JPH0873828A - Acryl-based pressure-sensitive adhesive composition - Google Patents
Acryl-based pressure-sensitive adhesive compositionInfo
- Publication number
- JPH0873828A JPH0873828A JP21305794A JP21305794A JPH0873828A JP H0873828 A JPH0873828 A JP H0873828A JP 21305794 A JP21305794 A JP 21305794A JP 21305794 A JP21305794 A JP 21305794A JP H0873828 A JPH0873828 A JP H0873828A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy compound
- sensitive adhesive
- adhesive composition
- acrylic
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- -1 Acryl Chemical group 0.000 title abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 7
- 125000003700 epoxy group Chemical group 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 description 35
- 230000001070 adhesive effect Effects 0.000 description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 239000000178 monomer Substances 0.000 description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000035882 stress Effects 0.000 description 8
- 239000002390 adhesive tape Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003522 acrylic cement Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 1
- 239000006185 dispersion Substances 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
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 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
- 238000010998 test method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、アクリル系ポリマーを主
な接着成分とする感圧接着剤組成物に関する。さらに詳
しくは本発明は、粘着力が強く、耐熱性に優れると共
に、一定の荷重をかけ続けたときに、剥離しにくい感圧
接着剤組成物に関する。TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive composition containing an acrylic polymer as a main adhesive component. More specifically, the present invention relates to a pressure-sensitive adhesive composition that has high adhesive strength, excellent heat resistance, and is difficult to peel off when a constant load is continuously applied.
【０００２】[0002]
【発明の技術的背景】近年、アクリル系ポリマ―からな
る感圧接着剤は、工業用粘着テープ、粘着シート、ラベ
ル、液晶表示板用等の種々の分野で使用されている。こ
うした感圧接着剤は、高い接着力を有していると共に、
用途の多様化に伴って高い耐熱性を有することも必要に
なってきている。BACKGROUND OF THE INVENTION In recent years, pressure-sensitive adhesives made of acrylic polymers have been used in various fields such as industrial adhesive tapes, adhesive sheets, labels and liquid crystal display boards. These pressure-sensitive adhesives have high adhesive strength and
With the diversification of applications, it is also necessary to have high heat resistance.
【０００３】ところで、このような感圧接着剤において
は、壁掛けフックの接着剤のように常に一定の荷重がか
かる条件下で使用されるものがある。こうした条件で使
用される接着剤は本質的に初期接着力が高いことが必要
になるが、初期接着力が高いだけでは必ずしも定荷重剥
離性（一定の比較的軽い荷重を長期間かけ続けたときの
剥離しにくさ）および保持力は高くならない。こうした
定荷重剥離性および保持力を向上させるには、接着剤に
かかる応力（剥離力）が接着剤と被着体との界面に直接
作用する前に、この応力を接着剤内で分散・吸収する必
要がある。Some pressure-sensitive adhesives, such as wall-hanging hook adhesives, are used under conditions in which a constant load is always applied. Adhesives used under such conditions essentially need to have high initial adhesive strength, but high initial adhesive strength does not necessarily mean constant load peelability (when a certain relatively light load is continuously applied for a long period of time). It is difficult to peel off) and the holding power does not become high. In order to improve such constant load releasability and holding force, before the stress (peeling force) applied to the adhesive acts directly on the interface between the adhesive and the adherend, this stress is dispersed and absorbed in the adhesive. There is a need to.
【０００４】そこで、本発明者は、感圧接着剤の定荷重
剥離性および保持力を向上させるべく研究を重ねた結
果、アクリル系接着剤に特定のエポキシ化合物を用いて
アクリル系接着剤の分子間に比較的低い密度で架橋構造
を形成することにより、接着剤の定荷重剥離性および保
持力が著しく向上するとの知見を得て本発明を完成し
た。Therefore, the present inventor has conducted extensive research to improve the constant-load releasability and holding power of the pressure-sensitive adhesive, and as a result, the molecule of the acrylic adhesive has been modified by using a specific epoxy compound for the acrylic adhesive. The present invention has been completed based on the finding that by forming a crosslinked structure with a relatively low density in the meantime, the constant load peelability and the holding force of the adhesive are significantly improved.
【０００５】なお、特開平4-18478号公報には、重量平
均分量が１０００〜３００００のテレケリックオリゴマ
ーをアクリル系接着剤に配合することが開示されてい
る。このテレケリックオリゴマーは、分子末端に２個以
上の官能基を有するオリゴマーであり、この官能基とし
てはイソシアネート基、エポキシ基、アミノ基、カルボ
キシル基、水酸基などであり、主鎖部分は、ポリオキシ
エチレン鎖、ポリオキシプロピレン鎖等で形成されてい
る。そして、この実施例３には、アクリル酸n-ブチル・
アクリル酸共重合体（モノマー重量組成；９:１）１０
０重量部に、重量平均分子量２０００の２官能エポキシ
系テレケリックオリゴマー０.５重量部を配合した例が
示されている。しかしながら、こうした接着剤におい
て、エポキシ基を有するテレケリックオリゴマーによっ
て形成される均一な架橋構造によって、この接着剤にか
かる応力が、三次元的に分散されて吸収されるのであ
り、上記公報に記載されているような分子量の大きなテ
レケリックオリゴマーを用いてもアクリルポリマーとの
相溶性が悪く、均一な架橋が形成されないため高温にお
ける応力分散効果が小さい。即ち、接着剤にかかる応力
を分散させて吸収するには、アクリルポリマー間に低密
度で均一な架橋構造が形成され、しかもこうして形成さ
れた架橋構造が、接着剤の凝集力を損なわない程度に形
成されていることが必要になるのである。Japanese Patent Application Laid-Open No. 4-18478 discloses that a telechelic oligomer having a weight average amount of 1,000 to 30,000 is mixed with an acrylic adhesive. This telechelic oligomer is an oligomer having two or more functional groups at the molecular ends, and the functional groups include an isocyanate group, an epoxy group, an amino group, a carboxyl group, a hydroxyl group, etc. It is formed of an ethylene chain, a polyoxypropylene chain, or the like. And, in this Example 3, n-butyl acrylate.
Acrylic acid copolymer (monomer weight composition; 9: 1) 10
An example is shown in which 0.5 part by weight of a bifunctional epoxy telechelic oligomer having a weight average molecular weight of 2000 is mixed with 0 part by weight. However, in such an adhesive, the stress applied to the adhesive is three-dimensionally dispersed and absorbed by the uniform cross-linked structure formed by the telechelic oligomer having an epoxy group, which is described in the above publication. Even if such a telechelic oligomer having a large molecular weight is used, the compatibility with the acrylic polymer is poor and a uniform crosslink is not formed, so that the stress dispersion effect at high temperature is small. That is, in order to disperse and absorb the stress applied to the adhesive, a low-density and uniform crosslinked structure is formed between the acrylic polymers, and the crosslinked structure thus formed does not impair the cohesive force of the adhesive. It needs to be formed.
【０００６】[0006]
【発明の目的】本発明は定荷重剥離強度が特に優れたア
クリル系感圧接着剤を提供することを目的としている。OBJECTS OF THE INVENTION It is an object of the present invention to provide an acrylic pressure-sensitive adhesive having particularly excellent constant load peel strength.
【０００７】さらに本発明は、高温における接着強度が
高く、しかも定荷重剥離強度の高いアクリル系感圧接着
剤を提供することを目的としている。Another object of the present invention is to provide an acrylic pressure-sensitive adhesive which has a high adhesive strength at high temperature and a high constant load peel strength.
【０００８】[0008]
【発明の概要】本発明のアクリル系感圧接着剤組成物
は、アクリル系ポリマーとエポキシ化合物とからなるア
クリル系感圧接着剤組成物であって、該アクリル系ポリ
マーは、カルボキシル基を有する繰り返し単位を０.５
〜２０重量部の量で含有しており、該エポキシ化合物
が、エポキシ当量２５０〜４００の直鎖状のグリシジル
系２官能エポキシ化合物であり、かつ該アクリル系ポリ
マー１００重量部に対して、該エポキシ化合物を０.０
２〜２重量部の量で含有することを特徴としている。SUMMARY OF THE INVENTION The acrylic pressure-sensitive adhesive composition of the present invention is an acrylic pressure-sensitive adhesive composition comprising an acrylic polymer and an epoxy compound, wherein the acrylic polymer has a repeating group having a carboxyl group. Unit is 0.5
To 20 parts by weight, the epoxy compound is a linear glycidyl-based bifunctional epoxy compound having an epoxy equivalent of 250 to 400, and the epoxy compound is added to 100 parts by weight of the acrylic polymer. Compound to 0.0
It is characterized in that it is contained in an amount of 2 to 2 parts by weight.
【０００９】上述のようにアクリル系感圧接着剤にエポ
キシ化合物を配合することは既に知られており、エポキ
シ化合物を含有することによってアクリル系感圧接着剤
の耐熱保持力は向上する。ところが、こうして従来から
使用されていたエポキシ化合物では定荷重剥離性（一定
の比較的軽い荷重を長時間かけたときの剥離しにくさ）
が弱点となっていた。しかし、特定のエポキシ化合物を
特定量配合して架橋構造を形成すると、従来アクリル系
感圧接着剤の弱点とされていた定荷重剥離性が著しく向
上する。It is already known to mix an epoxy compound with an acrylic pressure-sensitive adhesive as described above, and the heat-resistant holding power of the acrylic pressure-sensitive adhesive is improved by containing the epoxy compound. However, the epoxy compounds conventionally used in this way have constant load peelability (difficulty in peeling when a constant and relatively light load is applied for a long time).
Was a weak point. However, when a specific amount of a specific epoxy compound is blended to form a crosslinked structure, the constant load releasability, which has hitherto been a weak point of the acrylic pressure-sensitive adhesive, is significantly improved.
【００１０】さらに、このようなエポキシ化合物により
架橋構造を形成することにより、熱時の接着性も向上す
る。Further, by forming a crosslinked structure with such an epoxy compound, the adhesiveness at the time of heating is also improved.
【００１１】[0011]
【発明の具体的説明】次に本発明のアクリル系感圧接着
剤組成物について具体的に説明する。本発明のアクリル
系感圧接着剤組成物は、アクリル系ポリマーと特定のエ
ポキシ化合物とを含有している。DETAILED DESCRIPTION OF THE INVENTION Next, the acrylic pressure-sensitive adhesive composition of the present invention will be specifically described. The acrylic pressure-sensitive adhesive composition of the present invention contains an acrylic polymer and a specific epoxy compound.
【００１２】アクリル系ポリマーは、接着の主成分とな
るものであり、通常は、炭素原子数１〜１８程度のアル
キル基を有する（メタ）アクリル酸アルキルエステルモ
ノマーとカルボキシル基を有する単量体とを共重合させ
ることにより製造される。The acrylic polymer is a main component for adhesion, and is usually composed of a (meth) acrylic acid alkyl ester monomer having an alkyl group having about 1 to 18 carbon atoms and a monomer having a carboxyl group. It is manufactured by copolymerizing.
【００１３】ここで使用される（メタ）アクリル酸アル
キルエステルモノマーの例としては、（メタ）アクリル
酸メチル、（メタ）アクリル酸エチル、（メタ）アクリ
ル酸n-プロピル、（メタ）アクリル酸sec-プロピル、
（メタ）アクリル酸n-ブチル、（メタ）アクリル酸sec-
ブチル、（メタ）アクリル酸tert-ブチル、（メタ）ア
クリル酸イソアミル、（メタ）アクリル酸n-ヘキシル、
（メタ）アクリル酸シクロヘキシル、（メタ）アクリル
酸n-オクチル、（メタ）アクリル酸イソオクチル、（メ
タ）アクリル酸2-エチルヘキシル、（メタ）アクリル酸
ウンデシルおよび（メタ）アクリル酸ラウリル等を挙げ
ることができる。Examples of the (meth) acrylic acid alkyl ester monomer used here include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, sec. (Meth) acrylic acid. -Propyl,
N-Butyl (meth) acrylate, sec- (meth) acrylate
Butyl, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate,
Examples include cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, undecyl (meth) acrylate, and lauryl (meth) acrylate. it can.
【００１４】この（メタ）アクリル酸アルキルエステル
は、通常はアクリル系ポリマー中に６０〜９９.５重量
部の量で共重合している。また、本発明のアクリル系ポ
リマーを形成するカルボキシル基を有する単量体として
は、（メタ）アクリル酸、イタコン酸、クロトン酸、マ
レイン酸、マレイン酸モノブチルおよびβ-カルボキシ
エチルアクリレート等のカルボキシル基を含有するモノ
マーを挙げることができる。The (meth) acrylic acid alkyl ester is usually copolymerized in the acrylic polymer in an amount of 60 to 99.5 parts by weight. Further, as the monomer having a carboxyl group forming the acrylic polymer of the present invention, a carboxyl group such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, monobutyl maleate and β-carboxyethyl acrylate. The monomer contained can be mentioned.
【００１５】本発明の接着剤の主成分であるアクリル系
ポリマー中には、上記カルボキシル基を有する繰り返し
単位が０.５〜２０重量部の量、好ましくは１〜１０重
量部の量で共重合されている。このカルボキシル基を有
する基が０.５重量部より少ないと、エポキシ化合物と
の反応性が低下し、接着剤中に未反応のエポキシ基が残
存することが多くなり、また２０重量部を超えるとこの
アクリル系ポリマーのガラス転移温度が高くなり、常温
で良好な接着性能を示さなくなる。In the acrylic polymer which is the main component of the adhesive of the present invention, the repeating unit having a carboxyl group is copolymerized in an amount of 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight. Has been done. When the amount of the carboxyl group-containing group is less than 0.5 parts by weight, the reactivity with the epoxy compound is lowered, and unreacted epoxy groups often remain in the adhesive, and when it exceeds 20 parts by weight. The glass transition temperature of this acrylic polymer becomes high, and good adhesive performance is not exhibited at room temperature.
【００１６】また、本発明で使用するアクリル系ポリマ
ーには、上記の他にこのアクリル系ポリマーの特性を損
なわない範囲内で他の官能基を有するモノマーが共重合
していても良い。In addition to the above, the acrylic polymer used in the present invention may be copolymerized with a monomer having another functional group within a range not impairing the properties of the acrylic polymer.
【００１７】ここで他の官能基を有するモノマーの例と
しては、（メタ）アクリル酸2-ヒドロキシエチル、（メ
タ）アクリル酸2-ヒドロキシプロピルおよびアリルアル
コール等の水酸基を含有するモノマー；（メタ）アクリ
ルアミド、N-メチル（メタ）アクリルアミドおよびN-エ
チル（メタ）アクリルアミド等のアミド基を含有するモ
ノマー；N-メチロール（メタ）アクリルアミドおよびジ
メチロール（メタ）アクリルアミド等のアミド基とメチ
ロール基とを含有するモノマー、アミノメチル（メタ）
アクリレート、ジメチルアミノエチル（メタ）アクリレ
ートおよびビニルピリジン等のアミノ基を含有するモノ
マーのような官能基を有するモノマ−等を挙げることが
できる。Examples of monomers having other functional groups include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and monomers containing a hydroxyl group such as allyl alcohol; (meth) Monomers containing amide groups such as acrylamide, N-methyl (meth) acrylamide and N-ethyl (meth) acrylamide; containing amide groups such as N-methylol (meth) acrylamide and dimethylol (meth) acrylamide and methylol groups Monomer, aminomethyl (meth)
Examples thereof include monomers having a functional group such as an acrylate, dimethylaminoethyl (meth) acrylate, and a monomer containing an amino group such as vinylpyridine.
【００１８】さらに、上記のようなアクリル系モノマー
の他に、エチレン性二重結合を有するモノマーを使用す
ることができる。ここでエチレン性二重結合を有するモ
ノマーの例としては、マレイン酸ジブチル、マレイン酸
ジオクチルおよびフマル酸ジブチル等のα,β−不飽和
二塩基酸のジエステル；酢酸ビニル、プロピオン酸ビニ
ル等のビニルエステル；ビニルエーテル；スチレン、α
−メチルスチレンおよびビニルトルエン等のビニル芳香
族化合物；（メタ）アクリロニトリル等を挙げることが
できる。Further, in addition to the acrylic monomer as described above, a monomer having an ethylenic double bond can be used. Examples of the monomer having an ethylenic double bond include diesters of α, β-unsaturated dibasic acids such as dibutyl maleate, dioctyl maleate and dibutyl fumarate; vinyl esters such as vinyl acetate and vinyl propionate. ; Vinyl ether; styrene, α
-Vinyl aromatic compounds such as methylstyrene and vinyltoluene; (meth) acrylonitrile and the like.
【００１９】また、上記のようなエチレン性二重結合を
有するモノマーの他に、エチレン性二重結合を２個以上
有する化合物を併用することもできる。このような化合
物の例としては、ジビニルベンゼン、ジアリルマレー
ト、ジアリルフタレート、エチレングリコールジ（メ
タ）アクリレ−ト、トリメチロールプロパントリ（メ
タ）アクリレート、メチレンビス（メタ）アクリルアミ
ド等を挙げることができる。In addition to the above-mentioned monomer having an ethylenic double bond, a compound having two or more ethylenic double bonds can be used in combination. Examples of such compounds include divinylbenzene, diallylmaleate, diallylphthalate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, methylenebis (meth) acrylamide and the like.
【００２０】さらに、本発明では、例えば、エチレン、
プロピレン等のオレフィン類を共重合させることも可能
である。このようなアクリル系ポリマーは、有機溶媒中
に上記の単量体を投入し、窒素ガス等の不活性ガス雰囲
気下で、反応温度５０〜１００℃、反応時間２〜２０時
間反応させることにより製造することができる。この反
応に際しては、アゾビスイソブチロニトリルのような反
応開始剤を使用する。こうして得られたアクリル系ポリ
マーの重量平均分子量は、通常は１０００００〜１５０
００００の範囲内にある。また、上記のようにして有機
溶媒中で反応させることにより、アクリル系ポリマーは
有機溶媒溶液として得られる。こうして得られたアクリ
ル系ポリマーの有機溶媒溶液は、有機溶媒を分離せずそ
のまま使用することができる。Further, in the present invention, for example, ethylene,
It is also possible to copolymerize olefins such as propylene. Such an acrylic polymer is produced by introducing the above monomer into an organic solvent and reacting it in an inert gas atmosphere such as nitrogen gas at a reaction temperature of 50 to 100 ° C. for a reaction time of 2 to 20 hours. can do. In this reaction, a reaction initiator such as azobisisobutyronitrile is used. The weight average molecular weight of the acrylic polymer thus obtained is usually 100,000 to 150.
It is in the range of 0000. Further, the acrylic polymer is obtained as an organic solvent solution by reacting in the organic solvent as described above. The organic solvent solution of the acrylic polymer thus obtained can be used as it is without separating the organic solvent.
【００２１】本発明のアクリル系感圧接着剤は、特定の
エポキシ化合物を含有している。このエポキシ化合物
は、直鎖状の構造を有しており、その分子の両末端にエ
ポキシ基を有するグリシジル系２官能エポキシ化合物で
ある。The acrylic pressure-sensitive adhesive of the present invention contains a specific epoxy compound. This epoxy compound is a glycidyl-based bifunctional epoxy compound having a linear structure and having epoxy groups at both ends of the molecule.
【００２２】さらに、このエポキシ化合物のエポキシ当
量は２５０〜４００の範囲内にあることが必要である。
このエポキシ当量は、間接的にではあるが、エポキシ化
合物によって形成される架橋構造の長さを表している。
エポキシ化合物は、アクリル系ポリマー中のカルボキシ
ル基と結合して架橋構造を形成する。そして、エポキシ
当量が２５０〜４００のエポキシ化合物を使用すると、
アクリル系ポリマーとの間に均一な架橋構造が形成さ
れ、接着剤分子の間には緩い拘束状態が形成される。接
着剤層にかかった応力は、上記のように緩く拘束された
接着剤分子間で、均一な架橋構造の変形により吸収され
るものと考えられる。従って、エポキシ当量が２５０に
満たないエポキシ化合物を使用したのでは、アクリル系
ポリマーの凝集力が高くなり保持力は向上するものの架
橋構造の変形性が少ないため定荷重剥離性が悪くなる。
また、このエポキシ当量が４００を超えるエポキシ化合
物は、アクリル系ポリマーとの相溶性が低下し、架橋構
造が均一でないため変形性が悪く、保持力、定荷重剥離
性は低下する。Further, the epoxy equivalent of this epoxy compound must be in the range of 250 to 400.
This epoxy equivalent, although indirectly, represents the length of the crosslinked structure formed by the epoxy compound.
The epoxy compound bonds with the carboxyl group in the acrylic polymer to form a crosslinked structure. When an epoxy compound having an epoxy equivalent of 250 to 400 is used,
A uniform crosslinked structure is formed with the acrylic polymer, and a loosely bound state is formed between the adhesive molecules. It is considered that the stress applied to the adhesive layer is absorbed by the deformation of the uniform crosslinked structure between the adhesive molecules that are loosely constrained as described above. Therefore, if an epoxy compound having an epoxy equivalent of less than 250 is used, the cohesive force of the acrylic polymer is increased and the holding power is improved, but the crosslinkable structure is less deformable, so that the peelability under constant load is deteriorated.
Further, an epoxy compound having an epoxy equivalent of more than 400 has a low compatibility with an acrylic polymer and has a poor cross-linking structure so that the deformability is poor and the holding power and the constant load peeling property are lowered.
【００２３】本発明で使用することができるエポキシ化
合物の具体的な例を以下に示す。Specific examples of epoxy compounds that can be used in the present invention are shown below.
【００２４】[0024]
【化１】 Embedded image
【００２５】このようなエポキシ化合物は、主にアクリ
ル系ポリマー中のカルボキシル基と結合してアクリル系
ポリマー分子の間で均一な架橋構造を形成する。こうし
て形成された架橋構造は、アクリル系ポリマーを緩やか
に拘束する程度に形成されていることが必要であり、従
って、このエポキシ化合物をアクリル系ポリマー１００
重量部に対して、０.０２〜２重量部の量で使用して架
橋構造を形成することが必要である。このエポキシ化合
物の量が０.０２重量部に満たないと応力を吸収するの
に有効な密度の架橋構造を形成することができない。ま
た、２重量部を超えると架橋密度が高くなりすぎて、定
荷重剥離性が悪くなる。Such an epoxy compound mainly bonds with a carboxyl group in the acrylic polymer to form a uniform crosslinked structure between the acrylic polymer molecules. The crosslinked structure thus formed needs to be formed to such an extent that the acrylic polymer is gently restrained.
It is necessary to use 0.02 to 2 parts by weight based on parts by weight to form a crosslinked structure. If the amount of this epoxy compound is less than 0.02 part by weight, a crosslinked structure having a density effective for absorbing stress cannot be formed. On the other hand, if it exceeds 2 parts by weight, the crosslink density becomes too high and the peelability under constant load deteriorates.
【００２６】このようなエポキシ化合物による架橋構造
を迅速に形成するために、本発明では反応促進剤を使用
することが好ましい。この反応促進剤の例としては、イ
ミダゾールのようなアミノ化合物を挙げることができ
る。このような反応促進剤を使用する場合、反応促進剤
は、アクリル系ポリマー１００重量部に対して、通常は
０.０１〜５重量部、好ましくは０.１〜２重量部の量で
使用される。In the present invention, it is preferable to use a reaction accelerator in order to rapidly form a crosslinked structure by such an epoxy compound. Examples of this reaction promoter include amino compounds such as imidazole. When such a reaction accelerator is used, the reaction accelerator is generally used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the acrylic polymer. It
【００２７】本発明のアクリル系感圧接着剤組成物は、
通常、アクリル系ポリマーからなる主剤とエポキシ系架
橋剤成分とからなる２液型感圧接着剤として使用され
る。さらに、本発明の感圧接着剤組成物には、他の成分
を配合してもよい。The acrylic pressure-sensitive adhesive composition of the present invention comprises
Usually, it is used as a two-pack type pressure-sensitive adhesive consisting of a main agent made of an acrylic polymer and an epoxy crosslinking agent component. Further, the pressure-sensitive adhesive composition of the present invention may contain other components.
【００２８】本発明のアクリル系感圧接着剤組成物に配
合できる他の成分としては、タッキファイヤー、可塑剤
および染料等を挙げることができる。上記の他の成分と
しては、既に公知の成分を単独あるいは組み合わせて配
合することができる。Other components that can be added to the acrylic pressure-sensitive adhesive composition of the present invention include tackifiers, plasticizers and dyes. As the above-mentioned other components, already known components can be blended alone or in combination.
【００２９】本発明のアクリル系感圧接着剤組成物は、
通常の２液型感圧接着剤と同様に使用することができ
る。例えば、有機溶媒中に溶解若しくは分散しているア
クリル系ポリマー中に所定量のエポキシ化合物を加えて
充分に混合する。この際にタッキファイヤー等の他の成
分も必要により配合して混合する。The acrylic pressure-sensitive adhesive composition of the present invention comprises
It can be used in the same manner as an ordinary two-component pressure-sensitive adhesive. For example, a predetermined amount of an epoxy compound is added to an acrylic polymer which is dissolved or dispersed in an organic solvent, and they are mixed sufficiently. At this time, if necessary, other components such as a tackifier are blended and mixed.
【００３０】次いでこの混合物を剥離紙上に塗布し、溶
剤を除去後支持体上に転写し接着剤として使用すること
ができる。特に本発明のアクリル系感圧接着剤組成物
は、上記のように支持体上に転写した後、常温で５〜１
０日程度熟成させた後に使用することが好ましい。Then, this mixture can be coated on a release paper, and after removing the solvent, transferred onto a support to be used as an adhesive. In particular, the acrylic pressure-sensitive adhesive composition of the present invention, after being transferred onto a support as described above, has a temperature of 5 to 1 at room temperature.
It is preferably used after aging for about 0 days.
【００３１】本発明のアクリル系感圧接着剤組成物は、
金属、ガラス等との接着性が良好であり、高耐久用途の
工業用粘着テープ、工業用粘着シート、ラベル用接着
剤、液晶表示装置用の接着剤（特に基板上に偏光板ある
いは偏光板と位相差板との積層板を接着する際の接着
剤）等として有用性が高い。The acrylic pressure-sensitive adhesive composition of the present invention comprises
Good adhesion to metals, glass, etc., high-duty industrial adhesive tapes, industrial adhesive sheets, adhesives for labels, adhesives for liquid crystal display devices (especially polarizing plate or polarizing plate on substrate) It is highly useful as an adhesive when adhering a laminated plate to a retardation plate.
【００３２】[0032]
【発明の効果】本発明のアクリル系感圧接着剤組成物
は、アクリル系ポリマーと特定のエポキシ化合物とから
なるので、主としてアクリル系ポリマー間にこのエポキ
シ化合物による均一な架橋構造が形成され、この架橋構
造により接着剤に加わる応力を分散することができる。
従って、本発明のアクリル系感圧接着剤組成物は、特に
定荷重剥離強度に優れている。さらに、本発明のアクリ
ル系感圧接着剤組成物は、被着体に対する粘着力が高
く、特に高温条件下における粘着性、凝集性に優れてい
る。また、本発明の感圧接着剤組成物は高温例えば９０
℃付近での接着強度が高いので、耐熱性の接着剤として
特に特に優れている。Since the acrylic pressure-sensitive adhesive composition of the present invention comprises the acrylic polymer and the specific epoxy compound, a uniform crosslinked structure is mainly formed by the epoxy compound between the acrylic polymers. The crosslinked structure can disperse the stress applied to the adhesive.
Therefore, the acrylic pressure-sensitive adhesive composition of the present invention is particularly excellent in constant load peel strength. Furthermore, the acrylic pressure-sensitive adhesive composition of the present invention has a high adhesive force to an adherend, and is particularly excellent in adhesiveness and cohesiveness under high temperature conditions. Further, the pressure-sensitive adhesive composition of the present invention has a high temperature, for example, 90
It is particularly excellent as a heat-resistant adhesive because it has a high adhesive strength at around ° C.
【００３３】[0033]
【実施例】次に製造例および実施例を挙げ、本発明をさ
らに詳しく説明するが、本発明はこれらによって限定的
に解釈されるべきではない。なお、以下に示す実施例等
において「部」との表現は特に限定しない限り「重量
部」を表す。EXAMPLES The present invention will be described in more detail with reference to production examples and examples, but the present invention should not be construed as being limited thereto. In the following examples and the like, the expression "part" means "part by weight" unless otherwise specified.
【００３４】[0034]
【製造例１】 ［アクリル系ポリマーの製造］攪拌機、冷却管、温度計
および窒素導入管を備えた反応装置に、酢酸エチル８０
部、トルエン３０部、アクリル酸ブチル５０部、アクリ
ル酸2-エチルヘキシル４７部、アクリル酸２.５部およ
びメタアクリル酸2-ヒドロキシエチル０.５部を仕込ん
だ後、窒素気流下に系内温度が約７５℃となるまで昇温
した。[Production Example 1] [Production of acrylic polymer] Ethyl acetate 80 was added to a reactor equipped with a stirrer, a cooling pipe, a thermometer and a nitrogen introducing pipe.
Parts, 30 parts of toluene, 50 parts of butyl acrylate, 47 parts of 2-ethylhexyl acrylate, 2.5 parts of acrylic acid and 0.5 parts of 2-hydroxyethyl methacrylate, and then the system temperature under nitrogen flow. Was raised to about 75 ° C.
【００３５】この反応液にアゾビスイソブチロニトリル
０.２部を投入して反応を開始させ、２時間後にさらに
アゾビスイソブチロニトリルを０.３部追加して添加
し、反応液の温度を８０℃まで昇温し、この温度で５時
間攪拌を継続した。この反応液中に冷却トルエン４０部
を入れ、固形分が３９.１％、２３℃における粘度が４
８００cps、重量平均分子量（Ｍｗ）が５４万の重合体
溶液を得た。To this reaction solution, 0.2 part of azobisisobutyronitrile was added to start the reaction, and after 2 hours, 0.3 part of azobisisobutyronitrile was additionally added to the reaction solution. The temperature was raised to 80 ° C., and stirring was continued at this temperature for 5 hours. 40 parts of cooled toluene was added to this reaction solution to obtain a solid content of 39.1% and a viscosity at 23 ° C. of 4
A polymer solution having 800 cps and a weight average molecular weight (Mw) of 540,000 was obtained.
【００３６】[0036]
【実施例１】上記製造例１で得られた重合体１００部
（固形分、以下同じ）に対し架橋剤として、下式（１）
の構造を有するエポキシ当量が約２８０であるエポキシ
化合物［デナコール ＥＸ-８３２；ナガセ化成工業
（株）製］０.４部、架橋促進剤としてイミダゾ−ル０.
５部を添加し、剥離紙上に乾燥後の厚さが２５μｍとな
るように塗布し、乾燥後ポリエステルフィルムに転写し
た。Example 1 The following formula (1) was used as a cross-linking agent for 100 parts (solid content, hereinafter the same) of the polymer obtained in Production Example 1 above.
Epoxy compound having a structure of about 280 and an epoxy equivalent of about 280 [Denacol EX-832; manufactured by Nagase Kasei Kogyo Co., Ltd.] 0.4 part, and imidazole as a crosslinking accelerator.
5 parts was added and coated on a release paper so that the thickness after drying would be 25 μm, and transferred to a polyester film after drying.
【００３７】溶剤を乾燥器で除去後、２３℃で７日間熟
成して粘着テープを得た。After removing the solvent with a drier, it was aged at 23 ° C. for 7 days to obtain an adhesive tape.
【００３８】[0038]
【化２】 Embedded image
【００３９】[0039]
【実施例２】上記製造例１で得られた重合体１００部に
対し架橋剤として、下式（２）の構造を有するエポキシ
当量が約３８２であるエポキシ化合物［デナコール Ｅ
Ｘ-８４１；ナガセ化成工業（株）製］０.４部、架橋促
進剤としてイミダゾール０.５部を添加し、剥離紙上に
乾燥後の厚さが２５μｍとなるように塗布し、乾燥後ポ
リエステルフィルムに転写した。Example 2 An epoxy compound having a structure of the following formula (2) and an epoxy equivalent of about 382 was used as a crosslinking agent for 100 parts of the polymer obtained in the above Production Example 1 [Denacol E.
X-841; manufactured by Nagase Kasei Kogyo Co., Ltd.] 0.4 parts and 0.5 parts of imidazole as a crosslinking accelerator were added and coated on a release paper so as to have a thickness after drying of 25 μm. Transferred to film.
【００４０】溶剤を乾燥器で除去後、２３℃で７日間熟
成して粘着テープを得た。After removing the solvent with a drier, the adhesive tape was obtained by aging at 23 ° C. for 7 days.
【００４１】[0041]
【化３】 [Chemical 3]
【００４２】[0042]
【比較例１】製造例１で得られた重合体１００部に対し
架橋剤として、下式（３）の構造を有するエポキシ当量
が約１３５であるエポキシ化合物［デナコール ＥＸ-
８１０；ナガセ化成工業（株）製］０.０８部、架橋促
進剤としてイミダゾ−ル０.１部を添加し、剥離紙上に
乾燥後の厚さが２５μｍとなるように塗布し、乾燥後ポ
リエステルフィルムに転写した。Comparative Example 1 An epoxy compound having a structure of the following formula (3) and an epoxy equivalent of about 135 was used as a crosslinking agent for 100 parts of the polymer obtained in Production Example 1 [Denacol EX-
810; manufactured by Nagase Kasei Kogyo Co., Ltd.] 0.08 part, and 0.1 part of imidazole as a crosslinking accelerator are added and coated on a release paper so as to have a thickness after drying of 25 μm. Transferred to film.
【００４３】溶剤を乾燥器で除去後、２３℃で７日間熟
成して粘着テープを得た。After removing the solvent with a drier, it was aged at 23 ° C. for 7 days to obtain an adhesive tape.
【００４４】[0044]
【化４】 [Chemical 4]
【００４５】[0045]
【比較例２】製造例１で得られた重合体１００部に対し
架橋剤として、エポキシ当量が、約１００であるエポキ
シ化合物［テトラッドＸ；三菱瓦斯化学（株）製］０.
０３部を添加し、剥離紙上に乾燥後の厚さが２５μｍと
なるように塗布し、乾燥後ポリエステルフィルムに転写
した。Comparative Example 2 An epoxy compound having an epoxy equivalent of about 100 as a cross-linking agent for 100 parts of the polymer obtained in Production Example 1 [Tetrad X; manufactured by Mitsubishi Gas Chemical Co., Inc.]
03 parts was added and coated on a release paper so that the thickness after drying would be 25 μm, and transferred to a polyester film after drying.
【００４６】溶剤を乾燥器で除去後、２３℃で７日間熟
成して粘着テープを得た。After removing the solvent with a drier, it was aged at 23 ° C. for 7 days to obtain an adhesive tape.
【００４７】[0047]
【比較例３】製造例１で得られた重合体１００部に対し
架橋剤として、ポリイソシアネート化合物［コロネート
Ｌ；日本ポリウレタン（株）製］０.５部を添加し、剥
離紙上に乾燥後の厚さが２５μｍとなるように塗布し、
乾燥後ポリエステルフィルムに転写した。Comparative Example 3 To 100 parts of the polymer obtained in Production Example 1 was added 0.5 part of a polyisocyanate compound [Coronate L; manufactured by Nippon Polyurethane Co., Ltd.] as a cross-linking agent, which was dried on a release paper. Apply to a thickness of 25 μm,
After drying, it was transferred to a polyester film.
【００４８】溶剤を乾燥器で除去後、２３℃で７日間熟
成して粘着テープを得た。After removing the solvent with a drier, the adhesive tape was obtained by aging at 23 ° C. for 7 days.
【００４９】[0049]
【試験例】上記のように調製した、実施例１、２のテー
プおよび比較例１〜３の比較テープについて、粘着性能
を以下の通りの方法で調べた。この結果は、第１表に示
す。[Test Example] The adhesive performance of the tapes of Examples 1 and 2 and the comparative tapes of Comparative Examples 1 to 3 prepared as described above was examined by the following method. The results are shown in Table 1.
【００５０】（試験方法）粘着性能 粘着力 試験テープを２８０番の研磨材で研磨したＳＵＳ３０４
板およびガラス板に２kgのハンドローラーで１往復して
圧着させた。１時間放置後、この試験テープを剥離角度
１８０度、引張り速度３００mm／分の条件で剥離したと
きの強度を測定した（剥離温度２３℃（常温）および９
０℃、ｇ／２５mm）。(Test Method) Adhesive Performance Adhesive Strength SUS304 obtained by polishing a test tape with a No. 280 abrasive.
The plate and the glass plate were pressed back and forth once with a 2 kg hand roller. After being left for 1 hour, the strength when the test tape was peeled off at a peeling angle of 180 ° and a pulling speed of 300 mm / min was measured (peeling temperature 23 ° C (normal temperature) and 9
0 ° C, g / 25mm).
【００５１】 保持力 上記のＳＵＳ３０４板を被着体とし、貼付面積２０×
２０mm2の試験テ−プに荷重１kgをかけ、８０℃雰囲気
中、６０分後のずれを測定した（mm）。Holding power Using the above-mentioned SUS304 plate as an adherend, a pasting area of 20 ×
A load of 1 kg was applied to a 20 mm 2 test tape, and the deviation after 60 minutes was measured in an atmosphere of 80 ° C. (mm).
【００５２】 定荷重剥離性 試験テ−プをＳＵＳ３０４およびガラス板に貼り付け面
積が幅２０mm、長さ５０mmとなるように貼付し、８０℃
で剥離方向９０゜に２００ｇの荷重をかけた。こうして
加重をかけた試験テープの６０分経過後の剥がれ距離ま
たは落下時間を測定した（mmまたは分）。The constant load peelability test tape was attached to SUS304 and a glass plate so that the area was 20 mm in width and 50 mm in length, and the temperature was 80 ° C.
Then, a load of 200 g was applied in a peeling direction of 90 °. The peel distance or drop time after 60 minutes of the test tape thus loaded was measured (mm or minutes).
【００５３】上記の粘着力、定加重剥離性および保持力
について行った試験の結果を表１に示す。Table 1 shows the results of the tests conducted on the above-mentioned adhesive force, constant weight peelability and holding force.
【００５４】[0054]
【表１】 [Table 1]
【００５５】表１の結果より、本発明のアクリル系感圧
接着剤組成物のみが優れた粘着性能を示すことが明らか
である。From the results shown in Table 1, it is clear that only the acrylic pressure-sensitive adhesive composition of the present invention exhibits excellent tack performance.
Claims (1)
からなるアクリル系感圧接着剤組成物であって、 該アクリル系ポリマーは、カルボキシル基を有する繰り
返し単位を０.５〜２０重量部の量で含有しており、 該エポキシ化合物が、エポキシ当量２５０〜４００の直
鎖状のグリシジル系２官能エポキシ化合物であり、 かつ該アクリル系ポリマー１００重量部に対して、該エ
ポキシ化合物を０.０２〜２重量部の量で含有すること
を特徴とするアクリル系感圧接着剤組成物。1. An acrylic pressure-sensitive adhesive composition comprising an acrylic polymer and an epoxy compound, wherein the acrylic polymer contains a repeating unit having a carboxyl group in an amount of 0.5 to 20 parts by weight. The epoxy compound is a linear glycidyl-based bifunctional epoxy compound having an epoxy equivalent of 250 to 400, and 0.02 to 2 parts by weight of the epoxy compound is added to 100 parts by weight of the acrylic polymer. An acrylic pressure-sensitive adhesive composition, characterized in that it is contained in an amount of 1 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21305794A JP3498123B2 (en) | 1994-09-06 | 1994-09-06 | Acrylic pressure-sensitive adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21305794A JP3498123B2 (en) | 1994-09-06 | 1994-09-06 | Acrylic pressure-sensitive adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0873828A true JPH0873828A (en) | 1996-03-19 |
| JP3498123B2 JP3498123B2 (en) | 2004-02-16 |
Family
ID=16632822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21305794A Expired - Fee Related JP3498123B2 (en) | 1994-09-06 | 1994-09-06 | Acrylic pressure-sensitive adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3498123B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6709726B1 (en) * | 1997-10-21 | 2004-03-23 | Northstar Print Group | Peelable label |
| JP2006089564A (en) * | 2004-09-22 | 2006-04-06 | Dainippon Ink & Chem Inc | Adhesive for folding and fixing flexible printed circuit boards |
| JP2006521418A (en) * | 2004-01-20 | 2006-09-21 | エルジー・ケム・リミテッド | Acrylic pressure-sensitive adhesive composition for polarizing plate |
| JP2012097161A (en) * | 2010-10-29 | 2012-05-24 | Cheil Industries Inc | Adhesive composition |
-
1994
- 1994-09-06 JP JP21305794A patent/JP3498123B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6709726B1 (en) * | 1997-10-21 | 2004-03-23 | Northstar Print Group | Peelable label |
| US6921453B2 (en) * | 1997-10-21 | 2005-07-26 | Northstar Print Group | Peelable label |
| JP2006521418A (en) * | 2004-01-20 | 2006-09-21 | エルジー・ケム・リミテッド | Acrylic pressure-sensitive adhesive composition for polarizing plate |
| JP2006089564A (en) * | 2004-09-22 | 2006-04-06 | Dainippon Ink & Chem Inc | Adhesive for folding and fixing flexible printed circuit boards |
| JP2012097161A (en) * | 2010-10-29 | 2012-05-24 | Cheil Industries Inc | Adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3498123B2 (en) | 2004-02-16 |
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