JPH01221474A - Pressure-sensitive adhesive composition - Google Patents
Pressure-sensitive adhesive compositionInfo
- Publication number
- JPH01221474A JPH01221474A JP4727288A JP4727288A JPH01221474A JP H01221474 A JPH01221474 A JP H01221474A JP 4727288 A JP4727288 A JP 4727288A JP 4727288 A JP4727288 A JP 4727288A JP H01221474 A JPH01221474 A JP H01221474A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- parts
- addition
- pressure
- acrylic
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 50
- 239000000178 monomer Substances 0.000 claims abstract description 98
- 229920000642 polymer Polymers 0.000 claims abstract description 84
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 53
- 238000012644 addition polymerization Methods 0.000 claims abstract description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000009477 glass transition Effects 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001519 homopolymer Polymers 0.000 claims description 16
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 53
- 239000000853 adhesive Substances 0.000 abstract description 36
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 19
- 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 abstract description 19
- 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 abstract description 19
- 150000002148 esters Chemical class 0.000 abstract description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 239000011976 maleic acid Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- -1 isooctyl Chemical group 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000003431 cross linking reagent Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 238000012662 bulk polymerization Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- UXOFRFPVWFJROK-UHFFFAOYSA-N (2-ethenylphenyl)methanol Chemical compound OCC1=CC=CC=C1C=C UXOFRFPVWFJROK-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
- OUSXYCTXXLYBGJ-UHFFFAOYSA-N 1-ethenyl-2,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C=C)C(C(C)C)=C1 OUSXYCTXXLYBGJ-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- DBWWINQJTZYDFK-UHFFFAOYSA-N 2-ethenyl-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(C=C)=C1 DBWWINQJTZYDFK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- RAHRPJDILCRAIC-UHFFFAOYSA-N 3,3-dimethylbutan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)(C)C(C)OC(=O)C(C)=C RAHRPJDILCRAIC-UHFFFAOYSA-N 0.000 description 1
- URQYRMNIDDQKKW-UHFFFAOYSA-N 3,3-dimethylbutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(C)(C)C URQYRMNIDDQKKW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
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- 239000004971 Cross linker Substances 0.000 description 1
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- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
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- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
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- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 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
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- 238000004018 waxing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は常温および高温での接着特性にずくれかつ高
凝集力の感圧性接着剤組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a pressure-sensitive adhesive composition having excellent adhesive properties at room temperature and high temperature and having high cohesive strength.
近年、感圧性接着剤組成物の使用範囲が広がり、それに
伴って要求される特性も高度化する傾向にある。特に、
使用温度範囲が上がり、今迄以−ヒに高温での接着特性
が重要となってきている。In recent years, the range of use of pressure-sensitive adhesive compositions has expanded, and the required properties have also tended to become more sophisticated. especially,
As the operating temperature range has increased, adhesive properties at high temperatures have become more important than ever.
感圧性接着剤組成物は、ゴム系のものとアクリル系のも
のとに大別され、このうちゴム系のものは常温付近での
接着特性にすぐれているが、その反面耐熱性、耐候性に
劣り、このことから、高温での接着特性にずくれること
か望まれる用途に対しては、アクリル系のものが主に用
いられている。Pressure-sensitive adhesive compositions are broadly classified into rubber-based ones and acrylic-based ones. Of these, rubber-based ones have excellent adhesive properties near room temperature, but on the other hand, they have poor heat resistance and weather resistance. For this reason, acrylic-based materials are mainly used for applications where deterioration in adhesive properties at high temperatures is desired.
ところで、アクリル系ポリマーは、それ自身に粘着感が
あり、粘着付与樹脂を添加しなくとも感圧性接着剤とな
りうるが、粘着付与樹脂を添加したものに較べ、常温で
の接着力が弱い。このため、通常は他の感圧性接着剤に
おけるのと同様に粘着付与樹脂を添加して常温での接着
力を向上させるようにしている。By the way, acrylic polymers themselves have a sticky feel and can be used as pressure-sensitive adhesives without the addition of tackifying resins, but their adhesive strength at room temperature is weaker than those with tackifying resins added. For this reason, a tackifying resin is usually added to improve the adhesive strength at room temperature, similar to other pressure-sensitive adhesives.
ところが、粘着付与樹脂を添加すると、接着力の温度依
存性が大きくなり、高温ではむしろアクリル系ポリマー
単独よりも接着力が低下してくることがあるなど、高温
での接着特性については必ずしも満足できるものとはい
えなかった。However, when a tackifying resin is added, the temperature dependence of adhesive strength increases, and the adhesive strength at high temperatures may actually be lower than that of acrylic polymer alone, so the adhesive properties at high temperatures are not always satisfactory. It was nothing special.
このように、アクリル系の感圧性接名剤Ｎ、■成物は、
コム系のものに較べれは高温での接着特性にすぐれてい
るか、常温での接着力を確保したうえで高温においても
ずくれた接着特性を発揮させるという観点、つまり常温
での接着力と高温での接着力とを両立させるという観点
からＧＪ、なお充分に満足できるものとはいえなかった
。In this way, the acrylic pressure-sensitive contact material N,
Compared to com-based products, it has superior adhesive properties at high temperatures, or from the perspective of ensuring adhesive strength at room temperature and exhibiting adhesive properties that are loose at high temperatures. From the viewpoint of achieving both adhesive strength and adhesion, GJ was still not fully satisfactory.
したがって、この発明は、上記従来のアクリル系の感圧
性接着剤組成物の問題点を解消して、接着力の温度依存
性が小さく、常温はもちろん高温においてもすくれた接
着特性を発揮しろるアクリル系の感圧性接着剤組成物を
提供することをひとつの目的としている。また、この発
明の目的の他のひとつは、上記接着特性の改善に加えて
凝集力Ｑこもずくれたアクリル系の感圧性接着剤組成物
を提供することにある。Therefore, the present invention solves the problems of the conventional acrylic pressure-sensitive adhesive compositions mentioned above, has a small temperature dependence of adhesive strength, and exhibits excellent adhesive properties not only at room temperature but also at high temperatures. One objective is to provide an acrylic pressure sensitive adhesive composition. Another object of the present invention is to provide an acrylic pressure-sensitive adhesive composition that not only improves the adhesive properties described above but also has a low cohesive force Q.
この発明者らは、」−記の目的を達成するために鋭意検
削した結果、接着性ポリマーとじて、アクリル系ポリマ
ーに特定の、０ｉ量体を付加重合させてなる付加重合ポ
リマーを使用するとともに、この付加重合ポリマーとの
相溶性に劣る粘着付与樹脂を併用することにより、つま
りこの粘着付与樹脂と上記付加重合ポリマーとを混合し
てフィルム化したもののヘイズ値が上記相溶性の悪さを
示す特定範囲の値となるような組み合わせ構成とするこ
とにより、接着力の温度依存性が小さくなって、常温は
もちろん高温においてもずくれた接着特性を発揮し、そ
のうえ凝集力にもすぐれた感圧性接着剤組成物が得られ
るものであることを知り、この発明を完成するに至った
。The inventors, as a result of extensive research to achieve the above object, used an addition polymer formed by addition-polymerizing a specific Oi-mer to an acrylic polymer as an adhesive polymer. At the same time, by using a tackifier resin that has poor compatibility with this addition polymer, that is, the haze value of a film formed by mixing this tackifier resin and the above addition polymer shows the poor compatibility. By creating a combination structure that achieves values within a specific range, the temperature dependence of adhesive strength is reduced, and pressure-sensitive adhesives exhibit excellent adhesive properties not only at room temperature but also at high temperatures, and also have excellent cohesive strength. The present invention was completed based on the knowledge that a drug composition can be obtained.
すなわち、この発明は、アクリル酸もしくはメタクリル
酸と炭素数２〜１５の脂肪族アルコールとのエステルか
らなる主単量体に極性基含有不飽和単量体を加えた単量
体混合物を共重合させてなる室温で粘着性を有するアク
リル系ポリマーに、ポモポリマーないしコポリマーのガ
ラス転移点が２７３°Ｋ以上となりうる一種もしくは二
種以上のエヂレン性不飽和単量体を付加重合させて得ら
れる付加重合ポリマーと、この付加重合ポリマーとの相
溶性に劣る粘着付与樹脂とを含む感圧性接着剤組成物で
あって、上記付加重合ポリマーと上記粘着付与樹脂とを
混合してフィルム化したもののヘイズ値か１５〜９５％
の範囲にあることを特徴とする感圧性接着剤組成物に係
るものである。That is, this invention copolymerizes a monomer mixture in which a polar group-containing unsaturated monomer is added to a main monomer consisting of an ester of acrylic acid or methacrylic acid and an aliphatic alcohol having 2 to 15 carbon atoms. An addition polymer obtained by addition-polymerizing an acrylic polymer that is sticky at room temperature with one or more ethylenically unsaturated monomers that can have a pomopolymer or copolymer with a glass transition point of 273°K or higher. and a tackifier resin having poor compatibility with the addition polymer polymer, the haze value of a film obtained by mixing the addition polymer polymer and the tackifier resin is 15. ~95%
The present invention relates to a pressure-sensitive adhesive composition characterized in that the pressure-sensitive adhesive composition is in the following range.
なお、ト記のヘイズ値とは、付加重合ポリマーと粘着イ
」与樹脂とを混合してフィルム化したものに可視光を照
射したときの全透過光に対する拡散透過光の割合として
表わされるものである。すなわち、上記ヘイズ値は、付
加重合ポリマーと粘着付与樹脂との相溶性にすくれると
きは上記フィルムが透明となるためにこの値が小さくな
り、逆に上記相溶性に劣るときは上記フィルムに濁りが
生しるためこの値が大きくなる、というように、付加重
合ポリマーと粘着付与樹脂との相溶性の良否を示す尺度
となるものである。The haze value mentioned above is expressed as the ratio of diffusely transmitted light to the total transmitted light when visible light is irradiated on a film made by mixing an addition polymer and an adhesive agent resin. be. In other words, when the compatibility between the addition polymer and the tackifier resin is poor, the film becomes transparent and the haze value decreases; on the other hand, when the compatibility is poor, the film becomes cloudy. This value becomes large due to the formation of the tackifying resin, which is a measure of the compatibility between the addition polymer and the tackifying resin.
この明細書では、上記ヘイズ値の測定に際し、便宜」二
、透明なヘ−スフイルム上に付加重合ポリマーと粘着イ
」与樹脂との均一混合物を所定厚みに塗布乾燥してなる
複合フィルムを作製し、この複合フィルム全体の全光線
透過率と拡散透過率とを測定して、下記の式；
にしたがって算出したもので、上記のヘ−スフイルムと
しては７５μｍ厚のポリエステルフィルム（ヘイズ値０
．５）を適用し、上記混合物の乾燥厚めは５０μｍとし
、また全光線透過率と拡散透過率との測定は日本電色工
業株式会社製のオートマチックデジタルヘーズメータ（
ＮＤｉ（−２０Ｄ）を用いて行った。In this specification, for the purpose of measuring the haze value, a composite film is prepared by coating a transparent haze film with a homogeneous mixture of an addition polymer and a tackifier resin to a predetermined thickness and drying it. The total light transmittance and diffuse transmittance of the entire composite film were measured and calculated according to the following formula;
．． 5) was applied, the dry thickness of the above mixture was set to 50 μm, and the total light transmittance and diffuse transmittance were measured using an automatic digital haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
This was done using NDi (-20D).
なおまた、この明細書において、（メタ）アクリル酸ア
ルキルエステルとあるはアクリル酸アルキルエステルお
よび／またはメタクリル酸アルキルエステルを、（メタ
））２クリレートとあるはアクリレートおよび／または
メタクリレ−１・を、 （メタ）アクリル酸とあるはア
クリル酸および／またはメタクリル酸を、それぞれ意味
するものとする。Furthermore, in this specification, (meth)acrylic acid alkyl ester refers to acrylic acid alkyl ester and/or methacrylic acid alkyl ester, and (meth))2 acrylate refers to acrylate and/or methacrylate-1. (Meth)acrylic acid shall mean acrylic acid and/or methacrylic acid, respectively.
この発明におけるアクリル系ポリマーは、アクリル酸も
しくはメタクリル酸と炭素数２〜１５の脂肪族アルコー
ルとのエステルからなる主単量体に極性基含有不飽和単
量体を加えてなる、また必要に応してこれらと共重合可
能なビニル系単量体をさらに加えてなる単量体混合物を
常法により共重合させてなるものである。The acrylic polymer in this invention is made by adding an unsaturated monomer containing a polar group to the main monomer consisting of an ester of acrylic acid or methacrylic acid and an aliphatic alcohol having 2 to 15 carbon atoms, and if necessary, A monomer mixture obtained by further adding a vinyl monomer copolymerizable with these monomers is copolymerized by a conventional method.
主単量体としては、脂肪族アルコールのアルキル基がエ
チル基、ブチル基、５ｅｃ−ブチル基、イソブチル基、
ヘキシル基、ヘプチル基、オクチル基、イソオクチル基
、２−エナルヘキシル基などからなるアクリル酸もしく
はメタクリル酸のエステルが挙げられ、これらの一種ま
たは二種以上が用いられる。アルキル基の炭素数が２〜
１５の範囲外となると、感圧性接着剤としての特性が損
なわれるため、好ましくない。As the main monomer, the alkyl group of the aliphatic alcohol is an ethyl group, a butyl group, a 5ec-butyl group, an isobutyl group,
Examples include esters of acrylic acid or methacrylic acid consisting of hexyl, heptyl, octyl, isooctyl, 2-enalhexyl, etc., and one or more of these may be used. The number of carbon atoms in the alkyl group is 2 or more
If it is outside the range of 15, the properties as a pressure-sensitive adhesive will be impaired, which is not preferable.
極性基含有不飽和単量体としては、（メタ）アクリル酸
、イタコン酸、クロトン酸などのカルボキシル基含有単
量体、２−（メタ）アクリルアジドプロパンスルホン酸
の如きスルホン基含有単量体、（メタ）アクリドキシエ
チルホスフエートの如きリン酸基含有単量体、２−ヒド
ロキシエチル（メタ）アクリレート、２−ヒドロキシプ
ロピル（メタ）アクリレートなどの水酸基含有単量体、
Ｎ−Ｎ−ジメチル（エチル）アクリレート、ビス−Ｎ−
Ｎ−ジメチルアミノエチルマレエートなどのアミノ基含
有単量体、（メタ）アクリルアミド、Ｎ−メチロールア
クリルアミドなどのアミＦ基含有単量体、グリシジル（
メタ）アクリレートの如きエポキシ基含有単量体、アク
リロニトリルの如きニトリル基含有単量体などが挙げら
れる。これら極性基含有不飽和単量体は接着力の増大に
寄与するものであり、その一種または二種以上が用いら
れる。Examples of the polar group-containing unsaturated monomer include carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, and crotonic acid, sulfonic group-containing monomers such as 2-(meth)acrylazidopropanesulfonic acid, Phosphate group-containing monomers such as (meth)acridoxyethyl phosphate, hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
N-N-dimethyl(ethyl)acrylate, bis-N-
Amino group-containing monomers such as N-dimethylaminoethyl maleate, amine F group-containing monomers such as (meth)acrylamide and N-methylolacrylamide, glycidyl (
Examples include epoxy group-containing monomers such as meth)acrylate and nitrile group-containing monomers such as acrylonitrile. These polar group-containing unsaturated monomers contribute to increasing adhesive strength, and one or more of them may be used.
上記の主単量体および極性基含有不飽和単量体とともに
必要に応じて用いられるこれらと共重合可能なビニル系
単量体としては、たとえば酢酸ビニル、ビニルピロリド
ン、プロピオン酸ビニル、スチレンおよびその誘導体、
塩化ビニルなどが挙げられ、これらの一種または二種以
上が用いられこのよ・うな単量体混合物の組成としては
、主単量体が５０〜９９．９５重量％、極性基含有不飽
和単量体が２０〜０．０５重量％、共重合可能なビニル
系単量体が３０〜０重量％となるようにするのがよい。Examples of vinyl monomers that can be copolymerized with the above-mentioned main monomers and polar group-containing unsaturated monomers include vinyl acetate, vinyl pyrrolidone, vinyl propionate, styrene, and their like. derivative,
Examples include vinyl chloride, and the composition of such a monomer mixture in which one or more of these is used is 50 to 99.95% by weight of the main monomer, and unsaturated monomers containing polar groups. It is preferable that the copolymerizable vinyl monomer be 20 to 0.05% by weight and the copolymerizable vinyl monomer be 30 to 0% by weight.
主単量体および極性基含有不飽和単量体が上記範囲外と
なると接着特性上好ましい結果を得にくい。When the main monomer and the polar group-containing unsaturated monomer are outside the above range, it is difficult to obtain favorable results in terms of adhesive properties.
このような単量体構成からなるアクリル系ポリマーはそ
れ自体室温で粘着性を有するものであるが、分子量とし
てはＧＰＣ（ゲルパーミェーションクロマトグラフィー
）法による分子量分布曲線から測定される重量平均分子
量が約１０万以上、特に２０〜２００万程度の範囲にあ
るのが好ましい。Acrylic polymers made of such a monomer structure are sticky at room temperature, but the molecular weight is the weight average measured from the molecular weight distribution curve by GPC (gel permeation chromatography). It is preferable that the molecular weight is about 100,000 or more, particularly in the range of about 200,000 to 2,000,000.
この発明においては、このようなアクリル系ポリマーに
特定のエチレン性子飽和単量体を伺加重合させることに
より、付加重合ポリマーとする。In the present invention, an addition polymerization polymer is obtained by subjecting such an acrylic polymer to a specific ethylenic saturated monomer.
この付加重合ポリマーとしないで、アクリル系ポリマー
にそのまま後述の相溶性に劣る粘着付与樹脂を配合した
ときでも、常温および高温での接着特性の改良効果は認
められる。しかし、この発明のように、伺加重合ポリマ
ーとしたうえで上記粘着付与樹脂を配合すると、高温で
の接着特性がさらに一段と改善され、そのうえ凝集力の
大きな接着剤組成物が得られるのである。Even when the acrylic polymer is directly blended with a tackifying resin having poor compatibility, which will be described later, without forming this addition polymer, the effect of improving adhesive properties at room temperature and high temperature is observed. However, as in the present invention, when the above-mentioned tackifying resin is blended with the tackified polymer, the adhesive properties at high temperatures are further improved, and an adhesive composition with high cohesive strength can be obtained.
なお、余談ではあるが、イ」加重台のために使用する特
定のエチレン性不飽和単量体からホモポリマーないしコ
ポリマーを単独でつくり、これをアクリル系ポリマーに
ブレンドするだけでは、高温での接着特性や凝集力の大
幅な改善は認められない。また、付加重合のために使用
する特定のエチレン性不飽和単量体をアクリル系ポリマ
ーの合成時に一緒に添加して同時に共重合させてなるも
のを用いても、上記同様にこの発明の目的とするような
接着剤組成物は得られない。As an aside, it is important to note that simply making a homopolymer or copolymer from the specific ethylenically unsaturated monomer used for the weighting base and blending it with an acrylic polymer will result in poor adhesion at high temperatures. No significant improvement in properties or cohesion was observed. Furthermore, even if a specific ethylenically unsaturated monomer used for addition polymerization is added at the time of synthesis of the acrylic polymer and copolymerized at the same time, the object of the present invention will not be achieved as described above. It is not possible to obtain such an adhesive composition.
付加重合のために用いられる特定のエチレン性不飽和単
量体とは、そのホモポリマーないしコポリマーのガラス
転移点が２７３°Ｋ以上、好適には３００’に以上とな
りうる一種もしくは二種以上の、（：飽和単量体である
。ここて、ポモポリマーないしコポリマーのガラス転移
点が２７３°Ｋより低く ６なるものでは、高温での
接着力および凝集力の改善効果か充分に得られず不適当
である。The specific ethylenically unsaturated monomer used for addition polymerization is one or more monomers whose homopolymer or copolymer has a glass transition point of 273°K or higher, preferably 300°K or higher. (: It is a saturated monomer. Pomopolymers or copolymers whose glass transition point is lower than 273°K are unsuitable because they cannot sufficiently improve the adhesion and cohesive force at high temperatures. be.
なお、コポリマーのカラス転移点が２７３°Ｋ以上とな
りうる二種以上の不飽和単量体のなかには、各単量体の
ポモポリマーのガラス転移点がそれぞれ２７３°Ｋ以上
となりうる単量体混合物のほかに、ポモポリマーのカラ
ス転移点が２７３°ＫＪ４上となりうる不飽和単量体と
、ポモポリマーのカラス転移点が２７３°Ｋより低くな
る不飽和単量体との混合物も含まれる。後者の単量体混
合物はその組成比によってコポリマー としたときのカ
ラス転移点か２７３°Ｋ以上を示し・うるちのであれは
よい。たとえばアクリル酸ｎ−フチル（２７３°Ｋ以下
）：メタクリル酸メチル（３００°Ｋ以上）：イタコン
酸（３００’に以上）−］５：６５：１５の単量体混合
物はコポリマーのガラス転移点が２７３°Ｋ以」−とな
り、適用可能である。In addition, among the two or more unsaturated monomers that can make the copolymer have a glass transition point of 273°K or more, there are also monomer mixtures that can make the glass transition point of the pomopolymer of each monomer 273°K or more. Also included are mixtures of unsaturated monomers that can give the pomopolymer a glass transition temperature above 273°KJ4 and unsaturated monomers that can give the pomopolymer a glass transition temperature below 273°K. The latter monomer mixture exhibits a glass transition point of 273°K or higher when made into a copolymer depending on its composition ratio. For example, a monomer mixture of n-phthyl acrylate (below 273°K): methyl methacrylate (above 300°K): itaconic acid (above 300')-]5:65:15 has a copolymer glass transition point of 273°K or higher, and is applicable.
このような不飽和単量体としては、スチレン、酢酸ビニ
ル、アクリロニトリルおよびメタクリコニ１〜リルの群
から選ばれたそのホモポリマーのガラス転移点がいずれ
も３００°Ｋ以上となりうる不飽和単量体か、あるいは
アクリル酸エステル、メタクリル酸エステルもしくはス
チレン誘導体の群から選ばれたホモポリマーのガラス転
移点が２７３°Ｋ以上となりうる不飽和単量体（以下、
両群に属する不飽和単量体をＡ成分単量体と称する）が
とくに好適である。Such unsaturated monomers include unsaturated monomers selected from the group of styrene, vinyl acetate, acrylonitrile, and methacriconyl, whose homopolymers can all have a glass transition point of 300°K or higher. or an unsaturated monomer (hereinafter referred to as
Unsaturated monomers belonging to both groups are particularly preferred.
後者の群に属する不飽和単量体の具体例としては、アク
リル酸シクロヘキシル（２８９°Ｋ）、アクリル酸メチ
ル（２７９°Ｋ）、メタクリル酸ｎ −ブチル（２９３
°Ｋ）、Ｎ・Ｎジメチルアミノエチルメ＝ククリレ−ト
（２８９°Ｋ）、メタクリル酸ヘキサデシル（２８８°
Ｋ）、メタクリル酸２−メトキシエチル（２８６°Ｋ）
、４−ブチルスチレン（２７９°Ｋ）などのホモポリマ
ーのガラス転移点が２７３°Ｋ以上となりうる不飽和単
量体かあり、またメタクリル酸２−ブチル（３１８°Ｋ
）、３・３−ジメチルブチルメタクリレート（３１８°
Ｋ）、３・３−ジメチル−２−ブチルメタクリレート（
３８１°Ｋ）、メタクリル酸エチル（３３８°Ｋ）、ク
リシシルメタクリレ−＋１３１９°Ｋ）、イソボロニル
メタクリレ−１−（３８３°Ｋ）、メタクリル酸イソブ
チル（３２６°Ｋ）、イソプロピルメタクリレート（３
５４°Ｋ）、メタクリル酸メチル（３７８°Ｋ）、メタ
クリル酸エスル（３７８°Ｋ）、ｎ−プロピルメタクリ
レート （３０８°Ｋ）、イソボロニルアクリレート
（３６７°Ｋ）、４−ｔｅｒｔ−ブチルスチレン（４０
３°Ｋ）、２・４−ジイソプロピルスチレン（４４１°
Ｋ）、２・５−ジメチルスチレン（４１６°Ｋ）、３・
４−ジエチルスチレン（３８２°Ｋ）、２−ヒドロキシ
メチルスチレン（４３３°Ｋ）、４−メチルスチレン（
３６６’Ｋ）、２−メチルスチレン（３６６°Ｋ）など
のホモポリマーのガラス転移点が３００°Ｋ以上となり
うる不飽和単量体がある。これら後者の群に属する不飽
和単量体のなかでもホモポリマーのガラス転移点が３０
０°Ｋ以上となりうるものが特に望ましい。Specific examples of unsaturated monomers belonging to the latter group include cyclohexyl acrylate (289°K), methyl acrylate (279°K), and n-butyl methacrylate (293°K).
°K), N-N dimethylaminoethyl methacrylate (289 °K), hexadecyl methacrylate (288 °K),
K), 2-methoxyethyl methacrylate (286°K)
, 4-butylstyrene (279°K) and other unsaturated monomers whose homopolymer glass transition temperature can be 273°K or higher, and 2-butyl methacrylate (318°K)
), 3,3-dimethylbutyl methacrylate (318°
K), 3,3-dimethyl-2-butyl methacrylate (
381°K), ethyl methacrylate (338°K), chrysyl methacrylate (+1319°K), isobornyl methacrylate (383°K), isobutyl methacrylate (326°K), isopropyl methacrylate ( 3
54°K), methyl methacrylate (378°K), ester methacrylate (378°K), n-propyl methacrylate (308°K), isobornyl acrylate
(367°K), 4-tert-butylstyrene (40
3°K), 2,4-diisopropylstyrene (441°
K), 2,5-dimethylstyrene (416°K), 3.
4-diethylstyrene (382°K), 2-hydroxymethylstyrene (433°K), 4-methylstyrene (
There are unsaturated monomers whose homopolymer glass transition point can be 300°K or higher, such as 366'K) and 2-methylstyrene (366°K). Among these unsaturated monomers belonging to the latter group, the glass transition point of the homopolymer is 30
Particularly desirable is one that can have a temperature of 0°K or more.
この発明においてはこれらＡ成分単量体をその二つの群
の一方もしくは両方からアクリル系ポリマーの種類に応
じて一種もしくは二種以上を選定して使用するのがよい
が、さらにこれらＡ成分単量体とともにこれと共重合可
能でかつそのコポリマーのガラス転移点が２７３°Ｋ以
上となりうる不飽和単量体（以下、これをＢ成分単量体
と称する）を併用してもよい。In this invention, it is preferable to use one or more of these A component monomers selected from one or both of the two groups depending on the type of acrylic polymer; An unsaturated monomer (hereinafter referred to as component B monomer) which can be copolymerized with the monomer and whose copolymer has a glass transition point of 273°K or higher may be used together with the monomer.
このようなり成分単量体としては、アクリル酸、メタク
リル酸、イクコン酸なとのそのホモポリマーのガラス転
移点が２７３°Ｋ以上となりうる不飽和単量体や、アク
リル酸ｎ−ブチル、アクリル酸エチル、アクリル酸２−
エチルヘキシルなとそのホモポリマーのガラス転移点が
２７３°Ｋより低くなる不飽和単量体など一般のアクリ
ル系感圧接着剤に使用される単量体が一種もしくは二種
以上用いられる。Such component monomers include unsaturated monomers whose homopolymers such as acrylic acid, methacrylic acid, and ichonic acid can have a glass transition temperature of 273°K or higher, n-butyl acrylate, and acrylic acid. Ethyl, acrylic acid 2-
One or more monomers used in general acrylic pressure-sensitive adhesives, such as ethylhexyl and unsaturated monomers whose homopolymers thereof have a glass transition point lower than 273°K, are used.
これらＢ成分単量体の使用量は、コポリマーのガラス転
移点を決めるひとつの因子となるため、この点を勘案し
た上でＡ、Ｂ両成分単量体の種類に応して適宜決定ずれ
はよい。一般には、全単量体中９５重量％以下、好適に
は３０重量％以下とするのが好ましい。The amount of these component B monomers used is one of the factors that determines the glass transition point of the copolymer, so taking this into account, the amount of the B component monomer to be used can be determined as appropriate depending on the type of both component monomers A and B. good. In general, it is preferably 95% by weight or less, preferably 30% by weight or less based on the total monomers.
この発明においてこのようなエチレン性不飽和単量体を
室温で粘着性を有するアクリル系ポリマーに付加重合さ
せるに当たり、付加重合系内に有機溶剤を含ませた溶液
重合法や溶媒を全く使用しないバルク重合法のいずれを
採用してもよい。In this invention, when addition polymerizing such an ethylenically unsaturated monomer to an acrylic polymer that is sticky at room temperature, a solution polymerization method in which an organic solvent is included in the addition polymerization system or a bulk polymerization method that does not use any solvent is used. Any polymerization method may be employed.
溶液重合法によれば良好な重合作業性が得られるととも
に、使用する有機溶剤が重合反応時の連鎖移動剤として
効果的に作用して過度な付加重合反応を抑制し、室温で
粘着性を有するアクリル系ポリマーの分子量がもともと
高い場合などの重合反応時のケル化を防いたり、付加重
合ポリマーとこのポリマーとともに一部生成するポモポ
リマーないしコポリマーとを適度な分子量とするのに非
常に好結果を持たらす。According to the solution polymerization method, good polymerization workability is obtained, and the organic solvent used effectively acts as a chain transfer agent during the polymerization reaction to suppress excessive addition polymerization reaction, resulting in adhesiveness at room temperature. It has very good results in preventing kelization during the polymerization reaction when the acrylic polymer has a high molecular weight to begin with, and in adjusting the molecular weight of the addition polymer and the pomopolymer or copolymer partially formed with this polymer to an appropriate molecular weight. Tarasu.
このような有機溶剤の例としては、トルエン、ヘンセン
、キシレン、ヘキサン、ヘプタン、ｎ−オクタン、イソ
オクタン、酢酸エチル、アセトン、メチルエチルケトン
、メタノール、エタノール、イソプロパツールなどが挙
げられる。なお、これらの有機溶剤は室温で粘着性を有
するアクリル系ポリマーの合成に使用した有機溶剤をそ
のまま利用してもよい。Examples of such organic solvents include toluene, Hensen, xylene, hexane, heptane, n-octane, isooctane, ethyl acetate, acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, and the like. Incidentally, as these organic solvents, the organic solvents used in the synthesis of the acrylic polymer, which is sticky at room temperature, may be used as they are.
有機溶剤の使用量は、室温で粘着性を有するアクリル系
ポリマー１００重量部に対して通常５〜９００重量部、
好適には２５〜４００重量部程度であり、この量をあま
り多くしすぎると付加重合ポリマーの生成量が少なくな
りホモポリマーが多く生成してくるためこの発明の効果
が充分に得られなくなる。The amount of organic solvent used is usually 5 to 900 parts by weight per 100 parts by weight of the acrylic polymer that is sticky at room temperature.
The amount is preferably about 25 to 400 parts by weight, and if this amount is too large, the amount of addition polymerization polymer produced will decrease and a large amount of homopolymer will be produced, making it impossible to obtain sufficient effects of the present invention.
なお、有機溶剤の使用量の決定に当たっては、エチレン
性不飽和単量体の種類、この単量体ラジカルに対する有
機溶剤の連鎖移動のしやすさ、室温で粘着性を有するア
クリル系ポリマーの組成ないし分子量などを勘案し、そ
の他重合開始剤の種類ないし使用量なども考慮した方が
よい。The amount of organic solvent to be used should be determined based on the type of ethylenically unsaturated monomer, the ease of chain transfer of the organic solvent to the monomer radical, and the composition of the acrylic polymer, which is sticky at room temperature. It is better to take into consideration the molecular weight and other factors such as the type and amount of polymerization initiator used.
たとえばエチレン性不飽和単量体として酢酸ビニルを使
用するときは、好ましくはアクリル系ポサマー１’００
重量部に対して通常５〜７０重量部とするのがよく、酢
酸ビニル以外の前記入成分単量体を使用するときは同割
合が５〜４００重量部となるようにするのがよい。For example, when using vinyl acetate as the ethylenically unsaturated monomer, preferably acrylic posamer 1'00
The proportion is usually 5 to 70 parts by weight, and when the above-mentioned monomers other than vinyl acetate are used, the proportion is preferably 5 to 400 parts by weight.
また、一般に連鎖移動定数の小さい酢酸エチル、ヘンゼ
ンなどの有８！溶剤を使用したり分子量の非常に高いア
クリル系ポリマーに対しては溶剤の使用量を多くした方
か好ましく、逆に連鎖移動定数の大きいトルエン、イソ
プロパツールなどの有機溶剤を使用したり分子量の比較
的低いアクリル系ポリマーに対しては溶剤の使用量を少
なくした方がよい。In addition, there are compounds such as ethyl acetate and Hensen, which generally have small chain transfer constants. For acrylic polymers with very high molecular weights, it is preferable to use a large amount of solvent.On the contrary, it is preferable to use organic solvents such as toluene and isopropanol, which have large chain transfer constants, or for acrylic polymers with very high molecular weights. For relatively low acrylic polymers, it is better to use less solvent.
一方、このような溶剤を含ませないバルク重合法では、
室温で粘着性を有するアクリル系ポリマーとしてその分
子量ができるだけ低いものを選定し、また分子量の高い
アクリル系ポリマーを使用するときは重合系内に適宜の
連鎖移動剤を含ませて重合時のゲル化防止や付加重合反
応が過度に進みすぎないように配慮するのがよい。On the other hand, in bulk polymerization methods that do not contain such solvents,
Select an acrylic polymer with the lowest possible molecular weight that is sticky at room temperature, and when using an acrylic polymer with a high molecular weight, include an appropriate chain transfer agent in the polymerization system to prevent gelation during polymerization. It is advisable to take precautions to prevent the addition polymerization reaction from proceeding excessively.
上記の連鎖移動剤としては、たとえばチオグリコール、
千オグリコール酸、ブチルメルカプクン、ラウリルメル
カプタンなどの従来公知の連鎖移動剤が広く含まれる。Examples of the above chain transfer agent include thioglycol,
A wide range of conventionally known chain transfer agents such as 1000-glycolic acid, butyl mercapkun, and lauryl mercaptan are included.
使用量はエチレン性不飽和単量体１００重量部に対して
０．０１〜０．１重量部、好適には０．０３〜０．６重
量部程度でよい。The amount used may be about 0.01 to 0.1 part by weight, preferably about 0.03 to 0.6 part by weight, per 100 parts by weight of the ethylenically unsaturated monomer.
このような溶液重合ないしバルク重合において室温で粘
着性を有するアクリル系ポリマーとエチレン性不飽和単
量体との配合割合は、一般にアクリル系ポリマー１．０
０重量部に対してエチレン性不飽和単量体が５〜２００
重量部、好適には１０〜１５０重量部である。この量が
あまりに多くなりすぎると接着特性と凝集力との両立か
難しくなるため、好ましくない。In such solution polymerization or bulk polymerization, the blending ratio of the acrylic polymer, which is sticky at room temperature, and the ethylenically unsaturated monomer is generally 1.0% of the acrylic polymer.
5 to 200 ethylenically unsaturated monomers per 0 parts by weight
parts by weight, preferably 10 to 150 parts by weight. If this amount is too large, it becomes difficult to achieve both adhesive properties and cohesive force, which is not preferable.
もちろん、このような使用量は重合反応時のゲル化防止
や付加重合反応が過度に進みすぎないように、使用する
アクリル系ポリマーの組成ないし分子量やエチレン性不
飽和車量体の種類により、また溶液重合法を採用するか
バルク重合法を採用するかにより、さらに溶液重合法で
は使用する有機溶剤の種類により適宜決定すべきであり
、その最適範囲は種々の態様においてかなり相違する。Of course, the amount used depends on the composition and molecular weight of the acrylic polymer used and the type of ethylenically unsaturated polymer, in order to prevent gelation during the polymerization reaction and to prevent the addition polymerization reaction from proceeding too much. It should be determined appropriately depending on whether a solution polymerization method or a bulk polymerization method is employed, and in addition, in the case of a solution polymerization method, the type of organic solvent used, and the optimum range differs considerably in various embodiments.
一般的には、分子量の高いアクリル系ポリマーを使用す
るときは分子量の低いアクリル系ポリマーを使用すると
きに較へて、またエチレン性不飽和単量体として酢酸ビ
ニル以外の前記Ａ成分単量体を使用する場合は同単量体
として酢酸ビニルを使用する場合に較べて、またバルク
重合法を採用するときは溶液重合法を採用するときに較
べて、さらに溶液重合法において連鎖移動定数の小さい
有機溶剤を使用するときは同定数の大きいものを使用す
るときに較べて、それぞれエチレン性不飽和単量体の使
用量を少なくした方がよい。Generally, when using an acrylic polymer with a high molecular weight, compared to when using an acrylic polymer with a low molecular weight, the above A component monomer other than vinyl acetate is used as an ethylenically unsaturated monomer. When using vinyl acetate as the same monomer, the chain transfer constant is smaller when using bulk polymerization method than when using solution polymerization method. When using an organic solvent, it is better to use a smaller amount of each ethylenically unsaturated monomer than when using one with a large number of identifications.
また、エチレン性不飽和単量体の中にはこれに含まれる
官能基とアクリル系ポリマー中に含まれる官能基との反
応性の強いものもあり、このような場合は両者の反応に
よるケル化を防止する観点からもその使用量を適宜の範
囲に設定しなければならない。In addition, some ethylenically unsaturated monomers have strong reactivity between the functional groups contained in them and the functional groups contained in acrylic polymers, and in such cases, kelization due to the reaction between the two may occur. The amount used must be set within an appropriate range from the perspective of preventing this.
この発明における付加重合開始反応は光、電子線などの
エネルギーで行わせることもできるが、通常は室温で粘
着性を有するアクリル系ポリマーの合成に使用される一
般のラジカル重合触媒を使用して行えばよい。この触媒
にはアゾヒスイソブチロニトリルのようなアゾ系化合物
や各種の有機過酸化物などが含まれ、とくに有機過酸化
物を使用すると接着力と凝集力との改善に好結果が持た
らされる。Although the addition polymerization initiation reaction in this invention can be carried out using energy such as light or electron beams, it is usually carried out using a general radical polymerization catalyst used in the synthesis of acrylic polymers that are sticky at room temperature. That's fine. This catalyst contains azo compounds such as azohisisobutyronitrile and various organic peroxides, and the use of organic peroxides has shown particularly good results in improving adhesive strength and cohesive strength. Ru.
このような有機過酸化物としては、ヘンゾイルバーオキ
ザイド、クメンハイドロパーオキサイド、ジーｔｅｒｔ
−ブチルパーオキサイド、ｔｅｒｔ−プチルパーオキシ
ヘンゾエート、ラウロイルパーオキサイド、ケトンパー
オギサイド、ｔｅｒｔ−ブチルパーオキシ２−エチルヘ
キサノエート、メチルエチルケ１−ンパーオキサイド、
シクロヘキサノンパーオキザイＦなどがある。これらの
有機過酸化物やアゾ系化合物などの重合触媒の使用量は
、エチレン性不飽和単量体１００重量部に対して０．０
１〜５重量部、好ましくは０．０５〜３重量部程度であ
る。Such organic peroxides include henzoyl peroxide, cumene hydroperoxide, and tert.
-butyl peroxide, tert-butyl peroxyhenzoate, lauroyl peroxide, ketone peroxide, tert-butyl peroxy 2-ethylhexanoate, methyl ethyl chenene peroxide,
Examples include cyclohexanone peroxai F. The amount of polymerization catalysts such as organic peroxides and azo compounds used is 0.0 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer.
The amount is about 1 to 5 parts by weight, preferably about 0.05 to 3 parts by weight.
付加重合反応の温度は、重合触媒の使用量とともに得ら
れる付加重合ポリマーの分子量に大きく影響するため、
必要とする分子量に応して適宜設定するのがよく、一般
には７０℃以上の温度下で行えはよい。The temperature of the addition polymerization reaction, as well as the amount of polymerization catalyst used, greatly affects the molecular weight of the resulting addition polymer.
It is preferable to set the temperature appropriately according to the required molecular weight, and it is generally preferable to carry out the reaction at a temperature of 70° C. or higher.
このようにして得られる重合反応物は、ポリマー成分と
して一部エチレン性不飽和単量体のホモポリマーないし
コポリマーを含み、また未反応の室温で粘着性を有する
アクリル系ポリマーを含んでいるか、主に上記ポリマー
にエチレン性不飽和単量体がイ」加重合した付加重合ポ
リマーを含むものである。The polymerization reaction product obtained in this way contains a homopolymer or copolymer of an ethylenically unsaturated monomer as a polymer component, and also contains an unreacted acrylic polymer that is sticky at room temperature, or mainly contains an acrylic polymer that is sticky at room temperature. It contains an addition polymer in which an ethylenically unsaturated monomer is polymerized with the above polymer.
この付加重合ポリマーにおける付加物の分子量はほぼホ
モポリマーないしコポリマーの分子量に一致し、前記付
加重合反応の条件の選定によって種々変化させうるが、
一般には重量平均分子量が１、０００〜２００．０００
程度、好ましくは５，０００〜７０．０００程度である
。上記付加物の重量平均分子量はＧＰＣ法による分子量
分布曲線から容易に測定することかできる。The molecular weight of the adduct in this addition polymerization almost corresponds to the molecular weight of the homopolymer or copolymer, and can be varied depending on the selection of the conditions of the addition polymerization reaction.
Generally, the weight average molecular weight is 1,000 to 200,000.
degree, preferably about 5,000 to 70,000. The weight average molecular weight of the above-mentioned adduct can be easily measured from a molecular weight distribution curve by GPC method.
なお、上述のとおり、この発明にいう付加重合ポリマー
には未反応のアクリル系ポリマーやエチレン性不飽和単
量体のホモポリマーないしコポリマーが含まれているた
め、この付加重合ポリマーをこれ単独で、つまり後述の
粘着付与樹脂と混合しないでフィルム化したものにつき
、前記同様にしてヘイズ値を測定すると、付加重合前の
アクリル系ポリマーに較べて高くなるが、未反応のアク
リル系ポリマーやエチレン性不飽和単量体のホモポリマ
ーないしコポリマーは付加重合ポリマーとの相溶性が良
好であるため、アクリル系ポリマーと上記ホモポリマー
ないしコポリマーとの単なる混合に較べれば、そのヘイ
ズ値は小さくなる。As mentioned above, since the addition polymer referred to in the present invention includes an unreacted acrylic polymer or a homopolymer or copolymer of an ethylenically unsaturated monomer, this addition polymer can be used alone, In other words, if the haze value is measured in the same manner as above for a film formed without mixing with the tackifying resin described below, it will be higher than that of the acrylic polymer before addition polymerization, but it will be higher than that of the acrylic polymer before addition polymerization. Since the homopolymer or copolymer of the saturated monomer has good compatibility with the addition polymer, the haze value thereof becomes smaller than when the acrylic polymer is simply mixed with the homopolymer or copolymer.
つまり、上記細塊重合ポリマーのヘイズ値が高くなる場
合、付加重合か不完全でほとんどホモポリマーないしコ
ポリマーになっていることを意味し、この発明の付加重
合ポリマーとしては適さない。すなわち、この発明にい
う（−１加重合ポリマーはこれ単独の上記ヘイズ値が通
常１０％以下、より一般的には７％以下となるものであ
って、このような付加重合ポリマーに後述の特定の粘着
付与樹脂を配合するごとにより、接着特性の大幅な改善
を図りうるのである。In other words, when the haze value of the above-mentioned fine block polymerization polymer becomes high, it means that the addition polymerization is incomplete and almost becomes a homopolymer or a copolymer, which is not suitable as the addition polymerization polymer of the present invention. In other words, the (-1 polymerization polymer referred to in this invention) has a haze value of usually 10% or less, more generally 7% or less, and the addition polymerization polymer has the following specified haze value. Adhesive properties can be significantly improved by adding a tackifier resin.
この発明における粘着付与樹脂としては、上記の付加重
合ポリマーとの相溶性に劣るもの、つまり前記ヘイズ値
が１５〜９５％の範囲となるものか選択使用される。な
お、このヘイズ値は、付加重合ポリマーと粘着（４与樹
脂とを混合してフィルム化したものの前記測定値のほか
、上記混合物にこの種の接着剤に通常配合される各種架
橋剤を加えあるいは加えずして架橋処理してフィルム化
したものの前記測定値をも含むものである。The tackifying resin used in this invention is selected from those having poor compatibility with the above-mentioned addition polymerization polymer, that is, those having the haze value in the range of 15 to 95%. Note that this haze value is not only the above-mentioned measured value of a film made by mixing an addition polymer polymer and an adhesive resin, but also a value obtained by adding various cross-linking agents that are usually added to this type of adhesive to the above-mentioned mixture, or This also includes the above-mentioned measured values for films formed by crosslinking without addition.
このような粘着付与樹脂を上記（＝ｊ加重合ポリマーと
組み合わせ使用することにより、常温での接着力のほか
、高温での接着力にすぐれ、しかも高凝集力の感圧性接
着剤組成物を得ることが可能となる。これに対し、従来
では、アクリル系ポリマーとの相溶性にすくれる粘着付
与樹脂が好ましいものとされ、前記ヘイズ値が通常５以
下となる粘着付与樹脂が使用されていたが、この場合特
に高温での接着力か大きく低下する欠点を免れなかつた
。By using such a tackifying resin in combination with the above-mentioned (=j polymerization polymer), a pressure-sensitive adhesive composition having excellent adhesive strength at room temperature and high temperature as well as high cohesive strength can be obtained. On the other hand, in the past, tackifying resins that were highly compatible with acrylic polymers were preferred, and tackifying resins with a haze value of usually 5 or less were used. However, in this case, there was a drawback that the adhesion strength was significantly reduced, especially at high temperatures.
このように、この発明では、付加重合ポリマーとともに
これとの相溶性に劣る粘着付与樹脂を用いることにより
、従来のアクリル系ポリマーとこれとの相溶性にすくれ
る粘着付与樹脂を用いたものに較べ、高温での接着力を
大幅に改善でき、また凝集力の面でも良好な結果が得ら
れることを見い出したものであるが、この理由は以下の
如く推測される。In this way, in this invention, by using a tackifying resin with poor compatibility with the addition polymer, the tackifying resin is more compatible with the conventional acrylic polymer than with conventional acrylic polymers. It was discovered that the adhesive strength at high temperatures can be significantly improved, and good results can also be obtained in terms of cohesive strength.The reason for this is speculated as follows.
まず、従来の接着剤組成物では、そのフィルム化などに
際して架橋処理されるのが普通であり、その際アクリル
系ポリマーか分子量分布を有してかつそのうちの高分子
量のポリマー成分がより架橋されやすいことなどから、
通常は架橋部分と未架橋部分とが生じることになる。こ
こで、前記従来の相溶性にすぐれる粘着付与樹脂を用い
たものでは、これとアクリル系ポリマーとが均一に混合
されて透明な感圧性接着剤組成物が得られるという利点
を有するものの、上記の架橋部分上未架橋部分とに粘着
付与樹脂か均一に存在するために、これが加熱されると
、架橋部分を含めてすべての部分が均一に可塑化される
傾向が強く、この可塑化によって全体が軟化し、ひいて
は凝集力の低下を引きおこすことになる。その結果、高
温では感圧性接着剤組成物と被着体との間でぶ集破壊が
生じやすくなり、接着力が大きく低下するものと思われ
る。First, conventional adhesive compositions are usually crosslinked when they are made into a film, and at that time, acrylic polymers have a molecular weight distribution and high molecular weight polymer components are more likely to be crosslinked. Because of this,
Usually, there will be a crosslinked portion and an uncrosslinked portion. Here, although the conventional method using a tackifying resin with excellent compatibility has the advantage that the tackifying resin and the acrylic polymer can be uniformly mixed to obtain a transparent pressure-sensitive adhesive composition, Because the tackifying resin is uniformly present on the crosslinked and uncrosslinked parts of becomes soft, which in turn causes a decrease in cohesive force. As a result, it is thought that at high temperatures, the pressure-sensitive adhesive composition and the adherend are more likely to collide and break, resulting in a significant decrease in adhesive strength.
これに対し、この発明に係る付加重合ポリマーとの相溶
性に劣る粘着付与樹脂を用いたものでは、これと付加重
合ポリマーとの均一混合性に欠けるために全体として濁
りのある感圧性接着剤組成物が得られる。これは付加重
合ポリマーと粘着付与樹脂とが相互に相分離しでいるこ
とを示唆するものである。そして、かかる相分離により
、架橋部分への粘着付与樹脂の入り込みが少な（なるこ
とが予測され、その結果高温下における架橋部分での可
塑化がおこりにくくなり、接着剤全体としての凝集力の
低下が抑制されるので、接着力の低下が抑えられるもの
と思われる。また、上記付加重合ポリマーは既述のとお
りこれ自体凝集力にすくれたものであるが、これに上記
特定の粘着付与樹脂を配合したときには、上記すぐれた
凝集力をそのまま維持しうるちのと思われる。On the other hand, when using a tackifying resin having poor compatibility with the addition polymer according to the present invention, the pressure sensitive adhesive composition is cloudy as a whole due to lack of uniform miscibility with the addition polymer. You can get things. This suggests that the addition polymer and the tackifying resin are phase separated from each other. It is predicted that due to such phase separation, the tackifying resin will enter the crosslinked portion less, and as a result, plasticization will be less likely to occur in the crosslinked portion at high temperatures, and the cohesive strength of the adhesive as a whole will decrease. It is thought that the decrease in adhesive strength is suppressed because the above-mentioned addition polymerization polymer itself has a weak cohesive strength as mentioned above, but in addition to this, the above-mentioned specific tackifying resin It seems that when it is blended, the above-mentioned excellent cohesive force is maintained as it is.
この発明において用いられる粘着付与樹脂の種類は特に
問われない。代表的なものとして、ロジンまたはその誘
導体が挙げられ、その他α−ピネンやβ−ピネン重合体
、ジテルペン重合体、α−ピネン−フェノール共重合体
などのテルペンまたはその誘導体が好ましく用いられる
。これらの粘着付与樹脂は、その軟化点が７５℃以上、
通常１１０〜１９０℃であるのが、高温での接着力を向
上させる観点から好ましい。しかし、常温での接着力の
維持のために、上記高軟化点の粘着付与樹脂とともに、
軟化点が７５℃未満の低軟化点の粘着付与樹脂やその他
の公知の可塑剤を併用しても差し支えない。これらの低
軟化点の粘着付与樹脂やその他の可塑剤は、前記高軟化
点の粘着付与樹脂との合計量中５０重量％以下とされて
いるのがよい。The type of tackifying resin used in this invention is not particularly limited. A typical example is rosin or a derivative thereof, and other terpenes or derivatives thereof such as α-pinene, β-pinene polymer, diterpene polymer, and α-pinene-phenol copolymer are preferably used. These tackifying resins have a softening point of 75°C or higher,
Generally, the temperature is preferably 110 to 190°C from the viewpoint of improving adhesive strength at high temperatures. However, in order to maintain adhesive strength at room temperature, along with the above-mentioned high softening point tackifying resin,
A tackifying resin with a low softening point of less than 75° C. and other known plasticizers may be used in combination. These low softening point tackifying resins and other plasticizers are preferably contained in an amount of 50% by weight or less based on the total amount of the high softening point tackifying resin.
この発明に係る前記代表的な粘着付与樹脂として例示し
たロジンまたはその誘導体のうち、後者の誘導体には、
部分不均化または不均化ロジン、水添ロジン、マレイン
酸変性ロジン、重合ロジン、ホルムアルデヒド変性ロジ
ンなどのほか、これらの金属塩やその他ジエチレングリ
コール、グリセリン、ペンタエリスリトールなどとのエ
ステル類が包含される。Among the rosin or its derivatives exemplified as the representative tackifying resin according to the present invention, the latter derivative includes:
Includes partially disproportionated or disproportionated rosin, hydrogenated rosin, maleic acid-modified rosin, polymerized rosin, formaldehyde-modified rosin, etc., as well as metal salts of these and other esters with diethylene glycol, glycerin, pentaerythritol, etc. .
この発明においては、上述の如き粘着付与樹脂の中から
その一種または二種以上を選択使用するが、その際併用
する付加重合ポリマーの種類に応じてこれと混合してフ
ィルム化したもののヘイズ値が既述のとおり１５〜９５
％の範囲となるようにすることが肝要であり、より好ま
しくは上記ヘイズ値が２５〜９０％、実用的には４０〜
８０％の範囲となるようにするのがよい。In this invention, one or more tackifying resins are selected from among the tackifying resins mentioned above, and depending on the type of addition polymer used in combination, the haze value of the film formed by mixing this with the tackifying resin varies depending on the type of addition polymer used in combination. As mentioned above, 15-95
%, more preferably the haze value is 25 to 90%, practically 40 to 90%.
It is preferable to set it within a range of 80%.
ここで、上記ヘイズ値が１５％未満となると、高温での
接着力や凝集力を満足できず、また９５％を超えると、
常温での接着力（やタック）が不足するため、いずれも
不適当である。すなわち、上記ヘイズ値が１５〜９５％
の範囲となるようにすることにより、常温および高温で
の接着力を満足し、また高凝集力を有するものとしうる
のである。Here, if the haze value is less than 15%, the adhesive strength and cohesive force at high temperatures cannot be satisfied, and if it exceeds 95%,
Both are unsuitable because they lack adhesive strength (or tack) at room temperature. That is, the haze value is 15 to 95%.
By adjusting the adhesive strength within this range, it is possible to satisfy adhesive strength at room temperature and high temperature, and to have high cohesive strength.
なお、上記のヘイズ値は、主に付加重合ポリマーの種類
に応じてこれと併用する粘着付与樹脂の種類を選択する
ことにより決められるが、その他粘着（４与樹脂の使用
量も上記ヘイズ値を決めるひとつの因子となる。粘着付
与樹脂の使用量は、付加重合ポリマーの特質を損なうこ
とのないように、一般に付加重合ポリマー１００重量部
に対して３重量部以上、好ましくは５〜７０重量部の範
囲とするのが適当である。したがって、この範囲内で、
付加重合ポリマーと粘着付与樹脂との種類を勘案して、
前記ヘイズ値が１５〜９５％の範囲となるように、粘着
付与樹脂の使用量を適宜決定すればよい。The above haze value is determined mainly by selecting the type of tackifying resin used in conjunction with the addition polymer depending on the type of addition polymer, but the amount of tackifying resin used also depends on the above haze value. This is one determining factor.The amount of tackifying resin used is generally 3 parts by weight or more, preferably 5 to 70 parts by weight, based on 100 parts by weight of the addition polymer, so as not to impair the properties of the addition polymer. Therefore, within this range,
Considering the types of addition polymerization polymer and tackifier resin,
The amount of the tackifier resin to be used may be appropriately determined so that the haze value is in the range of 15 to 95%.
この発明の感圧性接着剤組成物は、以上の付加重合ポリ
マーと粘着付与樹脂とを必須成分として含むほか、凝集
力の向上のため通常架橋剤を含ませることができる。こ
の架橋剤としては、従来公知のもの、たとえばイソシア
ネート系架橋剤、メラミン系架橋剤、エポキシ系架橋剤
、過酸化物系架橋剤などが挙げられる。使用量は、付加
重合ポリマー１００重量部に対して通常２０重量部以下
とするのがよい。このような架橋剤を用いる代わりに、
あるいは架橋剤を使用したうえで、電子線や紫外線の照
射によって架橋処理することもできる。The pressure-sensitive adhesive composition of the present invention contains the above-described addition polymerization polymer and tackifying resin as essential components, and can also contain a crosslinking agent to improve cohesive force. Examples of the crosslinking agent include conventionally known crosslinking agents, such as isocyanate crosslinking agents, melamine crosslinking agents, epoxy crosslinking agents, and peroxide crosslinking agents. The amount used is usually 20 parts by weight or less per 100 parts by weight of the addition polymerization polymer. Instead of using such crosslinkers,
Alternatively, after using a crosslinking agent, crosslinking treatment can be performed by irradiation with an electron beam or ultraviolet rays.
また、この発明の感圧性接着剤組成物には、必要に応じ
て従来公知の各種添加剤、たとえば可ワ剤、軟化剤、充
填剤、顔料、染料などを含ませるようにしてもよい。こ
れらの添加剤は、この種の接着剤組成物に適用される通
常の使用量でよい。The pressure-sensitive adhesive composition of the present invention may also contain various conventionally known additives, such as waxing agents, softeners, fillers, pigments, and dyes, as required. These additives may be used in the usual amounts applied to adhesive compositions of this type.
以上のように、この発明においては、アクリル系ポリマ
ーに特定のエチレン性不飽和単量体を付加重合させてな
る付加重合ポリマーを用いるとともに、この付加重合ポ
リマーに対してこれとの相溶性に劣る、つまり付加重合
ポリマーと混合してフィルム化したもののヘイズ値が大
きくなるような粘着付与樹脂を用いるようにしたことに
より、従来のアクリル系の感圧性接着剤にはみられない
接着力の温度依存性の小さい、常温および高温での接着
特性、特に高温での接着特性にず（れ、そのうえ凝集力
にもず（れる感圧性接着剤組成物を提供できるという格
別の効果か奏し得られるものである。As described above, in this invention, an addition polymer formed by addition polymerizing a specific ethylenically unsaturated monomer to an acrylic polymer is used, and the addition polymer has poor compatibility with the addition polymer. In other words, by using a tackifying resin that increases the haze value when mixed with an addition polymer to form a film, the temperature dependence of adhesive strength, which is not seen with conventional acrylic pressure-sensitive adhesives, has been achieved. The present invention has the special effect of providing a pressure-sensitive adhesive composition that has low adhesive properties at room temperature and high temperature, particularly exhibits poor adhesive properties at high temperatures, and also exhibits low cohesive strength. be.
以下に、この発明の実施例を記載してより具体的に説明
する。なお、以下において部とあるは重量部を意味する
ものとする。また、以下に記述される重量平均分子量は
ＧＰＣ法による分子量分布曲線から測定した値である。EXAMPLES Below, examples of the present invention will be described in more detail. In addition, in the following, parts shall mean parts by weight. Moreover, the weight average molecular weight described below is a value measured from a molecular weight distribution curve by GPC method.
実施例１
アクリル酸ｎ−ブチル７０部、アクリル酸２−エチルヘ
キシル３０部およびアクリル酸３部からなる単量体混合
物１００部、トルエン５０部、酢酸エチル１５０部およ
びヘンゾイルパーオキザイド０．１部を三つロフラスコ
に投入し、窒素置換しながら６０分間撹拌したのち、６
２℃に昇温して７時間重合反応を行った。得られたポリ
マー溶液は室温で粘着性を有する重量平均分子量が約５
１万のアクリル系ポリマーを含むものであった。Example 1 100 parts of a monomer mixture consisting of 70 parts of n-butyl acrylate, 30 parts of 2-ethylhexyl acrylate, and 3 parts of acrylic acid, 50 parts of toluene, 150 parts of ethyl acetate, and 0.1 part of henzoyl peroxide. was poured into a three-necked flask, stirred for 60 minutes while purging with nitrogen, and then
The temperature was raised to 2°C and a polymerization reaction was carried out for 7 hours. The resulting polymer solution is sticky at room temperature and has a weight average molecular weight of about 5.
It contained 10,000 acrylic polymers.
つぎに、このポリマー溶液を５０℃に冷却したのち、上
記のアクリル系ポリマー１００部（単量体混合物の部数
に相当する）に対してメタクリル酸メチル２０部とアク
リル酸２部とからなる単量体混合物（コポリマーのガラ
ス転移点３７６°Ｋ）および上記の単量体混合物１００
部に対してヘンゾイルパーオギザイド１部を添加し、系
内ヲ３０分間窒素置換したのち、７５℃に昇温しで４時
間付力ロ重合反応を行った。Next, after cooling this polymer solution to 50°C, a monomer consisting of 20 parts of methyl methacrylate and 2 parts of acrylic acid was added to 100 parts of the above acrylic polymer (corresponding to the number of parts of the monomer mixture). (copolymer glass transition temperature 376°K) and the above monomer mixture 100
1 part of henzoyl perogizide was added to the reactor, and after purging the system with nitrogen for 30 minutes, the temperature was raised to 75° C. and a force polymerization reaction was carried out for 4 hours.
このようにして得られた付加重合ポリマーはその付加物
の重量平均分子量か２５，０００であった。The addition polymer thus obtained had a weight average molecular weight of 25,000, which is the weight average molecular weight of the adduct.
この付加重合ポリマーを含む溶液に、付加重合ポリマー
１００部に対してマレイン酸変性ロジンのペンタエリス
リ１〜−ルエステル（軟化点１２９℃）３０部とイソシ
アネート系架橋剤（トリレンジイソシアネート化合物）
３部とを加えて、均一に混合することにより、この発明
の感圧性接着剤組酸物の溶液とした。In a solution containing this addition polymer, 30 parts of pentaerythrityl ester of maleic acid-modified rosin (softening point 129°C) and an isocyanate crosslinking agent (tolylene diisocyanate compound) are added to 100 parts of the addition polymer.
3 parts and mixed uniformly to obtain a solution of the pressure-sensitive adhesive composition acid of the present invention.
この組成物の特性を評価するために、７５ ｔｔ ｍ厚
のポリエステルフィルム」−に乾燥厚みが５０μｍとな
るように塗布、乾燥して、感圧性接着テープを作製した
。なお、この接着テープのヘイズ値は５１％であった。In order to evaluate the properties of this composition, a pressure-sensitive adhesive tape was prepared by applying the composition to a 75 ttm thick polyester film to a dry thickness of 50 μm and drying. Note that the haze value of this adhesive tape was 51%.
実施例２
アクリル酸ｎ−ブチル４５部、アクリル酸２−エチルヘ
キシル４０部、メタクリル酸メチル１０部およびアクリ
ル酸５部からなる単量体混合物１００部、酢酸エチル３
００部およびヘンヅイルバーオキサイド０．１部を三つ
ロフラスコに投入し、以下、実施例１と全く同様にして
重量平均分子量が約６５万の室温で粘着性を有するアク
リル系ポリマーを含むポリマー溶液を形成した。この溶
液を室温下で減圧乾燥し、再びトルエンに熔解して４０
重量％溶液を調製した。Example 2 100 parts of a monomer mixture consisting of 45 parts of n-butyl acrylate, 40 parts of 2-ethylhexyl acrylate, 10 parts of methyl methacrylate, and 5 parts of acrylic acid, 3 parts of ethyl acetate
00 parts of Hensylver oxide and 0.1 part of Hensylver oxide were put into a three-necked flask, and the following procedure was carried out in exactly the same manner as in Example 1 to prepare a polymer containing an acrylic polymer having a weight average molecular weight of about 650,000 and having tackiness at room temperature. A solution was formed. This solution was dried under reduced pressure at room temperature, dissolved again in toluene, and
A weight percent solution was prepared.
このポリマー溶液に、ポリマー１００部に対しメタクリ
ル酸メチル６０部、アクリル酸ｎ−ブチル４０部および
アクリル酸５部からなる単量体温合物（コポリマーのガ
ラス転移点２８１’Ｋ）６０部とヘンゾイルパーオギザ
イｌ’ ０．９部を加えて、３０分間窒素置換させたの
ち、８５℃に昇温して６時間付加重合反応を行った。To this polymer solution, 60 parts of a monomer polymer (glass transition point of copolymer 281'K) consisting of 60 parts of methyl methacrylate, 40 parts of n-butyl acrylate, and 5 parts of acrylic acid (copolymer glass transition point 281'K) and Henzoyl were added to 100 parts of the polymer. After adding 0.9 part of Perogyzyl' and purging with nitrogen for 30 minutes, the temperature was raised to 85° C. and an addition polymerization reaction was carried out for 6 hours.
このようにして得られた付加重合ポリマーはその付加物
の重量平均分子量が６９，０００であった。The addition polymer thus obtained had a weight average molecular weight of 69,000.
このイ」加重合ポリマーを含む溶液に、付加重合ポリマ
ー１００部に対して重合ロジンのペンクエリスリトール
エステル（軟化点１２０℃）３０部とイソシアネート系
架橋剤（実施例１に記載のものと同じ）３部とを加えて
、均一に混合することにより、この発明の感圧性接着剤
組成物の溶液とした。この溶液から実施例１と同様にし
て作製した感圧性接着テープのヘイズ値は６２％であっ
た。Add 30 parts of penquerythritol ester of polymerized rosin (softening point: 120°C) and 3 parts of an isocyanate crosslinking agent (same as described in Example 1) to 100 parts of the addition polymerized polymer to the solution containing the polymerized polymer. A solution of the pressure-sensitive adhesive composition of the present invention was prepared by adding 1.0 parts and uniformly mixing. A pressure-sensitive adhesive tape produced from this solution in the same manner as in Example 1 had a haze value of 62%.
実施例３
アクリル酸ｎ−ブチル５０部とアクリル酌２−エチルヘ
キシル５０部と酢酸ビニル５部とアクリル酸５部からな
るｉ量体混合物１００部、酢酸エチル１００部、トルエ
ン１００部およびヘンゾイルバーオキザイド０１部を三
つロフラスコに投入し、以下実施例１と同様にして重量
平均分子量が約３９万の室温で粘着性のあるアクリル系
ポリマーを含む溶液を形成した。Example 3 100 parts of an i-mer mixture consisting of 50 parts of n-butyl acrylate, 50 parts of 2-ethylhexyl acrylate, 5 parts of vinyl acetate, and 5 parts of acrylic acid, 100 parts of ethyl acetate, 100 parts of toluene, and hexyl alcohol. One part of Zyde 0 was put into a three-hole flask, and the same procedure as in Example 1 was carried out to form a solution containing an acrylic polymer having a weight average molecular weight of about 390,000 and being sticky at room temperature.
このポリマー溶液に、ポリマー１００部に対しスチレン
３０部とアクリル酸３部との単量体混合物（コポリマー
のガラス転移点３７２°Ｋ）と上記混合物１００部に対
しヘンジイルパーオキサイド１部とを加え、３０分間窒
素置換させたのち、８０℃に昇温しで４時間付加重合反
応を行った。To this polymer solution were added a monomer mixture of 30 parts of styrene and 3 parts of acrylic acid (glass transition point of the copolymer: 372°K) per 100 parts of the polymer, and 1 part of hendiyl peroxide per 100 parts of the above mixture. After purging with nitrogen for 30 minutes, the temperature was raised to 80° C. and an addition polymerization reaction was carried out for 4 hours.
このようにして得られた付加重合ポリマーはその付加物
の重量平均分子量が１８．０００であった。The addition polymer thus obtained had a weight average molecular weight of 18.000.
このイ」加重台ポリマーを含む溶液に、イ」加重台ポリ
マー１００部に対してマレイン酸変性重合ロジンのペン
タエリスリトールエステル（軟化点１６８℃）２０部と
イソシアネート系架橋剤（実施例１に記載のものと同じ
）３部とを加えて、均一に混合することにより、この発
明の感圧性接着剤組成物の溶液とした。この溶液から実
施例１と同様にして作製した感圧性接着テープのヘイズ
値は７８％であった。To this solution containing the A' weighted base polymer, 20 parts of pentaerythritol ester of maleic acid-modified polymerized rosin (softening point 168°C) and an isocyanate crosslinking agent (as described in Example 1) were added to the solution containing the A' weighted base polymer (100 parts of the A' weighted base polymer). A solution of the pressure-sensitive adhesive composition of the present invention was prepared by adding 3 parts of the same as above and mixing uniformly. A pressure-sensitive adhesive tape produced from this solution in the same manner as in Example 1 had a haze value of 78%.
実施例４
マレイン酸変性ロジンのペンタエリスリト−ルエステル
（軟化点１２９℃）３０部の代わりに、芳香族変性テル
ペン炭化水素樹脂（軟化点１１０℃）２０部を使用した
以外は、実施例１と同様にして感圧性接着剤組成物の溶
液を調製した。この溶液から実施例１と同様にして作製
した感圧性接着テープのヘイズ値は５８％であった。Example 4 Same as Example 1 except that 20 parts of aromatic modified terpene hydrocarbon resin (softening point 110°C) was used instead of 30 parts of maleic acid-modified rosin pentaerythritol ester (softening point 129°C). A solution of a pressure sensitive adhesive composition was prepared in the same manner. A pressure-sensitive adhesive tape produced from this solution in the same manner as in Example 1 had a haze value of 58%.
実施例５
アクリル酸ｎ−ブチル７０部、アクリル酸２−エチルヘ
キシル３０部、アクリル酸２−ヒドロキシエチル１部お
よびアクリル酸０５部からなる単量体混合物１００部、
酢酸エチル３００部およびヘンソイルパーオキサイド０
．２部を三つロフラスコ乙こ投入し、以下、実施例１と
全く同様にして重量平均分子量が約７０万の室温で粘着
性を有するアクリル系ポリマーを含むポリマー溶液を形
成した。Example 5 100 parts of a monomer mixture consisting of 70 parts of n-butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 1 part of 2-hydroxyethyl acrylate, and 0.5 parts of acrylic acid,
300 parts of ethyl acetate and 0 parts of hensoil peroxide
．． Two parts were put into a three-hole flask, and the same procedure as in Example 1 was carried out to form a polymer solution containing an acrylic polymer having a weight average molecular weight of approximately 700,000 and having tackiness at room temperature.
このポリマー溶液に、ポリマー１００部に対しメタクリ
ル酸メチル１５部とヘンヅイルバーオキザイド０．２部
を加えて、３０分間窒素置換させたのち、７７℃に昇温
して６時間付加重合反応を行った。To this polymer solution, 15 parts of methyl methacrylate and 0.2 parts of hendyl oxide were added to 100 parts of the polymer, and after purging with nitrogen for 30 minutes, the temperature was raised to 77°C and an addition polymerization reaction was carried out for 6 hours. I did it.
このようにして得られた付加重合ポリマーはその付加物
の重量平均分子量が４３．０００であった。The addition polymer thus obtained had a weight average molecular weight of 43.000.
この付加重合ポリマーを含む溶液に、イ」加重台ポリマ
ー１００部に対してロジンフェノール樹脂（軟化点１５
４℃）３０部とイソシアネート系架橋剤（実施例１に記
載のものと同じ）３部とを加えて、均一に混合すること
により、この発明の感圧性接着剤組成物の溶液とした。In the solution containing this addition polymer, rosin phenol resin (softening point 15
4°C) and 3 parts of an isocyanate-based crosslinking agent (same as described in Example 1) were added and mixed uniformly to prepare a solution of the pressure-sensitive adhesive composition of the present invention.
この溶液から実施例１と同様にして作製した感圧性接着
テープのヘイズ値は６５％であった。A pressure-sensitive adhesive tape produced from this solution in the same manner as in Example 1 had a haze value of 65%.
比較例Ｉ
実施例１の付加重合ポリマーの代わりに、付加重合を行
う前のアクリル系ポリマーを使用した以外は、実施例１
と同様にして感圧性接着剤組成物の溶液を調製した。こ
の溶液から実施例１と同様にして作製した感圧性接着テ
ープのヘイズ値は４７％であった。Comparative Example I Example 1 except that an acrylic polymer before addition polymerization was used instead of the addition polymerization polymer of Example 1.
A solution of the pressure-sensitive adhesive composition was prepared in the same manner as above. A pressure-sensitive adhesive tape produced from this solution in the same manner as in Example 1 had a haze value of 47%.
比較例２
マレイン酸変性ロジンのペンタエリスリトールエステル
（軟化点１２９℃）３０部の代わりに、水添ロジンのグ
リセリンエステル（軟化点７９℃）３０部を使用した以
外は、実施例１と同様にして感圧性接着剤組成物の溶液
を調製した。この溶液から実施例１と同様にして作製し
た感圧性接着テープのヘイズ値は７％であった。Comparative Example 2 The same procedure as in Example 1 was carried out, except that 30 parts of glycerin ester of hydrogenated rosin (softening point 79°C) was used instead of 30 parts of pentaerythritol ester (softening point 129°C) of maleic acid-modified rosin. A solution of a pressure sensitive adhesive composition was prepared. A pressure-sensitive adhesive tape produced from this solution in the same manner as in Example 1 had a haze value of 7%.
比較例３
マレイン酸変性重合ロジンのペンタエリスリトールエス
テル（軟化点１６８℃）２０部の代わりに、ロジンのグ
リセリンエステル（軟化点８５℃）２０部を使用した以
外は、実施例３と同様にして感圧性接着剤組成物の溶液
を調製した。この溶液から実施例１と同様にして作製し
た感圧性接着テープのヘイズ値は９％であった。Comparative Example 3 Sensitization was carried out in the same manner as in Example 3, except that 20 parts of glycerin ester of rosin (softening point 85°C) was used instead of 20 parts of pentaerythritol ester (softening point 168°C) of maleic acid-modified polymerized rosin. A solution of a pressure sensitive adhesive composition was prepared. A pressure-sensitive adhesive tape produced from this solution in the same manner as in Example 1 had a haze value of 9%.
比較例４
実施例３のイ」加重台ポリマーの代わりに付加重合を行
う前のアクリル系ポリマーを使用し、かつマレイン酸変
性重合ロジンのペンタエリスリト−ルエステル（軟化点
１６８℃）２０部の代わりにロジンフェノール（軟化点
１３０℃） ２５ ？ｓｒＩヲ使用し、それ以外は実
施例３と同様にして感圧性接着剤組成物の溶液を調製し
た。この溶液から実施例１と同様にして作製した感圧性
接着テープのヘイズ値は２％であった。Comparative Example 4 An acrylic polymer before addition polymerization was used in place of the weighted base polymer A of Example 3, and 20 parts of pentaerythritol ester (softening point 168°C) of maleic acid-modified polymerized rosin was used. Rosin phenol (softening point 130℃) 25? A solution of a pressure-sensitive adhesive composition was prepared in the same manner as in Example 3 except that srI was used. A pressure-sensitive adhesive tape produced from this solution in the same manner as in Example 1 had a haze value of 2%.
以上の実施例１〜５および比較例１〜４の各感圧性接着
剤組成物の接着力および凝集力を調べるために、各実施
例および比較例で作製した感圧性接着テープを用いて以
下の接着力試験および保持力試験を行った。その結果は
、下記の表に示されるとおりであった。In order to investigate the adhesive strength and cohesive force of each pressure-sensitive adhesive composition of Examples 1 to 5 and Comparative Examples 1 to 4, the pressure-sensitive adhesive tapes prepared in each Example and Comparative Example were used as follows. An adhesion test and a holding power test were conducted. The results were as shown in the table below.
〈接着力試験〉
２０℃、６５％Ｒｌ（の雰囲気中で供試テープ（２０部
幅）をステンレス板上に２ ｋｇゴムロ＝ラー１往復の
荷重にて貼り合わせ、その後２０℃および８０℃の温度
雰囲気下で１時間放置した。放置後、各温度雰囲気下で
１８０度方向に３００ｍｍ／分の引張り速度で引きヱ１
］がし、そのときの抵抗力を接着力として測定した。<Adhesion test> The sample tape (20 parts width) was bonded to a stainless steel plate in an atmosphere of 65% Rl at 20°C under a load of 1 reciprocation of a 2 kg rubber roller, and then the tape was bonded at 20°C and 80°C. It was left in a temperature atmosphere for 1 hour.After being left in a temperature atmosphere, it was pulled at a pulling speed of 300 mm/min in a 180 degree direction under each temperature atmosphere.
] and the resistance force at that time was measured as the adhesive force.
〈保持力試験〉
供試テープ（］０鰭幅）をヘークライト板にＩＱ ｍｍ
Ｘ ２ Ｑ ｍｍの接着面積となるように貼り付け、
これを４０ ’Ｃ雰囲気中に投入し、５００ｇの荷重を
かｉ：ｌ ２時間後のずれ距離を測定した。<Retention force test> IQ mm
Paste so that the adhesive area is X 2 Q mm,
This was placed in a 40'C atmosphere, a load of 500 g was applied to it, and the displacement distance was measured after 2 hours.
」二記表の結果から明らかなように、この発明に係る実
施例１〜５の感圧性接着テープは、常温での接着力にず
くれるだけでなく、高温での接着力の低下が比較例２−
４の接着テープに比し大きく抑制されており、接着力の
温度依存性の小さいすくれた接着特性を発揮し、かつ凝
集力にもずくれたものであることが判る。As is clear from the results in Table 2, the pressure-sensitive adhesive tapes of Examples 1 to 5 according to the present invention not only exhibit weak adhesive strength at room temperature, but also exhibit a decrease in adhesive strength at high temperatures compared to the comparative example. 2-
It can be seen that the adhesive strength was greatly suppressed compared to the adhesive tape No. 4, and it exhibited a weak adhesive property with low temperature dependence of adhesive force, and also had a weak cohesive force.
なお、比較例１の感圧性接着テープは、アクリル系ポリ
マーをこの発明のように付加重合ポリマーとすることな
くこれをそのままこれとの相溶性に劣る粘着付与樹脂と
組み合わせて感圧性接着剤組成物を構成させるようにし
たものであるが、この場合比較例２〜４に比し高温での
接着力を改善することはできるが、上記この発明の実施
例１〜５に比し劣っており、また凝集力の面でもこの発
明のものに比し劣っている。The pressure-sensitive adhesive tape of Comparative Example 1 was prepared by combining the acrylic polymer with a tackifying resin that is less compatible with the acrylic polymer without converting it into an addition-polymerized polymer as in the present invention, thereby forming a pressure-sensitive adhesive composition. In this case, the adhesion strength at high temperatures can be improved compared to Comparative Examples 2 to 4, but it is inferior to Examples 1 to 5 of the present invention, It is also inferior to that of the present invention in terms of cohesive force.
特許出願人 日東電気工業株式会社Patent applicant: Nitto Electric Industry Co., Ltd.
Claims (5)
５の脂肪族アルコールとのエステルからなる主単量体に
極性基含有不飽和単量体を加えた単量体混合物を共重合
させてなる室温で粘着性を有するアクリル系ポリマーに
、ホモポリマーないしコポリマーのガラス転移点が２７
３°Ｋ以上となりうる一種もしくは二種以上のエチレン
性不飽和単量体を付加重合させて得られる付加重合ポリ
マーと、この付加重合ポリマーとの相溶性に劣る粘着付
与樹脂とを含む感圧性接着剤組成物であつて、上記付加
重合ポリマーと上記粘着付与樹脂とを混合してフィルム
化したもののヘイズ値が１５〜９５％の範囲にあること
を特徴とする感圧性接着剤組成物。(1) Acrylic acid or methacrylic acid and carbon number 2-1
A homopolymer or The glass transition point of the copolymer is 27
A pressure-sensitive adhesive comprising an addition polymer obtained by addition polymerizing one or more ethylenically unsaturated monomers that can have a temperature of 3°K or more, and a tackifier resin having poor compatibility with the addition polymer. 1. A pressure-sensitive adhesive composition, characterized in that the above-mentioned addition polymerization polymer and the above-mentioned tackifying resin are mixed and formed into a film, and the haze value of the film is in the range of 15 to 95%.
系ポリマー１００重量部に対して５〜２００重量部使用
した請求項（１）に記載の感圧性接着剤組成物。(2) The pressure-sensitive adhesive composition according to claim (1), wherein 5 to 200 parts by weight of the ethylenically unsaturated monomer for addition polymerization is used per 100 parts by weight of the acrylic polymer.
ののヘイズ値が１０％以下である請求項（１）または（
２）に記載の感圧性接着剤組成物。(3) Claim (1) or (3) wherein the haze value of the addition polymerized polymer formed into a film alone is 10% or less.
2) The pressure-sensitive adhesive composition according to item 2).
（１）〜（３）のいずれかに記載の感圧性接着剤組成物
。(4) The pressure-sensitive adhesive composition according to any one of claims (1) to (3), wherein the tackifying resin has a softening point of 75°C or higher.
重量部に対して５〜７０重量部の範囲にある請求項（１
）〜（４）のいずれかに記載の感圧性接着剤組成物。(5) Tackifying resin content: addition polymerization polymer 100
Claim (1) in which the amount is in the range of 5 to 70 parts by weight.
) to (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4727288A JPH01221474A (en) | 1988-02-29 | 1988-02-29 | Pressure-sensitive adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4727288A JPH01221474A (en) | 1988-02-29 | 1988-02-29 | Pressure-sensitive adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01221474A true JPH01221474A (en) | 1989-09-04 |
Family
ID=12770655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4727288A Pending JPH01221474A (en) | 1988-02-29 | 1988-02-29 | Pressure-sensitive adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01221474A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0953059A (en) * | 1995-06-07 | 1997-02-25 | Nippon Shokubai Co Ltd | Adhesive composition |
| JP2000303049A (en) * | 1995-06-07 | 2000-10-31 | Nippon Shokubai Co Ltd | Solvent-type adhesive composition |
| JP2002003796A (en) * | 2000-06-27 | 2002-01-09 | Nitto Denko Corp | Adhesive composition and pressure-sensitive adhesive using the same and adhesive sheets thereof |
| JP2002003799A (en) * | 2000-06-27 | 2002-01-09 | Nitto Denko Corp | Adhesive sheets |
| US7109266B2 (en) | 2002-02-27 | 2006-09-19 | Nitto Denko Corporation | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
| JP2010159333A (en) * | 2009-01-07 | 2010-07-22 | Nitto Denko Corp | Light-diffusible adhesive composition, light diffusible adhesive layer and light-diffusible adhesive sheet |
-
1988
- 1988-02-29 JP JP4727288A patent/JPH01221474A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0953059A (en) * | 1995-06-07 | 1997-02-25 | Nippon Shokubai Co Ltd | Adhesive composition |
| JP2000303049A (en) * | 1995-06-07 | 2000-10-31 | Nippon Shokubai Co Ltd | Solvent-type adhesive composition |
| JP2002003796A (en) * | 2000-06-27 | 2002-01-09 | Nitto Denko Corp | Adhesive composition and pressure-sensitive adhesive using the same and adhesive sheets thereof |
| JP2002003799A (en) * | 2000-06-27 | 2002-01-09 | Nitto Denko Corp | Adhesive sheets |
| US7109266B2 (en) | 2002-02-27 | 2006-09-19 | Nitto Denko Corporation | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
| US7326462B2 (en) | 2002-02-27 | 2008-02-05 | Nitto Denko Corporation | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
| US7576156B2 (en) | 2002-02-27 | 2009-08-18 | Nitto Denko Corporation | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
| JP2010159333A (en) * | 2009-01-07 | 2010-07-22 | Nitto Denko Corp | Light-diffusible adhesive composition, light diffusible adhesive layer and light-diffusible adhesive sheet |
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