JP5726411B2 - Emulsion type adhesive and adhesive tape using the same - Google Patents
Emulsion type adhesive and adhesive tape using the same Download PDFInfo
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- JP5726411B2 JP5726411B2 JP2009237215A JP2009237215A JP5726411B2 JP 5726411 B2 JP5726411 B2 JP 5726411B2 JP 2009237215 A JP2009237215 A JP 2009237215A JP 2009237215 A JP2009237215 A JP 2009237215A JP 5726411 B2 JP5726411 B2 JP 5726411B2
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- 230000001070 adhesive effect Effects 0.000 title claims description 26
- 239000000853 adhesive Substances 0.000 title claims description 25
- 239000002390 adhesive tape Substances 0.000 title description 6
- 239000000839 emulsion Substances 0.000 title description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 61
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- 239000002562 thickening agent Substances 0.000 claims description 21
- 229920003169 water-soluble polymer Polymers 0.000 claims description 16
- 244000043261 Hevea brasiliensis Species 0.000 claims description 15
- 229920003052 natural elastomer Polymers 0.000 claims description 15
- 229920001194 natural rubber Polymers 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 14
- 239000005060 rubber Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 229920003051 synthetic elastomer Polymers 0.000 claims description 8
- 239000005061 synthetic rubber Substances 0.000 claims description 8
- 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 7
- 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 7
- 239000011342 resin composition Substances 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 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 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- -1 pentaerythritol ester Chemical class 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 claims description 2
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 238000002156 mixing Methods 0.000 description 10
- 230000003712 anti-aging effect Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Description
本発明は、エマルジョン型粘着剤及びこれを用いた粘着テープに関する。 The present invention relates to an emulsion-type pressure-sensitive adhesive and a pressure-sensitive adhesive tape using the same.
粘着剤の形態としては、溶剤型、ホットメルト型、硬化性液状樹脂型、エマルジョン型などが知られている。これらのうち溶剤型粘着剤は、粘着力が強く、種々の配合が容易であるため広く用いられてきた。しかしながら、揮発性有機化合物が世界的に問題となっており、揮発性有機化合物を含有しない粘着剤が望まれている。 As the form of the pressure-sensitive adhesive, a solvent type, a hot melt type, a curable liquid resin type, an emulsion type, and the like are known. Among these, solvent-type pressure-sensitive adhesives have been widely used because of their strong adhesive strength and ease of various blending. However, volatile organic compounds are a problem worldwide, and pressure-sensitive adhesives that do not contain volatile organic compounds are desired.
エマルジョン型粘着剤は、揮発性有機化合物を含まない上、塗布に特別の装置を必要とせず、かつ、保存も容易であることから、溶剤型粘着剤の代替品として注目されている。また、天然ゴムや合成ゴムをエマルジョン化した、いわゆるゴムエマルジョン型粘着剤を各種フィルム上に塗布乾燥して得られる粘着テープも検討されている（例えば、特許文献１参照。）。 The emulsion-type pressure-sensitive adhesive does not contain a volatile organic compound, does not require a special device for coating, and is easy to store, and thus has attracted attention as an alternative to the solvent-type pressure-sensitive adhesive. In addition, pressure-sensitive adhesive tapes obtained by applying so-called rubber emulsion-type pressure-sensitive adhesives obtained by emulsifying natural rubber or synthetic rubber onto various films and drying have been studied (for example, see Patent Document 1).
本発明は、エマルジョン型粘着剤及びこのエマルジョン型粘着剤を用いた粘着テープを提供することを課題とする。 An object of the present invention is to provide an emulsion-type pressure-sensitive adhesive and a pressure-sensitive adhesive tape using the emulsion-type pressure-sensitive adhesive.
即ち本発明は、天然ゴムと合成ゴムを１０：９０〜９０：１０の割合で混合したゴム混合物１００質量部と、粘着付与樹脂５０〜１５０質量部と、水溶性高分子増粘剤０．１〜５質量部とを、固形分換算で４０〜６０質量％有するエマルジョン型粘着剤である。エマルジョン型粘着剤は、その粘度が、２０００〜１００００ｍＰａ・ｓであるものが好ましく、パラレルプレート型レオメータにて、温度４０℃、剪断速度３０００ｓ−１の条件で剪断をかけた際に、剪断をかけた後の粘度が２倍になるために要する時間が１８００秒以上、増粘後のＴＩ値が７．０〜９．０であることが好ましい。
エマルジョン型粘着剤に用いる水溶性高分子増粘剤は、粘度３０００〜２００００ｍＰａ・ｓのものが好ましい。
エマルジョン型粘着剤は、塩化ビニル樹脂などをフィルム状にして得られたフィルム基材の少なくとも一方の面に塗布乾燥させることにより、粘着テープとして用いることができる。
That is, the present invention relates to 100 parts by mass of a rubber mixture in which natural rubber and synthetic rubber are mixed at a ratio of 10:90 to 90:10, 50 to 150 parts by mass of a tackifier resin, and a water-soluble polymer thickener 0.1. It is an emulsion-type pressure-sensitive adhesive having 40 to 60% by mass in terms of solid content. The emulsion type pressure-sensitive adhesive preferably has a viscosity of 2000 to 10000 mPa · s. When the shear is applied at a temperature of 40 ° C. and a shear rate of 3000 s-1 using a parallel plate rheometer, the emulsion type adhesive is subjected to shearing. It is preferable that the time required for the viscosity after doubling is 1800 seconds or more and the TI value after thickening is 7.0 to 9.0.
The water-soluble polymer thickener used for the emulsion-type pressure-sensitive adhesive preferably has a viscosity of 3000 to 20000 mPa · s.
The emulsion-type pressure-sensitive adhesive can be used as a pressure-sensitive adhesive tape by applying and drying at least one surface of a film substrate obtained by forming a film of vinyl chloride resin or the like.
エマルジョン型粘着剤及びこのエマルジョン型粘着剤を用いた粘着テープが得られる。 An emulsion-type pressure-sensitive adhesive and a pressure-sensitive adhesive tape using this emulsion-type pressure-sensitive adhesive are obtained.
エマルジョン型粘着剤のゴム混合物は、天然ゴムと合成ゴムを１０：９０〜９０：１０の混合比で混合して得られるものである。天然ゴムの混合量が少なくなると、得られるエマルジョン型粘着剤の粘着力が得られない場合があり、合成ゴムの混合量が少なくなると、得られるエマルジョン型粘着剤の耐老化性が得られない場合がある。ゴム混合物の天然ゴムと合成ゴムの混合比は、２０：８０〜８０：２０の範囲がより好ましい。 The rubber mixture of the emulsion type adhesive is obtained by mixing natural rubber and synthetic rubber at a mixing ratio of 10:90 to 90:10. When the amount of natural rubber is reduced, the adhesive strength of the resulting emulsion-type pressure-sensitive adhesive may not be obtained. When the amount of synthetic rubber is reduced, the resulting emulsion-type pressure-sensitive adhesive may not be resistant to aging. There is. The mixing ratio of natural rubber and synthetic rubber in the rubber mixture is more preferably in the range of 20:80 to 80:20.
天然ゴムとしては、特に限定するものではないが、濃縮原料天然ゴム、有機過酸化物前加硫天然ゴムなどがある。工業的に好ましくは濃縮原料天然ゴムが用いられる。 Examples of natural rubber include, but are not limited to, concentrated raw material natural rubber and organic peroxide pre-vulcanized natural rubber. Industrially preferably, a concentrated raw material natural rubber is used.
合成ゴムとしては、特に限定するものではないが、スチレン・ブタジエンゴム、ポリイソプレンゴム、ポリイソブチレンゴム、ブチルゴム、スチレングラフト天然ゴム、天然ゴムにメチルメタクリレートをグラフト重合させたメチルメタクリレートグラフト化天然ゴムなどがある。 The synthetic rubber is not particularly limited, but styrene / butadiene rubber, polyisoprene rubber, polyisobutylene rubber, butyl rubber, styrene grafted natural rubber, methyl methacrylate grafted natural rubber obtained by grafting methyl methacrylate to natural rubber, etc. There is.
粘着付与樹脂は、得られるエマルジョン型粘着剤の粘着力を調整するために配合するものである。粘着付与樹脂は、軟化点及び各成分との相溶性を有するものを用いることが好ましい。また、環球法により測定された軟化点が２０〜１８０℃のものが好ましい。軟化点が２０℃未満の粘着付与樹脂を配合すると、得られるエマルジョン型粘着剤の粘着特性が低下することがある。一方、軟化点が１８０℃を超える粘着付与樹脂を配合すると、粘着付与樹脂をエマルジョン化した時の安定性が低下することがある。本発明に適した粘着付与樹脂としては、テルペン樹脂、ロジン樹脂、水添ロジン樹脂、クマロン・インデン樹脂、スチレン樹脂、脂肪族及び脂環族などの石油樹脂、水添した脂肪族及び脂環族などの石油樹脂、テルペン−フェノール樹脂、キシレン樹脂、その他の脂肪族炭化水素樹脂や芳香族炭化水素樹脂などがある。粘着付与樹脂は、これらの化合物から少なくとも１種以上の樹脂を選択して用いればよい。特に、初期粘着力を向上させるためには、軟化点６５〜１５０℃の石油樹脂の脂環族飽和炭化水素樹脂や軟化点８０〜１５０℃のポリテルペン樹脂、軟化点８０〜１５０℃の水添ロジンのグリセリンエステルなどを用いるとよい。 The tackifying resin is blended in order to adjust the adhesive strength of the obtained emulsion-type pressure-sensitive adhesive. It is preferable to use a tackifying resin having a softening point and compatibility with each component. Further, those having a softening point of 20 to 180 ° C. measured by the ring and ball method are preferable. When a tackifying resin having a softening point of less than 20 ° C. is blended, the adhesive properties of the resulting emulsion-type adhesive may be deteriorated. On the other hand, when a tackifying resin having a softening point exceeding 180 ° C. is blended, stability when the tackifying resin is emulsified may be lowered. Suitable tackifying resins for the present invention include terpene resins, rosin resins, hydrogenated rosin resins, coumarone / indene resins, styrene resins, aliphatic and alicyclic petroleum resins, hydrogenated aliphatic and alicyclic groups. And other petroleum resins, terpene-phenol resins, xylene resins, other aliphatic hydrocarbon resins and aromatic hydrocarbon resins. The tackifying resin may be selected from at least one resin selected from these compounds. In particular, in order to improve the initial adhesive strength, an alicyclic saturated hydrocarbon resin of a petroleum resin having a softening point of 65 to 150 ° C., a polyterpene resin having a softening point of 80 to 150 ° C., and a hydrogenated rosin having a softening point of 80 to 150 ° C. It is preferable to use glycerin ester or the like.
粘着付与樹脂は、ゴム混合物１００質量部に対して、５０〜１５０質量部の範囲で用いる。粘着付与樹脂の配合量が５０質量部未満では、得られるエマルジョン型粘着剤の粘着力が発揮されない場合がある。１５０質量部を超えて配合してしまうと、得られるエマルジョン型粘着剤の凝集力が低下する場合がある。粘着付与樹脂の配合量は、７０〜１２０質量部の範囲がより好ましい。 The tackifying resin is used in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the rubber mixture. When the blending amount of the tackifying resin is less than 50 parts by mass, the adhesive force of the obtained emulsion-type adhesive may not be exhibited. If it exceeds 150 parts by mass, the resulting cohesive force of the emulsion-type pressure-sensitive adhesive may decrease. As for the compounding quantity of tackifying resin, the range of 70-120 mass parts is more preferable.
水溶性高分子増粘剤は、得られるエマルジョン型粘着剤の粘度を調整するために配合するものである。水溶性高分子増粘剤としては、変性ポリアクリル、ポリエーテル、ウレタン変性ポリエーテルなどがある。 The water-soluble polymer thickener is blended in order to adjust the viscosity of the obtained emulsion-type pressure-sensitive adhesive. Examples of the water-soluble polymer thickener include modified polyacryl, polyether, and urethane-modified polyether.
水溶性高分子増粘剤は、天然ゴムと合成ゴムのゴム混合物１００質量部に対して０．１〜５質量部の範囲で用いる。水溶性高分子増粘剤の配合量が０．１質量部未満では、得られるエマルジョン型粘着剤の粘度が低くなり、壁面などへ塗布した際に液垂れなどの問題が発生する場合がある。５質量部を超えて配合してしまうと、得られるエマルジョン型粘着剤の粘度が高くなり、粘着剤を均一に塗布できなくなる場合がある。水溶性高分子増粘剤の配合量は、０．３〜１．０質量部の範囲がより好ましい。 The water-soluble polymer thickener is used in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the rubber mixture of natural rubber and synthetic rubber. When the blending amount of the water-soluble polymer thickener is less than 0.1 parts by mass, the viscosity of the resulting emulsion-type pressure-sensitive adhesive becomes low, and problems such as dripping may occur when applied to a wall surface or the like. If the blending amount exceeds 5 parts by mass, the viscosity of the resulting emulsion-type pressure-sensitive adhesive increases, and the pressure-sensitive adhesive may not be applied uniformly. As for the compounding quantity of a water-soluble polymer thickener, the range of 0.3-1.0 mass part is more preferable.
エマルジョン型粘着剤は、上述の化合物を、固形分換算で３０〜６０質量％となるようにエマルジョン化させて得られるものである。
化合物の濃度が３０質量％未満であると、増粘剤による増粘効果が低下してしまう場合がある。化合物の濃度が６０質量％を超えてしまうと、エマルジョン型粘着剤の貯蔵安定性が低下する場合がある。エマルジョン型粘着剤の固形分濃度は、４０〜５０質量％の範囲がより好ましい。
The emulsion-type pressure-sensitive adhesive is obtained by emulsifying the above-described compound so as to be 30 to 60% by mass in terms of solid content.
If the concentration of the compound is less than 30% by mass, the thickening effect by the thickener may be lowered. If the concentration of the compound exceeds 60% by mass, the storage stability of the emulsion-type pressure-sensitive adhesive may be lowered. The solid content concentration of the emulsion-type pressure-sensitive adhesive is more preferably in the range of 40 to 50% by mass.
エマルジョン型粘着剤にはその特性を損なわない限り、さらに各種添加剤を追加することができる。このような添加剤としては特に限定されないが、例えば、湿潤剤、増粘剤、老化防止剤などを挙げることができる。湿潤剤を配合すると、エマルジョン型粘着剤の表面張力を下げることができ、粘着テープを製造する際に、フィルム基材への濡れ性を改善できるようになる。湿潤剤としては、例えば、陰イオン性界面活性剤、陽イオン性界面活性剤、非イオン性界面活性剤及び両性界面活性剤などを使用できる。好ましくは、ゴム混合物と結合しにくい、陰イオン性界面活性剤、非イオン性界面活性剤及び両性界面活性剤が用いられる。 Various additives can be further added to the emulsion-type pressure-sensitive adhesive as long as the properties thereof are not impaired. Such an additive is not particularly limited, and examples thereof include a wetting agent, a thickening agent, and an antiaging agent. When a wetting agent is blended, the surface tension of the emulsion-type pressure-sensitive adhesive can be lowered, and the wettability to the film substrate can be improved when the pressure-sensitive adhesive tape is produced. As the wetting agent, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant can be used. Preferably, an anionic surfactant, a nonionic surfactant and an amphoteric surfactant that are difficult to bind to the rubber mixture are used.
湿潤剤の配合量は、ゴム混合物１００質量部に対して、０．１〜１５質量部が好ましい。湿潤剤の配合量が０．１質量部未満では、エマルジョン型粘着剤のフィルム基材への濡れ性改善効果が得られない場合がある。１５質量部を超えて配合してしまうと、エマルジョン型粘着剤のゴム成分と石油樹脂成分との相溶性が阻害され、さらにはエマルジョン型粘着剤の粘着力が低下する場合がある。 As for the compounding quantity of a wetting agent, 0.1-15 mass parts is preferable with respect to 100 mass parts of rubber mixtures. If the blending amount of the wetting agent is less than 0.1 part by mass, the effect of improving the wettability of the emulsion-type pressure-sensitive adhesive to the film substrate may not be obtained. If it exceeds 15 parts by mass, the compatibility between the rubber component of the emulsion-type pressure-sensitive adhesive and the petroleum resin component is inhibited, and the adhesive strength of the emulsion-type pressure-sensitive adhesive may be lowered.
老化防止剤は、例えば、フェノール系老化防止剤、アミン系老化防止剤、ベンズイミダゾール系老化防止剤、ジチオカルバミン酸塩系老化防止剤及びリン系老化防止剤等の単独物または混合物を挙げることができる。好ましくは、フェノール系老化防止剤が用いられる。 Examples of the anti-aging agent include phenol-based anti-aging agents, amine-based anti-aging agents, benzimidazole-based anti-aging agents, dithiocarbamate-based anti-aging agents and phosphorus-based anti-aging agents, and the like. . Preferably, a phenolic anti-aging agent is used.
老化防止剤の配合量は、ゴム混合物１００質量部に対して０．１〜５質量部が好ましい。老化防止剤の配合量が０．１質量部未満では、酸素や光の存在下で得られたエマルジョン型粘着剤が劣化する場合がある。５質量部を超えて配合してしまうとエマルション型粘着剤の粘着力が低下することがある。 As for the compounding quantity of an anti-aging agent, 0.1-5 mass parts is preferable with respect to 100 mass parts of rubber mixtures. When the blending amount of the antioxidant is less than 0.1 parts by mass, the emulsion-type pressure-sensitive adhesive obtained in the presence of oxygen or light may deteriorate. If it exceeds 5 parts by mass, the adhesive strength of the emulsion-type pressure-sensitive adhesive may decrease.
エマルジョン型粘着剤は、その粘度が２０００〜１００００ｍＰａ・ｓであることが望ましい。粘度が２０００ｍＰａ・ｓ未満であると壁面などへ塗布した際に液垂れなどの問題が発生する場合がある。１００００ｍＰａ・ｓを越えてしまう水溶性高分子増粘剤添加量では、得られるエマルジョン型粘着剤の粘度が高くなり、粘着剤を均一に塗布できなくなる場合がある。エマルジョン型粘着剤の粘度を調整するためには、固形分濃度を調整するか、配合する水溶性高分子増粘剤の配合量を調整すればよい。 The emulsion-type pressure-sensitive adhesive desirably has a viscosity of 2000 to 10,000 mPa · s. When the viscosity is less than 2000 mPa · s, problems such as dripping may occur when applied to a wall surface or the like. When the amount of the water-soluble polymer thickener added exceeds 10,000 mPa · s, the viscosity of the resulting emulsion-type pressure-sensitive adhesive increases, and the pressure-sensitive adhesive may not be applied uniformly. In order to adjust the viscosity of the emulsion-type pressure-sensitive adhesive, the solid content concentration may be adjusted, or the blending amount of the water-soluble polymer thickener to be blended may be adjusted.
一般に、エマルジョン型粘着剤は、コーンプレート型レオメータ、例えば、ＭＣＲ３００（Ｐａａｒ Ｐｈｉｓｉｃａ社製）ｃｐ５０−２を用い、４０℃、３０００ｓ−１の一定条件下で剪断力を連続的にかけたときに、粘度が急激に上昇する現象が見られる。
本発明のエマルジョン型粘着剤は、上述の条件で剪断力をかけた際の粘度が、測定開始直後の粘度の２倍になるために要する時間が、測定開始から１８００秒以上であることが望ましい。このようなエマルジョン型粘着剤は、いわゆる貯蔵安定性にすぐれるものである。エマルジョン型粘着剤の粘度の上昇を抑えるためには、エマルジョン型粘着剤の固形分濃度を低く設定すればよい。
In general, an emulsion type adhesive has a viscosity when a cone plate type rheometer such as MCR300 (manufactured by Paar Phisica) cp50-2 is used and a shearing force is continuously applied under a constant condition of 40 ° C. and 3000 s-1. There is a phenomenon in which the value rises rapidly.
In the emulsion-type pressure-sensitive adhesive of the present invention, it is desirable that the time required for the viscosity when the shearing force is applied under the above-mentioned conditions to be twice the viscosity immediately after the start of measurement is 1800 seconds or more from the start of measurement. . Such an emulsion-type pressure-sensitive adhesive is excellent in so-called storage stability. In order to suppress an increase in the viscosity of the emulsion-type pressure-sensitive adhesive, the solid content concentration of the emulsion-type pressure-sensitive adhesive may be set low.
エマルジョン型粘着剤は、フィルム基材の少なくとも一方の面に塗布乾燥させることで、粘着テープとすることができる。 The emulsion-type pressure-sensitive adhesive can be formed into a pressure-sensitive adhesive tape by applying and drying on at least one surface of the film substrate.
エマルジョン型粘着剤をフィルム基材に塗布する方法としては、公知の方法を用いることができる。特に限定するものではないが、例えば、ナイフコーター、ロールコーター、コンマコーター、リップコーター、ダイコーターなどを用いて塗布すればよい。 A known method can be used as a method of applying the emulsion-type pressure-sensitive adhesive to the film substrate. Although it does not specifically limit, For example, what is necessary is just to apply | coat using a knife coater, a roll coater, a comma coater, a lip coater, a die coater etc.
フィルム基材としては、塩化ビニル樹脂組成物が好適に用いられる。塩化ビニル樹脂組成物は、ポリ塩化ビニルを含有していれば特に制限されない。塩化ビニル樹脂組成物の樹脂成分全量に対するポリ塩化ビニルの割合は、例えば、５０質量％以上、好ましくは８０質量％以上、さらに好ましくは９０〜１００質量％である。なお、塩化ビニル樹脂組成物は、樹脂成分以外に、必要に応じて、公知の添加物（例えば、安定剤、可塑剤など）を含有していてもよい。 As the film substrate, a vinyl chloride resin composition is suitably used. The vinyl chloride resin composition is not particularly limited as long as it contains polyvinyl chloride. The ratio of polyvinyl chloride with respect to the total amount of resin components of the vinyl chloride resin composition is, for example, 50% by mass or more, preferably 80% by mass or more, and more preferably 90 to 100% by mass. In addition to the resin component, the vinyl chloride resin composition may contain a known additive (for example, a stabilizer, a plasticizer, etc.) as necessary.
フィルム基材の厚みは特に制限されず、例えば、１０〜５００μｍ、好ましくは７０〜２００μｍ、さらに好ましくは８０〜１６０μｍである。なお、フィルム基材は単層の形態を有していてもよく、また、複層の形態を有していてもよい。
なお、フィルム基材には、必要に応じて、背面処理、帯電防止処理、プライマー処理などの各種処理が施すこともできる。
The thickness in particular of a film base material is not restrict | limited, For example, it is 10-500 micrometers, Preferably it is 70-200 micrometers, More preferably, it is 80-160 micrometers. In addition, the film base material may have a single layer form, and may have a multiple layer form.
In addition, various processes, such as a back surface process, an antistatic process, and a primer process, can also be given to a film base material as needed.
粘着剤層の厚みは、例えば、５〜１００μｍ、好ましくは１０〜５０μｍである。これより薄いと粘着力が低下して、得られる粘着テープの巻付け作業性が低下することがある。一方これより厚くなると、塗工性能が悪くなることがある。 The thickness of the pressure-sensitive adhesive layer is, for example, 5 to 100 μm, preferably 10 to 50 μm. If it is thinner than this, the adhesive strength is lowered, and the winding workability of the obtained adhesive tape may be lowered. On the other hand, if it is thicker than this, the coating performance may deteriorate.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
表１および表２において、「粘度の立ち上がり時間」とは、Ｐａａｒ Ｐｈｉｓｉｃａ社製のコーンプレート型レオメータＭＣＲ３００ ｃｐ５０−２を用い、４０℃、３０００ｓ−１の一定条件下で剪断力を連続的にかけたとき凝集物、皮張りの発生により測定される粘度が急激に上昇するのに要する時間であり、この時間が１８００秒以上のものを○、１８００秒未満のものを×とした。 In Tables 1 and 2, “viscosity rise time” means that a shear force was continuously applied under constant conditions of 40 ° C. and 3000 s-1 using a cone plate rheometer MCR300 cp50-2 manufactured by Paar Phisica. The time required for the viscosity measured by the occurrence of agglomerates and skinning to rise rapidly is shown. The time is 1800 seconds or more, and the time less than 1800 seconds is x.
表１および表２において、「増粘剤粘度」「粘着剤粘度」は、ＪＩＳ Ｚ ８８０３，８．項「単一円筒形回転粘度計による粘度測定方法」に準じて測定した。なお、測定はＢ型粘度計（東京計器社製）ローター：Ｎｏ．３、回転数：６ｒｐｍ、測定温度：２３℃にて行った。 In Tables 1 and 2, “Thickener viscosity” and “Adhesive viscosity” are JIS Z 8803,8. It was measured according to the term “viscosity measurement method using a single cylindrical rotational viscometer”. The measurement was conducted using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) rotor: No. 3. Rotation speed: 6 rpm, measurement temperature: 23 ° C.
表１および表２において、「粘着剤ＴＩ値」とは粘度測定にて使用したＢ型粘度計を用いて、回転数６０ｒｐｍと６ｒｐｍの粘度の比（６０ｒｐｍ／６ｒｐｍ）にてチクソトロピー性を評価した。 In Tables 1 and 2, the “adhesive TI value” is a thixotropic property evaluated using a B-type viscometer used in the viscosity measurement at a ratio of the viscosity of 60 rpm to 6 rpm (60 rpm / 6 rpm). .
「試験板粘着力」とは、ＪＩＳ Ｃ ２１０７， １０． 項「粘着力」の１１．４．１項に規定されている「試験板粘着力試験の準備」に準拠して測定した。 “Test plate adhesive strength” means JIS C 2107, 10. It was measured in accordance with “Preparation for test plate adhesive strength test” defined in the section “11.4.1” of the term “Adhesive strength”.
表１および表２において、「自背面粘着力」とは、ＪＩＳ Ｃ ２１０７ １０． 項「粘着力」の１１．４．２項に規定されている「背面粘着力試験の準備」に準拠して測定した。 In Tables 1 and 2, “self-rear adhesive strength” means JIS C 2107 10. It was measured in accordance with “Preparation for Back Adhesion Test” defined in the section “11.4.2” of the item “Adhesion”.
表１および表２において、「保持力」とは、ＪＩＳ Ｚ ０２３７， １３ 項「保持力」に準拠して測定した。 In Tables 1 and 2, “holding force” was measured according to JIS Z 0237, item 13 “holding force”.
表１および表２において、「塗工性」とは、基材に粘着剤を塗布する際に液垂れがなく、また粘着剤を塗布した後の粘着剤層の厚みが均一なものを○、そうでないものを×とした。 In Tables 1 and 2, “coatability” means that there is no dripping when the adhesive is applied to the substrate, and that the thickness of the adhesive layer after applying the adhesive is uniform. Those not so were marked with x.
（実施例１）本実施例におけるエマルジョン型粘着剤は、固形分質量比で天然ゴム（ＥＸＣＥＬＴＥＸ‐ＨＬＸ ＬＡ‐ＴＺ）２０質量部、スチレン・ブタジエンゴム（イーテックス社製ＫＴ４６１５Ｂ）４０質量部、ＮＲ−ｇｒａｆｔ−ＭＭＡ（ムサシノケミカル社製ＭＧ３０）４０質量部、粘着付与樹脂（荒川化学社製Ｅ−２００）３０質量部、石油樹脂（荒川化学社製ＡＰ−１１００−ＮＴ）７０質量部、潤滑剤としてジアルキルスルフォコハク酸ナトリウム塩（花王社製ペレックスＯＴ−Ｐ）１質量部、水溶性高分子増粘剤（ＡＤＥＫＡ社製アデカノールＵＨ−７５６ＶＦ）０．３質量部を、水に固形分換算で５０質量％となるようにエマルジョン化させたものである。
また、フィルム基材は、ポリ塩化ビニル樹脂（大洋塩ビ社製）１００質量部、可塑剤としてのＤＯＰ（ジェイプラス社製）５０質量部、安定剤としてのＣａ−Ｚｎ系安定剤（水澤化学社製）２質量部を混合して塩化ビニル樹脂組成物を調整し、得られた塩化ビニル樹脂組成物を、カレンダー成形機を用いて厚さ１６０μｍのフィルム状に成形したものである。得られたフィルム基材の一方の面にプライマーを積層し、さらにエマルジョン型粘着剤を塗布乾燥して、粘着剤層の厚みが２０±１μｍの粘着テープを作成した。この粘着テープを用いて、試験板粘着力、背面粘着力、保持力を評価した。
(Example 1) The emulsion-type pressure-sensitive adhesive in this example is 20 parts by mass of natural rubber (EXCELEX-HLX LA-TZ), 40 parts by mass of styrene-butadiene rubber (KT4615B manufactured by Etex Co., Ltd.), and NR. -Graft-MMA (MG30 manufactured by Musashino Chemical Co.) 40 parts by mass, 30 parts by mass of tackifier resin (E-200 manufactured by Arakawa Chemical Co., Ltd.), 70 parts by mass of petroleum resin (AP-1100-NT manufactured by Arakawa Chemical Co., Ltd.), lubricant 1 part by weight of dialkylsulfosuccinic acid sodium salt (Perox OT-P manufactured by Kao Co., Ltd.), 0.3 part by weight of a water-soluble polymer thickener (ADEKA NOL UH-756VF manufactured by ADEKA Co., Ltd.) in water as a solid content Emulsified so as to be 50% by mass.
In addition, the film base material is 100 parts by mass of polyvinyl chloride resin (manufactured by Taiyo PVC Co.), 50 parts by mass of DOP (manufactured by J-Plus) as a plasticizer, and a Ca—Zn-based stabilizer (Mizusawa Chemical Co., Ltd.) as a stabilizer. Manufactured) 2 parts by mass are mixed to prepare a vinyl chloride resin composition, and the resulting vinyl chloride resin composition is molded into a film having a thickness of 160 μm using a calendar molding machine. A primer was laminated on one surface of the obtained film base material, and an emulsion-type pressure-sensitive adhesive was further applied and dried to prepare a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer thickness of 20 ± 1 μm. Using this adhesive tape, the test plate adhesive strength, back adhesive strength, and holding strength were evaluated.
（実施例２）粘着付与樹脂、水溶性高分子増粘剤の配合を表１に示した比率とし、純水を加えることによって固形分を表１に示した値に調整した以外は、実施例１と同様にして粘着テープを作成して評価を行った。評価結果を表１に示す。 (Example 2) Example except that the composition of the tackifying resin and the water-soluble polymer thickener was set to the ratio shown in Table 1, and the solid content was adjusted to the value shown in Table 1 by adding pure water. In the same manner as in No. 1, an adhesive tape was prepared and evaluated. The evaluation results are shown in Table 1.
（実施例３〜１０）ゴム混合物及び粘着付与樹脂の配合を表１に示した比率とした以外は、実施例１と同様にして粘着テープを作成して評価を行った。評価結果を表１に示す。なお、表１中、水溶性高分子増粘剤（ＳＮ−８１２）は、サンノプコ社製のＳＮシックナーＡ-８１２、水溶性高分子増粘剤（ＵＨ−４５０ＶＦ）は、ＡＤＥＫＡ製のアデカノールＵＨ-４５０ＶＦ、水溶性高分子増粘剤（ＵＨ-７５６ＶＦ）はＡＤＥＫＡ製のアデカノールＵＨ-７５６ＶＦである。 (Examples 3 to 10) An adhesive tape was prepared and evaluated in the same manner as in Example 1 except that the ratio of the rubber mixture and the tackifying resin was changed to the ratio shown in Table 1. The evaluation results are shown in Table 1. In Table 1, the water-soluble polymer thickener (SN-812) is SN thickener A-812 manufactured by San Nopco, and the water-soluble polymer thickener (UH-450VF) is Adecanol UH- manufactured by ADEKA. 450 VF, a water-soluble polymer thickener (UH-756VF) is Adecanol UH-756VF manufactured by ADEKA.
（比較例１〜４）粘着付与樹脂や水溶性高分子増粘剤の配合を表２に示した比率とした以外は、実施例１と同様にして粘着テープを作成して評価を行った。評価結果を表２に示す。 (Comparative Examples 1 to 4) A pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1 except that the ratio of tackifying resin and water-soluble polymer thickener was changed to the ratio shown in Table 2. The evaluation results are shown in Table 2.
表１から明らかなように、本発明の各実施例の粘着テープは、粘度の立ち上がり時間が遅く、熱や剪断に対する安定性に優れ、且つ粘着力、保持力は適正な範囲にあり、塗工も問題なく行えた。 As is apparent from Table 1, the adhesive tape of each example of the present invention has a slow rise time of viscosity, excellent stability against heat and shear, and has an adhesive force and a holding force in appropriate ranges. It was possible without problem.
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