JP2009263494A - Water-based pressure-sensitive adhesive composition for low-temperature and rough surface - Google Patents
Water-based pressure-sensitive adhesive composition for low-temperature and rough surface Download PDFInfo
- Publication number
- JP2009263494A JP2009263494A JP2008114533A JP2008114533A JP2009263494A JP 2009263494 A JP2009263494 A JP 2009263494A JP 2008114533 A JP2008114533 A JP 2008114533A JP 2008114533 A JP2008114533 A JP 2008114533A JP 2009263494 A JP2009263494 A JP 2009263494A
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- JP
- Japan
- Prior art keywords
- weight
- sensitive adhesive
- acrylic
- pressure
- acrylic copolymer
- 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
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 111
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 39
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 38
- 230000009477 glass transition Effects 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229920006243 acrylic copolymer Polymers 0.000 claims description 70
- 239000000178 monomer Substances 0.000 claims description 69
- -1 acrylate ester Chemical class 0.000 claims description 63
- 230000001070 adhesive effect Effects 0.000 claims description 42
- 239000000853 adhesive Substances 0.000 claims description 41
- 239000000839 emulsion Substances 0.000 claims description 23
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 abstract description 19
- 229920006113 non-polar polymer Polymers 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 description 34
- 239000010410 layer Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000003995 emulsifying agent Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 239000003945 anionic surfactant Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 7
- 229940001584 sodium metabisulfite Drugs 0.000 description 7
- 235000010262 sodium metabisulphite Nutrition 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000002562 thickening agent Substances 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 229940049920 malate Drugs 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-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
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 239000001913 cellulose Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- YSEKNCXYRGKTBJ-UHFFFAOYSA-N dimethyl 2-hydroxybutanedioate Chemical compound COC(=O)CC(O)C(=O)OC YSEKNCXYRGKTBJ-UHFFFAOYSA-N 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
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Abstract
Description
本発明は、ダンボールのような粗面やポリオレフィンのような非極性ポリマーのフィルム又は成形品に対し、優れた接着力、殊に、優れた低温接着力を有すると共に、接着力の経時安定性にも優れた感圧接着剤層を形成することのできるアクリル系水性感圧接着剤組成物に関し、詳しくは、特定のガラス転移点を有するアクリル系共重合体、並びに、並びに、特定組成で且つ特定のガラス転移点を有するαーオレフィンー飽和脂肪酸ビニルエステル系共重合体および粘着付与樹脂をそれぞれ特定量配合してなるアクリル系水性感圧接着剤組成物であって、該組成物中に分散しているこれらアクリル系共重合体の平均粒子径が特定範囲であるアクリル系水性感圧接着剤組成物に関する。 The present invention has excellent adhesive strength, particularly excellent low-temperature adhesive strength, on the rough surface such as corrugated cardboard and nonpolar polymer film or molded product such as polyolefin, and the stability of adhesive strength over time. In particular, the present invention relates to an acrylic water-based pressure-sensitive adhesive composition capable of forming an excellent pressure-sensitive adhesive layer, and more specifically, an acrylic copolymer having a specific glass transition point, and a specific composition and specific An acrylic water-based pressure-sensitive adhesive composition comprising a specific amount of an α-olefin-saturated fatty acid vinyl ester copolymer and a tackifying resin each having a glass transition point of, and dispersed in the composition The present invention relates to an acrylic water-based pressure-sensitive adhesive composition in which the average particle size of these acrylic copolymers is in a specific range.
感圧接着剤の用途は、テープ、シート、ラベル、ステッカー、壁紙等の多方面にわたっており、被着体の材質もプラスチック、金属、ガラス、陶磁器、紙、布、木材、生鮮食料品等と広範囲にわたっている。 Applications of pressure-sensitive adhesives are wide-ranging, such as tapes, sheets, labels, stickers, wallpaper, etc., and the materials of adherends are wide-ranging such as plastic, metal, glass, ceramics, paper, cloth, wood, and fresh foods. Over.
従来、感圧接着剤の主原料として、天然ゴム、合成ゴム、エチレン−酢酸ビニル共重合体、アクリル系共重合体等が、有機溶媒に溶解された形態で又は水に分散された形で用いられてきた。これらの中でも、水に分散された形、すなわち水分散型のアクリル系共重合体を主原料とする感圧接着剤は、有機溶剤を含有せず、火災の発生や環境衛生上の問題がないので、次第に広く使用されるようになってきた。 Conventionally, natural rubber, synthetic rubber, ethylene-vinyl acetate copolymer, acrylic copolymer, etc. are used as the main raw materials for pressure sensitive adhesives in a form dissolved in an organic solvent or dispersed in water. Has been. Among these, a pressure-sensitive adhesive mainly composed of a water-dispersed acrylic copolymer, that is, a water-dispersed acrylic copolymer does not contain an organic solvent, and does not cause fire or environmental health problems. So it has become increasingly popular.
しかしながら、水分散型アクリル系共重合体を主原料とする感圧接着剤は、溶剤型アクリル系共重合体を主原料とする感圧接着剤に比較して、耐水性や接着力、特に低温での接着力やポリオレフィンのような非極性ポリマーのフィルムや成形品に対する接着力が不足しがちであるという問題点があった。 However, pressure-sensitive adhesives based on water-dispersed acrylic copolymers are more resistant to water resistance and adhesion, especially at low temperatures, compared to pressure-sensitive adhesives based on solvent-based acrylic copolymers. There is a problem in that the adhesive strength of the film and the non-polar polymer film or molded product such as polyolefin tend to be insufficient.
水分散型アクリル系共重合体を主原料とする感圧接着剤の上記のような問題点を改良する代表的な試みとして、例えば特開昭60-84371号公報（特許文献１）には、水性媒体と樹脂分からなり、該樹脂分が特定のアクリル系単量体を共重合してなるガラス転移点−30〜−60℃の範囲のアクリル系共重合体50〜95重量％、及び、軟化点が70〜130℃の範囲にある不均化ロジンエステル50〜５重量％からなる水性エマルジョン型接着剤組成物が開示されている。この接着剤組成物は、従来のアクリル系エマルジョンに対し特定の不均化ロジンエステルを特定量配合することによって、特にポリオレフィンに対する接着力を改良しようとするものである。 As a representative attempt to improve the above-mentioned problems of the pressure-sensitive adhesive mainly composed of a water-dispersed acrylic copolymer, for example, JP-A-60-84371 (Patent Document 1) 50% to 95% by weight of an acrylic copolymer having a glass transition point in the range of -30 to -60 ° C, which is composed of an aqueous medium and a resin, and the resin is copolymerized with a specific acrylic monomer, and softening An aqueous emulsion adhesive composition comprising 50-5% by weight of a disproportionated rosin ester having a point in the range of 70-130 ° C is disclosed. This adhesive composition is intended to improve the adhesive strength particularly to polyolefin by blending a specific amount of a specific disproportionated rosin ester with a conventional acrylic emulsion.
しかしながら上記提案の接着剤組成物は、ポリオレフィンなどの非極性ポリマーの被着体に対する接着力は確かに改良されるが、例えば、エマルジョン粒子が凝集して粗粒子となり易いなど機械的安定性が不十分であり、塗工時にノリスジ等が発生するなどの問題点がある。また得られる感圧接着シートは、例えば−10〜＋5℃程度の低温下で接着力が低下して被着体へ貼付できなくなったり、剥離時いわゆる不連続剥離となって被着体表面にしわが入ったりするなどの不都合が生じ易い。 However, although the above-mentioned proposed adhesive composition certainly improves the adhesion of non-polar polymers such as polyolefins to adherends, it has poor mechanical stability, for example, emulsion particles tend to aggregate and become coarse particles. It is sufficient, and there are problems such as generation of noisiness during coating. In addition, the pressure-sensitive adhesive sheet obtained has a low adhesive strength at a low temperature of, for example, about −10 to + 5 ° C. and cannot be applied to the adherend, or becomes a so-called discontinuous peel at the time of peeling, and the surface of the adherend is wrinkled. Inconvenience such as entering easily occurs.
また、例えば特開平4-103685号公報（特許文献２）には、特定のアクリル系(共)重合体を主成分とするアクリル系樹脂エマルジョンに、軟化点が100℃以下である粘着付与樹脂のエマルジョンが配合され、該粘着付与樹脂のエマルジョン粒子の平均粒子径が１μmを超えていることを特徴とするエマルジョン型感圧接着剤が開示されている。 Further, for example, in Japanese Patent Application Laid-Open No. 4-103685 (Patent Document 2), an acrylic resin emulsion mainly composed of a specific acrylic (co) polymer has a softening point of 100 ° C. or less. An emulsion-type pressure-sensitive adhesive is disclosed, in which an emulsion is blended and the average particle diameter of the emulsion particles of the tackifying resin exceeds 1 μm.
しかしながら上記第２の提案の感圧接着剤は、その凝集力が不十分となりがちで、得られる感圧接着シートのスリット性、裁断性及び抜き打ち性等の二次加工性が低下したり、高温時や高温高湿時の感圧接着シートの保存安定性が悪くなったりすると共に、前記第１の提案と同様、低温下で接着力が低下するなどの問題点がある。 However, the pressure-sensitive adhesive of the second proposal tends to have insufficient cohesive force, resulting in a decrease in secondary workability such as slit property, cutting property and punching property of the resulting pressure-sensitive adhesive sheet, and high temperature. The storage stability of the pressure-sensitive adhesive sheet at the time or at high temperature and high humidity may be deteriorated, and the adhesive force may be reduced at a low temperature as in the first proposal.
本発明者らは上記特性を改良するため特開平７−２３３３５７号公報（特許文献３）、において、特定のゲル分率・組成のアクリル系組成物を2種類以上含む水分散型アクリル系感圧接着剤組成物 、および、特開平７−２３３３５８号公報（特許文献４）において特定のガラス転移温度・粒子径のアクリル系組成物を2種類以上含む水分散型アクリル系感圧接着剤組成物を提案し、上記問題を解決した。 In order to improve the above characteristics, the present inventors disclosed in Japanese Patent Application Laid-Open No. 7-233357 (Patent Document 3), a water-dispersed acrylic pressure sensitive material containing two or more kinds of acrylic compositions having a specific gel fraction and composition. An adhesive composition and a water-dispersed acrylic pressure-sensitive adhesive composition comprising two or more acrylic compositions having specific glass transition temperatures and particle sizes in JP-A-7-233358 (Patent Document 4) Proposed and solved the above problem.
しかしながら特許文献３、特許文献４に開示された水分散型アクリル系感圧接着剤組成物は、エマルジョン粒子の機械的安定性、塗工性、低温接着性などの問題点が発生したため、さらに本発明者らは特開平９−２７９１１３号公報（特許文献５）、特開平９−２８６９６３号公報（特許文献６）において、特定範囲のガラス転移点を有する特定平均粒子径範囲のアクリル系共重合体水性分散液に、特定範囲の軟化点、平均分子量及び平均粒子径を有する粘着付与樹脂の水性分散液を特定量配合した組成物において上記問題を解決した。 However, the water-dispersed acrylic pressure-sensitive adhesive compositions disclosed in Patent Document 3 and Patent Document 4 have problems such as mechanical stability of emulsion particles, coating properties, and low-temperature adhesiveness. Inventors disclosed in JP-A-9-279113 (Patent Document 5) and JP-A-9-286963 (Patent Document 6) have a specific average particle size range acrylic copolymer having a glass transition point in a specific range. The above problems have been solved in a composition in which a specific amount of an aqueous dispersion of a tackifying resin having a softening point, an average molecular weight and an average particle size within a specific range is blended with an aqueous dispersion.
しかしながら、特許文献５または特許文献６で提案された組成物においても低温接着性、特にダンボール等の粗面に対して、常温で十分な接着力を有しても、低温では接着力が低下してしまいバランスの取れた十分な接着性が得られなかったのである。
本発明の課題は、感圧接着剤としての本来の性質、すなわち、タック、常態接着力、凝集力、貯蔵安定性をバランスよく保持すると共に、非極性ポリマーのフィルムや成形品に対する接着力、殊に、粗面接着性や低温接着力に優れたアクリル系水性感圧接着剤組成物を得ることにある。 The object of the present invention is to maintain the original properties as a pressure-sensitive adhesive, i.e., tack, normal adhesive strength, cohesive strength, and storage stability in a well-balanced manner, and to adhere to nonpolar polymer films and molded articles, in particular. Another object is to obtain an acrylic water-based pressure-sensitive adhesive composition excellent in rough surface adhesion and low-temperature adhesion.
本発明者らは前記課題を解決すべく研究を重ねた結果、例えば、特定範囲のガラス転移点を有する特定平均粒子径範囲のアクリル系共重合体水性分散液に、特定のガラス転移点を有し特定平均粒子径範囲のアクリルエステル系共重合体水性分散液を特定量配合し、さらに粘着付与樹脂の水性分散液を特定量配合した組成物が、前記問題点をことごとく解消した卓越したアクリル系水性感圧接着剤組成物となることを見出だし、本発明を完成した。 As a result of repeated studies to solve the above problems, the present inventors have, for example, a specific glass transition point in an acrylic copolymer aqueous dispersion having a specific average particle size range and a specific range of glass transition point. A composition containing a specific amount of an acrylic ester copolymer aqueous dispersion having a specific average particle size range and a specific amount of an aqueous dispersion of a tackifying resin further eliminates the above problems. The present invention was completed by finding a water-based pressure-sensitive adhesive composition.
すなわち本発明の感圧接着剤組成物は、
ガラス転移点が-４０℃以下であるアクリル系共重合体（A） ８５〜９５重量％、
ガラス転移点が３０℃以上であるアクリル系共重合体（B） ５〜１５重量％
を含む アクリル系共重合体混合物１００重量部当り、
(C)
粘着付与樹脂 ２〜２５重量部含む、アクリル系水性感圧接着剤組成物であって、
該アクリル系共重合体(A)の分散粒子の平均粒子径が０．３μm〜０．７μmであり、
且つ、アクリル系共重合体（B）の分散粒子の平均粒子径が０．５μm以下であって、
２３°CでのSUS基材への接着力が１２００ｇ／２５ｍｍ以上であり、かつダンボール基材へ-１０°Cでの接着力がSUS基材への２３°Cでの接着力の９０％以上であることを特徴とする。
That is, the pressure-sensitive adhesive composition of the present invention is
85 to 95% by weight of an acrylic copolymer (A) having a glass transition point of −40 ° C. or less,
Acrylic copolymer (B) having a glass transition point of 30 ° C. or higher 5 to 15% by weight
Per 100 parts by weight of the acrylic copolymer mixture containing
(C)
An acrylic water-based pressure-sensitive adhesive composition containing 2 to 25 parts by weight of a tackifying resin,
The average particle diameter of the dispersed particles of the acrylic copolymer (A) is 0.3 μm to 0.7 μm,
And the average particle diameter of the dispersed particles of the acrylic copolymer (B) is 0.5 μm or less,
Adhesive strength to SUS substrate at 23 ° C is 1200g / 25mm or more, and adhesive strength to corrugated cardboard substrate at -10 ° C is 90% or more of adhesive strength to SUS substrate at 23 ° C It is characterized by being.
以下本発明を詳細に説明する。本発明の共重合体成分(A)であるアクリル系共重合体は、特に限定されるものではないが、得られる感圧接着剤組成物の諸物性の優秀さの観点から、下記単量体(a-1)〜(a-3)、 The present invention will be described in detail below. The acrylic copolymer that is the copolymer component (A) of the present invention is not particularly limited, but from the viewpoint of excellent physical properties of the resulting pressure-sensitive adhesive composition, the following monomers are used. (a-1) to (a-3),
(a-1) 下記一般式で表され、その単独重合体のガラス転移点が−２０°C以下であるアクリル酸エステル ５０〜９９．９重量％、 (a-1) 50-99.9% by weight of an acrylic acid ester represented by the following general formula and having a glass transition point of the homopolymer of −20 ° C. or lower,
ＣＨ2＝ＣＨ−ＣＯＯＲ1（式中、Ｒ1は炭素数２〜１２の直鎖もしくは分枝アルキル基を示す） CH2 = CH-COOR1 (wherein R1 represents a linear or branched alkyl group having 2 to 12 carbon atoms)
(a-2) 炭素数３〜５のα,β-不飽和モノ-又はジ-カルボン酸 ０．３〜２重量％、 (a-2) 0.3 to 2% by weight of α, β-unsaturated mono- or dicarboxylic acid having 3 to 5 carbon atoms,
(a-3)上記単量体(a-1)，(a-２)と共重合可能な、該単量体(a-1)〜(a-２)以外の共単量体 ０〜４５重量％、 (a-3) Comonomers other than the monomers (a-1) to (a-2) that can be copolymerized with the monomers (a-1) and (a-2) weight%,
を乳化共重合してなるアクリル系共重合体であって、該アクリル系共重合体のガラス転移点が−４０°C以下のアクリル系共重合体であるのが好ましい。 It is preferable that the acrylic copolymer is obtained by emulsion copolymerization, and the acrylic copolymer has a glass transition point of −40 ° C. or lower.
前記単量体(a-1)は、一般式ＣＨ2＝ＣＨ−ＣＯＯＲ1で表わされるアクリル酸エステルであり、そのＲ1は炭素数２〜１２の直鎖もしくは分枝アルキル基を示し、且つ、その単独重合体のガラス転移点が−２０°C以下のものである。 The monomer (a-1) is an acrylate ester represented by the general formula CH2 = CH-COOR1, wherein R1 represents a linear or branched alkyl group having 2 to 12 carbon atoms, The glass transition point of the polymer is -20 ° C or lower.
そのような基Ｒ1の例としては、エチル基、n-プロピル基、n-ブチル基、i-ブチル基、n-ヘキシル基、n-オクチル基、i-オクチル基、2-エチルヘキシル基、n-ノニル基、i-ノニル基、n-デシル基、n-ドデシル基などを挙げることができる。これらの中、必須成分として用いられる単量体のアルキル基Ｒ1としては、n-ブチル基、n-ヘキシル基、n-オクチル基、i-オクチル基、2-エチルヘキシル基、n-ノニル基、i-ノニル基、n-デシル基などの炭素数４〜10の直鎖もしくは分枝アルキル基が好ましい。 Examples of such groups R1 are ethyl, n-propyl, n-butyl, i-butyl, n-hexyl, n-octyl, i-octyl, 2-ethylhexyl, n- Nonyl group, i-nonyl group, n-decyl group, n-dodecyl group and the like can be mentioned. Among these, the alkyl group R1 of the monomer used as an essential component includes n-butyl group, n-hexyl group, n-octyl group, i-octyl group, 2-ethylhexyl group, n-nonyl group, i A linear or branched alkyl group having 4 to 10 carbon atoms such as -nonyl group and n-decyl group is preferred.
このような単量体(a-1)であるアクリル酸エステルの具体例としては、エチルアクリレート、n-プロピルアクリレート、n-ブチルアクリレート、i-ブチルアクリレート、n-ヘキシルアクリレート、n-オクチルアクリレート、i-オクチルアクリレート、2-エチルヘキシルアクリレート、n-ノニルアクリレート、i-ノニルアクリレート等を挙げることができ、
これらの単量体を単独もしくは２種以上混合して使用することができる。
Specific examples of the acrylic ester that is such a monomer (a-1) include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, Examples include i-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, i-nonyl acrylate,
These monomers can be used alone or in admixture of two or more.
単量体(a-１)の使用量は、単量体(a-１)〜(a-3)の合計１００重量％中、５０〜９９．９重量％、好ましくは５５〜９８重量％、であるのがよい。単量体(a-1)の使用量が該下限量以上であれば、形成される感圧接着剤層の接着力、タック及び凝集力のバランスが優れているので好ましく、一方、該上限量以下であれば、凝集力が不足するなどの不都合が生じないので好ましい。 The amount of the monomer (a-1) used is 50 to 99.9% by weight, preferably 55 to 98% by weight, in a total of 100% by weight of the monomers (a-1) to (a-3). It is good to be. If the amount of the monomer (a-1) used is equal to or greater than the lower limit amount, it is preferable because the balance of the adhesive force, tack and cohesive force of the pressure-sensitive adhesive layer to be formed is preferable. The following is preferable because inconveniences such as insufficient cohesive force do not occur.
前記単量体(a-2)は、炭素数３〜５のα,β-不飽和モノ-もしくはジ-カルボン酸であり、その具体例としては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸、シトラコン酸などを挙げることができる。これらの中では、アクリル酸、メタクリル酸の利用がより好ましい。 The monomer (a-2) is an α, β-unsaturated mono- or di-carboxylic acid having 3 to 5 carbon atoms, and specific examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid. , Fumaric acid, crotonic acid, citraconic acid and the like. Among these, use of acrylic acid or methacrylic acid is more preferable.
前記単量体(a-2)の使用量は、前記単量体(a-1)〜(a-3)の合計１００重量％中、一般にO.1〜５重量％、好ましくは０．２〜４重量％、より好ましくは０．３〜２重量％、であるのがよい。該単量体(a-2)の使用量が該上限量以下であれば、形成される感圧接着剤層のタック及び耐水接着性が低下するなどの不都合が生じないので好ましい。一方、該使用量が該下限値以上であれば、得られる感圧接着剤水性組成物の機械安定性及び得られる感圧接着剤層の接着力が適度であり凝集力にも優れているので、該使用量範囲において適当に選択利用するのがよい。 The amount of the monomer (a-2) used is generally O.1 to 5% by weight, preferably 0.2%, out of a total of 100% by weight of the monomers (a-1) to (a-3). It should be ˜4% by weight, more preferably 0.3-2% by weight. If the amount of the monomer (a-2) used is not more than the upper limit, it is preferable because there are no inconveniences such as a decrease in tackiness and water-resistant adhesion of the pressure-sensitive adhesive layer to be formed. On the other hand, if the amount used is greater than or equal to the lower limit, the mechanical stability of the resulting pressure-sensitive adhesive aqueous composition and the adhesive strength of the resulting pressure-sensitive adhesive layer are moderate and excellent in cohesive strength. Therefore, it is preferable to appropriately select and use within the usage amount range.
前記単量体(a-3)は、前記単量体(a-1)〜(a-2)と共重合可能な、該単量体(a-1)〜(a-2)以外の共単量体であり、例えば、前記(a-1)以外のアクリル酸エステルを挙げることができる。このようなアクリル酸エステルの具体例としては、メチルアクリレート、i-プロピルアクリレート、t-ブチルアクリレート、トリデシルアクリレート、ステアリルアクリレート、オレイルアクリレート（好ましくはメチルアクリレート）等を挙げることができる。 The monomer (a-3) is a copolymer other than the monomers (a-1) to (a-2) that can be copolymerized with the monomers (a-1) to (a-2). Examples of the monomer include acrylic acid esters other than the above (a-1). Specific examples of such an acrylic acid ester include methyl acrylate, i-propyl acrylate, t-butyl acrylate, tridecyl acrylate, stearyl acrylate, and oleyl acrylate (preferably methyl acrylate).
また共単量体(a-3)としては、例えば、メチルメタクリレート、エチルメタクリレート、n-プロピルメタクリレート、n-ブチルメタクリレート、i-ブチルメタクリレート、t-ブチルメタクリレート、n-オクチルメタクリレート、2-エチルヘキシルメタクリレート、i-デシルメタクリレート、ラウリルメタクリレート、トリデシルメタクリレート、セチルメタクリレート、ステアリルメタクリレート、オレイルメタクリレート、シクロヘキシルメタクリレート、ベンジルメタクリレート（好ましくはメチルメタクリレート）等のメタクリル酸エステル； Examples of the comonomer (a-3) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, and 2-ethylhexyl methacrylate. Methacrylic acid esters such as i-decyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, oleyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate (preferably methyl methacrylate);
例えば、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、「バーサチック酸ビニル」（商品名）（好ましくは酢酸ビニル）等の飽和脂肪酸ビニルエステル；例えば、スチレン、α-メチルスチレン、ビニルトルエン（好ましくはスチレン）等の芳香族ビニル単量体；及び、例えば、アクリロニトリル、メタクリロニトリル等（好ましくはアクリロニトリル）のシアン化ビニル単量体；よりえらばれた共単量体も同様に利用できる。 For example, saturated fatty acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, “vinyl versatate” (trade name) (preferably vinyl acetate); for example, styrene, α-methylstyrene, vinyltoluene (preferably styrene) And vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, etc. (preferably acrylonitrile); more selected comonomers can be used as well.
また共単量体(a-3)としては、例えば、ジメチルマレート、ジ-n-ブチルマレート、ジ-2-エチルヘキシルマレート、ジ-n-オクチルマレート、ジメチルフマレート、ジ-n-ブチルフマレート、ジ-2-エチルヘキシルフマレート、ジ-n-オクチルフマレート等のマレイン酸もしくはフマル酸のジエステル；も使用可能であり、前記共単量体を単独でまたは２種類以上混合して使用することができる。 Examples of the comonomer (a-3) include dimethyl malate, di-n-butyl malate, di-2-ethylhexyl malate, di-n-octyl malate, dimethyl fumarate, and di-n-butyl. Diesters of maleic acid or fumaric acid such as fumarate, di-2-ethylhexyl fumarate, di-n-octyl fumarate, etc. can also be used, and the above comonomer is used alone or in admixture of two or more. can do.
このような共単量体(a-3)の使用量は、前記単量体(a-1)〜(a-3)の合計１００重量％に対して、一般に０〜４５重量％、好ましくは０〜３０重量％、さらに好ましくは２〜１０重量％であるのがよい。該共単量体(a-3)の使用量は、その種類により変わるので一義的には決められないが、接着力とタックとのバランス及びこれらと凝集力とのバランスなどを所望に応じて調節するのに役立つので、そのような目的に合致するように上記範囲内の量で適宜に選択することができる。該共単量体(a-4)の使用量が上記範囲の上限値以下であれば、タックが小さくなり過ぎるなどの不都合が生じないので好ましい。また、該使用量を２重量％以上とすることにより接着力又は凝集力の向上が期待できる。 The amount of the comonomer (a-3) used is generally 0 to 45% by weight, preferably 100% by weight based on the total of the monomers (a-1) to (a-3), preferably It is good that it is 0 to 30% by weight, more preferably 2 to 10% by weight. The amount of the comonomer (a-3) used varies depending on the type of the monomer (a-3) and cannot be uniquely determined, but the balance between the adhesive force and the tack and the balance between the cohesive force and the like can be determined as desired. Since it is useful for adjustment, it can be appropriately selected in an amount within the above range to meet such purpose. If the amount of the comonomer (a-4) used is less than or equal to the upper limit of the above range, it is preferable because there is no inconvenience such as too small tack. In addition, when the amount used is 2% by weight or more, an improvement in adhesion or cohesion can be expected.
本発明に用いられるアクリル系共重合体は、好ましくは前記単量体(a-1)〜(a-3)を共重合してなるものであり、そのＴgは−40℃以下であることが必要である。Ｔgが該温度を超えて高温過ぎる場合は、得られる感圧接着剤層のタックが不足しがちとなり、−10℃などの低温下での接着力、特にダンボールや成形品への接着性が不十分となることがあり好ましくない。 The acrylic copolymer used in the present invention is preferably obtained by copolymerizing the monomers (a-1) to (a-3), and the Tg thereof is −40 ° C. or lower. is necessary. If the Tg exceeds the above temperature and is too high, the resulting pressure-sensitive adhesive layer tends to be insufficiently tacky, and adhesion at low temperatures such as −10 ° C., particularly adhesion to cardboard and molded products, is poor. This is not preferable because it may be sufficient.
前記Ｔｇは、下記〔１〕に示す計算式による。１／Ｔｇ＝Ｗ1 ／Ｔｇ1 ＋Ｗ2 ／Ｔｇ2 ＋・・・＋Ｗn ／Ｔｇn ・・・〔１〕式中、Ｔｇ、Ｔｇｎは、単独重合体のガラス転移温度（Ｔｇ）を絶対温度で表示し、Ｗｎは樹脂中の各単量体成分の重量分率を示す。
なお、ここでいう「単独重合体のガラス転移温度（Ｔｇ）」は、Ｌ. Ｅ. ニールセン著、小野木宣治訳「高分子の力学的性質」第１１〜３５頁に記載されている単量体のガラス転移温度が適用される。
The Tg is according to the calculation formula shown in [1] below. 1 / Tg = W 1 / Tg 1 + W 2 / Tg 2 +... + Wn / Tgn... [1] In the formula, Tg and Tgn represent the glass transition temperature (Tg) of the homopolymer in absolute temperature, and Wn represents The weight fraction of each monomer component in the resin is shown.
The “glass transition temperature (Tg) of the homopolymer” referred to here is a monomer described by LE Nielsen, translated by Nojiharu Onoki, “Mechanical properties of polymer”, pages 11 to 35. The glass transition temperature is applied.
本発明に用いられるアクリル系共重合体を製造する好適な方法としては、例えば、前記(a-1)〜(a-3)の単量体を、要すれば水溶性保護コロイドの存在下、適当な界面活性剤を重合用乳化剤として用いて、水系媒体中で乳化共重合する態様を挙げることができる。 As a suitable method for producing the acrylic copolymer used in the present invention, for example, the monomers (a-1) to (a-3), if necessary, in the presence of a water-soluble protective colloid, An embodiment in which an appropriate surfactant is used as an emulsifier for polymerization and emulsion copolymerization is carried out in an aqueous medium can be mentioned.
本発明において使用し得る上記の界面活性剤としては、特に限定されるものではなく、乳化重合に用いられる通常の各種界面活性剤を使用することができるが、得られる感圧接着剤層の耐水性のよさなどの観点から、分子内にラジカル重合可能な不飽和基を有する、所謂「反応性乳化剤」の使用が好ましい。 The surfactant that can be used in the present invention is not particularly limited, and various normal surfactants used in emulsion polymerization can be used. However, the water resistance of the resulting pressure-sensitive adhesive layer can be used. From the standpoint of good properties, it is preferable to use a so-called “reactive emulsifier” having an unsaturated group capable of radical polymerization in the molecule.
このような反応性乳化剤としては、例えば、「エレミノール JS-2」、「エレミノール RS-30」〔以上、三洋化成工業(株)製〕、「アクアロン
HS-10N」、「アクアロン HS-20N」〔以上、第一工業製薬(株)製〕、「アデカリアソープ SE-10N」〔旭電化工業(株)製〕、「ラテムル S-120」、「ラテムル
S-120A」、「ラテムル S-180」、「ラテムル S-180A」〔以上、花王(株)製〕等のアニオン系反応性乳化剤；例えば、「アクアロン RN-20」、「アクアロン
RN-30」、「アクアロン RN-50」〔以上、第一工業製薬(株)製〕、「アデカリアソープ NE-10」、「アデカリアソープ NE-20」、「アデカリアソープ
NE-30」〔旭電化工業(株)製〕、「RMA-564」、「RMA-568」、「RMA-1114」〔以上、日本乳化剤(株)製〕等のノニオン系反応性乳化剤；などを挙げることができる。
Examples of such reactive emulsifiers include “Eleminol JS-2”, “Eleminol RS-30” (manufactured by Sanyo Chemical Industries, Ltd.), “AQUALON”.
HS-10N, Aqualon HS-20N (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE-10N (Asahi Denka Kogyo Co., Ltd.), Latemul S-120, Latemul
Anionic reactive emulsifiers such as “S-120A”, “Latemul S-180”, “Latemul S-180A” (manufactured by Kao Corporation); for example, “AQUALON RN-20”, “AQUALON”
RN-30, Aqualon RN-50 (Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap NE-10, Adekaria soap NE-20, Adekaria soap
Nonionic reactive emulsifiers such as “NE-30” (Asahi Denka Kogyo Co., Ltd.), “RMA-564”, “RMA-568”, “RMA-1114” (Nippon Emulsifier Co., Ltd.); Can be mentioned.
前記反応性乳化剤の使用量は、前記単量体(a-1)〜(a-3)の合計100重量部に対して、例えば、0.05〜10重量部、好ましくは0.1〜５重量部程度の量を例示することができる。該使用量が該下限値以上であれば、得られるアクリル系水性感圧接着剤組成物の機械的安定性が良好であるので好ましく、一方、該上限値以下であれば、形成される感圧接着剤層の凝集力及び耐水性が優れているので好ましい。 The amount of the reactive emulsifier used is, for example, about 0.05 to 10 parts by weight, preferably about 0.1 to 5 parts by weight with respect to 100 parts by weight of the monomers (a-1) to (a-3). The amount can be exemplified. If the amount used is greater than or equal to the lower limit, the resulting acrylic aqueous pressure-sensitive adhesive composition is preferable because the mechanical stability is good. It is preferable because the cohesive force and water resistance of the adhesive layer are excellent.
また前記の乳化共重合に際しては、前記反応性乳化剤と共に、従来公知のノニオン系界面活性剤類やアニオン系界面活性剤類など各種界面活性剤を重合用乳化剤として併用することができる。 In the emulsion copolymerization, various surfactants such as conventionally known nonionic surfactants and anionic surfactants can be used in combination with the reactive emulsifier as an emulsifier for polymerization.
上記ノニオン系界面活性剤類として、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキル（もしくはアルケニル）エーテル類；例えば、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類；例えば、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタントリオレエート等のソルビタン高級脂肪酸エステル類； Examples of the nonionic surfactants include polyoxyethylene alkyl (or alkenyl) ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; for example, polyoxyethylene octylphenyl ether, Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate;
例えば、ポリオキシエチレンソルビタンモノラウレート等のポリオキシエチレンソルビタン高級脂肪酸エステル類；例えば、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレート、ポリオキシエチレンモノオレエート等のポリオキシエチレン高級脂肪酸エステル類；例えば、オレイン酸モノグリセライド、ステアリン酸モノグリセライド等のグリセリン高級脂肪酸エステル類；例えば、ポリオキシエチレン・ポリオキシプロピレン・ブロックコポリマー；等を例示することができる。 For example, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate; for example, polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate Glycerin higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride; for example, polyoxyethylene / polyoxypropylene block copolymer;
また前記アニオン系界面活性剤類としては、例えば、オレイン酸ナトリウム、ステアリン酸ナトリウム等の高級脂肪酸塩類；例えば、ドデシルベンゼンスルホン酸ナトリウム等のアルキルアリールスルホン酸塩類；例えば、ラウリル硫酸ナトリウム、オレイル硫酸ナトリウム等のアルキル（もしくはアルケニル）硫酸エステル塩類；例えば、ポリエキシエチレンラウリルエーテル硫酸ナトリウム、ポリエキシエチレンオレイルエーテル硫酸アンモニウム等のポリオキシエチレンアルキル（もしくはアルケニル）エーテル硫酸エステル塩類； Examples of the anionic surfactants include higher fatty acid salts such as sodium oleate and sodium stearate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate; for example, sodium lauryl sulfate and sodium oleyl sulfate. Alkyl (or alkenyl) sulfate esters such as polyoxyethylene alkyl (or alkenyl) ether sulfates such as sodium polyoxyethylene lauryl ether sulfate and ammonium polyoxyethylene oleyl ether sulfate;
例えば、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルアリールエーテル硫酸エステル塩類；モノオクチルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、ポリオキシエチレンラウリルスルホコハク酸ナトリウム等のアルキルスルホコハク酸エステル塩及びその誘導体類；等を例示することができる。 For example, polyoxyethylene alkylaryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate; alkyl sulfosuccinate salts such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof And the like.
これらの界面活性剤を重合用乳化剤として用いる場合には、これらを適宜組合わせて使用するのがよく、その使用量としては一般に前記単量体(a-1)〜(a-3)の合計１００重量部に対して０〜１０重量部程度の量を例示できる。 When these surfactants are used as polymerization emulsifiers, they are preferably used in appropriate combination, and the amount used is generally the sum of the monomers (a-1) to (a-3). An amount of about 0 to 10 parts by weight can be exemplified with respect to 100 parts by weight.
またこれらの界面活性剤は、重合用乳化剤として用いるほか、得られる感圧接着剤水性組成物の機械安定性の向上や離型材（シリコーン樹脂等で離型処理した紙又はプラスチックフイルム）への塗工性の改良等を目的として、前記水性乳化共重合後にしばしば後添加される。例えば、転写法（該感圧接着剤組成物を離型材上に塗布して乾燥させ感圧接着剤層を形成させた後、該感圧接着剤層上に該基材を重ね加圧し、該基材上に該感圧接着剤層を転写する方法）が採用される場合には、前記アニオン系界面活性剤中に例示したスルホコハク酸エステル塩系アニオン系界面活性剤がしばしば用いられる。 These surfactants are used as an emulsifier for polymerization, improve the mechanical stability of the resulting pressure-sensitive adhesive aqueous composition, and apply to a release material (paper or plastic film release-treated with a silicone resin or the like). For the purpose of improving workability, it is often post-added after the aqueous emulsion copolymerization. For example, a transfer method (after applying the pressure-sensitive adhesive composition onto a release material and drying to form a pressure-sensitive adhesive layer, the substrate is overlaid and pressurized on the pressure-sensitive adhesive layer, When the method of transferring the pressure-sensitive adhesive layer onto a substrate is employed, the sulfosuccinic acid ester salt-based anionic surfactant exemplified in the anionic surfactant is often used.
本発明に好適に用いられるアクリル系共重合体水性分散液の好適な製造方法としては、例えば前記(a-1)〜(a-3)の単量体を、前記の如き界面活性剤を重合用乳化剤として用いて、例えばポリビニルアルコールなどの水溶性保護コロイドの存在下に、水系媒体中で乳化共重合するのが好ましい。 As a preferred method for producing an acrylic copolymer aqueous dispersion suitably used in the present invention, for example, the monomers (a-1) to (a-3) are polymerized with the surfactants as described above. As an emulsifier, it is preferable to carry out emulsion copolymerization in an aqueous medium in the presence of a water-soluble protective colloid such as polyvinyl alcohol.
上記の水溶性保護コロイドとしては、例えば、部分ケン化ポリビニルアルコール、完全ケン化ポリビニルアルコール、変性ポリビニルアルコール等のポリビニルアルコール（以下、PVAと略記することがある）類；例えば、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース塩等のセルロース誘導体；及びグアガムなどの天然多糖類；などが挙げられ、これらは、単独でも複数種併用の態様でも利用できる。 Examples of the water-soluble protective colloid include polyvinyl alcohols (hereinafter sometimes abbreviated as PVA) such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; for example, hydroxyethyl cellulose, hydroxypropyl Cellulose derivatives such as cellulose and carboxymethylcellulose salts; and natural polysaccharides such as guar gum; and the like can be used alone or in a combination of plural kinds.
これらの水溶性保護コロイドの中、乳化共重合のしやすさ、得られる感圧接着剤層の凝集力の優秀さなどの観点より、PVA類を用いるのが好ましく、部分ケン化PVA及び／又は変性PVAであって、平均重合度が500以下のものを用いるのが特に好ましい。水溶性保護コロイドの使用量としては、前記単量体(a-1)〜(a-4)の合計100重量部当り０〜２重量部程度である。 Among these water-soluble protective colloids, PVAs are preferably used from the viewpoints of ease of emulsion copolymerization and excellent cohesive strength of the resulting pressure-sensitive adhesive layer, and partially saponified PVA and / or It is particularly preferable to use a modified PVA having an average degree of polymerization of 500 or less. The amount of the water-soluble protective colloid used is about 0 to 2 parts by weight per 100 parts by weight in total of the monomers (a-1) to (a-4).
更に、乳化共重合に際しては、例えば、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩類；t-ブチルハイドロパーオキシド、クメンハイドロパーオキシド、p-メンタンハイドロパーオキシドなどの有機過酸化物類、過酸化水素などの重合開始剤を使用することができる。これらも一種もしくは複数種併用のいずれの態様でも利用できる。これらの重合開始剤は、前記単量体(a-1)〜(a-4)の合計１００重量部に対して、０．１〜１重量部程度の量用いるのが好ましい。 Further, in emulsion copolymerization, for example, persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide In addition, polymerization initiators such as hydrogen peroxide can be used. These can also be used in any form of one kind or a combination of plural kinds. These polymerization initiators are preferably used in an amount of about 0.1 to 1 part by weight with respect to a total of 100 parts by weight of the monomers (a-1) to (a-4).
また、水性乳化共重合に際して、所望により、還元剤を使用することができる。その例としては、アスコルビン酸、酒石酸、クエン酸、ブドウ糖、ホルムアルデヒドスルホキシラート金属塩等の還元性有機化合物；チオ硫酸ナトリウム、亜硫酸ナトリウム、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウム等の還元性無機化合物を例示できる。これら還元剤は、前記単量体(a-1)〜(a-3)の合計１００重量部に対して、、０．１〜１重量部程度の量用いるのが好ましい。 In the aqueous emulsion copolymerization, a reducing agent can be used as desired. Examples include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxylate metal salts; reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. It can be illustrated. These reducing agents are preferably used in an amount of about 0.1 to 1 part by weight with respect to a total of 100 parts by weight of the monomers (a-1) to (a-3).
更にまた、水性乳化共重合に際して、前記の重量平均分子量範囲の共重合体を得るために連鎖移動剤を使用することができ、このような連鎖移動剤としては、例えば、n-ドデシルメルカプタン、t-ドデシルメルカプタン、n-ブチルメルカプタン、2-エチルヘキシルチオグリコレート、2-メルカプトエタノール、トリクロロブロモメタン等を挙げることができる。これら連鎖移動剤は、前記単量体(a-1)〜(a-3)の合計100重量部に対して０〜１重量部程度の量用いるのが好ましい。 Furthermore, in the case of aqueous emulsion copolymerization, a chain transfer agent can be used in order to obtain a copolymer having the above weight average molecular weight range. Examples of such chain transfer agents include n-dodecyl mercaptan, t -Dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, trichlorobromomethane and the like. These chain transfer agents are preferably used in an amount of about 0 to 1 part by weight with respect to 100 parts by weight of the total of the monomers (a-1) to (a-3).
本発明に用いるアクリル系共重合体の乳化共重合において好適に採用される共重合温度は、約４０〜１００℃、特には約６０〜９０℃である。 The copolymerization temperature suitably employed in the emulsion copolymerization of the acrylic copolymer used in the present invention is about 40 to 100 ° C, particularly about 60 to 90 ° C.
かくして得られたアクリル系共重合体の水性分散液中の共重合体粒子の平均粒子径は、０．３μmを超えていることが必要であり、好ましくは０．３〜０．７μmである。平均粒子径が該下限値未満と小さ過ぎると、得られる感圧接着剤層の凝集力が不足したり、得られる感圧接着シートの経時安定性や二次加工性が低下したりするので好ましくない。一方、該上限値以下であれば、感圧接着剤層形成に際しての成膜性が優れており、また該水性分散液の製造に当たって好ましくない凝集物の発生がほとんどないので好ましい。 The average particle size of the copolymer particles in the aqueous dispersion of the acrylic copolymer thus obtained needs to exceed 0.3 μm, and preferably 0.3 to 0.7 μm. If the average particle diameter is too small and less than the lower limit value, the cohesive force of the resulting pressure-sensitive adhesive layer is insufficient, or the time-dependent stability and secondary processability of the resulting pressure-sensitive adhesive sheet are reduced, which is preferable. Absent. On the other hand, if it is less than the upper limit value, the film-forming property in forming the pressure-sensitive adhesive layer is excellent, and there is almost no generation of undesired aggregates in the production of the aqueous dispersion, which is preferable.
なお本明細書において、共重合体の平均粒子径は、日本化学会編「新実験化学講座４ 基礎技術３ 光(II)」第725〜741頁（昭和51年７月20日丸善株式会社発行）に記載された動的光散乱法（以下、DLS法ということがある）により測定された値である。 In this specification, the average particle size of the copolymer is the pp. 725 to 741 (published Maruzen Co., Ltd., July 20, 1976). ) Is a value measured by the dynamic light scattering method described below (hereinafter also referred to as DLS method).
なお上記の平均粒子径の測定に際して、アクリル系共重合体が前記のように粘着付与樹脂や界面活性剤、顔料、無機充填剤等の添加物と共に水系媒体中に分散されたアクリル系水性感圧接着剤組成物の形態をなしているときには、前記同様、遠心分離等の適宜の分離手段により該組成物からアクリル系共重合体の水性分散液を分離してから測定することができる。 In the measurement of the average particle size, the acrylic copolymer is dispersed in an aqueous medium together with additives such as a tackifier resin, a surfactant, a pigment, and an inorganic filler as described above. When it is in the form of an adhesive composition, it can be measured after separating an aqueous dispersion of an acrylic copolymer from the composition by an appropriate separation means such as centrifugation as described above.
前記のようにして得ることのできるアクリル系共重合体の水性分散液は、必要に応じてアンモニア水等によってpH調節できる。このような分散液は、固形分濃度
30〜70重量％、好ましくは45〜65重量％、粘度50〜3000cps（BH型回転粘度計、25℃、20rpm；粘度測定条件以下同様)、pH２〜８程度であるのがよい。
The aqueous dispersion of the acrylic copolymer that can be obtained as described above can be adjusted in pH with aqueous ammonia or the like, if necessary. Such a dispersion has a solids concentration
30 to 70% by weight, preferably 45 to 65% by weight, a viscosity of 50 to 3000 cps (BH type rotational viscometer, 25 ° C., 20 rpm; the same as in the viscosity measurement conditions below) and a pH of about 2 to 8.
本発明のアクリル系水性感圧接着剤組成物は、共重合体成分として前述したようなアクリル系共重合体(A)とともに、アクリル系共重合体（B)を含んでなるものである。 The acrylic water-based pressure-sensitive adhesive composition of the present invention comprises the acrylic copolymer (B) together with the acrylic copolymer (A) as described above as a copolymer component.
上記のアクリル系共重合体（B)は、下記単量体(b-1)〜(b-3)〔但し、(b-1)〜(b-3)の合計を100重量％とする〕、 The acrylic copolymer (B) is composed of the following monomers (b-1) to (b-3) (provided that the total of (b-1) to (b-3) is 100% by weight) ,
(b-1) 下記一般式で表され、その単独重合体のガラス転移点が−８０°C以上であるアクリル酸エステル０〜５０重量％、 (b-1) 0 to 50% by weight of an acrylate ester represented by the following general formula and having a glass transition point of the homopolymer of −80 ° C. or higher,
ＣＨ2＝ＣＨ−ＣＯＯＲ1（式中、Ｒ1は炭素数２〜１２の直鎖もしくは分枝アルキル基を示す） CH2 = CH-COOR1 (wherein R1 represents a linear or branched alkyl group having 2 to 12 carbon atoms)
(b-2) 炭素数３〜５のα,β-不飽和モノ-又はジ-カルボン酸 ０〜５重量％、 (b-2) 0 to 5% by weight of α, β-unsaturated mono- or di-carboxylic acid having 3 to 5 carbon atoms,
(b-3)上記単量体(b-1)，(b-2)と共重合可能な、該単量体(b-1)〜(b-２)以外の共単量体４５〜１００重量％、 (b-3) Comonomers 45 to 100 other than the monomers (b-1) to (b-2), which are copolymerizable with the monomers (b-1) and (b-2). weight%,
を乳化共重合してなるアクリル系共重合体であって、該アクリル系共重合体のガラス転移点が ３０°C以上のアクリル系共重合体であるのが好ましい。 An acrylic copolymer obtained by emulsion copolymerization is preferably an acrylic copolymer having a glass transition point of 30 ° C. or higher.
前記単量体(b-1)は、一般式ＣＨ2＝ＣＨ−ＣＯＯＲ1で表わされるアクリル酸エステルであり、そのＲ1は炭素数２〜１２の直鎖もしくは分枝アルキル基を示し、且つ、その単独重合体のガラス転移点が−２０°C以下のものである。 The monomer (b-1) is an acrylate ester represented by the general formula CH2 = CH-COOR1, wherein R1 represents a linear or branched alkyl group having 2 to 12 carbon atoms, The glass transition point of the polymer is -20 ° C or lower.
そのような基Ｒ1の例としては、エチル基、n-プロピル基、n-ブチル基、i-ブチル基、n-ヘキシル基、n-オクチル基、i-オクチル基、2-エチルヘキシル基、n-ノニル基、i-ノニル基、n-デシル基、n-ドデシル基などを挙げることができる。これらの中、必須成分として用いられる単量体のアルキル基Ｒ1としては、n-ブチル基、n-ヘキシル基、n-オクチル基、i-オクチル基、2-エチルヘキシル基、n-ノニル基、i-ノニル基、n-デシル基などの炭素数４〜10の直鎖もしくは分枝アルキル基が好ましい。 Examples of such groups R1 are ethyl, n-propyl, n-butyl, i-butyl, n-hexyl, n-octyl, i-octyl, 2-ethylhexyl, n- Nonyl group, i-nonyl group, n-decyl group, n-dodecyl group and the like can be mentioned. Among these, the alkyl group R1 of the monomer used as an essential component includes n-butyl group, n-hexyl group, n-octyl group, i-octyl group, 2-ethylhexyl group, n-nonyl group, i A linear or branched alkyl group having 4 to 10 carbon atoms such as -nonyl group and n-decyl group is preferred.
このような単量体(b-1)であるアクリル酸エステルの具体例としては、エチルアクリレート、n-プロピルアクリレート、n-ブチルアクリレート、i-ブチルアクリレート、n-ヘキシルアクリレート、n-オクチルアクリレート、i-オクチルアクリレート、2-エチルヘキシルアクリレート、n-ノニルアクリレート、i-ノニルアクリレート等を挙げることができ、
これらの単量体を単独もしくは２種以上混合して使用することができる。
Specific examples of the acrylic acid ester which is such a monomer (b-1) include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, Examples include i-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, i-nonyl acrylate,
These monomers can be used alone or in admixture of two or more.
単量体(b-１)の使用量は、単量体(b-１)〜(b-3)の合計１００重量％中、０〜５０ 重量％、好ましくは１０〜４０重量％、であるのがよい。単量体(b-1)の使用量が該下限量以上であれば、形成される感圧接着剤層の接着力、タック及び凝集力のバランスが優れているので好ましく、一方、該上限量以下であれば、凝集力が不足するなどの不都合が生じないので好ましい。 The amount of the monomer (b-1) used is 0 to 50% by weight, preferably 10 to 40% by weight, out of a total of 100% by weight of the monomers (b-1) to (b-3). It is good. If the amount of the monomer (b-1) used is not less than the lower limit amount, it is preferable because the balance of the adhesive force, tack and cohesive force of the formed pressure-sensitive adhesive layer is excellent, while the upper limit amount The following is preferable because inconveniences such as insufficient cohesive force do not occur.
前記単量体(b-２)は、炭素数３〜５のα,β-不飽和モノ-もしくはジ-カルボン酸であり、その具体例としては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸、シトラコン酸などを挙げることができる。これらの中では、アクリル酸、メタクリル酸の利用がより好ましい。 The monomer (b-2) is an α, β-unsaturated mono- or di-carboxylic acid having 3 to 5 carbon atoms, and specific examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid. , Fumaric acid, crotonic acid, citraconic acid and the like. Among these, use of acrylic acid or methacrylic acid is more preferable.
単量体(b-２)の使用量は、前記単量体(b-1)〜(b-３)の合計100重量％中、一般に０〜５重量％、好ましくは０〜４重量％、特に好ましくは ０．５〜３重量％である。該単量体(b-２)の使用量が該上限量を超えて多過ぎては、形成される感圧接着剤層のタック及び耐水性が低下することがあり好ましくない。一方、該使用量が 重量％以上であれば、得られる感圧接着剤水性組成物の機械安定性及び得られる感圧接着剤層の接着力が適度であり凝集力にも優れているので、該使用量範囲において適当に選択利用するのがよい。 The amount of the monomer (b-2) used is generally 0 to 5% by weight, preferably 0 to 4% by weight, out of a total of 100% by weight of the monomers (b-1) to (b-3). Particularly preferred is 0.5 to 3% by weight. If the amount of the monomer (b-2) used exceeds the upper limit, the tack and water resistance of the formed pressure-sensitive adhesive layer may be lowered, which is not preferable. On the other hand, if the amount used is not less than wt%, the mechanical stability of the resulting pressure-sensitive adhesive aqueous composition and the adhesive strength of the resulting pressure-sensitive adhesive layer are moderate and excellent in cohesion. It is preferable to select and use appropriately within the usage range.
前記単量体(b-３)は、単量体(b-1)、(b-２)と共重合可能で且つ該単量体(b-1)、(b-２)以外の共単量体であり、このような単量体(b-３)としては、アクリル酸エステル、メタクリル酸エステル、芳香族ビニル単量体、シアン化ビニル単量体、マレイン酸もしくはフマル酸エステル等を使用することができる。 The monomer (b-3) is copolymerizable with the monomers (b-1) and (b-2) and is a copolymer other than the monomers (b-1) and (b-2). As such a monomer (b-3), acrylic acid ester, methacrylic acid ester, aromatic vinyl monomer, vinyl cyanide monomer, maleic acid or fumaric acid ester are used. can do.
このような共単量体(b-３)の使用量は、前記単量体(b-1)〜(b-３)の合計100重量％に対して、一般に４５〜１００重量％、好ましくは５６〜９０重量％、特に好ましくは５７〜８９重量％である。該共単量体(b-３)の使用量は、その種類により変わるので一義的には決められないが、接着力とタックとのバランス及びこれらと凝集力とのバランスなどを所望に応じて調節するのに役立つので、そのような目的に合致するように上記範囲内の量で適宜に選択することができる。該共単量体(b−３)の使用量が上記範囲の上限値を超えて多過ぎては、二次加工性が悪くなることがあり好ましくない。 The amount of the comonomer (b-3) used is generally 45 to 100% by weight, preferably 100% by weight, preferably 100% by weight of the monomers (b-1) to (b-3). It is 56 to 90% by weight, particularly preferably 57 to 89% by weight. The amount of the comonomer (b-3) used varies depending on the type of the monomer (b-3) and cannot be uniquely determined. Since it is useful for adjustment, it can be appropriately selected in an amount within the above range to meet such purpose. If the amount of the comonomer (b-3) used exceeds the upper limit of the above range, the secondary processability may deteriorate, which is not preferable.
本発明に用いられるアクリル系共重合体（B)は、前記単量体(b-1)〜(b-３)を共重合してなるものであり、そのガラス転移点Ｔgは３０〜７０℃であることが必要である。Ｔgが該上限温度を超えて高温の場合は、得られる感圧接着剤層のタック、低温接着性及び曲面接着性が不足しがちとなり、また、該下限温度未満の場合には、感圧接着シートなどの二次加工性が悪くなるので好ましくない。 The acrylic copolymer (B) used in the present invention is obtained by copolymerizing the monomers (b-1) to (b-3), and has a glass transition point Tg of 30 to 70 ° C. It is necessary to be. When Tg is higher than the upper limit temperature, the resulting pressure-sensitive adhesive layer tends to have insufficient tack, low-temperature adhesiveness and curved surface adhesiveness. This is not preferable because secondary workability of a sheet or the like is deteriorated.
本発明に用いられるアクリル系共重合体（B)の共重合体粒子の平均粒子径は、０．５μｍ以下が必要であり、好ましくは０．２〜０．４μmである。平均粒子径が該下限値未満と小さ過ぎると、凝集力不足が起こり、一方、該上限値以下であれば、 接着力、タックや凝集力のバランスが取れる。 The average particle diameter of the copolymer particles of the acrylic copolymer (B) used in the present invention is required to be 0.5 μm or less, preferably 0.2 to 0.4 μm. If the average particle diameter is too small, such as less than the lower limit value, cohesive force will be insufficient.
本発明のアクリル系水性感圧接着剤組成物は、共重合体成分として、前記アクリル系共重合体(A) ８５〜９５重量％、好ましくは８８〜９２重量％並びに、前記アクリル系共重合体（B)
５〜１５重量％ 好ましくは８〜１２重量％、〔但し、(A)及び(B)の合計が100重量％である〕を含んでなるものである。
The acrylic water-based pressure-sensitive adhesive composition of the present invention comprises, as a copolymer component, 85 to 95% by weight, preferably 88 to 92% by weight of the acrylic copolymer (A), and the acrylic copolymer. (B)
5 to 15% by weight, preferably 8 to 12% by weight, wherein the sum of (A) and (B) is 100% by weight.
上記共重合体成分(B)の配合量が上記上限値を超えて多過ぎると、得られる感圧接着剤層のタックが不足がちであり、また凝集力及び耐水性も低下することが多いので好ましくない。一方、該共重合体成分(B)の配合量が上記下限値未満と少な過ぎては、得られる感圧接着剤層の凝集力不足が発生して、曲面に対する接着性が不十分となったり、二次加工性が悪くなりがちであり好ましくない。 If the amount of the copolymer component (B) exceeds the above upper limit and is too much, the pressure-sensitive adhesive layer obtained tends to be insufficient in tack, and the cohesive force and water resistance often decrease. It is not preferable. On the other hand, if the blending amount of the copolymer component (B) is too small and less than the above lower limit value, the resulting pressure-sensitive adhesive layer has insufficient cohesive force, resulting in insufficient adhesion to the curved surface. , Secondary workability tends to deteriorate, which is not preferable.
本発明のアクリル系水性感圧接着剤組成物は、前述したようなアクリル系共重合体(A)、アクリル系共重合体(B)とともに、必須成分として粘着付与樹脂(C)を含んでなるものである。 The acrylic water-based pressure-sensitive adhesive composition of the present invention comprises a tackifier resin (C) as an essential component together with the acrylic copolymer (A) and the acrylic copolymer (B) as described above. Is.
上記の粘着付与樹脂(C)としては、例えば、クマロン・インデン樹脂、テルペン樹脂、テルペン・フェノール樹脂、ロジン樹脂、p-t-ブチルフェノール・アセチレン樹脂、フェノール・ホルムアルデヒド樹脂、キシレン・ホルムアルデヒド樹脂、石油系炭化水素樹脂、水素添加炭化水素樹脂、テレピン系樹脂等を使用することができ、低温接着力及び曲面接着性のよさ等の観点から、テルペン・フェノール樹脂、ロジン樹脂、石油系炭化水素樹脂の使用が好ましい。 Examples of the tackifying resin (C) include, for example, coumarone / indene resin, terpene resin, terpene / phenol resin, rosin resin, pt-butylphenol / acetylene resin, phenol / formaldehyde resin, xylene / formaldehyde resin, petroleum hydrocarbon. Resin, hydrogenated hydrocarbon resin, turpentine resin, etc. can be used, and from the viewpoints of low temperature adhesive strength and curved surface adhesion, use of terpene / phenol resin, rosin resin, petroleum hydrocarbon resin is preferable. .
本発明に用いられる粘着付与樹脂(C)の軟化点は、70〜180℃、好ましくは100〜160℃、特に好ましくは120〜150℃であることが必要である。粘着付与樹脂(C)の軟化点が該下限値未満と低過ぎては、得られる感圧接着剤層の凝集力が低下する傾向にあるので好ましくなく、一方該上限値を超えて高過ぎては、低温接着力の向上が不十分になりがちとなるので好ましくない。なお粘着付与樹脂の軟化点の測定は、JIS
K-2531の環球法に従って測定された値である。
The softening point of the tackifier resin (C) used in the present invention needs to be 70 to 180 ° C, preferably 100 to 160 ° C, and particularly preferably 120 to 150 ° C. If the softening point of the tackifier resin (C) is too low as less than the lower limit value, it is not preferable because the cohesive force of the resulting pressure-sensitive adhesive layer tends to decrease, while exceeding the upper limit value is too high. Is not preferable because the improvement in low-temperature adhesion tends to be insufficient. The measurement of the softening point of tackifying resin is JIS
It is a value measured according to the ring and ball method of K-2531.
また本発明に好適に用いることのできる粘着付与樹脂は、その重量平均分子量（以下Ｍwと略記することがある）が、5000以下、特には2000〜4000であることが必要である。Ｍwの値が該上限値を超えて大きすぎては、得られる感圧接着剤層の常態接着力、低温接着力、曲面接着性等の接着物性が低下する傾向にあるので好ましくない。一方該下限値以上であれば、得られる感圧接着剤層の凝集力の低下などの不都合が生じることがないので好ましい。なお本発明における粘着付与樹脂のＭwは、GPC法により測定したポリスチレン換算の値をいう。 The tackifying resin that can be suitably used in the present invention needs to have a weight average molecular weight (hereinafter sometimes abbreviated as Mw) of 5000 or less, particularly 2000 to 4000. If the value of Mw exceeds the upper limit, it is not preferable because the adhesive properties such as normal adhesive strength, low temperature adhesive strength, and curved surface adhesiveness of the resulting pressure-sensitive adhesive layer tend to decrease. On the other hand, if it is more than the lower limit value, there is no inconvenience such as a decrease in cohesive force of the resulting pressure-sensitive adhesive layer, which is preferable. In addition, Mw of the tackifier resin in this invention means the value of polystyrene conversion measured by GPC method.
本発明に用いる粘着付与樹脂(C)の水系媒体中の分散粒子の平均粒子径は、0.3μm以下であることが必要であり、好ましくは0.05〜0.28μmである。平均粒子径が該上限値を超えて大き過ぎると、前記アクリル系共重合体との相溶性が悪くなって、得られる感圧接着剤層の接着力が不足したり、得られる感圧接着シートの経時安定性や二次加工性が低下したりするので好ましくない。一方、市販品等としての入手の容易さから該下限値以上であることが好ましい。なお本発明において、粘着付与樹脂の平均粒子径は前記アクリル系共重合体におけると同様に測定して得られた値である。 The average particle size of the dispersed particles in the aqueous medium of the tackifier resin (C) used in the present invention needs to be 0.3 μm or less, preferably 0.05 to 0.28 μm. If the average particle diameter is too large exceeding the upper limit, the compatibility with the acrylic copolymer is deteriorated, the adhesive force of the resulting pressure-sensitive adhesive layer is insufficient, or the resulting pressure-sensitive adhesive sheet This is not preferable because the aging stability and secondary workability of the steel deteriorate. On the other hand, it is preferable that it is more than this lower limit from the ease of acquisition as a commercial item etc. In the present invention, the average particle diameter of the tackifying resin is a value obtained by measurement in the same manner as in the acrylic copolymer.
さらに上記のＭw及び平均粒子径の測定に際して、アクリル系共重合体が前記のように粘着付与樹脂や界面活性剤、顔料、無機充填剤等の添加物と共に水系媒体中に分散されたアクリル系水性感圧接着剤組成物の形態をなしているときには、前記同様、遠心分離等の適宜の分離手段により該組成物からアクリル系共重合体の水性分散液を分離してから測定することができる。 Further, when the above Mw and average particle diameter are measured, the acrylic copolymer is dispersed in an aqueous medium together with additives such as a tackifier resin, a surfactant, a pigment, and an inorganic filler as described above. When the pressure-sensitive adhesive composition is in the form, it can be measured after separating the aqueous dispersion of the acrylic copolymer from the composition by an appropriate separation means such as centrifugation as described above.
このような粘着付与樹脂(C)としては、例えば、「スーパーエステル Ｅ−７８８」，「スーパーエステル E-625A」、「スーパーエステル E-635」〔以上荒川化学工業(株)製〕、「ハリエスター
SK-130D」、「ハリエスター SK-508」〔以上ハリマ化成(株)製〕等のロジン樹脂；例えば、「YSポリスター E-1250」、「YSポリスター
T-1300」、〔ヤスハラケミカル(株)製〕等のテルペン・フェノール樹脂；例えば、「QME-125ps」、「QME-800」〔以上東邦化学工業(株)製〕等の石油系炭化水素樹脂；などの商品名で市販されているものが好適に使用される。
Examples of such a tackifier resin (C) include “Superester E-788”, “Superester E-625A”, “Superester E-635” (manufactured by Arakawa Chemical Industries, Ltd.), Star
Rosin resins such as “SK-130D” and “Harry Star SK-508” (manufactured by Harima Chemicals Co., Ltd.); for example, “YS Polystar E-1250”, “YS Polystar
Terpene / phenol resins such as “T-1300” and “Yasuhara Chemical Co., Ltd.”; for example, petroleum hydrocarbon resins such as “QME-125ps” and “QME-800” [above Toho Chemical Industry Co., Ltd.]; What is marketed with a brand name, such as, is used suitably.
本発明のアクリル系水性感圧接着剤組成物は、共重合体成分として、前記アクリル系共重合体(A)70〜98重量％、好ましくは75〜96重量％、及び、前記粘着付与樹脂(C)２〜30重量％、好ましくは４〜25重量％〔但し、(A)及び(C)の合計が100重量％である〕を含んでなるものである。該粘着付与樹脂(C)の配合量が上記上限値を超えて多過ぎると、得られる感圧接着剤層のタックが不足がちとなり、また凝集力、低温接着力及び耐水接着性も低下することが多いので好ましくない。一方、該粘着付与樹脂(C)の配合量が上記下限値未満と少な過ぎては、得られる感圧接着剤層の非極性ポリマーに対する接着力が不十分となったり、二次加工性が悪くなりがちであり好ましくない。 The acrylic water-based pressure-sensitive adhesive composition of the present invention comprises, as a copolymer component, 70 to 98% by weight of the acrylic copolymer (A), preferably 75 to 96% by weight, and the tackifying resin ( C) 2 to 30% by weight, preferably 4 to 25% by weight (provided that the sum of (A) and (C) is 100% by weight). If the amount of the tackifying resin (C) exceeds the above upper limit, the resulting pressure-sensitive adhesive layer tends to have insufficient tack, and the cohesive strength, low-temperature adhesive strength and water-resistant adhesiveness will also decrease. Because there are many, it is not preferable. On the other hand, if the amount of the tackifying resin (C) is too small and less than the above lower limit, the adhesive force of the resulting pressure-sensitive adhesive layer to the nonpolar polymer becomes insufficient, or the secondary processability is poor. It tends to be distorted and is not preferable.
本発明のアクリル系水性感圧接着剤組成物は、製造の容易性などの観点から、前記のアクリル系共重合体(A)前記アクリル系共重合体（B)及び前記粘着付与樹脂(C)をそれぞれ水性分散液の形で混合し、必要に応じてこれに適宜の配合物を添加・配合することにより調製することが好ましい。 The acrylic water-based pressure-sensitive adhesive composition of the present invention includes the acrylic copolymer (A), the acrylic copolymer (B), and the tackifier resin (C) from the viewpoint of ease of production. It is preferable to prepare each by mixing them in the form of an aqueous dispersion, and adding and blending an appropriate blend to this if necessary.
本発明のアクリル系水性感圧接着剤組成物を用いて、感圧接着層を形成させる方法としては、紙又はプラスチックフイルム等の基材の上に該感圧接着剤組成物を直接塗布して乾燥させる直接法が採用できる。また転写法、すなわち、シリコーン樹脂等で離型処理した紙又はプラスチックフィルム等の離型材上に、該感圧接着剤組成物を塗布して乾燥させ感圧接着剤層を形成させた後、該感圧接着剤層上に該基材を重ねて加圧し、該基材上に該感圧接着剤層を転写する方法も利用できる。 As a method for forming a pressure-sensitive adhesive layer using the acrylic water-based pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition is directly applied onto a substrate such as paper or plastic film. A direct drying method can be adopted. In addition, the pressure-sensitive adhesive composition is applied on a release material such as paper or plastic film that has been subjected to a release treatment with a silicone resin or the like, and dried to form a pressure-sensitive adhesive layer. It is also possible to use a method in which the base material is stacked on the pressure-sensitive adhesive layer and pressed, and the pressure-sensitive adhesive layer is transferred onto the base material.
上記転写法では、通常、各種の増粘剤を用いて本発明の組成物を増粘して用いる。このような増粘剤としては、ポリアクリル酸ナトリウム、前記PVA類、前記セルロース誘導体、アルカリ性で増粘する水性分散型ポリ(メタ)アクリル酸系共重合体増粘剤等を例示することができる。これらの増粘剤の使用量は、所望の粘度に応じて適宜きめることができ、前記アクリル系共重合体100重量部に対して固形分として０〜10重量部、好ましくは０〜５重量部の範囲である。 In the above transfer method, the composition of the present invention is usually used after being thickened using various thickeners. Examples of such a thickener include sodium polyacrylate, the PVA, the cellulose derivative, and an aqueous dispersion type poly (meth) acrylic acid copolymer thickener that thickens with an alkali. . The amount of these thickeners used can be determined appropriately according to the desired viscosity, and is 0 to 10 parts by weight, preferably 0 to 5 parts by weight as a solid content with respect to 100 parts by weight of the acrylic copolymer. Range.
また、本発明の感圧接着剤組成物を、所望の性能を損なわない限り、例えば、合成ゴム、天然ゴム、エチレン−酢酸ビニル共重合樹脂等の各種変性用樹脂を添加して使用することができる。 Further, the pressure-sensitive adhesive composition of the present invention may be used by adding various modifying resins such as synthetic rubber, natural rubber, and ethylene-vinyl acetate copolymer resin, as long as the desired performance is not impaired. it can.
これら各種変性用樹脂の添加量は、非極性ポリマーへの接着力と凝集力のバランスの観点から適宜選択でき、前記共重合体成分(A)及び(B)の合計100重量部に対して、例えば、０〜60重量部、好ましくは、０〜30重量部のごとき添加量を例示できる。 The addition amount of these various modifying resins can be appropriately selected from the viewpoint of the balance between the adhesive force and cohesive force to the nonpolar polymer, and with respect to a total of 100 parts by weight of the copolymer components (A) and (B), For example, 0-60 weight part, Preferably, addition amount like 0-30 weight part can be illustrated.
さらに本発明の感圧接着剤組成物には、必要に応じて、可塑剤、湿潤剤、着色剤、無機質充填剤、安定剤、消泡剤、防腐剤、防黴剤等を添加して使用することができる。 Furthermore, the pressure-sensitive adhesive composition of the present invention is used by adding a plasticizer, a wetting agent, a colorant, an inorganic filler, a stabilizer, an antifoaming agent, an antiseptic, an antifungal agent, etc., as necessary. can do.
かくして得られる本発明のアクリル系水性感圧接着剤組成物は、一般に、固形分濃度５０〜６５重量％、粘度２０００〜７０００cps、pH６〜９程度がよく、また、転写法に用いる場合には、固形分濃度５０〜６５重量％、粘度３０００〜６０００cps、pH７〜９が好適である。 The acrylic water-based pressure-sensitive adhesive composition of the present invention thus obtained generally has a solid content of 50 to 65% by weight, a viscosity of 2000 to 7000 cps, and a pH of 6 to 9, and when used in a transfer method, A solid content concentration of 50 to 65% by weight, a viscosity of 3000 to 6000 cps, and a pH of 7 to 9 are suitable.
また本発明のアクリル系水性感圧接着剤組成物の ２３°CでのSUS基材への初期接着力が１２００ｇ／２５ｍｍ以上であることが必要であり、 好ましくは、１３００ ｇ／２５ｍｍ以上 特に好ましくは１５００ｇ／２５ｍｍ以上 であるのがよい。 In addition, it is necessary that the initial adhesive force of the acrylic aqueous pressure-sensitive adhesive composition of the present invention to the SUS substrate at 23 ° C. is 1200 g / 25 mm or more, preferably 1300 g / 25 mm or more. Is preferably 1500 g / 25 mm or more.
さらに本発明のアクリル系水性感圧接着剤組成物の ダンボール基材へ-１０°Cでの接着力が２３°Cでの接着力の９０％以上であることを特徴とが必要であり、 好ましくは、９５％以上 特に好ましくは１００％以上 であるのがよい。 Furthermore, the acrylic water-based pressure-sensitive adhesive composition of the present invention is characterized in that the adhesive strength at −10 ° C. to the corrugated cardboard substrate is 90% or more of the adhesive strength at 23 ° C. Is 95% or more, particularly preferably 100% or more.
以下、比較例、参考例と共に実施例を挙げて本発明について更に詳しく説明する。なお、試験用感圧接着シートの作成、並びに、該感圧接着シートの常態接着力、タック、凝集力、低温接着力、曲面接着性、耐水接着性、断裁性及び接着力経時変化率等の各種物性測定法は以下のとおりである。 Hereinafter, the present invention will be described in more detail with reference to examples together with comparative examples and reference examples. Note that the pressure-sensitive adhesive sheet for testing was prepared, and the normal adhesive strength, tack, cohesive strength, low-temperature adhesive strength, curved surface adhesiveness, water-resistant adhesiveness, cutting property, and adhesive force change rate of the pressure-sensitive adhesive sheet, etc. Various physical property measuring methods are as follows.
(1) 試験用感圧接着シートの作成離型材上に、感圧接着剤組成物のサンプルを、乾燥後の感圧接着剤層が20±３g／m2になるように塗布し、100℃で90秒熱風循環式乾燥機にて乾燥し、ついで上質紙＜55＞に転写して感圧接着シートを作成する。 (1) Preparation of test pressure-sensitive adhesive sheet A sample of the pressure-sensitive adhesive composition was applied on the release material so that the pressure-sensitive adhesive layer after drying was 20 ± 3 g / m 2, at 100 ° C. Dry with a hot air circulating dryer for 90 seconds, and then transfer to high-quality paper <55> to create a pressure-sensitive adhesive sheet.
(2) 接着力の測定JIS R-6253に規定する#280の耐水研磨紙で磨いたSUS 304のステンレス鋼板（以下、SUSと略称することがある）及びポリエチレン板（以下、PE板と略称することがある）（JIS
K-6768に規定する方法で表面張力γ0＝33dyn／cmのもの）に、前(1)項で作成した試験用感圧接着シートより切り出した試験片をJIS Z-0237の方法に従って圧着し、24時間後、23℃、65％RH、剥離速度300mm／分の条件でその剥離強度(g／25mm)を測定する。
(2) Measurement of adhesive strength SUS 304 stainless steel plate (hereinafter abbreviated as SUS) and polyethylene plate (hereinafter abbreviated as PE plate) polished with # 280 water-resistant abrasive paper specified in JIS R-6253 ) (JIS
The test piece cut out from the pressure-sensitive adhesive sheet for test created in the previous section (1) is pressure-bonded according to the method of JIS Z-0237 to the surface tension γ0 = 33 dyn / cm by the method specified in K-6768. After 24 hours, the peel strength (g / 25 mm) is measured under the conditions of 23 ° C., 65% RH, and peel speed of 300 mm / min.
(3) 低温接着力 前(1)項で作成した感圧接着シートより切り出した試験片及び 表面未処理 一般ダンボールを-1０℃の恒温室に24時間以上放置後、-1０℃でJIS Zー0237の方法に従って圧着し、-1０℃で20分間放置後、-1０℃、剥離速度300mm／分の条件下で剥離強度(g／25mm)を測定する。 (3) Low-temperature adhesive strength Specimens cut from the pressure-sensitive adhesive sheet prepared in the previous section (1) and untreated surface General corrugated cardboard is allowed to stand in a temperature-controlled room at -10 ° C for 24 hours or more and then JIS Z- Crimping is performed according to the method of 0237, and after standing for 20 minutes at −10 ° C., the peel strength (g / 25 mm) is measured under the conditions of −10 ° C. and peel speed of 300 mm / min.
(４) タックの測定J. Dow法に準じ、傾斜角30゜の斜面に前(1)項作成の試験用感圧接着シートより切り出した試験片（長さ100mm）を貼り付け、該試験片の斜面上方100mmの位置より径ｘ／32インチの大きさのスチールボールをころがし、試料上で停止する最大径のボールの大きさｘで表示する。 (4) Measurement of tack In accordance with J. Dow method, a test piece (length 100mm) cut out from the pressure-sensitive adhesive test sheet prepared in the previous section (1) was attached to a slope with an inclination angle of 30 °. A steel ball having a diameter of x / 32 inches is rolled from a position 100 mm above the slope of the surface, and the maximum diameter of the ball that stops on the sample is displayed as x.
(５) 凝集力の測定前(2)項と同様に処理したSUS板に、前(1)項作成の試験用感圧接着シートより切り出した試験片を、その貼着面積が25×25mm2になるように貼り付け、２kgローラーを１往復して圧着する。これを40℃×30％RHの雰囲気下で１kgの静荷重を資料に架け、荷重が落下するまでの時間を測定する。 (5) Before the measurement of cohesive force, a test piece cut from the test pressure-sensitive adhesive sheet prepared in (1) above was applied to a SUS plate treated in the same manner as in (2) above, and the bonding area was 25 x 25 mm2. Attaching the 2kg roller and reciprocating it once. Place a 1kg static load on the material in an atmosphere of 40 ° C x 30% RH, and measure the time until the load drops.
(6) 曲面接着性前(1)項で作成した感圧接着シートから10×20mm2の試験片を切り出し、φ=10mmのポリエチレン製の棒〔前(2)項で用いたPE板と同様の材質のもの〕に貼り付け、23℃、65％RHの条件下24時間放置した後の、試験片の棒からの浮きの様子を観察する。 (6) Curved surface adhesiveness Cut out a 10 x 20 mm2 test piece from the pressure-sensitive adhesive sheet prepared in the previous section (1), φ = 10 mm polyethylene rod [same as the PE plate used in the previous section (2) After the sample is left for 24 hours under conditions of 23 ° C and 65% RH, the specimen is observed to float from the rod.
○；浮きなし△；少し浮き有り×；完全に浮き上がり ○: No lift △; Slightly lift ×: Full lift
参考例１
[アクリル共重合体（Ａ）の作製]
温度計、撹拌機、窒素導入管および還流冷却器を備えた反応器内にイオン交換水185重量部を仕込み、窒素置換を行った。一方、別の容器にイオン交換水180重量部並びに乳化重合用の界面活性剤として「DKS NL-600」〔ポリオキシエチレンラウリルエーテル型ノニオン系界面活性剤（有効成分濃度100重量％）；第一工業製薬(株)製〕７重量部及び「ハイテノールNF-17」〔ポリオキシエチレンジスチリルフェニルエーテル硫酸エステルアンモニウム塩型アニオン系界面活性剤（有効成分濃度95重量％）；第一工業製薬（株）製〕7.4重量部を仕込んで撹拌溶解し、次いでこれにブチルアクリレート（BA）459.2重量部、2-エチルヘキシルアクリレート（EHA）189重量部、メチルメタクリレート（MMA）47.6重量部及びアクリル酸（AA）4.2重量部からなる単量体混合物を加えて撹拌し、単量体乳化液を得た。
Reference example 1
[Preparation of acrylic copolymer (A)]
Into a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, 185 parts by weight of ion-exchanged water was charged, and nitrogen substitution was performed. On the other hand, in a separate container, 180 parts by weight of ion-exchanged water and “DKS NL-600” [polyoxyethylene lauryl ether type nonionic surfactant (active ingredient concentration: 100% by weight)] as a surfactant for emulsion polymerization; Kogyo Seiyaku Co., Ltd.] 7 parts by weight and “Hitenol NF-17” [polyoxyethylene distyryl phenyl ether sulfate ammonium salt type anionic surfactant (active ingredient concentration 95% by weight); 7.4 parts by weight, and dissolved with stirring, followed by 459.2 parts by weight of butyl acrylate (BA), 189 parts by weight of 2-ethylhexyl acrylate (EHA), 47.6 parts by weight of methyl methacrylate (MMA) and acrylic acid (AA ) A monomer mixture consisting of 4.2 parts by weight was added and stirred to obtain a monomer emulsion.
反応器の内容物を窒素気流下に撹拌しながら加熱し、反応器内の水温が70℃に達した時点で、重合開始剤及び還元剤として過硫酸アンモニウム（APS）及びメタ重亜硫酸ナトリウム（SMBS）をそれぞれ0.1重量部添加した後、単量体乳化液、並びに8重量％濃度のAPS水溶液及びSMBS水溶液それぞれ35重量部を逐次添加して70℃で約3時間重合反応を行った。重合反応終了後、同温度で約１時間攪拌を継続してから冷却し、次いで25％アンモニア水を4重量部添加してpＨ調整し、アクリル系共重合体の水性分散液（Ａ-1）を得た。この水性分散液は、固形分62.4重量％、pH６.8、粘度200mPa・s（25℃、BH型回転粘度計20rpm）、平均粒子径約0.5μmであった。また、このアクリル系共重合体の特性値は、ガラス転移点−56℃であった。 The reactor contents are heated with stirring under a nitrogen stream, and when the water temperature in the reactor reaches 70 ° C, ammonium persulfate (APS) and sodium metabisulfite (SMBS) are used as polymerization initiators and reducing agents. After adding 0.1 parts by weight of each, 35 parts by weight of each of the monomer emulsion and the 8% by weight APS aqueous solution and SMBS aqueous solution were sequentially added, and a polymerization reaction was performed at 70 ° C. for about 3 hours. After completion of the polymerization reaction, stirring was continued for about 1 hour at the same temperature, followed by cooling. Then, 4 parts by weight of 25% ammonia water was added to adjust the pH, and an aqueous dispersion of acrylic copolymer (A-1) Got. This aqueous dispersion had a solid content of 62.4% by weight, a pH of 6.8, a viscosity of 200 mPa · s (25 ° C., BH type rotational viscometer 20 rpm), and an average particle size of about 0.5 μm. The characteristic value of this acrylic copolymer was a glass transition point of −56 ° C.
参考例２
アクリル系モノマーを表１に示すように換える以外は参考例１と同様にしてアクリル系共重合体の水性分散液（Ａ−２）を得た。この水性分散液の特性値を表１に示した。
Reference example 2
An acrylic copolymer aqueous dispersion (A-2) was obtained in the same manner as in Reference Example 1 except that the acrylic monomer was changed as shown in Table 1. The characteristic values of this aqueous dispersion are shown in Table 1.
参考例３
アクリル系モノマーを表１に示すように換える以外は参考例１と同様にしてアクリル系共重合体の水性分散液を調整したが、モノマーの共重合性が悪くて水性分散液が得られなかった。
Reference example 3
An aqueous dispersion of an acrylic copolymer was prepared in the same manner as in Reference Example 1 except that the acrylic monomer was changed as shown in Table 1. However, an aqueous dispersion was not obtained due to poor copolymerization of the monomer. .
参考例４
[アクリル共重合体（Ｂ）の作製]
温度計、撹拌機、窒素導入管および還流冷却器を備えた反応器内にイオン交換水180重量部を仕込み、窒素置換を行った。一方、別の容器にイオン交換水110重量部並びに乳化重合用の界面活性剤として「ラテムルE-118B」〔ポリオキシエチレンアルキルエーテル型アニオン系界面活性剤（有効成分濃度26重量％）；花王株式会社製〕７重量部を仕込んで撹拌溶解し、次いでこれにブチルアクリレート（BA）108重量部、メチルメタクリレート（MMA）480重量部及びアクリル酸（AA）4.2重量部からなる単量体混合物を加えて撹拌し、単量体乳化液を得た。
Reference example 4
[Preparation of acrylic copolymer (B)]
In a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, 180 parts by weight of ion-exchanged water was charged to perform nitrogen replacement. On the other hand, 110 parts by weight of ion-exchanged water in a separate container and “Latemul E-118B” [polyoxyethylene alkyl ether type anionic surfactant (active ingredient concentration: 26% by weight)] as a surfactant for emulsion polymerization; Kao Corporation Company made] 7 parts by weight was charged and dissolved with stirring, and then a monomer mixture consisting of 108 parts by weight of butyl acrylate (BA), 480 parts by weight of methyl methacrylate (MMA) and 4.2 parts by weight of acrylic acid (AA) was added thereto. And stirred to obtain a monomer emulsion.
反応器の内容物を窒素気流下に撹拌しながら加熱し、反応器内の水温が70℃に達した時点で、重合開始剤及び還元剤として過硫酸アンモニウム（APS）及びメタ重亜硫酸ナトリウム（SMBS）をそれぞれ0.1重量部添加した後、単量体乳化液、並びに8重量％濃度のAPS水溶液及びSMBS水溶液それぞれ60重量部を逐次添加して60℃で約4時間重合反応を行った。重合反応終了後、同温度で約１時間攪拌を継続してから冷却し、アクリル系共重合体の水性分散液（Ｂ−１）を得た。この水性分散液は、固形分55.5重量％、pH2.2、粘度200mPa・s（25℃、BH型回転粘度計20rpm）、平均粒子径約0.2μmであった。また、このアクリル系共重合体の特性値は、ガラス転移点60℃であった。 The reactor contents are heated with stirring under a nitrogen stream, and when the water temperature in the reactor reaches 70 ° C, ammonium persulfate (APS) and sodium metabisulfite (SMBS) are used as polymerization initiators and reducing agents. Then, 0.1 parts by weight of each was added, 60 parts by weight of each of the monomer emulsion, 8% by weight APS aqueous solution and SMBS aqueous solution were sequentially added, and a polymerization reaction was performed at 60 ° C. for about 4 hours. After completion of the polymerization reaction, stirring was continued for about 1 hour at the same temperature, followed by cooling to obtain an aqueous dispersion (B-1) of an acrylic copolymer. This aqueous dispersion had a solid content of 55.5% by weight, pH 2.2, a viscosity of 200 mPa · s (25 ° C., BH type rotational viscometer 20 rpm), and an average particle size of about 0.2 μm. The characteristic value of the acrylic copolymer was a glass transition point of 60 ° C.
参考例５〜７
アクリル系モノマーを表１に示すように換える以外は参考例１と同様にしてアクリル系共重合体の水性分散液（Ｂ-２〜Ｂ−４）を得た。これらの水性分散液の特性値を表２に示した。
Reference Examples 5-7
An acrylic copolymer aqueous dispersion (B-2 to B-4) was obtained in the same manner as in Reference Example 1 except that the acrylic monomer was changed as shown in Table 1. The characteristic values of these aqueous dispersions are shown in Table 2.
実施例１ アクリル系水性感圧接着剤組成物の作製
実施例１のアクリル系共重合体の水性分散液（Ａ-1）285重量部、アクリル系共重合体水性分散液（Ｂ-1）15重量部に粘着付与樹脂の水性分散液「スーパーエステルE-788」 〔重合ロジンエステル樹脂、固形分濃度50重量部％、軟化点160℃、重量平均分子量3000、平均粒子径0.4μｍ；荒川化学工業（株）製〕8重量部、固形分濃度40重量％のジオクルスルホコハク酸ナトリウム型アニオン系界面活性剤2.6重量部を添加し、次いでアクリル系アルカリ増粘剤及びアンモニア水を添加してｐＨ7.5、粘度4500mPa・s（25℃、BM型回転粘度計60rpm）のアクリル系水性感圧接着剤組成物を得た。
Example 1 Preparation of acrylic aqueous pressure-sensitive adhesive composition Acrylic copolymer aqueous dispersion (A-1) 285 parts by weight of Example 1, acrylic copolymer aqueous dispersion (B-1) 15 Aqueous dispersion of tackifier resin "Superester E-788" in parts by weight [Polymerized rosin ester resin, solid content concentration 50% by weight, softening point 160 ° C, weight average molecular weight 3000, average particle size 0.4μm; Arakawa Chemical Industries (Made by Co., Ltd.) 8 parts by weight, 2.6 parts by weight of a sodium dioctylsulfosuccinate anionic surfactant having a solid content of 40% by weight, and then an acrylic alkaline thickener and aqueous ammonia are added to adjust the pH to 7. 5. An acrylic water-based pressure-sensitive adhesive composition having a viscosity of 4500 mPa · s (25 ° C., BM type rotational viscometer 60 rpm) was obtained.
この組成物を用いて、前記(1)の方法に従い試験用の感圧接着シートを作成し、各種物性測定法(２)〜(８)に従って感圧接着シートの物性測定を行った。感圧接着剤組成物の配合組成、使用した粘着付与樹脂の種類とその特性値、得られる組成物の特性値を表３に、感圧接着シートの諸物性を表４に示す。 Using this composition, a pressure-sensitive adhesive sheet for testing was prepared according to the method (1), and the physical properties of the pressure-sensitive adhesive sheet were measured according to various physical property measurement methods (2) to (8). Table 3 shows the compounding composition of the pressure-sensitive adhesive composition, the types and characteristic values of the tackifying resin used, and the characteristic values of the resulting composition. Table 4 shows the physical properties of the pressure-sensitive adhesive sheet.
実施例２〜3及び比較例１〜2
実施例１において、アクリル系共重合体の水性分散液（Ａ-1）、アクリル系共重合体の水性分散液（Ｂ-1）及び粘着付与樹脂の水性分散液（E-７８８）の使用割合を変え、又は、アクリル系共重合体の水性分散液（Ａ-1）のみを用いて粘着付与樹脂の水性分散液を使用しない以外は実施例１と同様にしてアクリル系水性感圧接着剤組成物を得、以下同様にして感圧接着シートを作成して該感圧接着シートの物性測定を行った。感圧接着剤組成物の配合組成、使用した粘着付与樹脂の種類とその特性値、得られる組成物の特性値を表３に、感圧接着シートの諸物性を表４に示す。
Examples 2-3 and Comparative Examples 1-2
In Example 1, the ratio of the acrylic copolymer aqueous dispersion (A-1), the acrylic copolymer aqueous dispersion (B-1), and the tackifier resin aqueous dispersion (E-788). Or an acrylic aqueous pressure-sensitive adhesive composition in the same manner as in Example 1 except that only an aqueous dispersion of acrylic copolymer (A-1) is used and no aqueous dispersion of tackifying resin is used. Thereafter, a pressure-sensitive adhesive sheet was prepared in the same manner, and the physical properties of the pressure-sensitive adhesive sheet were measured. Table 3 shows the compounding composition of the pressure-sensitive adhesive composition, the types and characteristic values of the tackifying resin used, and the characteristic values of the resulting composition. Table 4 shows the physical properties of the pressure-sensitive adhesive sheet.
実施例４〜６及び比較例３
実施例１において、参考例１のアクリル系共重合体の水性分散液（Ａ-1）を用いる代わりに、アクリル系共重合体の水性分散液（Ａ-２）、 （Ｂ−２）〜（Ｂ−３）をそれぞれ用いる以外は実施例１と同様にしてアクリル系水性感圧接着剤組成物を得、以下同様にして感圧接着シートを作成して該感圧接着シートの物性測定を行った。感圧接着剤の配合組成、使用した粘着付与樹脂の種類とその特性値、得られる組成物の特性値を表３に、感圧接着シートの諸物性を表４に示す。
Examples 4 to 6 and Comparative Example 3
In Example 1, instead of using the acrylic copolymer aqueous dispersion (A-1) of Reference Example 1, an acrylic copolymer aqueous dispersion (A-2), (B-2) to (B-2)-( Acrylic water-based pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that each of B-3) was used. A pressure-sensitive adhesive sheet was prepared in the same manner, and the physical properties of the pressure-sensitive adhesive sheet were measured. It was. Table 3 shows the composition of the pressure-sensitive adhesive, the type of tackifying resin used, its characteristic values, and the characteristic values of the resulting composition. Table 4 shows the physical properties of the pressure-sensitive adhesive sheet.
比較例４
実施例１において、粘着付与樹脂を用いない 以外は実施例１と同様にしてアクリル系水性感圧接着剤組成物を得、以下同様にして感圧接着シートを作成して該感圧接着シートの物性測定を行った。感圧接着剤の配合組成、使用した粘着付与樹脂の種類とその特性値、得られる組成物の特性値を表３に、感圧接着シートの諸物性を表４に示す。
Comparative Example 4
In Example 1, an acrylic water-based pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that no tackifying resin was used, and a pressure-sensitive adhesive sheet was prepared in the same manner to prepare the pressure-sensitive adhesive sheet. Physical properties were measured. Table 3 shows the composition of the pressure-sensitive adhesive, the type of tackifying resin used, its characteristic values, and the characteristic values of the resulting composition. Table 4 shows the physical properties of the pressure-sensitive adhesive sheet.
Claims (4)
８５〜９５重量％、ガラス転移点が３０℃以上であるアクリル系共重合体（B） ５〜１５重量％
を含むアクリル系共重合体混合物 １００重量部当り、
粘着付与樹脂（Ｃ） を ２〜２５ 重量部含む アクリル系水性感圧接着剤組成物であって、
該アクリル系共重合体(A)の分散粒子の平均粒子径が０．３μm〜０．７μmであり、
且つ、アクリル系共重合体（B）の分散粒子の平均粒子径が０．３μm以下であって、
２３°CでのSUS基材への接着力が１２００ｇ/２5mm以上であり、
かつ ダンボール基材への-１０°Cでの接着力が２３°CでのSUS基材への接着力の９０％以上であることを特徴とするアクリル系水性感圧接着剤組成物。 Acrylic copolymer having a glass transition point of -40 ° C or lower (A)
85 to 95% by weight, acrylic copolymer (B) having a glass transition point of 30 ° C. or higher 5 to 15% by weight
Per 100 parts by weight of an acrylic copolymer mixture containing
An acrylic water-based pressure-sensitive adhesive composition containing 2 to 25 parts by weight of a tackifier resin (C),
The average particle diameter of the dispersed particles of the acrylic copolymer (A) is 0.3 μm to 0.7 μm,
And the average particle diameter of the dispersed particles of the acrylic copolymer (B) is 0.3 μm or less,
Adhesive strength to SUS substrate at 23 ° C is 1200g / 25mm or more,
An acrylic water-based pressure-sensitive adhesive composition characterized in that the adhesive strength at −10 ° C. to a corrugated cardboard substrate is 90% or more of the adhesive strength to a SUS substrate at 23 ° C.
下記一般式で表され、その単独重合体のガラス転移点が−20℃以下であるアクリル酸エステル ５０〜９９．９重量％、ＣＨ2＝ＣＨ−ＣＯＯＲ1（式中、Ｒ1は炭素数２〜１２の直鎖もしくは分枝アルキル基を示す）
(a-2) 炭素数３〜５のα,β-不飽和モノ-又はジ-カルボン酸０．３〜２重量％、
(a-3) 上記単量体(a-1)〜(a-2)と共重合可能な、該単量体(a-1)，(a-2)以外の共単量体
０〜４５重量％、を乳化共重合してなるアクリル系共重合体である請求項１記載のアクリル系水性感圧接着剤組成物。 Acrylic copolymer (A) is the following monomers (a-1) ~ (a-3), (a-1)
50-99.9 wt% acrylate ester represented by the following general formula and having a glass transition point of the homopolymer of −20 ° C. or lower, CH 2 ═CH—COOR 1 (wherein R 1 has 2 carbon atoms) Represents a linear or branched alkyl group of ~ 12)
(a-2) 0.3 to 2% by weight of an α, β-unsaturated mono- or di-carboxylic acid having 3 to 5 carbon atoms,
(a-3) Comonomers 0 to 45 other than the monomers (a-1) and (a-2), which are copolymerizable with the monomers (a-1) to (a-2). The acrylic water-based pressure-sensitive adhesive composition according to claim 1, which is an acrylic copolymer obtained by emulsion copolymerization in weight%.
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Cited By (9)
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| WO2013099801A1 (en) * | 2011-12-28 | 2013-07-04 | 住友化学株式会社 | Aqueous adhesive |
| WO2013150770A1 (en) * | 2012-04-06 | 2013-10-10 | 日東電工株式会社 | Adhesive composition, adhesive layer, adhesive sheet, surface protective sheet, optical surface-protective sheet, and optical film with surface protective sheet |
| JP2014533757A (en) * | 2011-11-18 | 2014-12-15 | スリーエム イノベイティブ プロパティズ カンパニー | Pressure sensitive adhesive composition |
| JP2016117785A (en) * | 2014-12-18 | 2016-06-30 | ヘンケルジャパン株式会社 | Aqueous adhesive |
| JP2019210482A (en) * | 2014-12-18 | 2019-12-12 | ヘンケルジャパン株式会社 | Aqueous adhesive |
| EP3719087A4 (en) * | 2017-11-29 | 2021-09-01 | Sumitomo Chemical Company, Limited | Coating liquid for forming gas barrier layer |
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| JP7468110B2 (en) | 2020-04-17 | 2024-04-16 | ａｒｔｉｅｎｃｅ株式会社 | Water-based pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and method for producing water-based pressure-sensitive adhesive |
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| JP2014533757A (en) * | 2011-11-18 | 2014-12-15 | スリーエム イノベイティブ プロパティズ カンパニー | Pressure sensitive adhesive composition |
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| EP3719087A4 (en) * | 2017-11-29 | 2021-09-01 | Sumitomo Chemical Company, Limited | Coating liquid for forming gas barrier layer |
| JP7468110B2 (en) | 2020-04-17 | 2024-04-16 | ａｒｔｉｅｎｃｅ株式会社 | Water-based pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and method for producing water-based pressure-sensitive adhesive |
| CN113698898A (en) * | 2020-05-22 | 2021-11-26 | 东洋油墨Sc控股株式会社 | Aqueous pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and process for producing aqueous pressure-sensitive adhesive |
| CN113698898B (en) * | 2020-05-22 | 2024-03-15 | 东洋油墨Sc控股株式会社 | Water pressure sensitive adhesive, pressure sensitive adhesive sheet, and method for producing water pressure sensitive adhesive |
| WO2023105120A1 (en) * | 2021-12-10 | 2023-06-15 | Upm Raflatac Oy | Linerless adhesive label |
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