JP2011190419A - Water-based removable type adhesive and adhesive tape - Google Patents
Water-based removable type adhesive and adhesive tape Download PDFInfo
- Publication number
- JP2011190419A JP2011190419A JP2010060050A JP2010060050A JP2011190419A JP 2011190419 A JP2011190419 A JP 2011190419A JP 2010060050 A JP2010060050 A JP 2010060050A JP 2010060050 A JP2010060050 A JP 2010060050A JP 2011190419 A JP2011190419 A JP 2011190419A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- water
- weight
- pressure
- peelable pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 33
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 16
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 26
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 68
- 239000000178 monomer Substances 0.000 claims description 37
- 239000004094 surface-active agent Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000002978 peroxides Chemical class 0.000 claims description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 2
- -1 2-ethylhexyl Chemical group 0.000 description 30
- 230000035882 stress Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000000123 paper Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011111 cardboard Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
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- 238000004873 anchoring Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
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- 229920005989 resin Polymers 0.000 description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
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- 239000002985 plastic film Substances 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 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 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- KQSMCAVKSJWMSI-UHFFFAOYSA-N 2,4-dimethyl-1-n,1-n,3-n,3-n-tetrakis(oxiran-2-ylmethyl)benzene-1,3-diamine Chemical compound CC1=C(N(CC2OC2)CC2OC2)C(C)=CC=C1N(CC1OC1)CC1CO1 KQSMCAVKSJWMSI-UHFFFAOYSA-N 0.000 description 1
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- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
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- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- SFHANYOFMGEJCT-UHFFFAOYSA-N octyl 2-sulfanylpropanoate Chemical compound CCCCCCCCOC(=O)C(C)S SFHANYOFMGEJCT-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QUANRIQJNFHVEU-UHFFFAOYSA-N oxirane;propane-1,2,3-triol Chemical compound C1CO1.OCC(O)CO QUANRIQJNFHVEU-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000007883 water-soluble azo polymerization initiator Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、粘着ラベル、マスキングテープおよびシート、表面保護フィルム等に使用でき、粘着性に優れ、各種被着体(金属板、ガラス、プラスチック板、紙等)に貼り付け後長期間放置した後でも容易に剥離できる水系再剥離型粘着剤及びそれを用いた粘着テープに関する。 The present invention can be used for pressure-sensitive adhesive labels, masking tapes and sheets, surface protection films, etc., has excellent adhesiveness, and is left for a long time after being attached to various adherends (metal plate, glass, plastic plate, paper, etc.) However, the present invention relates to an aqueous re-peelable pressure-sensitive adhesive that can be easily peeled and a pressure-sensitive adhesive tape using the same.
従来、値札ラベルや宅配便の宛名ラベル等では、使用中にラベルが剥がれないように、強粘着型の粘着剤が使用されていた。しかし、ラベルの貼付後に経時で被着体への密着性が上がり過ぎるため、後で剥がす際には糊残りや紙基材の破れが発生していた。 Conventionally, a strong adhesive type adhesive has been used for price tag labels, courier address labels, and the like so that the labels do not peel off during use. However, the adhesiveness to the adherend is excessively increased over time after the label is pasted, and therefore, adhesive residue and tearing of the paper base material occurred when peeling off later.
そのため被着体から容易に剥離できるように、再剥離型の感圧性接着剤が従来から提案されている。
特許文献1には、架橋性単量体と水溶性アゾ系重合開始剤を用い平均粒子径が100nm以下のアクリル系共重合体に対し、アジリジン基を有する架橋剤を配合する事により耐水性、耐湿熱性に優れ、被着体表面を汚染する事なく再剥離性に優れた水性エマルジョン型粘着剤が開示されている。しかしこの粘着剤は、架橋密度が高くなりすぎて、例えばダンボールなどの粗面に対する粘着性が得られない。
Therefore, a re-peelable pressure-sensitive adhesive has been conventionally proposed so that it can be easily peeled off from the adherend.
Patent Document 1 includes a crosslinkable monomer and a water-soluble azo polymerization initiator, an acrylic copolymer having an average particle size of 100 nm or less, and water resistance by blending a crosslinking agent having an aziridine group. An aqueous emulsion-type pressure-sensitive adhesive having excellent wet heat resistance and excellent removability without contaminating the adherend surface has been disclosed. However, this pressure-sensitive adhesive has an excessively high crosslinking density, and cannot provide adhesiveness to rough surfaces such as cardboard.
また、特許文献2には、架橋性単量体とアニオン型反応性界面活性剤を用い、70%以上の高ゲル分率に架橋させたアクリル系共重合体に対し、架橋剤としてエマルジョン型オキサゾリン系化合物を配合する事により、経時での粘着力上昇が少なく、かつ再剥離時における被着体への耐汚染性に優れた再剥離型水性粘着剤組成物が開示されている。しかしこの粘着剤は凝集力が高い上、さらに架橋剤を用いているため架橋密度が高くなりすぎて、例えばダンボールなどの粗面に対する粘着性が得られない。 Patent Document 2 discloses an emulsion type oxazoline as a crosslinking agent for an acrylic copolymer crosslinked with a high gel fraction of 70% or more using a crosslinking monomer and an anionic reactive surfactant. There has been disclosed a re-peelable water-based pressure-sensitive adhesive composition in which an increase in adhesive force with time is small by blending a system compound and excellent in stain resistance to an adherend during re-peeling. However, this pressure-sensitive adhesive has a high cohesive force and further uses a cross-linking agent, so that the cross-linking density becomes too high and, for example, the pressure-sensitive adhesiveness to rough surfaces such as cardboard cannot be obtained.
また、特許文献3には、特定量のアクリル酸ブチル、不飽和カルボン酸と反応性界面活性剤を含むアクリル系共重合体に対し、粘着付与樹脂とエポキシ架橋剤を必須成分として含むことで、強粘着力ながら再剥離性良好な粘着シートが得られる旨が開示されている。しかしこの粘着剤は、高温高湿経時後の再剥離性が悪化する問題があった。 Patent Document 3 includes a tackifier resin and an epoxy crosslinking agent as essential components for an acrylic copolymer containing a specific amount of butyl acrylate, an unsaturated carboxylic acid and a reactive surfactant. It is disclosed that an adhesive sheet with good removability can be obtained while having strong adhesive strength. However, this pressure-sensitive adhesive has a problem that the removability after aging at high temperature and high humidity deteriorates.
本発明は、ダンボール等の粗面への粘着性に優れ、かつ被着体への貼り付け後、高温高湿で長時間放置された後でも被着体表面から容易に剥離できる粘着テープに使用できる水系再剥離型粘着剤を提供することを目的とする。 The present invention is used for an adhesive tape that has excellent adhesion to rough surfaces such as corrugated cardboard and can be easily peeled off from the surface of the adherend even after being left for a long time at high temperature and high humidity after being attached to the adherend. An object is to provide a water-based re-peelable pressure-sensitive adhesive.
本発明は、アクリル系樹脂(A)と、硬化剤(B)とを含む水系再剥離型粘着剤であって、
前記水系再剥離型粘着剤から形成してなる断面積4mm2の乾燥皮膜の、応力−歪み曲線における200%歪み時の応力値が0.01〜0.03N/mm2であり、
最大応力時の歪みが800〜1300%であり、最大応力値が0.04〜0.08N/mm2 であることを特徴とする水系再剥離型粘着剤に関する。
The present invention is an aqueous re-peelable pressure-sensitive adhesive containing an acrylic resin (A) and a curing agent (B),
The stress value at the time of 200% strain in the stress-strain curve of a dry film having a cross-sectional area of 4 mm 2 formed from the water-based re-peelable pressure-sensitive adhesive is 0.01 to 0.03 N / mm 2
The present invention relates to a water-based re-peelable pressure-sensitive adhesive having a strain at a maximum stress of 800 to 1300% and a maximum stress value of 0.04 to 0.08 N / mm 2 .
また、本発明は、アクリル系樹脂(A)が、少なくとも2−エチルヘキシルアクリレート(A−1)とブチルアクリレート(A−2)を合計90.0〜99.9重量%を含む単量体混合物を非反応性界面活性剤の存在下で、重合開始剤として過酸化物と還元剤を用いて共重合してなるであって、
(A−1)/(A−2)の重量比が55/45〜25/75であり、
硬化剤(B)がエポキシ化合物であり、さらに、ポリオール(C)を含むことを特徴とする上記発明の水性再剥離型粘着剤に関する。
Further, the present invention provides a monomer mixture in which the acrylic resin (A) contains at least 2-ethylhexyl acrylate (A-1) and butyl acrylate (A-2) in a total amount of 90.0 to 99.9% by weight. Copolymerized using a peroxide and a reducing agent as a polymerization initiator in the presence of a non-reactive surfactant,
The weight ratio of (A-1) / (A-2) is 55 / 45-25 / 75,
The curing agent (B) is an epoxy compound, and further contains a polyol (C), and relates to the aqueous re-peelable pressure-sensitive adhesive according to the invention described above.
また本発明は、上記発明の水系再剥離型粘着剤から形成してなる乾燥皮膜の酢酸エチル抽出残分が45〜75重量%であることを特徴とする水系再剥離型粘着剤に関する。 The present invention also relates to an aqueous re-peelable pressure-sensitive adhesive characterized in that the ethyl acetate extraction residue of a dry film formed from the water-based re-peelable pressure-sensitive adhesive of the invention is 45 to 75% by weight.
また本発明は、アクリル系樹脂(A)から形成してなる乾燥皮膜のテトラヒドロフラン溶出分の重量平均分子量が25〜45万であることを特徴とする上記発明の水系再剥離型粘着剤に関する。 The present invention also relates to the water-based re-peelable pressure-sensitive adhesive according to the invention, wherein the dry film formed from the acrylic resin (A) has a weight average molecular weight of 25 to 450,000 for the elution of tetrahydrofuran.
また、本発明は、上記発明の水系再剥離型粘着剤から形成してなる粘着剤層を含む粘着テープに関する。 Moreover, this invention relates to the adhesive tape containing the adhesive layer formed from the water-system re-peeling type adhesive of the said invention.
本発明により、ダンボール等の粗面への粘着性に優れ、かつ被着体への貼り付け後、高温高湿で長時間放置された後でも被着体表面から容易に剥離できる粘着テープに使用できる水系再剥離型粘着剤を提供することができた。 According to the present invention, it is excellent in adhesiveness to rough surfaces such as corrugated cardboard and used for an adhesive tape that can be easily peeled off from the adherend surface even after being left for a long time at high temperature and high humidity after being attached to the adherend. It was possible to provide a water-based re-peelable pressure sensitive adhesive.
本願の発明者は、応力―歪み曲線における初期の応力値と、その後の歪み(伸び)における最大応力値を所定の範囲内に制御することで、粗面への粘着性と高温高湿経時後の再剥離性が両立できることを見出した。
すなわち、本発明はアクリル系樹脂(A)と、硬化剤(B)とを含む水系再剥離型粘着剤に関するものであり、当該水系再剥離型粘着剤から形成した断面積4mm2の乾燥皮膜の、応力−歪み曲線における初期の応力値である200%歪み時の応力値が0.01〜0.03N/mm2であることが重要である。ここで応力値が0.01N/mm2未満のときは、粘着シートが高温高湿経時中または経時後に脱落や浮きが発生する恐れがある。また0.03N/mm2を越えると、粘着シートに紙基材を用いた場合、紙の破れが発生する恐れがある。
The inventor of the present application controls the initial stress value in the stress-strain curve and the maximum stress value in the subsequent strain (elongation) within a predetermined range, so that the adhesiveness to the rough surface and the high temperature and high humidity after aging It was found that re-peelability can be compatible.
That is, the present invention relates to an aqueous re-peelable pressure-sensitive adhesive containing an acrylic resin (A) and a curing agent (B), and a dry film having a cross-sectional area of 4 mm 2 formed from the aqueous re-peelable pressure-sensitive adhesive. It is important that the stress value at the time of 200% strain, which is the initial stress value in the stress-strain curve, is 0.01 to 0.03 N / mm 2 . Here, when the stress value is less than 0.01 N / mm 2 , the adhesive sheet may fall off or float during or after the high temperature and high humidity. If it exceeds 0.03 N / mm 2 , the paper may be torn when a paper base material is used for the pressure-sensitive adhesive sheet.
本発明において応力―歪み曲線とは、粘着剤層にかけた応力と、その応力による変形量(歪み)との関係を示す曲線である。そして、粘着剤の応力―歪み曲線と再剥離性との間には相関関係があると推測している。 In the present invention, the stress-strain curve is a curve showing the relationship between the stress applied to the pressure-sensitive adhesive layer and the amount of deformation (strain) caused by the stress. It is assumed that there is a correlation between the stress-strain curve of the adhesive and the removability.
ここで本発明において粘着力とは粘着テープを被着体へ貼付した後、引張り試験機等により測定した数値をいい、粘着性とは粘着テープを被着体へ貼付した後の粘着テープの被着体に対する密着性を意味する。 Here, in the present invention, the adhesive strength refers to a value measured by a tensile tester or the like after the adhesive tape has been applied to the adherend, and the adhesiveness refers to the adhesion of the adhesive tape after the adhesive tape has been applied to the adherend. It means adhesion to the body.
また、本発明では、さらに、粘着層が適度に歪み(伸び)、その歪みに対応する応力値が適切な範囲内であることが必要である。すなわち、断面積4mm2当たりの最大応力時の歪みが800〜1300%の範囲にあり、かつ最大応力値が0.04〜0.08N/mm2の範囲にあることが重要である。一方、前記数値範囲を満たさないと再剥離性が不足する恐れがある。 In the present invention, it is further necessary that the pressure-sensitive adhesive layer is appropriately distorted (elongated) and the stress value corresponding to the distortion is within an appropriate range. That is, it is important that the strain at the maximum stress per cross-sectional area of 4 mm 2 is in the range of 800 to 1300% and the maximum stress value is in the range of 0.04 to 0.08 N / mm 2 . On the other hand, if the numerical range is not satisfied, the removability may be insufficient.
本発明では、応力と歪みの関係は以下の方法により測定する。
1.剥離シート上に粘着剤層の乾燥厚さが0.05mmになるように粘着剤を塗工し、100℃で3分間乾燥する。さらに同様な作業で0.05mmの塗工物を3枚作成する。そして計4枚の塗工物を気泡が入らないように貼り合わせ、厚み0.2mm粘着剤塗工物を作成する。気泡が混入した場合は、オートクレーブ処理により脱気することもできる。
2.幅20mm、長さ24mm、厚み0.2mmサイズに試験サンプルを切断する。
3.引張試験機(EZ TEST、島津製作所社製)に試験サンプルを固定し、300mm/分で引っ張ることで応力〔N/mm2〕と歪み〔%〕を求める。測定雰囲気は、温度;23℃、湿度;55%RHである。
4.応力〔N/mm2〕は、サンプルの断面積あたりの強度であり、測定値である引張強度〔N〕とサンプルの厚み〔mm〕とサンプル幅〔mm〕から求めることができる。
5.上記3で求めた応力〔N/mm2〕をy軸とし、歪み〔%〕をx軸としてグラフを作成し、そのグラフから200%歪み時の応力値、最大応力時の歪み、最大応力値、最大歪み等各パラメータの数値を求める。
In the present invention, the relationship between stress and strain is measured by the following method.
1. A pressure-sensitive adhesive is coated on the release sheet so that the dry thickness of the pressure-sensitive adhesive layer is 0.05 mm, and dried at 100 ° C. for 3 minutes. Further, three 0.05 mm coated products are prepared in the same operation. Then, a total of four coated products are bonded so that bubbles do not enter, and a 0.2 mm thick adhesive coated product is created. When bubbles are mixed, it can be degassed by autoclaving.
2. A test sample is cut into a size of width 20 mm, length 24 mm, thickness 0.2 mm.
3. A test sample is fixed to a tensile tester (EZ TEST, manufactured by Shimadzu Corporation), and stress [N / mm 2 ] and strain [%] are obtained by pulling at 300 mm / min. Measurement atmosphere is temperature; 23 degreeC, humidity; 55% RH.
4). The stress [N / mm 2 ] is the strength per cross-sectional area of the sample, and can be obtained from the measured tensile strength [N], sample thickness [mm], and sample width [mm].
5. Create a graph with the stress [N / mm 2 ] obtained in 3 above as the y-axis and the strain [%] as the x-axis. From the graph, the stress value at the time of 200% strain, the strain at the maximum stress, and the maximum stress value The numerical value of each parameter such as maximum distortion is obtained.
本発明の水系再剥離粘着剤に用いるアクリル系樹脂(A)を説明する。
アクリル系樹脂(A)は、カルボキシル基含有エチレン性不飽和単量体、およびそれ以外のエチレン性不飽和単量体を含むエチレン性不飽和単量体混合物を乳化重合させてなるものである。
The acrylic resin (A) used for the aqueous re-peeling adhesive of the present invention will be described.
The acrylic resin (A) is obtained by emulsion polymerization of an ethylenically unsaturated monomer mixture containing a carboxyl group-containing ethylenically unsaturated monomer and other ethylenically unsaturated monomers.
エチレン性不飽和単量体としては、具体的には、例えば、
アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸−2−エチルヘキシル等のアクリル酸エステル類;
メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸2−エチルヘキシル、メタクリル酸シクロヘキシル等のメタクリル酸エステル類;
アクリル酸、メタクリル酸、イタコン酸、マレイン酸、2−メタクリロイルプロピオン酸等の不飽和基含有各種カルボン酸;
スチレン、α−メチルスチレン、ベンジルメタクリレート等の芳香族単量体;
酢酸ビニル、プロピオン酸ビニル、等のビニルエステル類;
ビニルピロリドンの如き複素環式ビニル化合物;
エチレン、プロピレン等の如きα−オレフィン類;
ブタジエンの如きジエン類;
グリシジルメタクリレート,アリルグリシジルエーテル等のグリシジル基含有単量体;
2−ヒドロキシエチルメタクリレート等の水酸基含有単量体;
ジメチルアミノエチルメタクリレート等のアミノ基含有単量体;
アクリルアミド等のカルボン酸アミド基含有単量体;
ジメチルビニルメトキシシラン等の不飽和結合含有シラン化合物;
アクリロニトリル等のシアノ基含有単量体;
ジビニルベンゼン等の多官能ビニル単量体;
などを挙げる事ができる。
As an ethylenically unsaturated monomer, specifically, for example,
Acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, acrylate-2-ethylhexyl;
Methacrylate esters such as ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate;
Various unsaturated group-containing carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-methacryloylpropionic acid;
Aromatic monomers such as styrene, α-methylstyrene, benzyl methacrylate;
Vinyl esters such as vinyl acetate and vinyl propionate;
Heterocyclic vinyl compounds such as vinylpyrrolidone;
Α-olefins such as ethylene and propylene;
Dienes such as butadiene;
Glycidyl group-containing monomers such as glycidyl methacrylate and allyl glycidyl ether;
Hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate;
Amino group-containing monomers such as dimethylaminoethyl methacrylate;
Carboxylic acid amide group-containing monomers such as acrylamide;
Unsaturated bond-containing silane compounds such as dimethylvinylmethoxysilane;
Cyano group-containing monomers such as acrylonitrile;
Polyfunctional vinyl monomers such as divinylbenzene;
And so on.
本発明では、上記それ以外のエチレン性不飽和単量体として、2−エチルヘキシルアクリレート(A−1)とブチルアクリレート(A−2)を併用することが好ましい。使用割合は全単量体100重量%中、90.0〜99.9重量%であることが好ましい。
さらに(A−1)/(A−2)の重量比が55/45〜25/75であることが好ましい。ブチルアクリレート(A−2)が45重量%未満のときは、紙基材の粘着テープとして用いた場合、再剥離時に基材が破断する恐れがある。逆に75重量%を越えると、被着体への糊残りが生じる恐れがある。
In the present invention, it is preferable to use 2-ethylhexyl acrylate (A-1) and butyl acrylate (A-2) in combination as the other ethylenically unsaturated monomers. The use ratio is preferably 90.0 to 99.9% by weight in 100% by weight of all monomers.
Furthermore, the weight ratio of (A-1) / (A-2) is preferably 55/45 to 25/75. When butyl acrylate (A-2) is less than 45% by weight, the substrate may be broken during re-peeling when used as an adhesive tape for a paper substrate. On the other hand, when it exceeds 75% by weight, there is a possibility that adhesive residue may be generated on the adherend.
本発明のアクリル系樹脂(A)のガラス転移温度は−70〜−10℃であることが好ましく、―65〜−50℃であることがより好ましい。ガラス転移温度が−10℃よりも高いと、紙基材への投錨性及び被着体への粘着性が不十分となり易い。他方、アクリル系樹脂(A)のガラス転移温度が−70℃より低いと、高温雰囲気下で再剥離性が劣る恐れがある。なお本発明において投錨性とは、基材に対する粘着剤層の密着性を意味する。 The glass transition temperature of the acrylic resin (A) of the present invention is preferably −70 to −10 ° C., more preferably −65 to −50 ° C. When the glass transition temperature is higher than −10 ° C., the anchoring property to the paper substrate and the adhesiveness to the adherend are likely to be insufficient. On the other hand, if the glass transition temperature of the acrylic resin (A) is lower than -70 ° C, the removability may be deteriorated in a high temperature atmosphere. In the present invention, the anchoring property means the adhesiveness of the pressure-sensitive adhesive layer to the substrate.
本発明におけるアクリル系樹脂(A)のガラス転移温度(Tg)は下記の式[I]により理論的に導かれる。
1/Tg=[(W1/Tg1)+(W2/Tg2)+・・・・(Wn/Tgn)]/100 [I]
ただし、
W1:単量体1の重量%、Tg1:単量体1のみから形成され得るホモポリマーのガラス転移温度(°K)、
W2:単量体2の重量%、Tg2:単量体2のみから形成され得るホモポリマーのガラス転移温度(°K)、
Wn:単量体nの重量%、Tgn:単量体nのみから形成され得るホモポリマーのガラス転移温度(°K)、
(ここに、W1+W2+・・・・+Wn=100)
尚、エチレン性不飽和単量体を水性媒体中で重合する際に界面活性剤として、エチレン性不飽和基を有するものを使用する場合には、エチレン性不飽和単量体の構成の特定及び共重合体のTgの計算に際して、エチレン性不飽和基を有する界面活性剤は単量体には含めないものとする。
そして、本発明で用いた単量体のガラス転移温度は以下の数値を用いた。アクリル酸(106℃)、メタクリル酸(186℃)、メタクリル酸メチル(105℃)、アクリル酸メチル(8℃)、アクリル酸エチル(−22℃)、アクリル酸ブチル(−52℃)、アクリル酸2−エチルヘキシル(−70℃)、スチレン(100℃)、メタクリル酸2−ヒドロキシエチル(55℃)である。
The glass transition temperature (Tg) of the acrylic resin (A) in the present invention is theoretically derived from the following formula [I].
1 / Tg = [(W1 / Tg1) + (W2 / Tg2) +... (Wn / Tgn)] / 100 [I]
However,
W1: wt% of monomer 1, Tg1: glass transition temperature (° K) of a homopolymer that can be formed from monomer 1 alone,
W2: wt% of monomer 2, Tg2: glass transition temperature (° K) of homopolymer that can be formed from monomer 2 alone,
Wn:% by weight of monomer n, Tgn: glass transition temperature (° K) of a homopolymer that can be formed only from monomer n,
(W1 + W2 + ... + Wn = 100)
When using an ethylenically unsaturated monomer having an ethylenically unsaturated group as a surfactant when polymerizing the ethylenically unsaturated monomer in an aqueous medium, In calculating the Tg of the copolymer, a surfactant having an ethylenically unsaturated group is not included in the monomer.
And the following numerical value was used for the glass transition temperature of the monomer used by this invention. Acrylic acid (106 ° C), methacrylic acid (186 ° C), methyl methacrylate (105 ° C), methyl acrylate (8 ° C), ethyl acrylate (-22 ° C), butyl acrylate (-52 ° C), acrylic acid They are 2-ethylhexyl (-70 degreeC), styrene (100 degreeC), and 2-hydroxyethyl methacrylate (55 degreeC).
乳化重合に用いる界面活性剤としてはアニオン界面活性剤単独でも、ノニオン界面活性剤との併用でも良い。使用量は、全単量体100重量部に対し0.1〜10重量部であることが好ましく、0.5〜5重量部であることがより好ましい。10重量部を超えると高温高湿経時後の再剥離性が低下する傾向にある。また0.1重量部未満のときは、重合安定性が低下する恐れがある。 The surfactant used for the emulsion polymerization may be an anionic surfactant alone or in combination with a nonionic surfactant. The amount used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of all monomers. If it exceeds 10 parts by weight, the removability after high temperature and high humidity tends to decrease. On the other hand, when the amount is less than 0.1 part by weight, the polymerization stability may be lowered.
本発明では、非反応性界面活性剤、すなわちラジカル重合性の官能基を有さない非反応性界面活性剤を使用することが好ましい。反応性界面活性剤を用いると紙基材への投錨性が悪化し、再剥離性が低下する恐れがある。 In the present invention, it is preferable to use a non-reactive surfactant, that is, a non-reactive surfactant having no radically polymerizable functional group. When the reactive surfactant is used, the anchoring property to the paper base material is deteriorated and the removability may be lowered.
本発明において用いられる界面活性剤のうち、非反応性界面活性剤としては、ドデシルベンゼンスルホン酸塩、ラウリル硫酸塩、アルキルジフェニルエーテルスルホン酸塩、ジアルキルスルホコハク酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、ポリオキシエチレン多環フェニルエーテル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩等のアニオン系界面活性剤;
ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテルなどのポリオキシエチレンアルキルフェニルエーテル類;
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などのポリオキシエチレンアルキルエーテル類;
ポリオキシエチレンジスチレン化フェニルエーテルなどのポリオキシ多環フェニルエーテル類;
ポリオキシエチレンソルビタン脂肪酸エステル等のノニオン系界面活性剤などが挙げられる。
Among the surfactants used in the present invention, as the non-reactive surfactant, dodecylbenzene sulfonate, lauryl sulfate, alkyl diphenyl ether sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkyl phenyl ether sulfate, Anionic surfactants such as polyoxyethylene polycyclic phenyl ether sulfate and polyoxyethylene alkyl ether sulfate;
Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether;
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether;
Polyoxypolycyclic phenyl ethers such as polyoxyethylene distyrenated phenyl ether;
Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters are listed.
本発明で、アクリル系樹脂(A)の合成に用いる重合開始剤は、ラジカル重合開始剤が好ましい。ラジカル重合開始剤は、アゾ系化合物や過酸化物等を用いることができる。その中でも過酸化物が好ましいが、過酸化物と還元剤を組み合わせて用いること(以下、レドックス開始剤ともいう)が特に好ましい。レドックス開始剤を用いることで、アクリル系樹脂(A)は分岐が少なく、リニアな分子構造になると推測しているが、このリニアな分子構造により再剥離性と粗面への粘着性の両立をより高レベルで達成できると推測している。
前記過酸化物としては、例えば、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩、アゾビスイソブチロニトリル及びその塩酸塩、2,2−アゾビス(2−アミジノプロパン)二塩酸塩、4,4−アゾビス(4−シアノ吉草酸)等のアゾ系開始剤、過酸化水素、ターシャリーブチルハイドロパーオキサド等が挙げられる。
前記還元剤としては、ピロ亜硫酸ソーダ、L−アスコルビン酸等が挙げられる。
レドックス開始剤の組合せとしては、例えば、過酸化物とアスコルビン酸との組み合わせ(過酸化水素水とアスコルビン酸との組み合わせ等)、過酸化物と鉄(II)塩との組み合わせ(過酸化水素水と鉄(II)塩との組み合わせ等)、過硫酸塩と亜硫酸水素ナトリウムとの組み合わせ等が挙げられる。そして本発明では再剥離性の面から、過硫酸アンモニウムとピロ亜硫酸ソーダとの組み合わせが好ましい。
In the present invention, the polymerization initiator used for the synthesis of the acrylic resin (A) is preferably a radical polymerization initiator. As the radical polymerization initiator, an azo compound, a peroxide, or the like can be used. Among these, peroxides are preferable, but it is particularly preferable to use a combination of peroxides and reducing agents (hereinafter also referred to as redox initiators). By using a redox initiator, it is estimated that the acrylic resin (A) has few branches and a linear molecular structure, but this linear molecular structure provides both removability and adhesion to a rough surface. I guess it can be achieved at a higher level.
Examples of the peroxide include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, azobisisobutyronitrile and its hydrochloride, and 2,2-azobis (2-amidinopropane) dihydrochloride. Azo initiators such as 4,4-azobis (4-cyanovaleric acid), hydrogen peroxide, tertiary butyl hydroperoxide and the like.
Examples of the reducing agent include sodium pyrosulfite and L-ascorbic acid.
As combinations of redox initiators, for example, a combination of peroxide and ascorbic acid (a combination of hydrogen peroxide solution and ascorbic acid), a combination of peroxide and iron (II) salt (hydrogen peroxide solution) And a combination of persulfate and sodium bisulfite, and the like. In the present invention, a combination of ammonium persulfate and sodium pyrosulfite is preferable from the viewpoint of removability.
重合開始剤の使用量は、全単量体の合計100重量部に対し0.3〜1重量部が好ましく、0.4〜0.8重量部がより好ましい。すなわち、1重量部より多いと高温高湿経時後の再剥離性が不足する恐れがある。また0.3重量部未満であると重合安定性が低下する恐れがある。 The amount of the polymerization initiator used is preferably 0.3 to 1 part by weight, more preferably 0.4 to 0.8 part by weight, based on 100 parts by weight of all monomers. That is, when the amount is more than 1 part by weight, the re-peelability after aging at high temperature and high humidity may be insufficient. Moreover, there exists a possibility that superposition | polymerization stability may fall that it is less than 0.3 weight part.
本発明では、乳化重合時の反応温度は80℃以下が好ましく、70℃以下がより好ましい。80℃を越えるとアクリル系樹脂(A)が分岐しやすく、再剥離性が低下する恐れがある。また反応温度は常温以上で行うことが好ましい。 In the present invention, the reaction temperature during emulsion polymerization is preferably 80 ° C. or lower, more preferably 70 ° C. or lower. If it exceeds 80 ° C., the acrylic resin (A) tends to branch and the removability may be reduced. Moreover, it is preferable to perform reaction temperature at normal temperature or more.
本発明において、アクリル系樹脂(A)の分子量の調節のため、連鎖移動剤を使用してもよい。
連鎖移動剤としては、例えば、チオール基や水酸基を有する化合物が一般に知られている。チオール基を有する化合物としては、例えば、ラウリルメルカプタン、2−メルカプトエチルアルコール、ドデシルメルカプタン、メルカプトコハク酸等のメルカプタン類や、メルカプトプロピオン酸n−ブチルやメルカプトプロピオン酸オクチル等のメルカプトプロピオン酸アルキルや、メルカプトプロピオン酸メトキシブチル等のメルカプトプロピオン酸アルコキシアルキルが挙げられる。また、メチルアルコール、n−プロピルアルコール、イソプロピルアルコール(IPA)、t−ブチルアルコール、ベンジルアルコール等のアルコール類があげられる。これらの中でも粘着剤の臭気及び凝集物の点から、イソプロピルアルコール等のアルコール類を使用することが好ましい。
In the present invention, a chain transfer agent may be used for adjusting the molecular weight of the acrylic resin (A).
As the chain transfer agent, for example, a compound having a thiol group or a hydroxyl group is generally known. Examples of the compound having a thiol group include mercaptans such as lauryl mercaptan, 2-mercaptoethyl alcohol, dodecyl mercaptan, mercaptosuccinic acid, and alkyl mercaptopropionates such as n-butyl mercaptopropionate and octyl mercaptopropionate, Examples include mercaptopropionate alkoxyalkyl such as methoxybutyl mercaptopropionate. Moreover, alcohols, such as methyl alcohol, n-propyl alcohol, isopropyl alcohol (IPA), t-butyl alcohol, benzyl alcohol, are mention | raise | lifted. Among these, it is preferable to use alcohols such as isopropyl alcohol from the viewpoint of the odor of the adhesive and the aggregates.
連鎖移動剤の使用量は、全単量体100重量部に対し0.01〜0.1重量部が好ましく、0.03〜0.07重量部がより好ましい。即ち、0.1重量部を超えると高温高湿経時後の再剥離性が低下する恐れがある。また0.01重量部未満のときは期待した効果が得られない恐れがある。 The amount of the chain transfer agent used is preferably from 0.01 to 0.1 parts by weight, more preferably from 0.03 to 0.07 parts by weight, based on 100 parts by weight of the total monomers. That is, if it exceeds 0.1 parts by weight, the removability after aging at high temperature and high humidity may be reduced. When the amount is less than 0.01 parts by weight, the expected effect may not be obtained.
本発明において使用される水性媒体としては、水が挙げられ、本発明の目的や効果を損なわない範囲で親水性の有機溶剤も必要に応じて使用することができる。 Examples of the aqueous medium used in the present invention include water, and a hydrophilic organic solvent can also be used as needed within a range that does not impair the objects and effects of the present invention.
得られたアクリル系樹脂(A)は、塩基化合物で中和して使用することが好ましい。塩基化合物としては、アンモニアや、アミン類として、モノエチルアミン、ジメチルエタノールアミン、メチルプロパノールアミンなどが使用される。これらは単独でも、2種以上を組み合わせて使用してもよい。 The obtained acrylic resin (A) is preferably used after being neutralized with a base compound. As the basic compound, ammonia, and as the amines, monoethylamine, dimethylethanolamine, methylpropanolamine and the like are used. These may be used alone or in combination of two or more.
本発明において、アクリル系樹脂(A)の平均粒子径は、150〜1000nm以上が好ましく、200〜800nmがより好ましい。平均粒子径が150nm未満では、エマルジョンの粘度が高くなりすぎ、粘着剤の塗工性が低下し良好な粘着テープが得られないおそれがある。一方、800nmを超えると、粘着剤の耐水性が低下し、また被着体に対する粘着力が低下するおそれがある。なお、この平均粒子径は、動的光散乱法(Microtrac社製 Nanotrac NPA150)を用いて求めた。 In this invention, 150-1000 nm or more is preferable and, as for the average particle diameter of acrylic resin (A), 200-800 nm is more preferable. If the average particle size is less than 150 nm, the viscosity of the emulsion becomes too high, and the applicability of the pressure-sensitive adhesive is lowered, and a good pressure-sensitive adhesive tape may not be obtained. On the other hand, when it exceeds 800 nm, the water resistance of the pressure-sensitive adhesive is lowered, and the adhesive strength to the adherend may be lowered. In addition, this average particle diameter was calculated | required using the dynamic light scattering method (Microtrac NPA150 NPA150).
本発明では、アクリル系樹脂(A)から形成してなる乾燥皮膜のテトラヒドロフラン可溶分のゲルパーミーエーションクロマトグラムの最大値を示す重量平均分子量が、20万〜60万であることが好ましく、25万〜45万であることがより好ましい。25万未満では高温高湿経時後の再剥離後に糊残りが発生する恐れがある。他方、60万を超えると紙基材への投錨性及び各被着体への粘着性が不十分となり易い。 In this invention, it is preferable that the weight average molecular weight which shows the maximum value of the gel permeation chromatogram of the tetrahydrofuran soluble part of the dry film formed from acrylic resin (A) is 200,000-600,000, 25 More preferably, it is 10,000 to 450,000. If it is less than 250,000, adhesive residue may occur after re-peeling after aging at high temperature and high humidity. On the other hand, when it exceeds 600,000, the anchoring property to the paper substrate and the adhesiveness to each adherend are likely to be insufficient.
本発明における分子量測定方法は以下の通りである。
すなわち、アクリル系樹脂(A)をポリエチレンテレフタレート(PET)フィルムに乾燥膜厚が約20g/m2となるように塗工し、25℃で24時間乾燥して得られた乾燥皮膜を、テトラヒドロフラン中に25℃で1日間浸漬する。その後、THFをフィルターで濾過後、GPC測定を行う。
なお、GPCの測定条件は以下のとおりである。
装置:Shodex GPC System−21〔昭和電工(株)製〕
カラム:Shodex KF−602.5を1本、Shodex KF−606Mを2本〔昭和電工(株)製〕の合計3本を連結して使用。
溶媒:テトラヒドロフラン
流速:0.5ml/min
温度:40℃
試料濃度:0.1wt%
試料注入量:50μl
The molecular weight measurement method in the present invention is as follows.
That is, the acrylic resin (A) was applied to a polyethylene terephthalate (PET) film so that the dry film thickness was about 20 g / m 2 and dried at 25 ° C. for 24 hours. Soak at 25 ° C. for 1 day. Then, after filtering THF with a filter, GPC measurement is performed.
The measurement conditions for GPC are as follows.
Apparatus: Shodex GPC System-21 [manufactured by Showa Denko KK]
Column: A total of three Shodex KF-602.5 and two Shodex KF-606M (manufactured by Showa Denko KK) are connected and used.
Solvent: Tetrahydrofuran Flow rate: 0.5 ml / min
Temperature: 40 ° C
Sample concentration: 0.1 wt%
Sample injection volume: 50 μl
本発明において、水系再剥離型粘着剤から形成した乾燥皮膜の酢酸エチル抽出残分が45〜75重量%であることが好ましい。45重量%未満では、高温高湿経時後における再剥離性が劣る恐れがある。他方、75重量%を超えると、紙基材への投錨性や各被着体への粘着性が不十分になる恐れがある。 In this invention, it is preferable that the ethyl acetate extraction residue of the dry film formed from the water-system re-peelable pressure-sensitive adhesive is 45 to 75% by weight. If it is less than 45% by weight, the removability after aging at high temperature and high humidity may be inferior. On the other hand, when it exceeds 75% by weight, the anchoring property to the paper substrate and the adhesiveness to each adherend may be insufficient.
本発明における酢酸エチル抽出残分の測定方法は以下の通りである。
すなわち、水系再剥離型粘着剤をポリエチレンテレフタレート(PET)フィルムに乾燥膜厚が約200μmとなるように塗工後、25℃で24時間乾燥させる。その粘着シートを5cm×5cmの大きさに切断し、その試験片に積層されている粘着剤層の重量を測定する(その重量をG1とする)。その試験片を50mlの酢酸エチルに23℃で1日放置する。続いて、試験片及びトルエン溶液を濾布で濾過した残渣を105℃で1時間乾燥させ、試験片に積層された粘着剤層の乾燥後の重量、及び溶液を濾過した残渣の乾燥後の重量を測定する(その合算重量をG2とする)。その後、(G2/G1)×100により算出する。
The method for measuring the ethyl acetate extraction residue in the present invention is as follows.
That is, the aqueous re-peelable pressure-sensitive adhesive is applied to a polyethylene terephthalate (PET) film so that the dry film thickness is about 200 μm, and then dried at 25 ° C. for 24 hours. The pressure-sensitive adhesive sheet is cut into a size of 5 cm × 5 cm, and the weight of the pressure-sensitive adhesive layer laminated on the test piece is measured (the weight is defined as G1). The specimen is left in 50 ml of ethyl acetate at 23 ° C. for 1 day. Subsequently, the residue obtained by filtering the test piece and the toluene solution with a filter cloth was dried at 105 ° C. for 1 hour, the weight after drying of the pressure-sensitive adhesive layer laminated on the test piece, and the weight after drying of the residue obtained by filtering the solution. Is measured (the combined weight is G2). Then, it is calculated by (G2 / G1) × 100.
また本発明の水性再剥離粘着剤は、粘着付与樹脂を含まないことが重要である。粘着付与樹脂を含むことで、粘着力と再剥離性を両立することが困難になるからである。 It is important that the aqueous re-peeling adhesive of the present invention does not contain a tackifying resin. It is because it becomes difficult to make adhesive force and removability compatible by including tackifying resin.
次に、本発明で用いる硬化剤(B)としては、カルボキシル基と架橋するものであれば特に限定されず、例えば、オキサゾリン系化合物、カルボジイミド系化合物、エポキシ系化合物、アジリジン系化合物、イソシアネート系化合物、メラミン系化合物、金属錯体等の金属系化合物、アミン系化合物等が挙げられるが、中でも特にエポキシ系化合物は特に高温高湿経時後の再剥離性に優れるため好ましい。
硬化剤の添加量としては、水系再剥離型粘着剤から形成した乾燥皮膜の酢酸エチル抽出残分が45〜75重量%になるような量が好ましい。
Next, the curing agent (B) used in the present invention is not particularly limited as long as it crosslinks with a carboxyl group. For example, an oxazoline compound, a carbodiimide compound, an epoxy compound, an aziridine compound, an isocyanate compound , Melamine compounds, metal compounds such as metal complexes, amine compounds, and the like. Among them, epoxy compounds are particularly preferable because they are particularly excellent in removability after aging at high temperature and high humidity.
The addition amount of the curing agent is preferably such that the ethyl acetate extraction residue of the dry film formed from the aqueous re-peelable pressure-sensitive adhesive is 45 to 75% by weight.
オキサゾリン系化合物としては、例えば、2位の炭素位置に不飽和炭素−炭素結合をもつ置換基を有する付加重合性2−オキサゾリン(例えば2−イソプロペニル−2−オキサゾリン)と他の不飽和単量体との共重合体等が挙げられる。 Examples of the oxazoline compound include addition-polymerizable 2-oxazoline (for example, 2-isopropenyl-2-oxazoline) having a substituent having an unsaturated carbon-carbon bond at the 2-position carbon position and other unsaturated monomer. And a copolymer with the body.
カルボジイミド系化合物としては、カルボジイミド基を少なくとも2個以上含有するもが挙げられる。 Examples of the carbodiimide compound include those containing at least two carbodiimide groups.
エポキシ系化合物としては、例えば、ビスフェノールA・エピクロルヒドリン型のエポキシ樹脂、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、レソーシノールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、ヒドロジェネイティッドビスフェノールAジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン、N,N,N’,N’−テトラグリシジルm−キシレンジアミン、1,3−ビス(N,N’−ジグリシジルアミノメチル)シクロヘキサン等が挙げられる。 Examples of the epoxy compound include bisphenol A / epichlorohydrin type epoxy resin, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl. Ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol di Glycidyl ether, propylene glycol diglyme Dil ether, polypropylene glycol diglycidyl ether, diglycidyl aniline, diglycidyl amine, N, N, N ′, N′-tetraglycidyl m-xylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) And cyclohexane.
本発明の水系再剥離型粘着剤は、ポリオール(C)を含むことも好ましい。これにより基材への投錨性が向上し、再剥離性も向上するため好ましい。
ポリオール(C)は、多価アルコール類から選ばれた少なくとも1種以上を使用することができる。特に、多価アルコール類のうち、常温で液状である多価のアルコール類、ポリオキシアルキレン類、及びポリオキシアルキレンのグリコールエーテル類、アルキルアミンのポリオキシアルキレン付加物等を使用することが好ましい。具体的には、エチレングリコール、数平均分子量が2000以下のポリアルキレングリコール、グリセリン、ポリグリセリン(例えばジグリセリン、ヘキサグリセリン、ヘキサグセリン、デカグリセリン)、グリセリンエチレンオキサイド付加物、グリセリンプロピレンオキサイド付加物、トリメチロールプロパンプロピレンオキサイド付加物、ソルビトールプロピレンオキサイド付加物、エチレンジアミンプロピレンオキサイド付加物、エチレンオキサイド/プロピレンオキサイド/エチレンオキサイドブロック体、アルキルアミンエチレンオキサイド付加物等が挙げられ、これらの群より選ばれた少なくとも1種以上使用することができる。より好ましくは、エチレングリコール、数平均分子量が2000以下のポリエチレングリコール、グリセリン、ポリグリセリンである。
The aqueous re-peelable pressure-sensitive adhesive of the present invention preferably contains a polyol (C). This is preferable because the anchoring property to the base material is improved and the removability is improved.
As the polyol (C), at least one selected from polyhydric alcohols can be used. In particular, among polyhydric alcohols, polyhydric alcohols that are liquid at normal temperature, polyoxyalkylenes, glycol ethers of polyoxyalkylenes, polyoxyalkylene adducts of alkylamines, and the like are preferably used. Specifically, ethylene glycol, polyalkylene glycol having a number average molecular weight of 2000 or less, glycerin, polyglycerin (for example, diglycerin, hexaglycerin, hexaglycerin, decaglycerin), glycerin ethylene oxide adduct, glycerin propylene oxide adduct, tri Examples include methylolpropane propylene oxide adduct, sorbitol propylene oxide adduct, ethylenediamine propylene oxide adduct, ethylene oxide / propylene oxide / ethylene oxide block, alkylamine ethylene oxide adduct, etc., and at least one selected from these groups More than seeds can be used. More preferred are ethylene glycol, polyethylene glycol having a number average molecular weight of 2000 or less, glycerin, and polyglycerin.
ポリオール(C)の使用量は、アクリル樹脂(A)100重量部に対して0.2〜10重量部が好ましい。使用量が0.2重量部より少ない場合は、使用した効果が得られず、10重量部を超える場合は、凝集力の低下により再剥離性が低下する恐れがある。 The amount of the polyol (C) used is preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the acrylic resin (A). When the amount used is less than 0.2 parts by weight, the used effect cannot be obtained, and when it exceeds 10 parts by weight, the removability may be lowered due to a decrease in cohesive force.
本発明の水系再剥離型粘着剤には、必要に応じて、一般の水性粘着剤種々の添加剤、例えば消泡剤、湿潤剤、着色顔料、増粘剤、可塑剤、酸化防止剤、紫外線吸収剤、防腐剤などを配合することができる。 The water-based re-peelable pressure-sensitive adhesive of the present invention includes various additives such as a general aqueous pressure-sensitive adhesive, such as an antifoaming agent, a wetting agent, a coloring pigment, a thickening agent, a plasticizer, an antioxidant, and an ultraviolet ray as necessary. Absorbers, preservatives and the like can be blended.
本発明の粘着テープついて説明する。本発明の粘着テープは上記水系再剥離型粘着剤からから形成してなる粘着剤層を含むものである。なお、本発明において、粘着テープは粘着シートともいい、これらを切り分けたものを粘着ラベルともいう。
粘着テープは、水系再剥離型粘着剤を剥離シートへ塗工し、乾燥した後に、基材と貼り合わせる転写塗工法、先に基材へ粘着剤を直接塗工し、乾燥後に剥離シートと貼り合わせる直接塗工法等により製造することができる。
The adhesive tape of the present invention will be described. The pressure-sensitive adhesive tape of the present invention includes a pressure-sensitive adhesive layer formed from the aqueous re-peelable pressure-sensitive adhesive. In the present invention, the pressure-sensitive adhesive tape is also referred to as a pressure-sensitive adhesive sheet, and a product obtained by separating these is also referred to as a pressure-sensitive adhesive label.
The adhesive tape is a transfer coating method in which a water-based re-peelable adhesive is applied to a release sheet, dried, and then bonded to the base material, and the adhesive is directly applied to the base material first, and then dried and attached to the release sheet. It can be manufactured by a direct coating method or the like.
基材は、紙、合成紙、プラスチックフィルム等を用いることが好ましく、いわゆるアンカー処理がされていても良い。また剥離シートは、紙やプラスチックフィルム等にシリコーン等の剥離処理を施したものを用いることが好ましい。 The substrate is preferably paper, synthetic paper, plastic film or the like, and may be subjected to so-called anchor treatment. Further, it is preferable to use a release sheet obtained by subjecting paper or a plastic film to a release treatment such as silicone.
水性粘着剤組成物の塗工方法としては特に制限されるものではなく、コンマコーター、ブレードコーター、グラビアコーター等のロールコーター、スロットダイコーター、リップコーター、カーテンコーター等の従来公知のコーティング装置を用いることができる。 The method for applying the aqueous pressure-sensitive adhesive composition is not particularly limited, and a conventionally known coating apparatus such as a roll coater such as a comma coater, a blade coater, or a gravure coater, a slot die coater, a lip coater, or a curtain coater is used. be able to.
粘着テープの粘着剤層の厚みは、0.1〜200μmが好ましく、1〜100μmがより好ましい。上記数値範囲外になると粘着力と再剥離性を両立できない恐れがある。 0.1-200 micrometers is preferable and, as for the thickness of the adhesive layer of an adhesive tape, 1-100 micrometers is more preferable. If it is out of the above numerical range, there is a possibility that both adhesive strength and removability cannot be achieved.
以下、実施例、比較例を挙げて本発明を詳細に説明するが、本発明は以下の実施例のみ
に限定されるものではない。なお、以下の「部」及び「%」は、それぞれ重量部及び「重量%」に基づく値である。
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited only to a following example. The following “parts” and “%” are values based on parts by weight and “% by weight”, respectively.
[実施例1]
還流冷却器、攪拌機、温度計、窒素導入管、原料投入口を具備する容積2Lの4つ口フ
ラスコに、イオン交換水23.4部を入れ、窒素を導入しつつ攪拌しながら、内温を70℃に加温した。単量体として、2−エチルヘキシルアクリレート(以後、「2−EHA」と略す)33部、ブチルアクリレート(以後、「BA」と略す)66部、アクリル酸(以後、「AA」と略す)1部、界面活性剤としてペレックスOT−P〔花王(株)製のアニオン型非反応性界面活性剤〕2.0部、イオン交換水20.8部の混合物をホモミキサーで乳化し、単量体エマルジョンを作製した。
上記の反応容器中に、得られた単量体エマルジョンのうち5%を添加し、同時に5%過硫酸アンモニウム(以後、「APS」と略す)水溶液0.4部及び2%ピロ亜硫酸ナトリウム(以後、「SMBS」と略す)水溶液0.5部を添加して乳化重合を開始した。
反応容器に5%APS水溶液及び2%SMBS水溶液を添加してから3分後に、上記単
量体エマルジョン及び5%APS水溶液3.6部及び2%SMBS水溶液4.5部を同時
に5時間かけて滴下した。この間反応容器内は好ましい温度の上限値70℃に保った。
滴下終了後、3時間70℃に保ち、熟成を行った。その後冷却を開始し、30℃まで冷
却し、アンモニア水を添加し中和することで、不揮発分濃度55.0%、pH7.0、粘度250mPa・sのアクリル樹脂エマルジョンを得た。
尚、単量体から求められるガラス転移温度(以下、「理論Tg」という)は−57℃であった。ポリマーのテトラヒドロフラン可溶分のゲルパーミーエーションクロマトグラムの最大値を示す重量平均分子量は41万であった。
[Example 1]
Put 23.4 parts of ion-exchanged water into a 2 L four-necked flask equipped with a reflux condenser, stirrer, thermometer, nitrogen inlet tube, and raw material inlet, and maintain the internal temperature while stirring while introducing nitrogen. Warmed to 70 ° C. As monomers, 33 parts of 2-ethylhexyl acrylate (hereinafter abbreviated as “2-EHA”), 66 parts of butyl acrylate (hereinafter abbreviated as “BA”), 1 part of acrylic acid (hereinafter abbreviated as “AA”) A mixture of 2.0 parts of PELEX OT-P (an anionic non-reactive surfactant manufactured by Kao Corporation) and 20.8 parts of ion-exchanged water as a surfactant was emulsified with a homomixer, and a monomer emulsion Was made.
In the above reaction vessel, 5% of the obtained monomer emulsion was added, and at the same time, 0.4 part of 5% aqueous solution of ammonium persulfate (hereinafter abbreviated as “APS”) and 2% sodium pyrosulfite (hereinafter referred to as “polysulfite”). Emulsion polymerization was started by adding 0.5 part of an aqueous solution (abbreviated as “SMBS”).
Three minutes after adding 5% APS aqueous solution and 2% SMBS aqueous solution to the reaction vessel, the monomer emulsion, 3.6 parts of 5% APS aqueous solution and 4.5 parts of 2% SMBS aqueous solution were simultaneously added over 5 hours. It was dripped. During this period, the inside of the reaction vessel was kept at a preferable upper limit of 70 ° C.
After completion of the dropwise addition, the mixture was kept at 70 ° C. for 3 hours and aged. Thereafter, cooling was started, and the mixture was cooled to 30 ° C. and neutralized by adding aqueous ammonia to obtain an acrylic resin emulsion having a nonvolatile content concentration of 55.0%, pH 7.0, and a viscosity of 250 mPa · s.
In addition, the glass transition temperature calculated | required from a monomer (henceforth "theoretical Tg") was -57 degreeC. The weight average molecular weight which shows the maximum value of the gel permeation chromatogram of the tetrahydrofuran soluble part of a polymer was 410,000.
得られたアクリル樹脂エマルジョン100部に対し、不揮発分換算にて、防腐剤:0.03部、濡れ剤:0.5部、消泡剤1.0部、ポリオールとしてプロピレングリコール1.8部を用いて、ホモミキサーにて増粘剤で粘度が3000mPa・s(BL型粘度計、25℃で#4ロータ/60rpmにて測定)になるように調製した組成物を得た。
さらに、当該組成物中のアクリル樹脂分の100重量部に対して、エポキシ系架橋剤(ナガセケムテックス株式会社製、商品名「デナコールEX−614B」)を0.5重量部添加し、水系再剥離型粘着剤を得た。
Preservative: 0.03 part, wetting agent: 0.5 part, antifoaming agent 1.0 part, and propylene glycol 1.8 parts as polyol with respect to 100 parts of the obtained acrylic resin emulsion. A composition prepared using a thickener with a homomixer so as to have a viscosity of 3000 mPa · s (BL type viscometer, measured at 25 ° C. with # 4 rotor / 60 rpm) was obtained.
Furthermore, 0.5 parts by weight of an epoxy crosslinking agent (manufactured by Nagase ChemteX Corp., trade name “Denacol EX-614B”) is added to 100 parts by weight of the acrylic resin content in the composition. A peelable adhesive was obtained.
[実施例2]
2EHAとBAの使用量を、2EHA49.5部、BA49.5部へ変更したこと以外は実施例1と同様に行い、水系再剥離型粘着剤を得た。
[Example 2]
An aqueous re-peelable pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the amounts of 2EHA and BA used were changed to 2EHA 49.5 parts and BA 49.5 parts.
[実施例3]
2EHAとBAの使用量を、2EHA33.0部、BA66.0部へ変更したこと以外は実施例1と同様に行い、水系再剥離型粘着剤を得た。
[Example 3]
A water-based re-peelable pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the amounts of 2EHA and BA used were changed to 2EHA 33.0 parts and BA 66.0 parts.
[実施例4]
プロピレングリコールを5.4部に増量した以外は実施例1と同様に行い、水系再剥離型粘着剤を得た。
[Example 4]
An aqueous re-peelable pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that propylene glycol was increased to 5.4 parts.
[実施例5]
プロピレングリコールを9.0部に増量した以外は実施例1と同様に行い、水系再剥離型粘着剤を得た。
[Example 5]
An aqueous re-peelable pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that propylene glycol was increased to 9.0 parts.
[実施例6]
プロピレングリコールをジプロピレングリコールに変更した以外は実施例1と同様に行い、水系再剥離型粘着剤を得た。
[Example 6]
An aqueous re-peelable pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that propylene glycol was changed to dipropylene glycol.
[実施例7]
プロピレングリコールをエチレングリコールに変更した以外は実施例1と同様に行い、水系再剥離型粘着剤を得た。
[Example 7]
An aqueous re-peelable pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that propylene glycol was changed to ethylene glycol.
[比較例1]
2EHAとBAの使用量を、2EHA15.0部、BA84.0部に変更したこと以外は実施例1と同様に行い、粘着剤を得た。
[Comparative Example 1]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the amounts of 2EHA and BA were changed to 2EHA 15.0 parts and BA 84.0 parts.
[比較例2]
2EHAとBAの使用量を、2EHA84.0部、BA15.0部に変更したこと以外は実施例1と同様に行い、粘着剤を得た。
[Comparative Example 2]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the amounts of 2EHA and BA used were changed to 2EHA 84.0 parts and BA 15.0 parts.
[比較例3]
重合開始剤を5%APS水溶液6.0gへ変更し、反応容器に一括添加し、反応温度を80℃に維持して反応したこと以外は実施例1と同様に行い、粘着剤を得た。
[Comparative Example 3]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the polymerization initiator was changed to 6.0 g of 5% APS aqueous solution, added to the reaction vessel at once, and the reaction was carried out while maintaining the reaction temperature at 80 ° C.
[比較例4]
合成中に連鎖移動剤としてイソプロピルアルコールを3部添加して合成したこと以外は実施例1と同様に行い、粘着剤を得た。
[Comparative Example 4]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 3 parts of isopropyl alcohol was added as a chain transfer agent during synthesis.
[比較例5]
界面活性剤を、反応性界面活性剤アクアロンKH−10(第一工業製薬製)に変更した以外は実施例1と同様に行い、粘着剤を得た。
[Comparative Example 5]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the surfactant was changed to the reactive surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku).
実施例および比較例で得られた粘着剤をアプリケーターで剥離シート上に乾燥膜厚20μmとなるように塗工し、100℃の乾燥オーブンで3分間乾燥させ、粘着剤層を形成した。次いで、剥離シート上に設けられた粘着剤層に、上質紙を貼り合わせ、粘着テープを作成した。 The pressure-sensitive adhesives obtained in Examples and Comparative Examples were applied on a release sheet with an applicator so as to have a dry film thickness of 20 μm, and dried in a drying oven at 100 ° C. for 3 minutes to form a pressure-sensitive adhesive layer. Subsequently, a quality paper was bonded to the pressure-sensitive adhesive layer provided on the release sheet to prepare a pressure-sensitive adhesive tape.
[物性評価]
<応力−歪み曲線>
上記方法で試験サンプルを作成し評価した。
[Evaluation of the physical properties]
<Stress-strain curve>
Test samples were prepared and evaluated by the above method.
<永久粘着力>
得られた粘着テープを23℃、50%RH環境下で、25mm×100mmにカットし試験片を作成した。試験片をSUS板(SUS304)、ダンボール(Kライナー 王子板紙社製)に対してそれぞれ貼付して試験サンプルとした。その試験サンプルをJIS Z0237に基づき、貼付24時間後の粘着力を180°引き剥がし法による引張り速度300mm/分にて測定した。
<Permanent adhesive strength>
The obtained adhesive tape was cut into 25 mm × 100 mm in an environment of 23 ° C. and 50% RH to prepare a test piece. The test pieces were attached to a SUS board (SUS304) and cardboard (K liner manufactured by Oji Paperboard Co., Ltd.) to obtain test samples. Based on JIS Z0237, the test sample was measured for adhesive strength 24 hours after application at a pulling speed of 300 mm / min by a 180 ° peeling method.
<熱湿経時後粘着力>
得られた粘着テープを23℃、50%RH環境下で、25mm×100mmにカットし試験片を作成した。試験片をステンレス板(SUS304)、ダンボール(Kライナー)に対してそれぞれ貼付して試験サンプルとした。その試験サンプルを23℃、50%RH環境下で1日間静置後、40℃、80%RH環境下で7日間静置したのちに23℃、50%RH環境下へと戻し、2時間静置後した。その試験サンプルをJIS Z0237に基づき、180°引き剥がし法による引張り速度300mm/分での粘着力を測定した。
<Adhesive strength after heat and humidity>
The obtained adhesive tape was cut into 25 mm × 100 mm in an environment of 23 ° C. and 50% RH to prepare a test piece. Test specimens were attached to a stainless steel plate (SUS304) and cardboard (K liner), respectively, to obtain test samples. The test sample was allowed to stand in a 23 ° C., 50% RH environment for 1 day, then left in a 40 ° C., 80% RH environment for 7 days, then returned to a 23 ° C., 50% RH environment, and allowed to stand for 2 hours. After that. The test sample was measured for adhesive strength at a pulling speed of 300 mm / min by 180 ° peeling method based on JIS Z0237.
<曲面貼付性>
得られた粘着テープを23℃、50%RH環境下で、25mm×100mmにカットし試験片を作成した。試験片を直径80mmφのボール紙の紙管に貼付した。そして23℃、50%RH環境下で3日間静置後、40℃、80%RH環境下で3日間放置したのちに23℃、50%RH環境下へと戻し、2時間静置後の試験片を剥がし、その状態を評価した。
○:剥がれ長さが3mm未満
△:剥がれ長さが3〜10mm
×:剥がれ長さが10mmより大きい
<Curved surface paste>
The obtained adhesive tape was cut into 25 mm × 100 mm in an environment of 23 ° C. and 50% RH to prepare a test piece. The test piece was attached to a paper tube of cardboard having a diameter of 80 mmφ. Then, after standing for 3 days in an environment of 23 ° C. and 50% RH, leaving it for 3 days in an environment of 40 ° C. and 80% RH, returning to an environment of 23 ° C. and 50% RH, and then allowing to stand for 2 hours The piece was peeled off and the state was evaluated.
○: Peeling length is less than 3 mm Δ: Peeling length is 3 to 10 mm
X: Peeling length is larger than 10 mm
<再剥離性>
上記曲面貼付性試験の評価後、試験片を手で剥がし、剥離状態を観察した。
○:被着体に粘着剤が残らない。
×CL:被着体に汚染または曇りがある
×PF:基材が破断する。
×CF:粘着剤層の凝集破壊がある。
以上の評価結果を表に示す。
<Removability>
After the evaluation of the curved surface sticking property test, the test piece was peeled off by hand, and the peeled state was observed.
○: No adhesive remains on the adherend.
* CL: The adherend is contaminated or clouded. * PF: The substrate is broken.
XCF: There is cohesive failure of the pressure-sensitive adhesive layer.
The above evaluation results are shown in the table.
表1において、界面活性剤および重合開始剤の使用量は、全単量体100重量部に対する使用量である。またポリオールおよび硬化剤の使用量は、アクリル系樹脂100重量部に対する使用量である In Table 1, the usage amount of the surfactant and the polymerization initiator is the usage amount based on 100 parts by weight of the total monomers. Moreover, the usage-amount of a polyol and a hardening | curing agent is a usage-amount with respect to 100 weight part of acrylic resins.
表1の結果から、比較例は、応力−歪み曲線が所定の数値範囲外であったため、粘着性と再剥離性を両立できなかった。
一方、実施例は、応力−歪み曲線が所定の数値範囲であったため、粗面への粘着性と高温高湿経時後の再剥離性を両立することができた。
From the result of Table 1, since the stress-strain curve was outside the predetermined numerical range, the comparative example could not achieve both adhesiveness and removability.
On the other hand, in the examples, the stress-strain curve was in a predetermined numerical range, and therefore, the adhesiveness to the rough surface and the re-peelability after aging at high temperature and high humidity were compatible.
Claims (5)
前記水系再剥離型粘着剤から形成した断面積4mm2の乾燥皮膜の、応力−歪み曲線における200%歪み時の応力値が0.01〜0.03N/mm2であり、
最大応力時の歪みが800〜1300%であり、最大応力値が0.04〜0.08N/mm2 であることを特徴とする水系再剥離型粘着剤。 An aqueous re-peelable pressure-sensitive adhesive containing an acrylic resin (A) and a curing agent (B),
The stress value at the time of 200% strain in the stress-strain curve of the dry film having a cross-sectional area of 4 mm 2 formed from the aqueous re-peelable pressure-sensitive adhesive is 0.01 to 0.03 N / mm 2 ,
A water-based re-peelable pressure-sensitive adhesive having a strain at a maximum stress of 800 to 1300% and a maximum stress value of 0.04 to 0.08 N / mm 2 .
硬化剤(B)がエポキシ化合物であり、さらに、ポリオール(C)を含むことを特徴とする請求項1記載の水性再剥離型粘着剤。 A non-reactive surfactant is a monomer mixture in which the acrylic resin (A) contains a total of 90.0 to 99.9% by weight of at least 2-ethylhexyl acrylate (A-1) and butyl acrylate (A-2). In the presence of a polymerization initiator using a peroxide and a reducing agent, and the weight ratio of (A-1) / (A-2) is 55/45 to 25/75. Yes,
The aqueous re-peelable pressure-sensitive adhesive according to claim 1, wherein the curing agent (B) is an epoxy compound and further contains a polyol (C).
An adhesive tape comprising an adhesive layer formed from the aqueous re-peelable adhesive according to claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2010060050A JP2011190419A (en) | 2010-03-17 | 2010-03-17 | Water-based removable type adhesive and adhesive tape |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP2010060050A JP2011190419A (en) | 2010-03-17 | 2010-03-17 | Water-based removable type adhesive and adhesive tape |
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JP2011190419A true JP2011190419A (en) | 2011-09-29 |
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JP2010060050A Pending JP2011190419A (en) | 2010-03-17 | 2010-03-17 | Water-based removable type adhesive and adhesive tape |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013112716A (en) * | 2011-11-28 | 2013-06-10 | Nitto Denko Corp | Protective sheet and method of manufacturing the same |
WO2020096011A1 (en) * | 2018-11-09 | 2020-05-14 | 日立化成株式会社 | Temporary protective film for producing semiconductor device, reel body, and method for producing semiconductor device |
WO2023013489A1 (en) * | 2021-08-02 | 2023-02-09 | 三菱ケミカル株式会社 | Adhesive agent composition, adhesive agent and adhesive sheet |
-
2010
- 2010-03-17 JP JP2010060050A patent/JP2011190419A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013112716A (en) * | 2011-11-28 | 2013-06-10 | Nitto Denko Corp | Protective sheet and method of manufacturing the same |
WO2020096011A1 (en) * | 2018-11-09 | 2020-05-14 | 日立化成株式会社 | Temporary protective film for producing semiconductor device, reel body, and method for producing semiconductor device |
JPWO2020096011A1 (en) * | 2018-11-09 | 2021-10-07 | 昭和電工マテリアルズ株式会社 | Temporary protective film for manufacturing semiconductor devices, reels, and methods for manufacturing semiconductor devices |
JP7151782B2 (en) | 2018-11-09 | 2022-10-12 | 昭和電工マテリアルズ株式会社 | Temporary protective film for manufacturing semiconductor device, reel body, and method for manufacturing semiconductor device |
WO2023013489A1 (en) * | 2021-08-02 | 2023-02-09 | 三菱ケミカル株式会社 | Adhesive agent composition, adhesive agent and adhesive sheet |
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