JP4716687B2 - Method and apparatus for producing adhesive tape or sheet - Google Patents
Method and apparatus for producing adhesive tape or sheet Download PDFInfo
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- JP4716687B2 JP4716687B2 JP2004216760A JP2004216760A JP4716687B2 JP 4716687 B2 JP4716687 B2 JP 4716687B2 JP 2004216760 A JP2004216760 A JP 2004216760A JP 2004216760 A JP2004216760 A JP 2004216760A JP 4716687 B2 JP4716687 B2 JP 4716687B2
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- pressure
- sensitive adhesive
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- adhesive tape
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- 239000002390 adhesive tape Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 title description 23
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 148
- 239000000203 mixture Substances 0.000 claims description 73
- 239000010410 layer Substances 0.000 claims description 52
- 239000012530 fluid Substances 0.000 claims description 48
- 239000003431 cross linking reagent Substances 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 34
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 27
- 230000001070 adhesive effect Effects 0.000 claims description 25
- 238000004898 kneading Methods 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000853 adhesive Substances 0.000 claims description 24
- 239000012790 adhesive layer Substances 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 3
- 239000000178 monomer Substances 0.000 description 13
- 239000006260 foam Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 238000005187 foaming Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 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 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 210000003855 cell nucleus Anatomy 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 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
- 239000003094 microcapsule Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 210000004940 nucleus Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 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
Images
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は厚みの薄い粘着剤層を備えた粘着テープ又はシート及び、微細な気泡を有する発泡粘着剤層を備えた発泡粘着テープ又はシートの製造方法に関する。本発明は又、厚みの薄い粘着剤層又は、微細な気泡構造を有する発泡粘着剤層を支持体上に設けた粘着テープ又はシートの製造装置に関するものである。 The present invention relates to a pressure-sensitive adhesive tape or sheet provided with a thin pressure-sensitive adhesive layer and a method for producing a foamed pressure-sensitive adhesive tape or sheet provided with a foamed pressure-sensitive adhesive layer having fine bubbles. The present invention also relates to an apparatus for producing an adhesive tape or sheet in which a thin adhesive layer or a foamed adhesive layer having a fine cell structure is provided on a support.
従来、粘着テープや粘着シートの製造において、厚みの薄い粘着剤層を形成する方法としては、粘着剤組成物を溶剤で希釈して支持体に塗布するなど、溶剤を用いるのが一般的である。環境対策の観点からは溶剤を使用せず薄層化できるコーティング手法の開発が望まれている。 Conventionally, in the production of pressure-sensitive adhesive tapes and pressure-sensitive adhesive sheets, as a method of forming a thin pressure-sensitive adhesive layer, it is common to use a solvent, such as diluting the pressure-sensitive adhesive composition with a solvent and applying it to a support. . From the viewpoint of environmental measures, it is desired to develop a coating method that can be thinned without using a solvent.
一方、粘着テープや粘着シートの粘着剤層を微細な発泡構造とすることにより、見かけの弾性率を低下させて、初期粘着性、粗面接着性、耐反撥性などの特性を向上させたり、粘着剤使用量の低減により材料費を削減することが行われている。しかし、厚みの薄い粘着剤層に微細な発泡構造を形成させることは困難であり、形成できたとしても持続させることが難しく、厚みの薄い粘着剤層中に、安定して残存する微細な発泡構造を形成することは困難であった。このような問題を解決する発泡粘着テープ又はシート製造方法として、熱分解型化学発泡剤を粘着剤層中に含有させて加熱する方法（特許文献１参照）、粘着剤層中にマイクロカプセルのような微小中空粒子を混合する方法（特許文献２参照）などが知られている。しかしこれらの方法では、発泡剤や微小中空粒子が均一に分散しにくい、微細セルが得られにくい、発泡セル構造の制御が困難である、コスト高となるなどの多くの問題がある。 On the other hand, by making the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet into a fine foam structure, the apparent elastic modulus is lowered, and the properties such as initial tackiness, rough surface adhesion, and repulsion resistance are improved. Reducing material costs by reducing the amount of adhesive used. However, it is difficult to form a fine foam structure in a thin pressure-sensitive adhesive layer, and even if it can be formed, it is difficult to maintain a fine foam structure that remains stably in a thin pressure-sensitive adhesive layer. It was difficult to form a structure. As a method for producing a foamed pressure-sensitive adhesive tape or sheet for solving such a problem, a method in which a heat-decomposable chemical foaming agent is contained in a pressure-sensitive adhesive layer and heated (see Patent Document 1), and a microcapsule is used in the pressure-sensitive adhesive layer. A method of mixing fine hollow particles (see Patent Document 2) is known. However, these methods have many problems such as difficulty in uniformly dispersing the foaming agent and fine hollow particles, difficulty in obtaining fine cells, difficulty in controlling the foam cell structure, and high costs.
その他、既存の粘着シートを高圧力の不活性ガス雰囲気下において粘着剤層中に該雰囲気ガスを溶解させた後、圧力を解放することで粘着剤層を発泡させる方法が開示されている（特許文献３、４参照）。しかしながら、この方法では、微細なセル構造を形成できるものの、粘着剤の塗工、乾燥といった従来の粘着シート製造工程に加えて、さらに発泡工程が必要となるため、工程が複雑となり、従来の粘着シートの製造コストに比べてコストアップは免れない。また、この発泡工程は主にバッチ式の圧力室内で行われるため、連続生産性という観点からは非常に不利である。
In addition, there is disclosed a method in which an existing pressure-sensitive adhesive sheet is foamed by releasing the pressure after dissolving the atmospheric gas in the pressure-sensitive adhesive layer under a high-pressure inert gas atmosphere (patent)
また、発泡粘着剤層を構成するポリマーの単量体を含む混合物を、加圧下、超臨界状態又は液体状態の不活性流体中で重合に付した後、得られた重合組成物を、前記圧力よりも低圧力下の支持体上に吐出、積層して発泡粘着剤層を形成させる方法が開示されている（特許文献５参照）。しかし、この方法では気泡が安定して残存しない。 In addition, a mixture containing a polymer monomer constituting the foamed pressure-sensitive adhesive layer is subjected to polymerization in an inert fluid in a supercritical state or a liquid state under pressure, and then the obtained polymerization composition is subjected to the pressure. A method is disclosed in which a foamed adhesive layer is formed by discharging and laminating on a support under a lower pressure (see Patent Document 5). However, in this method, bubbles do not remain stably.
本発明の目的は、上記問題に鑑み、溶剤を使用せずに厚みの薄い粘着剤層を形成することができる粘着テープ又はシートの製造方法を提供することである。又、微細且つ安定な気泡を有する発泡粘着剤層を備えた発泡粘着テープ又はシートの製造方法を提供することである。さらに上記厚みの薄い粘着剤層を備えた粘着テープ又はシートや、微細且つ安定な気泡を有する発泡粘着剤層を備えた発泡粘着テープ又はシートを、複雑な工程を経ることなく、生産効率よく製造できる製造装置を提供することである。 In view of the above problems, an object of the present invention is to provide a method for producing a pressure-sensitive adhesive tape or sheet that can form a thin pressure-sensitive adhesive layer without using a solvent. Moreover, it is providing the manufacturing method of the foaming adhesive tape or sheet | seat provided with the foaming adhesive layer which has a fine and stable bubble. Furthermore, it is possible to produce a pressure-sensitive adhesive tape or sheet having a thin pressure-sensitive adhesive layer and a foamed pressure-sensitive adhesive tape or sheet having a foamed pressure-sensitive adhesive layer having fine and stable bubbles without producing complicated processes. It is to provide a manufacturing apparatus that can.
本発明者らは、前記目的を達成するため鋭意研究を重ねた結果、粘着剤層を構成するポリマーを含む粘着剤組成物を、超臨界状態又は液体状態の不活性流体及び架橋剤と共に特定条件下で混練し、且つ特定条件下で支持体上に積層すると、不活性流体の混合量により、発泡構造を有しない厚みの薄い粘着剤層又は、微細且つ安定な気泡構造を有する発泡粘着剤層の何れかを任意に製造できることを見出した。又、このような方法で製造した発泡粘着剤層の気泡構造は、従来の方法により製造した発泡粘着剤の気泡に比べ微細であり、安定して残存する。本発明はこれらの知見に基づき完成されたものである。 As a result of intensive research to achieve the above object, the present inventors have determined that a pressure-sensitive adhesive composition containing a polymer constituting the pressure-sensitive adhesive layer is subjected to a specific condition together with an inert fluid and a crosslinking agent in a supercritical state or a liquid state. Under pressure and when laminated on a support under specific conditions, depending on the amount of inert fluid mixed, a thin adhesive layer having no foam structure or a foam adhesive layer having a fine and stable cell structure It was found that any of the above can be produced arbitrarily. Further, the cell structure of the foamed adhesive layer produced by such a method is finer than the cells of the foamed adhesive produced by the conventional method and remains stably. The present invention has been completed based on these findings.
すなわち、本発明は、粘着剤層を備えた粘着テープ又はシートの製造方法であって、
（１）粘着剤層を構成するポリマーを含む粘着剤組成物と粘着剤組成物中のポリマーを架橋させるための架橋剤を、加圧下、超臨界状態又は液体状態の不活性流体と共に混練する工程であって、前記架橋剤は、前記ポリマーを加圧下で超臨界状態又は液体状態の不活性流体と混練し、粘度を低減した粘着剤組成物に対し、注入する混練工程と、
（２）上記粘着剤組成物を、混練時の圧力よりも低圧力下の支持体上にダイスにより吐出、積層して粘着剤層を形成する工程、
を含むことを特徴とする粘着テープ又はシートの製造方法である。
That is, this invention is a manufacturing method of the adhesive tape or sheet | seat provided with the adhesive layer,
(1) A step of kneading a pressure-sensitive adhesive composition containing a polymer constituting the pressure-sensitive adhesive layer and a crosslinking agent for crosslinking the polymer in the pressure-sensitive adhesive composition together with an inert fluid in a supercritical state or a liquid state under pressure. The cross-linking agent is a kneading step of kneading the polymer with an inert fluid in a supercritical state or a liquid state under pressure, and injecting the pressure-sensitive adhesive composition with reduced viscosity ;
(2) A step of discharging and laminating the pressure-sensitive adhesive composition with a die on a support under a pressure lower than the pressure during kneading to form a pressure-sensitive adhesive layer;
It is a manufacturing method of the adhesive tape or sheet | seat characterized by including.
本発明において、超臨界状態又は液体状態の不活性流体の混合量が粘着剤組成物の固形分に対して０．２重量％以上２重量％未満であると、粘着剤中に発泡構造がほとんど形成されず、厚みの薄い粘着剤層を備えた粘着テープ又はシートを製造することができる。不活性流体の混合量が粘着剤組成物の固形分に対して２重量％以上では、不活性流体の気化により、平均気泡径１００μｍ以下の気泡が粘着剤層中に形成された発泡粘着テープ又はシートを製造することができる。 In the present invention, when the mixing amount of the inert fluid in the supercritical state or the liquid state is 0.2% by weight or more and less than 2% by weight with respect to the solid content of the pressure-sensitive adhesive composition, almost no foamed structure is present in the pressure-sensitive adhesive. An adhesive tape or sheet that is not formed and has a thin adhesive layer can be produced. When the mixing amount of the inert fluid is 2% by weight or more with respect to the solid content of the pressure-sensitive adhesive composition, the foamed pressure-sensitive adhesive tape in which bubbles having an average bubble diameter of 100 μm or less are formed in the pressure-sensitive adhesive layer by vaporization of the inert fluid or Sheets can be manufactured.
前記粘着剤層を構成するポリマーとして、例えばゴム系ポリマーやアクリル系ポリマーが挙げられる。また、前記不活性流体には二酸化炭素が含まれる。 Examples of the polymer constituting the pressure-sensitive adhesive layer include rubber polymers and acrylic polymers. The inert fluid contains carbon dioxide.
本発明は、また、粘着剤層を構成するポリマーを含む粘着剤組成物を加圧下で混練させるための耐圧容器、該耐圧容器に超臨界状態又は液体状態の不活性流体を供給するための不活性流体供給手段、該耐圧容器において前記ポリマーを加圧下で超臨界状態又は液体状態の不活性流体と混練し、粘度を低減した粘着剤組成物に対し、該粘着剤組成物中のポリマーを架橋させるための架橋剤を注入するための架橋剤供給手段、及び混練した粘着剤組成物を吐出するためのダイスを有する粘着テープ又はシート製造装置に係わるものである。
なお、本明細書では、上記の発明のほか、 粘着剤層を備えた粘着テープ又はシートの製造方法であって、
（１）粘着剤層を構成するポリマーを含む粘着剤組成物と粘着剤組成物中のポリマーを架橋させるための架橋剤を、加圧下、超臨界状態又は液体状態の不活性流体と共に混練する工程と、
（２）上記粘着剤組成物を、混練時の圧力よりも低圧力下の支持体上に吐出、積層して粘着剤層を形成する工程、
を含むことを特徴とする粘着テープ又はシートの製造方法、
及び、粘着剤層を構成するポリマーを含む粘着剤組成物を加圧下で混練させるための耐圧容器、該耐圧容器に超臨界状態又は液体状態の不活性流体を供給するための不活性流体供給手段、該耐圧容器に架橋剤を供給するための架橋剤供給手段、及び混練した粘着剤組成物を吐出するための吐出手段を有する粘着テープ又はシート製造装置についても説明する。
The present invention also provides a pressure-resistant container for kneading a pressure-sensitive adhesive composition containing a polymer constituting the pressure-sensitive adhesive layer under pressure, and a non-pressure for supplying an inert fluid in a supercritical state or a liquid state to the pressure-resistant container. An active fluid supply means, and the polymer in the pressure-sensitive adhesive composition is kneaded with an inert fluid in a supercritical state or a liquid state under pressure in the pressure vessel, and the polymer in the pressure-sensitive adhesive composition is cross-linked to the pressure-sensitive adhesive composition with reduced viscosity. The present invention relates to a cross-linking agent supply means for injecting a cross-linking agent for causing a pressure-sensitive adhesive and a pressure-sensitive adhesive tape or sheet manufacturing apparatus having a die for discharging a kneaded pressure-sensitive adhesive composition.
In the present specification, in addition to the above-described invention, a method for producing an adhesive tape or sheet having an adhesive layer,
(1) A step of kneading a pressure-sensitive adhesive composition containing a polymer constituting the pressure-sensitive adhesive layer and a crosslinking agent for crosslinking the polymer in the pressure-sensitive adhesive composition together with an inert fluid in a supercritical state or a liquid state under pressure. When,
(2) A step of forming the pressure-sensitive adhesive layer by discharging and laminating the pressure-sensitive adhesive composition on a support under a pressure lower than the pressure during kneading,
A method for producing a pressure-sensitive adhesive tape or sheet, comprising:
And a pressure-resistant container for kneading the pressure-sensitive adhesive composition containing the polymer constituting the pressure-sensitive adhesive layer under pressure, and an inert fluid supply means for supplying an inert fluid in a supercritical state or a liquid state to the pressure-resistant container An adhesive tape or sheet manufacturing apparatus having a cross-linking agent supply means for supplying a cross-linking agent to the pressure vessel and a discharge means for discharging the kneaded pressure-sensitive adhesive composition will also be described.
本発明によれば、厚みの薄い粘着剤層を備えた粘着テープ又はシートを有機溶剤を用いることなく形成でき、従来必要であった粘着剤の加熱乾燥工程を省略することができる。また、不活性流体の混合量を調節することにより、厚みの薄い粘着剤層中に発泡構造を有する発泡粘着テープ又はシート、あるいは発泡構造を有しない、より厚みの少ない粘着剤層を備えた粘着テープ又はシートの何れかを任意に製造することができる。本発明の発泡粘着テープ又はシートの製造に際しては、粘着剤の発泡と支持体上への積層を同時に行うことができ、製造工程は簡易である。得られる発泡粘着剤層の発泡構造は、微細であり、且つ安定に残存する。さらに、架橋剤を加圧下超臨界状態又は液体状態の不活性流体と共に混練するので、混練中に架橋反応が進行し、粘着剤組成物を支持体上に積層した後、架橋反応を促すための工程を設ける必要が無い。これにより、凝集力の高い粘着剤が簡易に得られる。 According to the present invention, a pressure-sensitive adhesive tape or sheet having a thin pressure-sensitive adhesive layer can be formed without using an organic solvent, and a heat-drying step of a pressure-sensitive adhesive that has been conventionally required can be omitted. Further, by adjusting the mixing amount of the inert fluid, a pressure-sensitive adhesive layer having a foam structure in a thin pressure-sensitive adhesive layer, or a pressure-sensitive adhesive layer having a smaller thickness and having no foam structure. Either tape or sheet can be produced arbitrarily. When the foamed adhesive tape or sheet of the present invention is produced, the adhesive can be foamed and laminated on the support at the same time, and the production process is simple. The foaming structure of the resulting foamed adhesive layer is fine and remains stable. Furthermore, since the cross-linking agent is kneaded with an inert fluid in a supercritical state or a liquid state under pressure, the cross-linking reaction proceeds during kneading, and after the pressure-sensitive adhesive composition is laminated on the support, the cross-linking reaction is promoted. There is no need to provide a process. Thereby, an adhesive with high cohesive force can be obtained easily.
本発明の方法では、粘着剤層を構成するポリマーを含む粘着剤組成物と、該ポリマーを架橋させるための架橋剤を、加圧下、超臨界状態又は液体状態の不活性流体と混練し、例えばスリットダイのような成形用出口オリフィスを有する金型から、前記混練時の圧力よりも低圧力下の支持体上に吐出、積層して粘着剤層を形成する。 In the method of the present invention, a pressure-sensitive adhesive composition containing a polymer constituting the pressure-sensitive adhesive layer and a crosslinking agent for crosslinking the polymer are kneaded with an inert fluid in a supercritical state or a liquid state under pressure, for example, A pressure-sensitive adhesive layer is formed by discharging and laminating from a mold having an outlet orifice for molding such as a slit die onto a support under a pressure lower than the pressure during the kneading.
粘着剤層を構成するポリマーとしては、公知の粘着特性を有するポリマーを用いることができ、特に制限されない。例えば、ゴム系ポリマー、アクリル系ポリマーなどが例示できる。 As a polymer which comprises an adhesive layer, the polymer which has a well-known adhesion characteristic can be used, and it does not restrict | limit in particular. For example, a rubber polymer, an acrylic polymer, etc. can be illustrated.
ゴム系ポリマーとしては例えば、天然ゴム、ブチルゴム、ブタジエンゴム、イソプレンゴム、スチレン−イソプレン−スチレン、スチレン−エチレン／ブチレン−スチレン、スチレン−エチレン／プロピレン−スチレン、スチレン−ブタジエン−スチレンなどの合成ゴム等が挙げられる。 Examples of rubber-based polymers include natural rubber, butyl rubber, butadiene rubber, isoprene rubber, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene, styrene-ethylene / propylene-styrene, synthetic rubber such as styrene-butadiene-styrene, etc. Is mentioned.
アクリル系ポリマーとしては、例えば、２種以上のアクリル酸エステルモノマーの共重合体、少なくともアクリル酸エステルモノマーと官能基含有不飽和モノマーとをモノマー成分とする共重合体などの、アクリル酸エステル共重合体が好ましい。前記アクリル酸エステルモノマーとしては、例えば、メチルアクリレート、エチルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、２−エチルヘキシルアクリレート、イソオクチルアクリレート、イソノニルアクリレートなどのアクリル酸Ｃ1-10アルキルエステルなどが挙げられるが、これらに限定されるものではない。 Examples of the acrylic polymer include a copolymer of two or more kinds of acrylic ester monomers, and a copolymer of acrylic esters such as a copolymer having at least an acrylic ester monomer and a functional group-containing unsaturated monomer as monomer components. Coalescence is preferred. Examples of the acrylate monomer include acrylic acid C 1-10 alkyl esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, and isononyl acrylate. However, it is not limited to these.
前記官能基含有不飽和モノマーとしては、例えば、アクリル酸、メタクリル酸、イタコン酸などのカルボキシル基含有モノマー；無水マレイン酸などの酸無水物；アクリルアミド、アクリロニトリル、ジメチルアミノエチルメタクリレートなどの窒素含有基（アミド基、シアノ基、アミノ基など）を有するモノマー；ヒドロキシエチルアクリレート、ヒドロキシプロピルメタクリレートなどのヒドロキシル基含有モノマー；グリシジルアクリレートなどのエポキシ基含有モノマー等が挙げられるが、これらに限定されるものではない。前記以外のモノマー成分として、酢酸ビニルなどのビニルエステル類；スチレン、ビニルトルエンなどの芳香族ビニル化合物；メタクリル酸メチル、メタクリル酸エチルなどのメタクリル酸エステルなどを含んでいてもよい。これらのモノマーを、公知の方法で重合に付し、適宜な粘着特性を有するポリマーとすればよい。 Examples of the functional group-containing unsaturated monomer include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, and itaconic acid; acid anhydrides such as maleic anhydride; nitrogen-containing groups such as acrylamide, acrylonitrile, and dimethylaminoethyl methacrylate ( Monomers having an amide group, cyano group, amino group, etc.); hydroxyl group-containing monomers such as hydroxyethyl acrylate and hydroxypropyl methacrylate; and epoxy group-containing monomers such as glycidyl acrylate, but are not limited thereto. . Other monomer components may include vinyl esters such as vinyl acetate; aromatic vinyl compounds such as styrene and vinyl toluene; and methacrylic esters such as methyl methacrylate and ethyl methacrylate. These monomers may be subjected to polymerization by a known method to form a polymer having appropriate adhesive properties.
粘着剤組成物には、上記ポリマーの他に、粘着剤に通常添加する添加剤、例えば、粘着付与樹脂、軟化剤、老化防止剤、充てん剤、着色剤などが含まれていてもよい。粘着剤組成物は予め調製し、ストランド状、ペレット状など適宜な状態に加工しておくとよい。 In addition to the above-mentioned polymer, the pressure-sensitive adhesive composition may contain additives usually added to the pressure-sensitive adhesive, such as tackifier resins, softeners, anti-aging agents, fillers, and colorants. The pressure-sensitive adhesive composition may be prepared in advance and processed into an appropriate state such as a strand or pellet.
本発明において使用する不活性流体としては、常温、常圧では気体であり且つ重合条件下で不活性な広範囲の物質を使用でき、その代表的な例として、ヘリウム、アルゴン等の希ガス類；窒素、二酸化炭素等の無機性ガス類などが挙げられる。これらの中でも、二酸化炭素は、超臨界状態又は液体状態において高分子材料に対する親和性が比較的高く、かつ環境への影響が少なく、コスト的にも有利であることから、最も好適に使用できる。 As the inert fluid used in the present invention, a wide range of substances which are gases at normal temperature and pressure and are inert under polymerization conditions can be used. Typical examples thereof include rare gases such as helium and argon; nitrogen, Examples thereof include inorganic gases such as carbon dioxide. Among these, carbon dioxide can be most suitably used because it has a relatively high affinity for the polymer material in the supercritical state or the liquid state, has little influence on the environment, and is advantageous in terms of cost.
超臨界状態または液体状態の不活性流体を粘着剤組成物と混練する際の圧力は、加圧下（特に高圧下）であればよく、用いる不活性流体の種類により、例えば１ＭＰａ〜４０ＭＰａ程度の範囲から適宜選択できる。例えば、不活性流体として二酸化炭素などを使用する場合、圧力は５ＭＰａ〜４０ＭＰａ程度の範囲が好ましい。 The pressure at the time of kneading the supercritical or liquid inert fluid with the pressure-sensitive adhesive composition may be under pressure (particularly under high pressure), for example, in the range of about 1 MPa to 40 MPa, depending on the type of inert fluid used. Can be selected as appropriate. For example, when carbon dioxide or the like is used as the inert fluid, the pressure is preferably in the range of about 5 MPa to 40 MPa.
また、混練温度も不活性流体の種類や使用する粘着剤組成物の種類に応じて適宜に選択できる。不活性流体として二酸化炭素などを使用する場合の温度は、例えば１００℃〜２００℃程度の範囲が好ましい。また、温度は、同一装置内で部分ごとに変化させてもよい。例えば、不活性流体として二酸化炭素などを用い、粘着剤組成物に天然ゴム系の混合物を用いる場合、混練部分の温度は１２０℃〜１４０℃、粘着剤組成物の吐出部分の温度は８０〜１００℃程度の範囲が好適である。 The kneading temperature can also be appropriately selected according to the type of inert fluid and the type of pressure-sensitive adhesive composition used. The temperature when carbon dioxide or the like is used as the inert fluid is preferably in the range of about 100 ° C. to 200 ° C., for example. Moreover, you may change temperature for every part within the same apparatus. For example, when carbon dioxide or the like is used as the inert fluid and a natural rubber-based mixture is used for the pressure-sensitive adhesive composition, the temperature of the kneading portion is 120 ° C. to 140 ° C., and the temperature of the discharge portion of the pressure-sensitive adhesive composition is 80 to 100. A range of about ° C is preferred.
本発明の粘着テープ及び粘着シートの製造方法においては、粘着剤組成物を架橋反応させるための架橋剤を注入し、混練する工程を有する。この架橋剤は、加圧下で超臨界状態又は液体状態の不活性流体と混練し、粘度を低減した粘着剤組成物に対し、高圧下で高圧ポンプを用いて注入するのが作業性の点から好ましい。ただし、粘着剤組成物に架橋剤を添加した後、加圧下、超臨界状態又は液体状態の不活性流体と混練することもできる。この工程により粘着剤組成物中のポリマーに高分子量化、三次元化構造が形成されて凝集力が高まり、粘着特性が向上するだけでなく、粘着剤組成物中に微細な気泡を発生させて発泡層を形成させる場合、微細気泡発生後の粘着剤組成物の物性が微細気泡が固定化される方向にシフトするため、安定した微細発泡構造を形成できるようになる。 In the manufacturing method of the adhesive tape and adhesive sheet of this invention, it has the process of inject | pouring and knead | mixing the crosslinking agent for carrying out the crosslinking reaction of an adhesive composition. From the viewpoint of workability, this cross-linking agent is kneaded with an inert fluid in a supercritical state or a liquid state under pressure and injected into a pressure-sensitive adhesive composition with a reduced pressure using a high-pressure pump under high pressure. preferable. However, after adding a crosslinking agent to the pressure-sensitive adhesive composition, it can be kneaded with an inert fluid in a supercritical state or a liquid state under pressure. By this process, the polymer in the pressure-sensitive adhesive composition has a high molecular weight, a three-dimensional structure is formed, the cohesive force is increased, the pressure-sensitive adhesive property is improved, and fine bubbles are generated in the pressure-sensitive adhesive composition. When the foam layer is formed, the physical properties of the pressure-sensitive adhesive composition after the generation of fine bubbles are shifted in the direction in which the fine bubbles are fixed, so that a stable fine foam structure can be formed.
架橋剤の種類は特に限定されず、公知の架橋剤の中から、用いる粘着剤組成物に適したものを選択して使用すればよい。例えば、カルボキシル基や水酸基を有するアクリル系ポリマーに対しては、この官能基と反応し得る多官能性化合物を用いることができる。このような化合物の例としては、ジフェニルメタンジイソシアネート、トリレンジイソシアネートなどのポリイソシアネート、ポリエポキシ化合物、各種金属塩、キレート化合物などを挙げることができる。架橋剤の使用量は、粘着剤を構成するポリマーの分子量等にもよるが、通常ポリマー１００重量部に対して０．５〜２０重量部の範囲とするのがよい。架橋剤の使用量が多すぎると、凝集力が高くなり、被着体との接着力が低下する。一般に、ポリマー分子量が大きいときは架橋剤の配合量を減らし、分子量が小さいときは架橋剤の配合量を増やすようにすると、良好な接着力が得られやすい。所望の特性が得られるように使用量を調節すればよい。 The kind of the crosslinking agent is not particularly limited, and a crosslinking agent suitable for the pressure-sensitive adhesive composition to be used may be selected from known crosslinking agents. For example, for an acrylic polymer having a carboxyl group or a hydroxyl group, a polyfunctional compound capable of reacting with this functional group can be used. Examples of such compounds include polyisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate, polyepoxy compounds, various metal salts, and chelate compounds. The amount of the crosslinking agent used is usually in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymer, although it depends on the molecular weight of the polymer constituting the pressure-sensitive adhesive. When there is too much usage-amount of a crosslinking agent, cohesion force will become high and the adhesive force with a to-be-adhered body will fall. Generally, when the polymer molecular weight is large, the amount of the crosslinking agent is decreased, and when the molecular weight is small, the amount of the crosslinking agent is increased. What is necessary is just to adjust usage-amount so that a desired characteristic may be acquired.
本発明では、加圧下で不活性流体及び架橋剤と共に混練した粘着剤組成物を、前記混練時の圧力よりも低圧力下の支持体上に吐出し、積層して粘着剤層を形成する。支持体としては、粘着テープに通常用いられる支持体であればよく、例えば、和紙、クラフト紙などの紙類；不織布；ポリオレフィン系樹脂、ポリエステル系樹脂、塩化ビニル樹脂などからなるプラスチックフィルムなどが挙げられる。支持体の厚みは特に限定されず、取扱性等を考慮して適宜選択できる。粘着剤組成物を支持体上に積層する際の圧力は、前記混練時の圧力よりも低ければよく、特に制限されないが、操作性の点から大気圧が好ましい。 In the present invention, the pressure-sensitive adhesive composition kneaded with an inert fluid and a crosslinking agent under pressure is discharged onto a support under a pressure lower than the pressure at the time of kneading and laminated to form a pressure-sensitive adhesive layer. The support may be any support that is usually used for pressure-sensitive adhesive tapes, and examples thereof include papers such as Japanese paper and craft paper; non-woven fabrics; plastic films made of polyolefin resins, polyester resins, vinyl chloride resins, and the like. It is done. The thickness of the support is not particularly limited and can be appropriately selected in consideration of handling properties. The pressure at which the pressure-sensitive adhesive composition is laminated on the support is not particularly limited as long as it is lower than the pressure during the kneading, but atmospheric pressure is preferable from the viewpoint of operability.
本発明の粘着テープ及び粘着シートの製造方法においては、加圧下、超臨界状態又は液体状態の不活性流体と混練することにより、粘着剤組成物の粘度を低減調整することができ、有機溶剤を用いることなしに厚みの薄い粘着剤層を形成することができる。さらに、不活性流体の混合量を調節することにより、微細な発泡構造を有する発泡粘着剤層又は、発泡構造ほをほとんど持たない、より厚みの少ない粘着剤層の何れかを任意に形成することができる。不活性流体の混合量を粘着剤組成物の固形分に対して２重量％以上とした場合には、粘着剤層中に微細な発泡構造を有する発泡粘着剤層を形成することができる。不活性流体の混合量を粘着剤組成物の固形分に対して０．２重量％以上２重量％未満とした場合には、粘着剤層中に気泡構造をほとんど有しない、より厚みの少ない（例えば１５〜５０μｍ）粘着剤層を形成することができる。 In the method for producing the pressure-sensitive adhesive tape and pressure-sensitive adhesive sheet of the present invention, the viscosity of the pressure-sensitive adhesive composition can be reduced and adjusted by kneading with an inert fluid in a supercritical state or a liquid state under pressure. A thin PSA layer can be formed without using it. Furthermore, by adjusting the mixing amount of the inert fluid, any one of a foamed adhesive layer having a fine foam structure or an adhesive layer having a smaller thickness and having almost no foamed structure can be arbitrarily formed. Can do. When the mixing amount of the inert fluid is 2% by weight or more based on the solid content of the pressure-sensitive adhesive composition, a foamed pressure-sensitive adhesive layer having a fine foam structure can be formed in the pressure-sensitive adhesive layer. When the mixing amount of the inert fluid is 0.2% by weight or more and less than 2% by weight with respect to the solid content of the pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer has almost no bubble structure, and has a smaller thickness ( For example, a pressure-sensitive adhesive layer can be formed.
本発明では、粘着テープ又はシートの接着面（粘着面）を保護するために、セパレータ（剥離ライナー）が用いられていてもよい。このようなセパレータとしては慣用の剥離紙などを使用できる。具体的には、例えば、剥離処理剤による剥離処理層を少なくとも一方の表面に有する基材の他、フッ素系ポリマーや無極性ポリマーからなる低接着性基材などを用いることができる。剥離処理剤としては特に限定されず、例えば、シリコーン系剥離処理剤、フッ素系剥離処理剤、長鎖アルキル系剥離処理剤などを用いることができる。なお、セパレータの厚さや形成方法などは特に限定されない。 In the present invention, a separator (release liner) may be used to protect the adhesive surface (adhesive surface) of the adhesive tape or sheet. As such a separator, a conventional release paper or the like can be used. Specifically, for example, a low-adhesive base material made of a fluorine-based polymer or a nonpolar polymer can be used in addition to a base material having a release treatment layer with a release treatment agent on at least one surface. The release treatment agent is not particularly limited, and for example, a silicone release treatment agent, a fluorine release treatment agent, a long-chain alkyl release treatment agent, or the like can be used. In addition, the thickness of a separator, a formation method, etc. are not specifically limited.
本発明の粘着テープ及び粘着シートの製造方法においては、粘着剤の発泡は、加圧下で粘着剤組成物と混練された不活性流体が気泡核を形成し、粘着剤組成物を支持体上へ吐出した瞬間、この気泡核が圧力の低下により気泡に成長することによって起こる。したがって、本発明の方法によれば、粘着剤の積層と発泡を同時に行うことが可能であり、製造工程が簡略化される。また、粘着剤組成物と架橋剤を加圧下、高温で混練するため、混練中に架橋反応が進行する。この架橋構造を有する粘着剤組成物は、本発明の方法によれば支持体上に小さな厚みで積層することができ、凝集強く保持力に優れた粘着剤層を簡易に製造できる。 In the method for producing the pressure-sensitive adhesive tape and pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive is foamed by the inert fluid kneaded with the pressure-sensitive adhesive composition under pressure to form cell nuclei, and the pressure-sensitive adhesive composition is placed on the support. This occurs when the bubble nuclei grow into bubbles due to a drop in pressure at the moment of discharge. Therefore, according to the method of the present invention, it is possible to simultaneously laminate and foam the pressure-sensitive adhesive, and the manufacturing process is simplified. Further, since the pressure-sensitive adhesive composition and the crosslinking agent are kneaded at high temperature under pressure, the crosslinking reaction proceeds during the kneading. According to the method of the present invention, the pressure-sensitive adhesive composition having a crosslinked structure can be laminated on the support with a small thickness, and a pressure-sensitive adhesive layer that is cohesive and excellent in holding power can be easily produced.
本発明の方法は、粘着剤層を構成するポリマーを加圧下で混練するための耐圧容器（高圧装置）、該耐圧容器に超臨界状態又は液体状態の不活性流体を供給するための不活性流体供給手段、架橋剤を供給するための架橋剤供給手段、及び混練した粘着剤組成物を吐出するための吐出手段を有する粘着テープ又はシート製造装置により実施できる。 The method of the present invention comprises a pressure vessel (high pressure device) for kneading the polymer constituting the pressure-sensitive adhesive layer under pressure, and an inert fluid for supplying a supercritical or liquid inert fluid to the pressure vessel. It can be carried out by an adhesive tape or sheet manufacturing apparatus having a supply means, a cross-linking agent supply means for supplying a cross-linking agent, and a discharge means for discharging the kneaded pressure-sensitive adhesive composition.
図１は本発明の粘着テープ又はシート製造装置の一例を示す概略図である。図１において、１、２はそれぞれ、粘着剤層を構成するポリマーを加圧下で混練するための耐圧容器、該耐圧容器に粘着剤組成物を供給するためのホッパーである。耐圧容器１としては、加圧下で混練可能な容器であれば特に限定されず、バッチ式の圧力容器、耐圧性を有する押出装置等の何れであってもよい。耐圧容器１として押出装置を用いる場合は、ホッパー２から粘着剤組成物を連続的に供給することができる。図１において３、４はそれぞれ不活性流体ボンベ、不活性ガス精密供給装置である。これらに必要に応じて配管、バルブ等を配置して不活性流体供給手段を構成している。図１において５、６はそれぞれ架橋剤液用容器、液体高圧ポンプである。これらに必要に応じて配管、バルブ等を配置して架橋剤供給手段が構成されている。図１において７は粘着剤組成物を吐出するための吐出手段である。吐出手段７としては、例えば、Ｔダイ、フィッシュテールダイなどのダイスが挙げられるが、粘着剤を薄層で吐出できる構造のものであれば、特に限定されるものではない。吐出手段７は加熱できる構造であることが好ましい。図１において８、９、１０はそれぞれ、支持体繰出部、セパレータ繰出部、巻取部である。支持体繰出部８から繰り出された支持体上に、吐出手段７により粘着剤組成物を塗布し、セパレータ繰出部９から繰り出されたセパレータにより粘着剤の粘着面を被覆保護する。支持体、粘着剤層、セパレータの三層よりなるセパレータ付き粘着テープ又はシートを巻取部１０で巻きとり、巻回された形態の粘着テープ又シートを製造する。
FIG. 1 is a schematic view showing an example of the pressure-sensitive adhesive tape or sheet manufacturing apparatus of the present invention. In FIG. 1, 1 and 2 are a pressure vessel for kneading the polymer constituting the pressure-sensitive adhesive layer under pressure and a hopper for supplying the pressure-sensitive adhesive composition to the pressure vessel. The pressure vessel 1 is not particularly limited as long as it is a vessel that can be kneaded under pressure, and may be any of a batch-type pressure vessel, a pressure-resistant extruder, and the like. When an extrusion apparatus is used as the pressure vessel 1, the pressure-sensitive adhesive composition can be continuously supplied from the
本発明において使用する耐圧装置１として、バッチ式の圧力容器を用いた場合は、さらに吐出手段開閉用のバルブを設置するのが好ましい。この場合、バルブを閉じた状態で粘着剤を調製した後、バルブの開放操作により、装置内外の圧力差を推進力として粘着剤を吐出手段７から吐出させ、発泡した粘着剤を支持体上に積層する。粘着剤の吐出速度はバルブの開閉度合いにより調整できる。 When a batch-type pressure vessel is used as the pressure-resistant device 1 used in the present invention, it is preferable to further install a valve for opening and closing the discharge means. In this case, after the pressure-sensitive adhesive is prepared with the valve closed, the pressure-sensitive adhesive is discharged from the discharge means 7 using the pressure difference between the inside and outside of the apparatus as a driving force, and the foamed pressure-sensitive adhesive is placed on the support. Laminate. The discharge speed of the adhesive can be adjusted by the degree of opening and closing of the valve.
耐圧装置１として耐圧押出装置を用いる場合は、例えば、粘着剤組成物と加圧された不活性流体とを連続的に供給して、耐圧押出装置内で粘着剤組成物を連続的に超臨界状態又は液体状態の不活性流体及び架橋剤と混練させ、これを押出装置先端に取り付けた吐出手段７より連続的に薄層に押出して、薄層化した粘着剤を支持体上に積層する。このように耐圧押出装置を用いる場合には、原料供給−混練−架橋−積層、又は原料供給−混練−架橋−発泡・積層の工程を一貫して行うことのできる連続生産プロセスが可能となるため、薄層粘着テープ又はシート製造装置あるいは発泡構造を有する薄層粘着テープ又は粘着シート製造装置として好適である。 When using a pressure-resistant extrusion apparatus as the pressure-resistant apparatus 1, for example, the pressure-sensitive adhesive composition and the pressurized inert fluid are continuously supplied, and the pressure-sensitive adhesive composition is continuously supercritical in the pressure-resistant extrusion apparatus. An inert fluid and a cross-linking agent in a state or a liquid state are kneaded, and this is continuously extruded into a thin layer from the discharge means 7 attached to the tip of the extrusion apparatus, and the thinned adhesive is laminated on the support. When the pressure-extrusion apparatus is used in this way, a continuous production process capable of consistently performing the steps of raw material supply-kneading-crosslinking-lamination or raw material supply-kneading-crosslinking-foaming / lamination becomes possible. It is suitable as a thin-layer adhesive tape or sheet manufacturing apparatus or a thin-layer adhesive tape or adhesive sheet manufacturing apparatus having a foamed structure.
以下実施例に基づき本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these.
（試験評価）
実施例及び比較例で作製した粘着テープを２５ｍｍ幅に切り取り、ステンレス板上に１ｋｇのローラー１往復で圧着し、室温で３０分放置後、１８０°剥離試験を実施し、粘着テープの対ステンレス板接着力を評価した。また同じく２５ｍｍ幅に切り取った粘着テープをステンレス板上に２５ｍｍ×２５ｍｍ面積となるように１ｋｇのローラー１往復で圧着し、４０℃中で３０分間放置後２ｋｇの荷重を吊り下げ、本発明の粘着テープの対ステンレス板保持力を評価した。評価結果をそれぞれ表１に示す。
(Test evaluation)
The pressure-sensitive adhesive tapes produced in the examples and comparative examples were cut to a width of 25 mm, pressure-bonded on a stainless steel plate by one reciprocation of a 1 kg roller, allowed to stand at room temperature for 30 minutes, and then subjected to a 180 ° peel test. Adhesive strength was evaluated. Similarly, the adhesive tape cut to a width of 25 mm is pressed on a stainless steel plate with a 1 kg roller so as to have an area of 25 mm × 25 mm. The holding force of the tape against the stainless steel plate was evaluated. The evaluation results are shown in Table 1, respectively.
（粘着剤組成物の調製）
１２０℃に加温した容器容量５リットルの加圧式ニーダー中に天然ゴム（ＳＶＲ：ムーニー粘度６０ＭＬ(1+4)100℃）１．５ｋｇを投入し４０ｒｐｍの速度で２分間混練した。次に軟化点１１５℃の石油系樹脂１．５ｋｇを３回に分割してトータル時間が１５分間となるように投入し混練した。最後に軟化点３０℃のテルペンフェノール系樹脂１５０ｇと、住友化学社製ゴム用老化防止剤、商品名「スミライザーＮＷ」３０ｇを投入し５分間混練し本発明に用いる粘着剤組成物を調製し、取り出した後引き伸ばして約φ１５ｍｍのストランド状に加工した。
(Preparation of adhesive composition)
1.5 kg of natural rubber (SVR: Mooney viscosity 60 ML (1 + 4) 100 ° C. ) was put into a pressure type kneader having a container capacity of 5 liters heated to 120 ° C. and kneaded for 2 minutes at a speed of 40 rpm. Next, 1.5 kg of a petroleum-based resin having a softening point of 115 ° C. was divided into three portions and charged so as to have a total time of 15 minutes. Finally, 150 g of a terpene phenolic resin having a softening point of 30 ° C. and an anti-aging agent for rubber manufactured by Sumitomo Chemical Co., Ltd., 30 g of a trade name “Sumilyzer NW” were added and kneaded for 5 minutes to prepare an adhesive composition used in the present invention. After taking out, it was stretched and processed into a strand of about φ15 mm.
（実施例１）
スクリュー部分が４ゾーンから構成され、フィード部分から１００℃、１２０℃、１４０℃、１４０℃に加熱したφ２５ｍｍ、Ｌ／Ｄ３０の単軸押出機に、１４０℃に加熱したフィッシュテールダイを設けた粘着剤塗工装置（図１参照）を用いて粘着テープを製造した。ホッパー部分から上記（粘着剤組成物の調製）で調製したストランド状の粘着剤組成物を投入し、２０ｒｐｍの回転数で混練した。二酸化炭素を、Ｌ／Ｄが１６の位置から炭酸ガス精密供給装置を用いて注入圧力が１５ＭＰａで、粘着剤組成物に対して１．４重量％となるように供給した。更にＬ／Ｄが１９の位置からＨＤＩ系イソシアネート架橋剤を粘着剤組成物の固形分に対して１重量％となるように注入圧力２０ＭＰａで供給した。
フィッシュテールダイの先端から、１００ｍｍ幅で５０μｍ厚みのポリエステルフィルム上に３０μｍの厚みで吐出し、本発明の粘着テープを作製した。
Example 1
Adhesive with screw part composed of 4 zones, φ25mm, L / D30 single screw extruder heated from feed part to 100 ° C, 120 ° C, 140 ° C, 140 ° C with fishtail die heated to 140 ° C The adhesive tape was manufactured using the agent coating apparatus (refer FIG. 1). The strand-shaped pressure-sensitive adhesive composition prepared in the above (Preparation of pressure-sensitive adhesive composition) was charged from the hopper part, and kneaded at a rotation speed of 20 rpm. Carbon dioxide was supplied from a position having an L / D of 16 using a carbon dioxide gas precision supply device so that the injection pressure was 15 MPa and 1.4 wt% with respect to the pressure-sensitive adhesive composition. Further, from the position where L / D was 19, the HDI isocyanate crosslinking agent was supplied at an injection pressure of 20 MPa so as to be 1% by weight with respect to the solid content of the pressure-sensitive adhesive composition.
From the tip of the fishtail die, it was discharged at a thickness of 30 μm onto a polyester film having a width of 100 mm and a thickness of 50 μm to produce an adhesive tape of the present invention.
（比較例１）
架橋剤を注入しなかった以外は実施例１と同様の操作を行い、粘着テープを作製した。
(Comparative Example 1)
An adhesive tape was prepared by performing the same operation as in Example 1 except that the crosslinking agent was not injected.
（実施例２）
スクリュー部分が４ゾーンから構成され、フィード部分から１００℃、１２０℃、１４０℃、１４０℃に加熱したφ２５ｍｍ、Ｌ／Ｄ３０の単軸押出機に、１４０℃に加熱したフィッシュテールダイを設けた粘着剤塗工装置（図１参照）を用いて粘着テープを製造した。ホッパー部分から（粘着剤組成物の調製）で調製したストランド状の粘着剤組成物を投入し、２０ｒｐｍの回転数で混練した。二酸化炭素を、Ｌ／Ｄが１６の位置から炭酸ガス精密供給装置を用いて注入圧力１５ＭＰａで、粘着剤組成物に対して５重量％となるように供給した。更にＬ／Ｄが１９の位置からＨＤＩ系イソシアネート架橋剤を粘着剤組成物の固形分に対して１重量％となるように注入圧力２０ＭＰａで供給した。
フィッシュテールダイの先端から１００ｍｍ幅で５０μｍ厚みのポリエステルフィルム上に１００μｍの厚みで吐出し、混練した超臨界状態の二酸化炭素を気化させ平均気泡径が４０μｍの発泡層を有する本発明の粘着テープを作製した。
作製した発泡粘着テープは２４時間後も気泡が安定して粘着剤層に保持されていた。
(Example 2)
Adhesive with screw part composed of 4 zones, φ25mm, L / D30 single screw extruder heated from feed part to 100 ° C, 120 ° C, 140 ° C, 140 ° C with fishtail die heated to 140 ° C The adhesive tape was manufactured using the agent coating apparatus (refer FIG. 1). The strand-shaped pressure-sensitive adhesive composition prepared in (Preparation of pressure-sensitive adhesive composition) from the hopper part was charged and kneaded at a rotation speed of 20 rpm. Carbon dioxide was supplied from the position where L / D was 16 using a carbon dioxide gas precision supply device at an injection pressure of 15 MPa so as to be 5% by weight with respect to the pressure-sensitive adhesive composition. Further, from the position where L / D was 19, the HDI isocyanate crosslinking agent was supplied at an injection pressure of 20 MPa so as to be 1% by weight with respect to the solid content of the pressure-sensitive adhesive composition.
The pressure-sensitive adhesive tape of the present invention having a foamed layer having an average cell diameter of 40 μm is discharged from a tip of a fishtail die on a polyester film having a width of 100 μm and a thickness of 50 μm, ejected at a thickness of 100 μm, and vaporizing kneaded supercritical carbon dioxide. Produced.
In the produced foamed adhesive tape, bubbles were stably held in the adhesive layer even after 24 hours.
（比較例２）
架橋剤を注入しなかった以外は、実施例２と同様の操作を行い、平均気泡径が６０μｍの発泡層を有する本発明の粘着テープを作製した。
作製した発泡粘着テープは２４時間後粘着剤層中の気泡がほとんど消失していた。
(Comparative Example 2)
The pressure-sensitive adhesive tape of the present invention having a foamed layer having an average cell diameter of 60 μm was prepared in the same manner as in Example 2 except that the crosslinking agent was not injected.
In the produced foamed adhesive tape, the bubbles in the pressure-sensitive adhesive layer almost disappeared after 24 hours.
１ 耐圧容器（高圧装置）
２ ホッパー
３ 不活性流体ボンベ
４ ガス精密供給装置
５ 架橋剤用容器
６ 液体高圧ポンプ
７ 粘着剤組成物吐出手段
８ 支持体繰出部
９ セパレータ繰出部
１０ 巻取部
1 Pressure vessel (high pressure device)
DESCRIPTION OF
Claims (6)
（１）粘着剤層を構成するポリマーを含む粘着剤組成物と粘着剤組成物中のポリマーを架橋させるための架橋剤を、加圧下、超臨界状態又は液体状態の不活性流体と共に混練する工程であって、前記架橋剤は、前記ポリマーを加圧下で超臨界状態又は液体状態の不活性流体と混練し、粘度を低減した粘着剤組成物に対し、注入する混練工程と、
（２）上記粘着剤組成物を、混練時の圧力よりも低圧力下の支持体上にダイスにより吐出、積層して粘着剤層を形成する工程、
を含むことを特徴とする粘着テープ又はシートの製造方法。 A method for producing an adhesive tape or sheet comprising an adhesive layer,
(1) A step of kneading a pressure-sensitive adhesive composition containing a polymer constituting the pressure-sensitive adhesive layer and a crosslinking agent for crosslinking the polymer in the pressure-sensitive adhesive composition together with an inert fluid in a supercritical state or a liquid state under pressure. The cross-linking agent is a kneading step of kneading the polymer with an inert fluid in a supercritical state or a liquid state under pressure, and injecting the pressure-sensitive adhesive composition with reduced viscosity ;
(2) A step of discharging and laminating the pressure-sensitive adhesive composition with a die on a support under a pressure lower than the pressure during kneading to form a pressure-sensitive adhesive layer;
The manufacturing method of the adhesive tape or sheet | seat characterized by including this.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004216760A JP4716687B2 (en) | 2004-07-26 | 2004-07-26 | Method and apparatus for producing adhesive tape or sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004216760A JP4716687B2 (en) | 2004-07-26 | 2004-07-26 | Method and apparatus for producing adhesive tape or sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006036870A JP2006036870A (en) | 2006-02-09 |
| JP4716687B2 true JP4716687B2 (en) | 2011-07-06 |
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| JP2004216760A Expired - Lifetime JP4716687B2 (en) | 2004-07-26 | 2004-07-26 | Method and apparatus for producing adhesive tape or sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5363204B2 (en) * | 2009-06-11 | 2013-12-11 | エア・ウォーター株式会社 | Cleaning method for slit nozzle of coating device |
| KR101866588B1 (en) | 2010-06-30 | 2018-06-11 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | (Meth)acryloyl Pressure-Sensitive Foam Adhesives |
| JP6787799B2 (en) * | 2017-01-24 | 2020-11-18 | 信越化学工業株式会社 | Adhesive molding method and pellicle manufacturing method by this molding method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63225684A (en) * | 1987-03-13 | 1988-09-20 | Nitto Electric Ind Co Ltd | Acrylic form pressure sensitive adhesive layer |
| JPH04185427A (en) * | 1990-11-20 | 1992-07-02 | Kotou Kogyo Kk | Manufacture of composite formed body sheet of polyolefin |
| JPH04260460A (en) * | 1990-09-21 | 1992-09-16 | Union Carbide Chem & Plast Co Inc | Device and method for spraying coating containing supercritical fluid as diluent from orifice |
| JPH06166767A (en) * | 1992-12-01 | 1994-06-14 | Sekisui Chem Co Ltd | Polyolefin resin foam |
| JPH093238A (en) * | 1995-06-19 | 1997-01-07 | Tonen Chem Corp | Production of fine porous membrane of thermoplastic resin |
| JP2000169802A (en) * | 1998-12-08 | 2000-06-20 | Nitto Denko Corp | Production of expanded tacky tape or sheet and apparatus for producing the same |
| JP2003281961A (en) * | 2002-03-26 | 2003-10-03 | Nitto Denko Corp | Adhesive tape for tactile switch, adhesive composition for tactile switch, and tactile switch |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000192007A (en) * | 1998-12-28 | 2000-07-11 | Nitto Denko Corp | Acrylic pressure sensitive adhesive composition and its production |
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2004
- 2004-07-26 JP JP2004216760A patent/JP4716687B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63225684A (en) * | 1987-03-13 | 1988-09-20 | Nitto Electric Ind Co Ltd | Acrylic form pressure sensitive adhesive layer |
| JPH04260460A (en) * | 1990-09-21 | 1992-09-16 | Union Carbide Chem & Plast Co Inc | Device and method for spraying coating containing supercritical fluid as diluent from orifice |
| JPH04185427A (en) * | 1990-11-20 | 1992-07-02 | Kotou Kogyo Kk | Manufacture of composite formed body sheet of polyolefin |
| JPH06166767A (en) * | 1992-12-01 | 1994-06-14 | Sekisui Chem Co Ltd | Polyolefin resin foam |
| JPH093238A (en) * | 1995-06-19 | 1997-01-07 | Tonen Chem Corp | Production of fine porous membrane of thermoplastic resin |
| JP2000169802A (en) * | 1998-12-08 | 2000-06-20 | Nitto Denko Corp | Production of expanded tacky tape or sheet and apparatus for producing the same |
| JP2003281961A (en) * | 2002-03-26 | 2003-10-03 | Nitto Denko Corp | Adhesive tape for tactile switch, adhesive composition for tactile switch, and tactile switch |
Also Published As
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| JP2006036870A (en) | 2006-02-09 |
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