive adhesive, that is, substantially free of solvent, has excellent heat fluidity before irradiation with ultraviolet light, and has good coating properties. However, as a result of diligent investigation for an acrylic compound having appropriate adhesive properties when irradiated with ultraviolet rays, an acrylic adhesive composition whose gel fraction and shear strength change within a certain range before and after ultraviolet irradiation. It was found that the product has the property.
[0008]
Moreover, as an example of such an adhesive composition, it discovered that there existed what mix | blended the specific acrylic copolymer, the polymerizable monomer, and the photoinitiator, and completed this invention.
[0009]
That is, the present invention is a pressure-sensitive adhesive composition that is substantially composed of an acrylic compound and does not contain a solvent, and has a gel fraction before irradiation with ultraviolet rays of 5% or less and a shear strength of 0.5 kg / cm 2 or less, after the irradiation with ultraviolet rays of 100 to 2000 mJ / cm 2, a gel fraction of 30-75%, which provides an ultraviolet-curable pressure-sensitive adhesive composition shear strength is 5 kg / cm 2 or more It is.
[0010]
The present invention also provides the following three components (a) to (c):
(A) Polymer having a weight average molecular weight of 50,000 to 180,000 consisting of acrylic acid and alkyl (meth) acrylate 100 parts by weight (b) Monomer having 3 or more acryloyl groups in the molecule 0.1 to 2 parts by weight ( c) The present invention provides an ultraviolet curable pressure-sensitive adhesive composition containing 0.5 to 5 parts by weight of benzophenones as a photoinitiator and having the above properties.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The pressure-sensitive adhesive composition of the present invention is an ultraviolet-curing type that is substantially composed of an acrylic compound that does not contain a solvent, and has a gel fraction of 5% or less and a shear strength of 0 before ultraviolet irradiation. 0.5 kg / cm 2 or less. By irradiating this with ultraviolet rays of 100 to 2000 mJ / cm 2 , the gel fraction becomes 30 to 75% and the shear strength becomes 5 kg / cm 2 or more.
[0012]
In consideration of the completion of the reaction of the system and polymer degradation due to excessive application of ultraviolet rays, the irradiation of the pressure-sensitive adhesive composition of the present invention is about 100 to 2000 mJ / cm 2 , preferably 100 to 1000 mJ / cm 2 . Moreover, when the gel fraction after ultraviolet irradiation is less than 30%, the cohesive force is lowered, and in the shear fracture, cohesive failure occurs on the paste surface, and the shear strength is reduced. On the other hand, when the gel fraction after ultraviolet irradiation exceeds 75%, the adhesiveness at the interface between the glue surface and the adherend is weakened and shear strength tends to be lowered in shear fracture. Therefore, in order for the shear strength to be 5 kg / cm 2 or more, the gel fraction is preferably 30 to 75%, more preferably 40 to 65%.
[0013]
As an example of the ultraviolet curable pressure-sensitive adhesive composition having the above properties, one composed of the following three components (a), (b) and (c) can be mentioned.
(A) Polymer having a weight average molecular weight of 50,000 to 180,000 consisting of acrylic acid and alkyl (meth) acrylate 100 parts by weight (b) Monomer having 3 or more acryloyl groups in the molecule 0.1 to 2 parts by weight ( c) Benzophenones as photoinitiators 0.5-5 parts by weight
Among these, as a main component of a polymer having a weight average molecular weight of 50,000 to 180,000 composed of acrylic acid and alkyl (meth) acrylate as component (a), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl ( (Meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, bexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n- Nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. Further, (meth) acrylic acid, vinyl acetate, styrene, acrylonitrile, acrylamide, diethylaminoethyl (meth) acrylate and the like may be copolymerized as necessary. These can be used alone or in combination of two or more as required, and the glass transition temperature (Tg) of the polymer is -20 ° C. or lower due to problems such as coating properties and adhesiveness. Is preferred. In addition, although the weight average molecular weight of a polymer is 5 to 180,000, when coating property and shear strength are considered, it is more preferable that it is 8 to 150,000.
[0015]
Specific examples of the monomer having three or more acryloyl groups in the molecule as component (b) include trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetra Examples thereof include acrylate and pentaerythritol hexaacrylate. These can be used alone or in combination of two or more.
[0016]
Furthermore, examples of the benzophenones as the photoinitiator as the component (c) include benzophenone and derivatives thereof, p-chlorobenzophenone, p-dimethylaminobenzophenone and the like. In particular, it is preferable to use benzophenone in view of physical properties.
[0017]
Among the above three components, the component (a) is produced by a radical polymerization method, and can be produced by a solution polymerization method, a bulk polymerization method, a suspension polymerization method or the like. However, it is necessary to make it solvent-free from the viewpoint of the working environment. In solvent polymerization, a process for removing the solvent is required, and in suspension polymerization, a separation / washing process is required. It is desirable to use bulk polymerization.
[0018]
The blending ratio for preparing the ultraviolet curable pressure-sensitive adhesive composition using the three components (a) to (c) is such that the component (b) is 0.1 to 2 weights with respect to 100 parts by weight of the component (a). Part and component (c) are 0.5 to 5 parts by weight. If component (b) exceeds 2 parts by weight, the gel fraction after ultraviolet irradiation exceeds 75%, and adhesion at the adherend interface The force decreases and the shear strength decreases. On the other hand, when the component (c) exceeds 5 parts by weight, the polymer is deteriorated, and the gel fraction and shear strength are decreased. From this, it is preferable that the component (b) is 0.5 to 1.5 parts by weight and the component (c) is 0.5 to 3 parts by weight.
[0019]
The reason why the ultraviolet curable pressure-sensitive adhesive composition of the present invention, for example, the pressure-sensitive adhesive composition prepared from the components (a) to (c) described above, exhibits high shear and high cohesive force when irradiated with ultraviolet rays is considered as follows. It is done.
[0020]
That is, when ultraviolet rays are irradiated, the component (b) is polymerized by the component (c) photoinitiator. Since this component (b) is a polyfunctional compound, it becomes a high-density cross-linked polymer, which is further entangled with the component (a) to form a coagulated cross-linked structure. And it is thought that gelation by hydrogen drawing occurs between the polymers obtained from the component (a) and the component (b), the gel fraction is increased, and high shear and high cohesive force are obtained.
[0021]
The ultraviolet curable pressure-sensitive adhesive composition of the present invention should satisfy the gel fraction and shear strength conditions before and after the ultraviolet irradiation, but is further applied on the premise that it is applied at 120 ° C. or less. Is considered, it is more preferable to have a viscosity of 30 to 300 ps, particularly 30 to 200 ps in a temperature range of 100 to 120 ° C.
[0022]
【The invention's effect】
The ultraviolet curable pressure-sensitive adhesive composition of the present invention described above has excellent heat fluidity before irradiation with ultraviolet rays, has good coating properties, and has adhesiveness / cohesiveness / shear after irradiation with ultraviolet rays. Since the strength and the like are improved, it can be said that the pressure-sensitive adhesive composition has extremely excellent processability.
Therefore, it can be widely used as an adhesive for double-sided tapes, packaging tapes, labels, and the like.
[0023]
【Example】
Next, although an Example, a comparative example, and a test example are given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples. In the examples, “part” means “part by weight”.
[0024]
Example 1
In a device equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and ultraviolet irradiation device, 98 parts of 2-ethylhexyl acrylate, 2 parts of acrylic acid, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1 was charged with 0.005 part and purged with nitrogen for 30 minutes while maintaining at 130 ° C. Next, the UV intensity in the polymerization system closest to the light source is set to 5.6 mW / cm 2 , and UV irradiation and cooling operation are alternately repeated for 10 seconds, and the temperature in the photopolymerization apparatus is set to 130 ± 2 ° C. While maintaining, polymerization was performed by irradiating UV until the total UV irradiation amount was 6000 mJ / cm 2 to obtain a solvent-free copolymer having a weight average molecular weight of 100,000. To the obtained copolymer, 0.5 part of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) and 1 part of benzophenone were added to obtain an ultraviolet curable adhesive having a melt viscosity of 102 ps at 120 ° C. .
[0025]
The obtained UV curable adhesive was melted at 120 ° C. and applied to a 50 μm-thick polyethylene terephthalate film so that the adhesive layer had a thickness of 25 μm. Immediately after application, 1000 mJ / cm 2 UV was irradiated. Further, a 38 μm thick silicon-treated polyethylene terephthalate film was applied to make an adhesive film.
[0026]
Example 2
An ultraviolet curable type having a melt viscosity of 95 ps at 120 ° C. by adding 1.5 parts of pentaerythritol triacrylate and 1 part of benzophenone to a solventless copolymer having a weight average molecular weight of 100,000 obtained in the same formulation as in Example 1. An adhesive was obtained. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0027]
Example 3
An ultraviolet curable pressure-sensitive adhesive having a melt viscosity of 101 ps at 120 ° C. by adding 1 part of pentaerythritol tetraacrylate and 1 part of benzophenone to a solventless copolymer having a weight average molecular weight of 100,000 obtained in the same formulation as in Example 1. Got. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0028]
Example 4
An ultraviolet curable pressure-sensitive adhesive having a melt viscosity at 120 ° C. of 105 ps by adding 1 part of pentaerythritol hexaacrylate and 1 part of benzophenone to a solventless copolymer having a weight average molecular weight of 100,000 obtained by the same formulation as in Example 1. Got. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0029]
Example 5
In the same apparatus as in Example 1, 98 parts of 2-ethylhexyl acrylate, 2 parts of acrylic acid, and 0.007 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 were charged. A nitrogen purge was performed in the same manner as in Example 1, and a polymerization reaction was performed under the same UV irradiation conditions as in Example 1 to obtain a solvent-free copolymer having a weight average molecular weight of 60,000. 1 part of pentaerythritol triacrylate and 1 part of benzophenone were added to the obtained copolymer to obtain an ultraviolet curable pressure-sensitive adhesive having a melt viscosity of 58 ps at 120 ° C. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0030]
Example 6
In the same apparatus as in Example 1, 98 parts of 2-ethylhexyl acrylate, 2 parts of acrylic acid, and 0.004 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 were charged. A nitrogen purge was performed in the same manner as in Example 1, and a polymerization reaction was performed under the same UV irradiation conditions as in Example 1 to obtain a solvent-free copolymer having a weight average molecular weight of 170,000. 1 part of pentaerythritol triacrylate and 1 part of benzophenone were added to the obtained copolymer to obtain an ultraviolet curable pressure-sensitive adhesive having a melt viscosity of 256 ps at 120 ° C. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0031]
Example 7
In the same apparatus as in Example 1, 98 parts of butyl acrylate, 2 parts of acrylic acid, and 0.005 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 were charged. A nitrogen purge was performed in the same manner as in Example 1, and a polymerization reaction was performed under the same UV irradiation conditions as in Example 1 to obtain a solvent-free copolymer having a weight average molecular weight of 110,000. 1 part of pentaerythritol triacrylate and 1 part of benzophenone were added to the obtained copolymer to obtain an ultraviolet curable pressure-sensitive adhesive having a melt viscosity of 128 ps at 120 ° C. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0032]
Example 8
A device equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with 96 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of acrylic acid, 100 parts of ethyl acetate, and 140 parts of methyl ethyl ketone, and 0.5 parts of azobisisonitrile. Was added. A polymerization reaction was performed in a nitrogen gas stream at 72 ° C. for 6 hours to obtain a copolymer solution having a weight average molecular weight of 140,000.
[0033]
All the solvent of the obtained polymer solution was volatilized, and 1 part by weight of pentaerythritol triacrylate and 1 part by weight of benzophenone were added thereto to obtain an ultraviolet curable adhesive having a melt viscosity of 148 ps at 120 ° C. About the obtained ultraviolet curing adhesive, it carried out similarly to Example 1, and obtained the adhesive film.
[0034]
Example 9
In the same apparatus as in Example 8, 48 parts by weight of 2-ethylhexyl acrylate, 48 parts by weight of butyl acrylate, 4 parts by weight of acrylic acid, 100 parts by weight of ethyl acetate and 30 parts by weight of methyl ethyl ketone were added, and 0.5 part of azobisisonitrile was added. Except for the above, polymerization was carried out in the same manner as in Example 9 to obtain a copolymer solution having a weight average molecular weight of 170,000.
After all the solvent of the obtained polymer solution was volatilized, 1 part by weight of pentaerythritol triacrylate and 1 part by weight of benzophenone were added thereto to obtain an ultraviolet curable adhesive having a melt viscosity of 268 ps at 120 ° C. About the obtained ultraviolet curing adhesive, it carried out similarly to Example 1, and obtained the adhesive film.
[0035]
Comparative Example 1
In the same apparatus as in Example 1, 98 parts of 2-ethylhexyl acrylate, 2 parts of acrylic acid, and 0.002 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 were charged. A nitrogen purge was performed in the same manner as in Example 1, and a polymerization reaction was performed under the same UV irradiation conditions as in Example 1 to obtain a solvent-free copolymer solution having a weight average molecular weight of 200,000. 1 part of pentaerythritol triacrylate and 1 part of benzophenone were added to the obtained copolymer to obtain an ultraviolet curable pressure-sensitive adhesive having a melt viscosity of 330 ps at 120 ° C. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0036]
Comparative Example 2
In the same apparatus as in Example 1, 98 parts of 2-ethylhexyl acrylate, 2 parts of acrylic acid, and 0.008 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 were charged. A nitrogen purge was performed in the same manner as in Example 1, and a polymerization reaction was performed under the same UV irradiation conditions as in Example 1 to obtain a solvent-free copolymer having a weight average molecular weight of 40,000. 1 part of pentaerythritol triacrylate and 1 part of benzophenone were added to the obtained copolymer to obtain an ultraviolet curable pressure-sensitive adhesive having a melt viscosity of 35 ps at 120 ° C. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0037]
Comparative Example 3
An ultraviolet curable pressure-sensitive adhesive having a melt viscosity of 98 ps at 120 ° C. by adding 1 part of diethylene glycol diacrylate and 1 part of benzophenone to a solventless copolymer having a weight average molecular weight of 100,000 obtained in the same formulation as in Example 1. Got. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0038]
Comparative Example 4
An ultraviolet curable pressure-sensitive adhesive having a melt viscosity of 112 ps at 120 ° C. was obtained from the solventless copolymer having a weight average molecular weight of 100,000 obtained in Example 1. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0039]
Comparative Example 5
One part of pentaerythritol triacrylate was added to the solventless copolymer having a weight average molecular weight of 100,000 obtained in the same formulation as in Example 1 to obtain an ultraviolet curable pressure-sensitive adhesive having a melt viscosity of 101 ps at 120 ° C. . The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0040]
Comparative Example 6
UV curable adhesive having a melt viscosity of 90 ps at 120 ° C. by adding 3 parts of pentaerythritol triacrylate and 1 part of benzophenone to the solventless copolymer having a weight average molecular weight of 100,000 obtained in the same formulation as in Example 1. An agent was obtained. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0041]
Comparative Example 7
UV curable adhesive having a melt viscosity at 120 ° C. of 102 ps by adding 1 part of pentaerythritol triacrylate and 6 parts of benzophenone to the solventless copolymer having a weight average molecular weight of 100,000 obtained in the same formulation as in Example 1. An agent was obtained. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0042]
Comparative Example 8
An ultraviolet curable adhesive having a melt viscosity at 120 ° C. of 102 ps by adding 1 part of pentaerythritol triacrylate and 1 part of benzoin to a solventless copolymer having a weight average molecular weight of 100,000 obtained in the same formulation as in Example 1. An agent was obtained. The obtained ultraviolet curable adhesive was used as an adhesive film in the same manner as in Example 1.
[0043]
Comparative Example 9
The ultraviolet curable adhesive obtained in Example 1 was melted at 120 ° C., applied to a 50 μm-thick polyethylene tetraphthalate film so that the pressure-sensitive adhesive layer had a thickness of 25 μm, and immediately after coating, 50 mJ / cm 2. Were irradiated with ultraviolet rays to form an adhesive film.
[0044]
Comparative Example 10
A pressure-sensitive adhesive film was obtained in the same manner as in Comparative Example 9 except that the UV irradiation amount was 2300 mJ / cm 2 .
[0045]
Test Examples The adhesive films prepared in Examples 1 to 9 and Comparative Examples 1 to 10 were measured for holding power, shear strength and gel fraction by the following methods. The results are shown in Table 1.
[0046]
(1) Measurement of holding power (a) Test sample As a test sample, the test piece which cut | disconnected the adhesive film prepared in Examples 1-9 and Comparative Examples 1-10 in 20 mm width was used.
[0047]
(B) As a tester, a holding power tester such as an instrument, etc., it is an air circulation type dryer that can be kept at 40 ± 1 ° C., the test surface of the test plate can be installed vertically, and a load of 1 kg is applied to the lower end of the sample Such a thing was used. Moreover, as a crimping | compression-bonding apparatus, the 2 kg steel roller with which the surface was coat | covered with rubber | gum was used. Furthermore, as a test plate, a SUS304 stainless steel plate having a thickness of 2.0 mm specified in JIS-G-4305 (cold rolled stainless steel plate) is 50 mm wide and 100 mm long (having holes for hooks). After cutting, the surface was well polished in the longitudinal direction with # 280 water-resistant abrasive paper as defined in JIS-R-6253, and used after being cleaned with ethyl acetate.
[0048]
(C) The measurement operation test piece was attached to the lower end of the test plate with an area of 20 × 20 mm, and was subjected to one reciprocating pressure bonding at a speed of 300 mm / min with a pressure bonding apparatus. A test plate is mounted in a testing machine maintained at 40 ± 1 ° C., left to stand for 20 minutes, and then a 1 kg load is applied to start measurement.
The holding force was the time until the test piece fell off the test plate, and when it did not drop even after 1 hour, the shifted distance was measured in units of 0.1 mm, and was taken as the value. The measurement is performed on two test pieces, and if it falls within 1 hour, the average value of the falling time is rounded to the unit of 1 minute, and if it is held for 1 hour, the average value of the shifted distance is rounded to the unit of 0.1 mm. Showed.
[0049]
(2) Shear strength (a) Test sample As a test sample, the test piece which cut | disconnected the adhesive film prepared in Examples 1-9 and Comparative Examples 1-10 in 20 mm width was used.
[0050]
(B) A constant-speed extension type tensile tester defined in JIS-B-7721 was used as a tester, instrument, or other tester. Further, the same crimping apparatus and test plate as those used for the holding force test were used.
[0051]
(C) The measurement operation test piece was attached to the lower end of the test plate with an area of 20 × 20 mm, and was subjected to one reciprocating pressure bonding at a speed of 300 mm / min with a pressure bonding apparatus. As shown in FIG. 1, the test plate and the test piece were fixed to the upper chuck and the lower chuck of the tensile tester, and were peeled off at a speed of 50 mm / min 20 minutes after the press bonding, and the strength of the fracture was recorded. This strength was converted per 1 cm 2 to obtain shear strength.
[0052]
(3) A sample having a gel fraction of 10 × 10 cm 2 was soaked in 100 g of ethyl acetate at 23 ° C. for 24 hours, filtered through a 200 mesh wire mesh, and the residue on the wire mesh was dried at 100 ° C. for 2 hours and weighed. Moreover, the weight of the 10 * 10 cm < 2 > base material which has not apply | coated the adhesive was also measured, and the gel fraction was computed from the following formula.
[Formula 1]
(Result)
[Table 1]
As is clear from the above results, the ultraviolet curable pressure-sensitive adhesive composition of the present invention has low shear strength and gel fraction before ultraviolet irradiation, but both shear strength and gel fraction are remarkably after ultraviolet irradiation. It becomes high and shows excellent holding power.
[Brief description of the drawings]
FIG. 1 is a drawing schematically showing how to attach a test plate and a test piece for measuring shear strength.
1……
Claims (2)
（ａ）アクリル酸及びアルキル（メタ）アクリレートからなる重量
平均分子量５〜１８万のポリマー １００重量部
（ｂ）分子内に３個以上のアクリロイル基を有する単量体 ０.１〜２重量部
（ｃ）光開始剤としてのベンゾフェノン類 ０.５〜５重量部
を含有し、実質的に溶剤を含まない粘着剤組成物であって、紫外線を照射する前の、１００〜１２０℃における粘度が３０〜３００ｐｓ、ゲル分率が５％以下、せん断強度が０.５ｋｇ／ｃｍ２以下であり、１００〜２０００ｍＪ／ｃｍ２の紫外線を照射した後は、ゲル分率が３０〜７５％、せん断強度が５ｋｇ／ｃｍ２以上となる紫外線硬化型粘着剤組成物。 The following three components (a) to (c)
(A) Weight consisting of acrylic acid and alkyl (meth) acrylate
100 parts by weight of polymer having an average molecular weight of 50,000 to 180,000
(B) 0.1-2 parts by weight of a monomer having 3 or more acryloyl groups in the molecule
(C) 0.5 to 5 parts by weight of benzophenones as photoinitiators
Contains, a pressure-sensitive adhesive composition substantially free of solvent, prior to irradiation with ultraviolet rays, a viscosity at 100 to 120 ° C. is 30～300Ps, gel fraction of 5% or less, the shear strength is 0. 5 kg / cm 2 or less, 100 to 2000 mJ / cm 2 after irradiation ultraviolet rays, a gel fraction of 30-75%, the ultraviolet-curable pressure-sensitive adhesive composition shear strength is 5 kg / cm 2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28636898A JP4362564B2 (en) | 1998-10-08 | 1998-10-08 | UV curable adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28636898A JP4362564B2 (en) | 1998-10-08 | 1998-10-08 | UV curable adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000109779A JP2000109779A (en) | 2000-04-18 |
| JP4362564B2 true JP4362564B2 (en) | 2009-11-11 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28636898A Expired - Lifetime JP4362564B2 (en) | 1998-10-08 | 1998-10-08 | UV curable adhesive composition |
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| Country | Link |
|---|---|
| JP (1) | JP4362564B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006273935A (en) * | 2005-03-28 | 2006-10-12 | Toray Coatex Co Ltd | Acrylic pressure-sensitive adhesive composition, pressure-sensitive adhesive tape using the composition and its manufacturing process |
| JP5052030B2 (en) * | 2005-04-12 | 2012-10-17 | 日本合成化学工業株式会社 | Adhesive sheet |
| JP5408640B2 (en) * | 2006-09-04 | 2014-02-05 | 日東電工株式会社 | Ultraviolet curable adhesive composition, ultraviolet curable adhesive sheet and method for producing the same |
| JP5087414B2 (en) | 2008-01-22 | 2012-12-05 | 日東電工株式会社 | Photocurable acrylic viscoelastic material composition, acrylic viscoelastic material, acrylic viscoelastic material layer tape or sheet, and production method thereof |
| JP5406456B2 (en) * | 2008-02-01 | 2014-02-05 | 株式会社日本触媒 | Ionizing radiation curable adhesive composition for re-peeling and use thereof |
| JP5921970B2 (en) * | 2012-06-21 | 2016-05-24 | 日東電工株式会社 | Thermally conductive adhesive composition |
| JP6168759B2 (en) * | 2012-12-06 | 2017-07-26 | 日東ライフテック株式会社 | Manufacturing method of adhesive sheet |
| JP6534841B2 (en) * | 2015-03-31 | 2019-06-26 | 株式会社フジシール | Lid label and package |
-
1998
- 1998-10-08 JP JP28636898A patent/JP4362564B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JP2000109779A (en) | 2000-04-18 |
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