JP5871452B2 - Adhesive for roll paper and roll paper - Google Patents
Adhesive for roll paper and roll paper Download PDFInfo
- Publication number
- JP5871452B2 JP5871452B2 JP2010078560A JP2010078560A JP5871452B2 JP 5871452 B2 JP5871452 B2 JP 5871452B2 JP 2010078560 A JP2010078560 A JP 2010078560A JP 2010078560 A JP2010078560 A JP 2010078560A JP 5871452 B2 JP5871452 B2 JP 5871452B2
- Authority
- JP
- Japan
- Prior art keywords
- paper
- adhesive
- roll
- weight
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000853 adhesive Substances 0.000 title claims description 117
- 230000001070 adhesive effect Effects 0.000 title claims description 114
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 35
- 150000001720 carbohydrates Chemical class 0.000 claims description 27
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 24
- 238000004804 winding Methods 0.000 claims description 21
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 19
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 17
- 239000008103 glucose Substances 0.000 claims description 17
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 16
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 7
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 7
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- 230000000052 comparative effect Effects 0.000 description 33
- 239000003795 chemical substances by application Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 26
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- 239000002518 antifoaming agent Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
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- 238000012360 testing method Methods 0.000 description 9
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- 239000000654 additive Substances 0.000 description 6
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- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- PNNNRSAQSRJVSB-SLPGGIOYSA-N Fucose Natural products C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C=O PNNNRSAQSRJVSB-SLPGGIOYSA-N 0.000 description 2
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/32—Water-activated adhesive, e.g. for gummed paper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2405/00—Presence of polysaccharides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2471/00—Presence of polyether
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sanitary Thin Papers (AREA)
Description
本発明は、トイレットペーパー及びキッチンタオル等のロール状ペーパー、ロール状ペーパーに塗布されるロール状ペーパー用接着剤、特にロール状ペーパーの巻き始めに塗布される接着剤（いわゆるピックアップ剤）に関する。 The present invention relates to roll paper such as toilet paper and kitchen towel, an adhesive for roll paper applied to the roll paper, particularly an adhesive (so-called pickup agent) applied to the beginning of winding of the roll paper.
ロール状ペーパーとは、例えば、キッチンペーパー、ペーパーウェス、ラッピングペーパー、トイレットペーパー及びペーパータオル等の紙がロール状に巻かれた紙製品をいい、有芯型と無芯型がある。有芯型のロール状ペーパーは、筒芯（紙管）に紙を緩く巻き付け、紙を所望の長さと外径を有するように巻き取ることにより製造されている。無芯型のロール状ペーパーは、細い巻芯（巻軸）に紙を緩く巻付け、次いで固く巻き付けて所望の長さと外径を有する製品とし、その後巻芯を抜いて製造されるか、有芯型の筒芯と同径の巻芯に紙を固く巻き付けて所望の長さと外径を有する製品とし、その後、巻芯を抜いて製造されている。 The roll paper refers to, for example, a paper product in which paper such as kitchen paper, paper waste, wrapping paper, toilet paper, and paper towel is wound into a roll shape, and includes a core type and a coreless type. The cored roll paper is manufactured by loosely winding paper around a cylindrical core (paper tube) and winding the paper to have a desired length and outer diameter. Uncore type roll paper is manufactured by winding the paper loosely around a thin core (winding shaft) and then winding it tightly to make a product with the desired length and outer diameter, and then removing the core or It is manufactured by winding paper tightly around a core having the same diameter as that of the core cylinder, to obtain a product having a desired length and outer diameter, and then removing the core.
ロール状ペーパーを製造する際、有芯型、無芯型を問わず、紙を巻き始める部分に、特殊な接着剤、いわゆるピックアップ剤が塗布され、芯（例えば、筒芯及び巻芯等であり、特に、紙管）とペーパーが接着される。 When manufacturing roll paper, regardless of whether it is a cored type or a coreless type, a special adhesive, so-called pickup agent, is applied to the part where the paper starts to be rolled, and a core (for example, a cylindrical core and a core) In particular, the paper tube) and the paper are bonded.
ピックアップ剤には、下記の性能が要求される：１）ピックアップ剤は芯に塗布された後、乾燥前の湿った状態で、芯と、ロール状に巻かれるペーパーを迅速に接着できること；及び、２）ピックアップ剤の乾燥後、接着されたペーパーを芯から簡単に剥離できること。従って、ピックアップ剤には、湿った状態での接着性（以下、「初期接着性」ともいう）及び乾燥後の剥離性（以下、単に「剥離性」ともいう）の双方に優れることが要求される。 The following performance is required for the pickup agent: 1) The pickup agent can be quickly bonded to the core and the paper wound in a roll shape in a wet state before drying after being applied to the core; and 2) After the pickup agent is dried, the adhered paper can be easily peeled off from the core. Accordingly, the pickup agent is required to be excellent in both adhesiveness in a wet state (hereinafter also referred to as “initial adhesiveness”) and peelability after drying (hereinafter also simply referred to as “peelability”). The
水、ポリビニルアルコール、エチルセルロース、ポリ酢酸ビニル、アクリル樹脂等を主成分とするピックアップ剤が公知である。しかし、これらのピックアップ剤は、初期接着性が高すぎるため、剥離性が不十分であるという問題がある。そこで、ピックアップ剤の剥離性を向上させることを目的として、ピックアップ剤に剥離調整剤を添加する方法が知られている（例えば、特許文献１及び特許文献２参照）。 A pickup agent mainly composed of water, polyvinyl alcohol, ethyl cellulose, polyvinyl acetate, acrylic resin or the like is known. However, these pick-up agents have a problem that the initial adhesiveness is too high and the peelability is insufficient. Therefore, a method of adding a release adjusting agent to the pickup agent is known for the purpose of improving the peelability of the pickup agent (see, for example, Patent Document 1 and Patent Document 2).
例えば、特許文献１は、でんぷん等の糖類を主成分とする糊に、剥離調整剤として脂肪酸エステルや脂肪酸アミドが添加されたピックアップ剤を開示する（特許文献１請求項１及び２、及び実施例等参照）。また、特許文献２は、剥離調整剤としてポリアルキレングリコールを用いることを開示する（特許文献２請求項１及び２、及び実施例参照）。 For example, Patent Document 1 discloses a pick-up agent in which a fatty acid ester or a fatty acid amide is added as a release adjusting agent to a paste such as starch as a main component (Patent Document 1, Claims 1 and 2 and Examples). Etc.). Moreover, patent document 2 discloses using polyalkylene glycol as a peeling regulator (refer patent document 2 claim 1 and 2 and an Example).
これらの特許文献１及び２に開示されたピックアップ剤は、剥離調整剤を含むので、剥離性に優れるため、芯からペーパーを容易に剥がすことができるが、初期接着性が不十分である。初期接着性に乏しいピックアップ剤をロール状ペーパーの巻き始めの箇所に塗布しても、湿った状態での接着力が低いため、芯とペーパーとを接着（即ち、ピックアップ）させることができないという問題がある。
ピックアップ剤の初期接着性と剥離性とのバランスをとるため、剥離調整剤の添加量を制御すると、ロール状ペーパーの塗工面がべたつき、剥離性が低下することがあった。
Since the pick-up agents disclosed in these Patent Documents 1 and 2 contain a release adjusting agent, they are excellent in releasability, so that the paper can be easily peeled off from the core, but the initial adhesiveness is insufficient. Even if a pickup agent with poor initial adhesiveness is applied to the beginning of the roll paper roll, the adhesive strength in the wet state is low, so the core and paper cannot be bonded (ie, picked up). There is.
In order to balance the initial adhesiveness and peelability of the pickup agent, when the amount of the release modifier added is controlled, the coated surface of the roll paper may become sticky and the peelability may be reduced.
本発明は、このような事情を鑑みなされたものであり、初期接着性が高く、塗工面をべたつかせることなく紙を容易に剥離させるロール状ペーパー用接着剤（特に、ピックアップ剤）、及びそのロール状ペーパー用接着剤が塗布されたロール状ペーパーを提供することを目的とする。 The present invention has been made in view of such circumstances, and has a high initial adhesiveness, and an adhesive for roll paper (especially a pick-up agent) that easily peels the paper without sticking the coated surface, and its It aims at providing the roll-shaped paper with which the adhesive agent for roll-shaped paper was apply | coated.
そこで、本研究者らは、鋭意研究を続けた結果、グルコースを含有する糖類に、特定の水性高分子及び特定の化合物を添加した接着剤は、「べたつき」を生じず、かつ初期接着性及び剥離性に優れ、特に、ピックアップ剤として有用であることを見出し、本発明を完成させるに至った。 Therefore, as a result of intensive research, the present researchers have found that an adhesive obtained by adding a specific aqueous polymer and a specific compound to a saccharide containing glucose does not cause “stickiness” and has an initial adhesive property and The present inventors have found that it is excellent in releasability and is particularly useful as a pickup agent, and has completed the present invention.
即ち、本発明は、一の要旨において、
（Ａ）糖類、（Ｂ）粘性調整剤及び（Ｃ）グリコール及び／又はトリオールを含むロール状ペーパー用接着剤であって、
（Ａ）糖類はグルコースを含み、
（Ｂ）粘性調整剤は、重量平均分子量２０，０００〜４，０００，０００の水性高分子を含むことを特徴とするロール状ペーパー用接着剤を提供する。
That is, the present invention in one aspect,
An adhesive for rolled paper containing (A) a saccharide, (B) a viscosity modifier and (C) glycol and / or triol,
(A) the saccharide contains glucose;
(B) The viscosity modifier includes an aqueous polymer having a weight average molecular weight of 20,000 to 4,000,000, and provides an adhesive for rolled paper.
本発明は、一の態様において、（Ａ）糖類が、更に、マルトースを含むロール状ペーパー用接着剤を提供する。
本発明は、他の態様において、重量平均分子量２０，０００〜４，０００，０００の水性高分子は、重量平均分子量２５，０００〜４００，０００のビニルピロリドン系重合体及び／又は重量平均分子量３００，０００〜３，５００，０００のアルキレンオキシド系重合体であるロール状ペーパー用接着剤を提供する。
本発明は、好ましい態様において、ロール状ペーパーの巻き始めに塗布されるロール状ペーパー用接着剤を提供する。
In one aspect, the present invention provides an adhesive for rolled paper in which (A) saccharide further contains maltose.
In another embodiment of the present invention, the aqueous polymer having a weight average molecular weight of 20,000 to 4,000,000 is a vinylpyrrolidone polymer having a weight average molecular weight of 25,000 to 400,000 and / or a weight average molecular weight of 300. The present invention provides an adhesive for rolled paper, which is an alkylene oxide polymer of 3,000 to 3,500,000.
In a preferred embodiment, the present invention provides an adhesive for roll paper applied at the beginning of winding of the roll paper.
本発明は、他の要旨において、上記ロール状ペーパー用接着剤が塗布されたロール状ペーパーを提供する。
本発明の他の要旨のロール状ペーパーは、上記ロール状ペーパー用接着剤が巻き始め部分に塗布されたことが好ましい。
In another aspect, the present invention provides a roll paper coated with the above adhesive for roll paper.
In the roll paper according to another aspect of the present invention, the roll paper adhesive is preferably applied to the winding start portion.
本発明に係るロール状ペーパー用接着剤は、（Ａ）糖類、（Ｂ）粘性調整剤及び（Ｃ）グリコール及び／又はトリオールを含むロール状ペーパー用接着剤であって、
（Ａ）糖類はグルコースを含み、
（Ｂ）粘性調整剤は、重量平均分子量２０，０００〜４，０００，０００の水性高分子を含むので、初期接着性及び剥離性の双方に優れ、更に、べたつきを生じない。
The adhesive for roll paper according to the present invention is an adhesive for roll paper containing (A) saccharide, (B) viscosity modifier and (C) glycol and / or triol,
(A) the saccharide contains glucose;
(B) Since the viscosity modifier contains an aqueous polymer having a weight average molecular weight of 20,000 to 4,000,000, it is excellent in both initial adhesion and peelability, and does not cause stickiness.
尚、本明細書では、「初期接着性」とは、ロール状ペーパーに接着剤が塗布された直後のウェットな状態での接着力のことをいう。「剥離性」とは、ロール状ペーパーを芯へ貼り付けるために塗布された接着剤が完全に乾燥した後、ロール状ペーパーが芯から剥離し易さを示す指標をいう。 In the present specification, “initial adhesiveness” refers to an adhesive force in a wet state immediately after an adhesive is applied to a roll paper. “Releasability” refers to an index indicating the ease with which a roll-shaped paper can be peeled off from the core after the adhesive applied to attach the roll-shaped paper to the core is completely dried.
本発明に係るロール状ペーパー用接着剤は、（Ａ）糖類が、更に、マルトースを含む場合、初期接着性が更に優れる。
本発明に係るロール状ペーパー用接着剤は、重量平均分子量２０，０００〜４，０００，０００の水性高分子は、重量平均分子量２５，０００〜４００，０００のビニルピロリドン系重合体及び／又は重量平均分子量３００，０００〜３，５００，０００のアルキレンオキシド系重合体を含む場合、初期タックがより高くなり、それに伴い初期接着性がより高くなる。
本発明に係るロール状ペーパー用接着剤は、ロール状ペーパーの巻き始めに塗布されて、ピックアップ剤として有用に使用することができる。
The adhesive for roll-shaped paper which concerns on this invention is further excellent in initial adhesiveness, when (A) saccharide | sugar contains maltose further.
The adhesive for roll paper according to the present invention is an aqueous polymer having a weight average molecular weight of 20,000 to 4,000,000, a vinylpyrrolidone polymer having a weight average molecular weight of 25,000 to 400,000, and / or a weight. When an alkylene oxide polymer having an average molecular weight of 300,000 to 3,500,000 is included, the initial tack becomes higher and the initial adhesiveness becomes higher accordingly.
The adhesive for rolled paper according to the present invention is applied at the beginning of winding of the rolled paper and can be usefully used as a pickup agent.
本発明に係るロール状ペーパーは、上記ロール状ペーパー用接着剤が塗布されることで、ペーパーが芯へ迅速に貼り付けられ、尚且つ、ペーパーの剥離性が向上する。
本発明に係るロール状ペーパーは、上記ロール状ペーパー用接着剤が巻き始め部分に塗布されるので、さらに、ペーパーが芯から剥がれ易くなる。
The roll-shaped paper according to the present invention is applied with the above-mentioned adhesive for roll-shaped paper, so that the paper is quickly attached to the core, and the peelability of the paper is improved.
In the roll-shaped paper according to the present invention, the above-mentioned adhesive for roll-shaped paper is applied to the winding start portion, and therefore the paper is easily peeled off from the core.
本発明に係るロール状ペーパー用接着剤は、（Ａ）糖類、（Ｂ）粘性調整剤及び（Ｃ）グリコール及び／又はトリオールを含む。
本発明において「（Ａ）糖類」とは、必須成分としてグルコースを含み、本発明が目的とするロール状ペーパー用接着剤を得ることができるものである限り、特に限定されるものではない。「グルコース」とは、代表的な単糖類の一種であり、ブドウ糖とも呼ばれる。（Ａ）糖類は、グルコース単独であってよいが、他の糖類を含むことが好ましい。「他の糖類」として、例えば、単糖類（グルコースを除く）、二糖類、三糖類、四糖類、多糖類、及びその他オリゴ糖を例示できる。
The adhesive for roll-shaped paper which concerns on this invention contains (A) saccharides, (B) viscosity modifier, and (C) glycol and / or triol.
In the present invention, the “(A) saccharide” is not particularly limited as long as it contains glucose as an essential component and can obtain the intended adhesive for rolled paper of the present invention. “Glucose” is a kind of typical monosaccharide and is also called glucose. (A) The saccharide may be glucose alone, but preferably contains other saccharides. Examples of “other saccharides” include monosaccharides (excluding glucose), disaccharides, trisaccharides, tetrasaccharides, polysaccharides, and other oligosaccharides.
「単糖類（グルコースを除く）」として、具体的に以下のものを例示できる。
プシコース、フルクトース、ソルボース、タガトース、アロース、アルトロース、マンノース、グロース、イドース、ガラクトース、タロース、フコース、フクロース、ラムノース等のヘキソース；
ケトトリオース（ジヒドロキシアセトン）、アルドトリオース（グリセルアルデヒド）等のトリオース；
エイリトリロース、エリトロース、トレオース等のテトロース；及び
リブロース、キシルロース、リボース、アラビノース、キシロース、リキソース、デオキシリボース等のペントース。
Specific examples of the “monosaccharide (excluding glucose)” include the following.
Hexoses such as psicose, fructose, sorbose, tagatose, allose, altrose, mannose, gulose, idose, galactose, talose, fucose, fucose, rhamnose;
Trioses such as ketotriose (dihydroxyacetone) and aldotriose (glyceraldehyde);
Tetroses such as eiritrirose, erythrose, and threose; and pentoses such as ribulose, xylulose, ribose, arabinose, xylose, lyxose, and deoxyribose.
「二糖類」として、例えば、スクロース、ラクトース、マルトース、トレハロース、ツラノース、セロビオースを例示でき、「三糖類」として、例えば、ラフィノース、エレジトース、マルトトリオースを例示でき、「四糖類」として、例えば、アカルボース、スタキオースを例示できる。
「多糖類」として、例えば、グリコーゲン、デンプン（アミロース、アミロペクチン）、セルロース、デキストリン、グルカン、Ｎ-アセチルグルコサミン、キチン質を例示できる。
「その他のオリゴ糖」として、例えば、フラクオリゴ糖、ガラクオリゴ糖、マンナンオリゴ糖を例示できる。
Examples of the “disaccharide” include sucrose, lactose, maltose, trehalose, turanose, and cellobiose. Examples of the “trisaccharide” include raffinose, elegitose, and maltotriose. Examples of the “tetrasaccharide” include, for example, Examples include acarbose and stachyose.
Examples of the “polysaccharide” include glycogen, starch (amylose, amylopectin), cellulose, dextrin, glucan, N-acetylglucosamine, and chitin.
Examples of “other oligosaccharides” include, for example, fructooligosaccharides, galactooligosaccharides, and mannan oligosaccharides.
これら「他の糖類」は、単独で又は組み合わせて用いることができる。
他の糖類として、単糖類（グルコールを除く）及び二糖類が好ましく、二糖類として、マルトースが好ましい。
従って、本発明に係るロール状ペーパー用接着剤は、（Ａ）糖類として、グルコース及びマルトースを含むことがより好ましい。
These “other saccharides” can be used alone or in combination.
Other saccharides are preferably monosaccharides (excluding glycol) and disaccharides, and the disaccharide is preferably maltose.
Therefore, it is more preferable that the adhesive for rolled paper according to the present invention contains glucose and maltose as the saccharide (A).
本発明において、（Ａ）糖類は、（Ｂ）粘性調整剤や（Ｃ）グリコール及び／又はトリオールと混合されるが、固形状態で混合されても、予め水に溶解されて液糖（シロップ）とされてから、（Ｂ）粘性調整剤や（Ｃ）グリコール及び／又はトリオールと混合されても良い。 In the present invention, (A) saccharide is mixed with (B) viscosity modifier and (C) glycol and / or triol, but even if mixed in a solid state, it is dissolved in water in advance and is liquid sugar (syrup). Then, it may be mixed with (B) a viscosity modifier or (C) glycol and / or triol.
本発明において、（Ｂ）粘性調整剤とは、重量平均分子量２０，０００〜４，０００，０００の水性高分子を含み、本発明が目的とするロール状ペーパー用接着剤を得ることができるものである限り、特に限定されるものではない。本発明において、「（Ｂ）粘性調整剤」に含まれる水溶性高分子として、例えば、ビニルピロリドン系重合体、アルキレンオキシド系重合体、ポリビニルアルコール等を例示することができる。 In the present invention, (B) the viscosity modifier includes an aqueous polymer having a weight average molecular weight of 20,000 to 4,000,000, and can obtain the adhesive for roll-shaped paper intended by the present invention. As long as it is, it is not particularly limited. In the present invention, examples of the water-soluble polymer contained in “(B) viscosity modifier” include vinylpyrrolidone polymers, alkylene oxide polymers, polyvinyl alcohol, and the like.
重量平均分子量２０，０００〜４，０００，０００の水性高分子は、重量平均分子量２５，０００〜４００，０００のビニルピロリドン系重合体及び／又は重量平均分子量３００，０００〜３，５００，０００のアルキレンオキシド系重合体のアルキレンオキシド系重合体であることが好ましい。そのようなビニルピロリドン系重合体及びアルキレンオキシド系重合体は、単独で用いられても、混合されて用いられても良い。 An aqueous polymer having a weight average molecular weight of 20,000 to 4,000,000 is a vinylpyrrolidone polymer having a weight average molecular weight of 25,000 to 400,000 and / or a weight average molecular weight of 300,000 to 3,500,000. The alkylene oxide polymer is preferably an alkylene oxide polymer. Such vinyl pyrrolidone polymers and alkylene oxide polymers may be used alone or in combination.
ビニルピロリドン系重合体の重量平均分子量は、２５，０００〜４００，０００であることが好ましく、２００，０００〜４００，０００であることがより好ましい。重量平均分子量が２５，０００〜４００，０００である場合、ロール状ペーパー用接着剤の初期接着性がより高くなる。
アルキレンオキシド系重合体の重量平均分子量は、３００，０００〜３，５００，０００であることが好ましく、３００，０００〜２，０００，０００であることがより好ましい。重量平均分子量が３００，０００〜３，５００，０００である場合、ロール状ペーパー用接着剤の初期接着性が向上する。
The weight average molecular weight of the vinylpyrrolidone polymer is preferably 25,000 to 400,000, more preferably 200,000 to 400,000. When the weight average molecular weight is 25,000 to 400,000, the initial adhesiveness of the adhesive for rolled paper is higher.
The weight average molecular weight of the alkylene oxide polymer is preferably 300,000 to 3,500,000, and more preferably 300,000 to 2,000,000. When the weight average molecular weight is 300,000 to 3,500,000, the initial adhesiveness of the adhesive for roll paper is improved.
本明細書では、重量平均分子量（Ｍｗ）とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）装置で測定され、単分散分子量ポリエチレングリコールで換算された重量平均分子量をいう。より具体的には、Ｗａｔｅｒｓ２６９０，２４８７，４１０を用い、ＲＩ及びＵＶのクロマトグラムを検出した。ＧＰＣカラムとして、ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅ ＰＷＸＬ、Ｕｌｔｒａｈｙｄｒｏｇｅｌ Ｌｉｎｅｒ、ＴＳＫｇeｌ ＧＭＰＷＸＬ、Ｕｌｙｒａｈｙｄｒｏｇｅｌ２５０（東ソー社製）を用いた。 In the present specification, the weight average molecular weight (Mw) refers to a weight average molecular weight measured with a gel permeation chromatography (GPC) apparatus and converted to monodisperse molecular weight polyethylene glycol. More specifically, RI and UV chromatograms were detected using Waters 2690, 2487, 410. As GPC columns, TSKgel SuperMultipore PWXL, Ultrahydrogel Liner, TSKgel GMPWXL, Ultrahydrogel 250 (manufactured by Tosoh Corporation) were used.
試料をアセトニトリル／０．１Ｍ ｐＨ７．０リン酸緩衝液（２０：８０）に溶解して、流速を０．６ｍｌ／ｍｉｎ、カラム温度を４０℃にて流した。
尚、標準物質としてエチレングリコール（ＥＧ）溶液と、分子量の異なる７種類の標準ポリエチレンオキサイド（ＰＥＯ）／ポリエチレングリコール（ＰＥＧ）を用いて準備した２種類のＰＥＯ／ＰＥＧ溶液（下記「ＳＴＤ−Ａ」及び「ＳＴＤ―Ｂ」）の計３種を使用して得た検量線を用いて、Ｍｗを求めた。ここで、ＳＴＤ−Ａは、Ｍｗ＝９２０，０００、１０７，０００及び２４，０００のＰＥＯと、Ｍｗ＝１，５００のＰＥＧを混合して得た。ＳＴＤ−Ｂは、Ｍｗ＝２５０，０００及び５０，０００のＰＥＯと、Ｍｗ＝３，０００のＰＥＧを混合して得た。
The sample was dissolved in acetonitrile / 0.1 M pH 7.0 phosphate buffer (20:80), and the flow rate was 0.6 ml / min and the column temperature was 40 ° C.
In addition, two types of PEO / PEG solutions prepared using ethylene glycol (EG) solution and seven types of standard polyethylene oxide (PEO) / polyethylene glycol (PEG) having different molecular weights as standard substances (hereinafter referred to as “STD-A”) And “STD-B”), Mw was determined using calibration curves obtained using a total of three types. Here, STD-A was obtained by mixing PEO with Mw = 920,000, 107,000 and 24,000, and PEG with Mw = 1,500. STD-B was obtained by mixing PEO with Mw = 250,000 and 50,000 and PEG with Mw = 3,000.
本発明において「ビニルピロリドン系重合体」とは、Ｎ−ビニルピロリドンから得られるビニルピロリドン単位を有する重合体をいい、本発明が目的とするロール状ペーパー用接着剤を得ることができる限り、特に限定されるものではない。ビニルピロリドン系重合体として、例えば、ポリビニルピロリドン及び／又はＮ−ビニルピロリドンを必須とするホモポリマー（単独重合体）、若しくは、必要に応じてその他の単量体を共重合して得られるコポリマー（共重合体）を例示することができ、これらを好適に使用することができる。 In the present invention, the “vinyl pyrrolidone polymer” refers to a polymer having a vinyl pyrrolidone unit obtained from N-vinyl pyrrolidone, and as long as the adhesive for roll paper targeted by the present invention can be obtained. It is not limited. As a vinylpyrrolidone polymer, for example, a homopolymer (homopolymer) essentially containing polyvinylpyrrolidone and / or N-vinylpyrrolidone, or a copolymer obtained by copolymerizing other monomers as required ( Copolymer)), and these can be preferably used.
ビニルピロリドン系重合体が共重合体である場合、Ｎ−ビニルピロリドンと共重合する単量体は、Ｎ−ビニルピロリドンと共重合可能なものであって、本発明が目的とするロール状ペーパー用接着剤を得ることができる限り、特に限定されるものではない。
具体的には、
（１）（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸−２−ヒドロキシエチル等の（メタ）アクリル酸エステル類；
（２）（メタ）アクリル酸アミド、Ｎ−モノエチル（メタ）アクリルアミド、Ｎ，Ｎ’−ジメチル（メタ）アクリルアミド、２−アクリルアミド−２−メチルプロパンスルホン酸等の（メタ）アクリルアミド誘導体類；
（３）（メタ）アクリル酸ジメチルアミノエチル、ジメチルアミノエチル（メタ）アクリルアミド、ビニルピリジン、ビニルイミダゾール等の塩基性不飽和単量体；
（４）ビニルホルムアミド、ビニルアセトアミド、ビニルオキサゾリドン、Ｎ−ビニルカプロラクタム等のビニルアミド類；
（５）（メタ）アクリル酸、イタコン酸、マレイン酸、フマル酸等のカルボキシル基含有不飽和単量体；
（６）無水マレイン酸、無水イタコン酸等の不飽和酸無水物類；
（７）プロピオン酸ビニル、酢酸ビニル等のビニルエステル類；
（８）ビニルエチレンカーボネート及びその誘導体；
（９）スチレン及びその誘導体；
（１０）ビニルスルホン酸及びその誘導体；
（１１）エチルビニルエーテル等のビニルエーテル類；
（１２）エチレン、プロピレン、ブタジエン等のオレフィン類
を例示できる。
When the vinylpyrrolidone-based polymer is a copolymer, the monomer copolymerized with N-vinylpyrrolidone is copolymerizable with N-vinylpyrrolidone, and is intended for roll papers intended by the present invention. As long as the adhesive can be obtained, it is not particularly limited.
In particular,
(1) (Meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid-2-hydroxyethyl;
(2) (meth) acrylamide derivatives such as (meth) acrylic acid amide, N-monoethyl (meth) acrylamide, N, N′-dimethyl (meth) acrylamide, 2-acrylamido-2-methylpropanesulfonic acid;
(3) Basic unsaturated monomers such as dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine, vinylimidazole;
(4) Vinylamides such as vinylformamide, vinylacetamide, vinyloxazolidone, N-vinylcaprolactam;
(5) carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, itaconic acid, maleic acid and fumaric acid;
(6) Unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride;
(7) Vinyl esters such as vinyl propionate and vinyl acetate;
(8) vinyl ethylene carbonate and its derivatives;
(9) Styrene and its derivatives;
(10) vinyl sulfonic acid and its derivatives;
(11) Vinyl ethers such as ethyl vinyl ether;
(12) Examples of olefins such as ethylene, propylene, and butadiene.
アルキレンオキシド系重合体は、アルキレンオキシドから誘導されるアルキレンオキシド単位を有する重合体であって、本発明が目的とするロール状ペーパー用接着剤を得ることができる限り、特に限定されるものではない。
そのようなアルキレンオキシドとして、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシドを例示できる。これらアルキレンオキシドの中でも、特にエチレンオキシドが本発明では好ましい。
The alkylene oxide polymer is a polymer having an alkylene oxide unit derived from an alkylene oxide, and is not particularly limited as long as the adhesive for roll paper targeted by the present invention can be obtained. .
Examples of such alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide. Among these alkylene oxides, ethylene oxide is particularly preferable in the present invention.
本発明では、アルキレンオキシド系重合体は、アルキレンオキシドと他の単量体との共重合体であってもよい。アルキレンオキシドと共重合する単量体は、本発明が目的とするロール状ペーパー用接着剤を得ることができる限り、特に限定されるものではないが、不飽和カルボン酸単量体及び／又はその塩であることが好ましい。不飽和カルボン酸単量体として、例えば、アクリル酸、メタクリル酸、アクリロキシプロピオン酸、シトラコン酸、イタコン酸、クロトン酸、マレイン酸、無水マレイン酸等を例示することができ、これらの中でも、アクリル酸、メタクリル酸が好ましい。また、不飽和カルボン酸単量体の塩として、例えば、前記不飽和カルボン酸単量体のナトリウム塩、カリウム塩等の金属塩及び、アンモニウム塩等を例示できる。 In the present invention, the alkylene oxide polymer may be a copolymer of an alkylene oxide and another monomer. The monomer copolymerized with the alkylene oxide is not particularly limited as long as the adhesive for roll paper targeted by the present invention can be obtained, but the unsaturated carboxylic acid monomer and / or its monomer A salt is preferred. Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, acryloxypropionic acid, citraconic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, etc. Among these, acrylic Acid and methacrylic acid are preferred. Examples of the salt of the unsaturated carboxylic acid monomer include metal salts such as sodium salt and potassium salt of the unsaturated carboxylic acid monomer, and ammonium salt.
（Ｂ）粘性調整剤が、上記水性高分子を含むことで、ロール状ペーパー用接着剤の初期接着性が向上する。本発明では、住友精化社の（商品名：ＰＥＯ＃２、ＰＥＯ＃３Ｚ、ＰＥＯ＃８Ｚ、ＰＥＯ＃１５Ｚ）や、日本触媒化学社の（商品名：ＰＶＰ Ｋ-３０、ＰＶＰ Ｋ-９０、ＰＶＰ Ｋ-８５）を、（Ｂ）粘性調整剤として好適に用いることができる。 (B) The initial adhesiveness of the adhesive for roll-shaped paper improves because a viscosity modifier contains the said aqueous polymer. In the present invention, (trade names: PEO # 2, PEO # 3Z, PEO # 8Z, PEO # 15Z) of Sumitomo Seika Co., Ltd. and (trade names: PVP K-30, PVP K-90, PVP K-85) can be suitably used as the (B) viscosity modifier.
（Ｂ）粘性調整剤は、ビニルピロリドン系重合体やアルキレンオキシド系重合体の他にも、本発明が目的とするロール状ペーパー用接着剤を得ることができる限り、
尿素、尿素化合物、ジシアンジアミド等の窒素含有物質や、
水酸化カルシウム、酸化カルシウム、炭酸ナトリウム、リン酸３ナトリウム、リン酸水素２アンモニウム、硼砂、フッ化ナトリウム、水ガラス、アンモニア水等の一般的に粘性調整剤とされるものを含有することができる。
(B) In addition to the vinyl pyrrolidone polymer and the alkylene oxide polymer, the viscosity modifier may be used as long as the adhesive for roll paper targeted by the present invention can be obtained.
Nitrogen-containing substances such as urea, urea compounds, dicyandiamide,
Commonly used as viscosity adjusting agents such as calcium hydroxide, calcium oxide, sodium carbonate, trisodium phosphate, diammonium hydrogen phosphate, borax, sodium fluoride, water glass, and aqueous ammonia can be contained. .
本発明に係るロール状ペーパー用接着剤は、（Ｃ）グリコール及び／又はトリオールを含む。
本発明に係る「（Ｃ）グリコール及び／又はトリオール」とは、Ｍｗが２０，０００未満であるグリコール及び／又はトリオールをいい、本発明が目的とするロール状ペーパー用接着剤を得ることができる限り、特に限定されるものではないが、常温常圧で液体であって、（Ａ）糖類と（Ｂ）粘性調整剤を溶解可能であることが好ましく、グリコールであることが、より好ましい。
The adhesive for roll paper according to the present invention contains (C) glycol and / or triol.
The “(C) glycol and / or triol” according to the present invention refers to a glycol and / or triol having an Mw of less than 20,000, and the intended adhesive for roll-shaped paper of the present invention can be obtained. As long as it is not particularly limited, it is preferably liquid at room temperature and normal pressure, and is preferably capable of dissolving (A) saccharide and (B) viscosity modifier, and more preferably glycol.
（Ｃ）グリコール及び／又はトリオールとして、例えば、
グリセリン等のトリオール；
エチレングリコール、ジプロピレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のグリコール；
を例示することができる。これらは、単独又は組み合わせて使用することができる。
（Ｃ）は、ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコールであってもよいが、Ｍｗは２０，０００未満であるので、（Ｂ）粘性調整剤に含まれるアルキレンオキシド系重合体とは、明確に異なる。
尚、本発明では、（Ｃ）グリコール及び／又はトリオールは、べたつき調整剤として作用する。（Ｃ）グリコール及び／又はトリオールは、そのまま用いても、溶媒と混合して用いてもよい。溶媒は、水性媒体、非水性媒体のいずれでもよく、両者の混合媒体でも良いが、水性媒体を含む媒体であることが好ましく、水性媒体であることがより好ましい。
(C) As glycol and / or triol, for example,
Triols such as glycerin;
Glycols such as ethylene glycol, dipropylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol;
Can be illustrated. These can be used alone or in combination.
(C) may be a polyalkylene glycol such as polyethylene glycol or polypropylene glycol, but since Mw is less than 20,000, (B) the alkylene oxide polymer contained in the viscosity modifier is clear. Different.
In the present invention, (C) glycol and / or triol acts as a stickiness adjuster. (C) Glycol and / or triol may be used as they are or mixed with a solvent. The solvent may be either an aqueous medium or a non-aqueous medium, and may be a mixed medium of both, but is preferably a medium containing an aqueous medium, and more preferably an aqueous medium.
上記（Ａ）糖類、（Ｂ）粘性調整剤及び（Ｃ）グリコール及び／又はトリオールは、そのままの状態、例えば、固体又は液体の状態で、混合されてもよいが、必要に応じて水性媒体に溶かされて、混合されてもよい。得られた混合物は、更に、水性媒体を用いて適宜所望の濃度に調節されて本発明に係るロール状ペーパー用接着剤が得られる。従って、本発明に係るロール状ペーパー用接着剤は、一般に水性接着剤である。本発明に係る接着剤は、水性媒体に均一に溶解していることが好ましい。
ここで、「水性媒体」とは、水道水、蒸留水又はイオン交換水等の一般的な水をいうが、水性媒体に溶解可能な有機溶剤であって、本発明に係る接着剤の成分と反応性の乏しい有機溶剤、例えば、アセトン及び酢酸エチル等を含んでもよく、更に水性媒体に溶解可能な単量体、オリゴマー、プレポリマー及び／又は樹脂等を含んでも良い。また後述するような各種添加剤等を含んでも良い。
The (A) saccharide, (B) viscosity modifier and (C) glycol and / or triol may be mixed as they are, for example, in a solid or liquid state, but if necessary, in an aqueous medium. It may be dissolved and mixed. The obtained mixture is further appropriately adjusted to a desired concentration using an aqueous medium to obtain the roll paper adhesive according to the present invention. Therefore, the adhesive for roll paper according to the present invention is generally an aqueous adhesive. The adhesive according to the present invention is preferably dissolved uniformly in an aqueous medium.
Here, the “aqueous medium” refers to general water such as tap water, distilled water, or ion exchange water, but is an organic solvent that is soluble in the aqueous medium, and includes the components of the adhesive according to the present invention. An organic solvent having poor reactivity, such as acetone and ethyl acetate, may be included, and a monomer, oligomer, prepolymer, and / or resin that can be dissolved in an aqueous medium may also be included. Further, various additives as described later may be included.
本発明では、（Ａ）〜（Ｃ）の総重量１００重量部に対し、（Ａ）糖類は、固形分として、１０〜９０重量部が配合されることが好ましく、２０〜７０重量部が配合されることがより好ましく、４０〜６０重量部が配合されることが特に好ましい。ロール状ペーパー用接着剤は、（Ａ）〜（Ｃ）の総重量１００重量部に対し（Ａ）糖類が１０〜９０重量部配合されることで、初期接着性及び剥離性のバランスにより優れ、不要な「べたつき」をより生じない。 In this invention, it is preferable that 10-90 weight part is mix | blended as (A) saccharide as solid content with respect to 100 weight part of total weight of (A)-(C), and 20-70 weight part is mix | blended. It is more preferable that 40 to 60 parts by weight is blended. The adhesive for roll-shaped paper is excellent in the balance of initial adhesiveness and peelability by blending 10 to 90 parts by weight of saccharide (A) with respect to 100 parts by weight of the total weight of (A) to (C). Unnecessary “stickiness” is less generated.
本発明では、（Ａ）〜（Ｃ）の総重量１００重量部に対し、（Ｂ）粘性調整剤は、固形分として、１〜１０重量部が配合されることが好ましく、１〜８重量部が配合されることがより好ましく、１〜７重量部が配合されることが特に好ましい。ロール状ペーパー用接着剤は、（Ａ）〜（Ｃ）の総重量１００重量部に対し（Ｂ）粘性調整剤が１〜１０重量部配合されることで、初期接着性及び剥離性のバランスにより優れ、不要な「べたつき」をより生じない。 In this invention, it is preferable that 1-10 weight part is mix | blended as (B) viscosity modifier as solid content with respect to 100 weight part of total weight of (A)-(C), 1-8 weight part Is more preferable, and 1 to 7 parts by weight is particularly preferable. The adhesive for roll paper is blended with 1 to 10 parts by weight of (B) viscosity modifier with respect to 100 parts by weight of the total weight of (A) to (C), so that the initial adhesiveness and peelability are balanced Excellent, less unwanted “stickiness”.
本発明では、（Ａ）〜（Ｃ）の総重量１００重量部に対し、（Ｃ）グリコール及び／又はトリオールは、１０〜７０重量部が配合されることが好ましく、２０〜７０重量部が配合されることがより好ましく、２０〜６０重量部が配合されることが特に好ましい。ロール状ペーパー用接着剤は、（Ａ）〜（Ｃ）の総重量１００重量部に対し（Ｃ）グリコール及び／又はトリオールが１０〜７０重量部配合されることで、初期接着性及び剥離性のバランスにより優れ、不要な「べたつき」をより生じない。 In the present invention, 10 to 70 parts by weight of (C) glycol and / or triol is preferably blended with respect to 100 parts by weight of the total weight of (A) to (C), and 20 to 70 parts by weight is blended. It is more preferable that 20 to 60 parts by weight is blended. The adhesive for roll-shaped paper is blended with 10 to 70 parts by weight of (C) glycol and / or triol with respect to 100 parts by weight of the total weight of (A) to (C). Excellent balance and less unwanted “stickiness”.
本発明では、（Ａ）〜（Ｃ）成分の総重量は、ロール状ペーパー用接着剤の総重量１００重量部に対し、１０〜９０重量部であることが好ましく、３０〜９０重量部であることがより好ましく、４０〜８０重量部であることが特に好ましい。（Ａ）〜（Ｃ）成分の総重量が１０〜９０重量部である場合、本発明のロール状ペーパー用接着剤は、初期接着性および剥離性に優れ、不要なべたつきを生じることはない。 In this invention, it is preferable that the total weight of (A)-(C) component is 10-90 weight part with respect to 100 weight part of total weight of the adhesive agent for roll-shaped paper, and is 30-90 weight part. More preferably, the amount is 40 to 80 parts by weight. When the total weight of the components (A) to (C) is 10 to 90 parts by weight, the adhesive for roll-shaped paper of the present invention is excellent in initial adhesiveness and peelability and does not cause unnecessary stickiness.
本発明のロール状ペーパー用接着剤は、成分（Ａ）〜（Ｃ）の他に、更に、架橋剤、可塑剤、消泡剤、防錆剤、防腐剤等の添加剤を必要に応じて適宜含むことができる。添加剤の配合方法は、特に限定されることはない。 In addition to the components (A) to (C), the adhesive for roll paper of the present invention may further contain additives such as a crosslinking agent, a plasticizer, an antifoaming agent, a rust inhibitor, and an antiseptic as necessary. It can be included as appropriate. The method for blending the additive is not particularly limited.
本発明のロール状ペーパー用接着剤を調製する場合、成分（Ａ）〜（Ｃ）と必要に応じて各種添加剤を配合した後、水性媒体を添加しても良いし、成分（Ａ）〜（Ｃ）を予め水性媒体に混合した後、各種添加剤を配合しても良い。 When preparing the adhesive for roll-shaped paper of this invention, after mix | blending components (A)-(C) and various additives as needed, an aqueous medium may be added, and component (A)- You may mix | blend various additives, after mixing (C) with an aqueous medium previously.
各種添加剤のうち、架橋剤として、例えば、酢酸亜鉛、酸化亜鉛、酢酸ジルコニウム、炭酸ジルコニウムアンモニウム等を例示できる。これらの架橋剤は、単独で又は組み合わせて使用することができる。 Among various additives, examples of the crosslinking agent include zinc acetate, zinc oxide, zirconium acetate, and ammonium zirconium carbonate. These crosslinking agents can be used alone or in combination.
消泡剤として、例えば、
ジメチルポリシロキサン、ポリオキシアルキレン変性シリコーン、有機変性ポリシロキサン、フッ素シリコーン等のシリコーン系消泡剤；
ヒマシ油、ゴマ油、アマニ油、動植物油等の油脂系消泡剤；
ステアリン酸、オレイン酸、パルミチン酸等の脂肪酸系消泡剤；
イソアミルステアリン酸、ジグリコールラウリン酸、ジステアリルコハク酸、ジステアリン酸、ソルビタンモノラウリン酸、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン、モノラウリン酸ブチルステアレート、ショ糖脂肪酸エステル、スルホン化リチノール酸のエチル酢酸アルキルエステル、天然ワックス等の脂肪酸エステル系消泡剤；
ポリオキシアルキレングリコールとその誘導体、ポリオキシアルキレンアルコール水和物、ジアミルフェノキシエタノール、３−ヘプタノール、２−エチルヘキサノール等のアルコール系消泡剤；
３−ヘプチルセルソルブ、ノニルセルソルブ−３−ヘプチルカルビトール等のエーテル系消泡剤；
トリブチルホスフェート、オクチルリン酸ナトリウム、トリス（ブトキシエチル）ホスフェート等のリン酸エステル系消泡剤；
ジアミルアミン等のアミン系消泡剤；
ポリアルキレンアマイド、アシレイトポリアミン、ジオクタデカノイルピペリジン等のアマイド系消泡剤；
ステアリン酸アルミニウム、ステアリン酸カルシウム、オレイン酸カリウム、ウールオレインのカルシウム塩等の金属石鹸系消泡剤；
ラウリルスルホン酸ナトリウム、ドデシルスルホン酸ナトリウム等のスルホン酸エステル系消泡剤等を例示することができる。
As an antifoaming agent, for example,
Silicone-based antifoaming agents such as dimethylpolysiloxane, polyoxyalkylene-modified silicone, organic-modified polysiloxane, and fluorine silicone;
Oil-based antifoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oils;
Fatty acid-based antifoaming agents such as stearic acid, oleic acid, palmitic acid;
Isoamyl stearic acid, diglycol lauric acid, distearyl succinic acid, distearic acid, sorbitan monolauric acid, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan, monolauric acid butyl stearate, sucrose fatty acid ester, sulfonated lithinolic acid Fatty acid ester antifoaming agents such as ethyl acetate alkyl ester and natural wax;
Alcohol-based antifoaming agents such as polyoxyalkylene glycol and derivatives thereof, polyoxyalkylene alcohol hydrate, diamylphenoxyethanol, 3-heptanol, 2-ethylhexanol;
Ether type antifoaming agents such as 3-heptylcellosolve and nonylcellosolve-3-heptylcarbitol;
Phosphate-based antifoaming agents such as tributyl phosphate, sodium octyl phosphate, tris (butoxyethyl) phosphate;
Amine-based antifoaming agents such as diamylamine;
Amide antifoaming agents such as polyalkylene amide, acylate polyamine, dioctadecanoyl piperidine;
Metal soap antifoaming agents such as aluminum stearate, calcium stearate, potassium oleate, calcium salt of wool olein;
Examples thereof include sulfonate ester antifoaming agents such as sodium lauryl sulfonate and sodium dodecyl sulfonate.
本発明に係るロール状ペーパー用接着剤は、消泡剤として、シリコーン系消泡剤を含有することが好ましい。シリコーン系消泡剤は、他の消泡剤と比べて肌に優しいので、トイレットペーパーやキッチンペーパーに塗工されるロール状ペーパー用接着剤の成分として好ましい。 It is preferable that the adhesive for roll-shaped paper which concerns on this invention contains a silicone type antifoamer as an antifoamer. Silicone-based antifoaming agents are gentler to the skin than other antifoaming agents, and thus are preferable as a component of an adhesive for roll-shaped paper applied to toilet paper or kitchen paper.
本発明に係るロール状ペーパー用接着剤は、ロール状に巻かれたペーパーに塗布されて使用される。ロール状ペーパーは、ペーパーがロール状に巻かれたものであれば良いが、一般的にはトイレットペーパーや、キッチンペーパー等の衛生薄葉紙がロール状に巻回されたものが挙げられる。ロール状に巻回されるペーパーは、１プライの単層紙でもよいが、吸水性等の点から２プライ以上の重ね紙であることが好ましい。 The adhesive for roll-shaped paper which concerns on this invention is apply | coated and used for the paper wound by roll shape. The roll paper may be any paper in which the paper is wound in a roll shape, but generally, a roll of sanitary thin paper such as toilet paper or kitchen paper is used. The paper wound in a roll shape may be a single-ply single-layer paper, but is preferably a two-ply or more overlapping paper from the viewpoint of water absorption.
ロール状ペーパー用接着剤が塗布される部位は、ロール状ペーパーのいずれの部分でも良いが、特にロール状ペーパーの巻き始めか、テールシール部（巻き終わり）に塗布されるのが本発明では好適である。本発明のロール状ペーパー用接着剤は、ロール状ペーパーの巻き始めに塗布されるピックアップ剤として、特に有効に使用される。
本明細書において、ピックアップ剤とは、芯にペーパーを巻き始める時に塗布される水性接着剤である。ピックアップ剤は、芯からペーパーを容易に剥がすために使用される。
The part to which the adhesive for roll-shaped paper is applied may be any part of the roll-shaped paper, but it is particularly preferable in the present invention to be applied to the start of winding of the roll-shaped paper or the tail seal part (end of winding). It is. The adhesive for roll-shaped paper of this invention is used especially effectively as a pick-up agent apply | coated at the beginning of winding of roll-shaped paper.
In this specification, the pickup agent is a water-based adhesive applied when paper starts to be wound around a core. The pick-up agent is used to easily peel the paper from the core.
本発明に係るロール状ペーパーは、上記ロール状ペーパー用接着剤が塗布されたトイレットペーパーやキッチンペーパー等であり、特にロール状ペーパーの巻き始めか、テールシール部（巻き終わり）に塗布されたものが好ましく、さらに好ましくは、巻き始めに塗布されたものが本発明では好適である。
本発明に係るロール状ペーパーの最も好ましい実施形態は、ペーパーの巻き始めに、ロール状ペーパー用接着剤がピックアップ剤として塗布されたトイレットペーパー、特に有芯型トイレットペーパーである。
The roll paper according to the present invention is toilet paper, kitchen paper, or the like to which the above-mentioned adhesive for roll paper is applied, and particularly applied to the start of the roll paper or the tail seal (winding end). More preferably, the coating applied at the beginning of winding is suitable in the present invention.
The most preferred embodiment of the roll-shaped paper according to the present invention is toilet paper, particularly cored-type toilet paper, in which an adhesive for roll-shaped paper is applied as a pickup agent at the beginning of paper winding.
本発明に係るロール状ペーパー接着剤を塗布する方式については、特別な方式を採用する必要はない。ホイール方式、ブレード方式、マウント方式、ノズル方式、スプレー方式等、一般的な方式が挙げられる。 It is not necessary to adopt a special method for the method of applying the roll paper adhesive according to the present invention. General methods such as a wheel method, a blade method, a mount method, a nozzle method, and a spray method are listed.
本発明では、初期接着性の高いロール状ペーパー用接着剤が塗布されているので、ロール状ペーパーの芯とペーパーとが迅速に貼り付けられる。さらに、本発明のロール状ペーパーは、剥離性に優れたロール状ペーパー用接着剤が塗布されているので、芯(巻き始め部分)や、テールシール（巻き終わり部分）からペーパーが容易に剥離し、最後まで無駄なく使用される。 In this invention, since the adhesive agent for roll-shaped paper with high initial adhesiveness is apply | coated, the core of roll-shaped paper and paper are affixed rapidly. Furthermore, since the roll-shaped paper of the present invention is coated with an adhesive for roll-shaped paper having excellent releasability, the paper can be easily peeled off from the core (winding start portion) and tail seal (winding end portion). It is used without waste until the end.
以下に本発明を実施例及び比較例を用いて説明するが、これらの例は本発明を説明するためのものであり、本発明を何ら限定するものではない。 The present invention will be described below with reference to examples and comparative examples, but these examples are for explaining the present invention and do not limit the present invention.
まず、ロール状ペーパー用接着剤の成分として、以下の成分を準備した。（）内に、商品名名及び製造会社名を記載した。尚、部とは重量部を意味し、「分子量」とは重量平均分子量（Ｍｗ）を意味する。
［（Ａ）糖類］
（A-1）グルコース（ブドウ糖ＴＤＨ、サンエイ糖化（株））
（A-2）液糖（サンシラップＲ７５、日本コーンスターチ（株））（サンシラップＲ７５は、グルコース、マルトース及びその他糖類が、７５重量％の濃度で、水に溶解された水溶液である。）
（A'-3）デキストリン（Dextrin Ｍｗ＝７５，０００、和光純薬工業（株））
（A'-4）カルボキシメチルセルロース（ＣＭＣ１２０５、ダイセル化学工業（株））
（A'-5）メチルセルロース（マーポローズ90EMP4000、松本油脂製薬（株））
First, the following components were prepared as components of the adhesive for roll paper. The name of the product and the name of the manufacturer are shown in (). “Part” means part by weight, and “molecular weight” means weight average molecular weight (Mw).
[(A) Sugar]
(A-1) Glucose (Glucose TDH, Sanei Saccharification Co., Ltd.)
(A-2) Liquid sugar (Sun syrup R75, Nippon Corn Starch Co., Ltd.) (Sun syrup R75 is an aqueous solution in which glucose, maltose and other sugars are dissolved in water at a concentration of 75% by weight.)
(A'-3) Dextrin (Dextrin Mw = 75,000, Wako Pure Chemical Industries, Ltd.)
(A'-4) Carboxymethylcellulose (CMC1205, Daicel Chemical Industries, Ltd.)
(A'-5) Methylcellulose (Marporose 90EMP4000, Matsumoto Yushi Seiyaku Co., Ltd.)
［（Ｂ）粘性調整剤］
ポリビニルピロリドン
（B-1）（PVPK-30 Mw＝２５，０００ 、日本触媒（株））
（B-2）（PVPK-85 Mw＝２５０，０００、日本触媒（株））
（B-3）（PVPK-90 Mw＝４００，０００、日本触媒（株））
ポリエチレンオキサイド
（B-4）（PEO＃2 Mw=３５０，０００ 、住友精化（株））
（B-5）（PEO＃3Z Mw=３４０，０００ 、住友精化（株））
（B-6）（PEO＃8Z Mw=２，０００，０００ 、住友精化（株））
（B-7）（PEO＃15Z Mw＝３，５００，０００、住友精化（株））
ポリビニルアルコール
（B-8）（ＪＰ-３３ Mw=１４５，０００、日本酢ビ・ポバール（株））
[(B) Viscosity modifier]
Polyvinylpyrrolidone (B-1) (PVPK-30 Mw = 25,000, Nippon Shokubai Co., Ltd.)
(B-2) (PVPK-85 Mw = 250,000, Nippon Shokubai Co., Ltd.)
(B-3) (PVPK-90 Mw = 400,000, Nippon Shokubai Co., Ltd.)
Polyethylene oxide (B-4) (PEO # 2 Mw = 350,000, Sumitomo Seika Co., Ltd.)
(B-5) (PEO # 3Z Mw = 340,000, Sumitomo Seika Co., Ltd.)
(B-6) (PEO # 8Z Mw = 2,000,000, Sumitomo Seika Co., Ltd.)
(B-7) (PEO # 15Z Mw = 3,500,000, Sumitomo Seika Co., Ltd.)
Polyvinyl alcohol (B-8) (JP-33 Mw = 145,000, Nippon Vinegar Poval Co., Ltd.)
［（Ｃ）グリコール及び／又はトリオール］
（C-1）ジエチレングリコール （ジエチレングリコール、和光純薬工業（株））
（C-2）トリエチレングリコール（トリエチレングリコール、和光純薬工業（株））
（C-3）ジプロピレングリコール（ジプロピレングリコール、和光純薬工業（株））
（C-4）ポリアルキレングリコール（ユニルーブ75DE170 Mw=５，０００、日油(株)）
［消泡剤］
（D-1）シリコーン系消泡剤 （KM72-F、信越化学工業（株））
[(C) glycol and / or triol]
(C-1) Diethylene glycol (Diethylene glycol, Wako Pure Chemical Industries, Ltd.)
(C-2) Triethylene glycol (Triethylene glycol, Wako Pure Chemical Industries, Ltd.)
(C-3) Dipropylene glycol (dipropylene glycol, Wako Pure Chemical Industries, Ltd.)
(C-4) Polyalkylene glycol (Unilube 75DE170 Mw = 5,000, NOF Corporation)
[Defoamer]
(D-1) Silicone-based antifoaming agent (KM72-F, Shin-Etsu Chemical Co., Ltd.)
実施例１〜１７のロール状ペーパー用接着剤を、以下の処方及び配合条件を用いて製造した。
実施例１
攪拌装置を備えたフラスコに、水を４０部、（A-1)を４４部、（B-3)を６部、（C-1)を５０部加えて、６０℃に加熱して１時間攪拌した。水、糖類、粘性調整剤及びグリコール類の混合液１４０部を得た。混合液を室温（２３℃）に冷却し、（D-1)１部を添加後、３０分間攪拌して実施例１のロール状ペーパー用接着剤を得た。
The adhesive for roll-shaped paper of Examples 1-17 was manufactured using the following prescription and compounding conditions.
Example 1
To a flask equipped with a stirrer, add 40 parts of water, 44 parts of (A-1), 6 parts of (B-3) and 50 parts of (C-1), and heat to 60 ° C. for 1 hour. Stir. 140 parts of a mixture of water, sugar, viscosity modifier and glycols was obtained. The mixture was cooled to room temperature (23 ° C.), 1 part of (D-1) was added, and the mixture was stirred for 30 minutes to obtain the adhesive for roll paper of Example 1.
実施例２
（A-1)４４部の替わりに、（A-2)５９部を用いたことを除いて、実施例１と同様の方法を用いて、実施例２のロール状ペーパー用接着剤を得た。
実施例３
(B-3)の替わりに（B-6)を用いたことを除いて、実施例１と同様の方法を用いて、実施例３のロール状ペーパー用接着剤を得た。
実施例４
（A-1)４４部の替わりに(A-2)５９部を用いたことを除いて、実施例３と同様の方法を用いて、実施例４のロール状ペーパー用接着剤を得た。
Example 2
(A-1) Instead of 44 parts, (A-2) 59 parts by weight was used, and the same method as in Example 1 was used to obtain an adhesive for rolled paper of Example 2. .
Example 3
Using the same method as in Example 1 except that (B-6) was used instead of (B-3), an adhesive for roll paper of Example 3 was obtained.
Example 4
The adhesive for roll-shaped paper of Example 4 was obtained using the same method as Example 3 except having used 59 parts of (A-2) instead of 44 parts of (A-1).
実施例５
(B-3)の替わりに(B-1)を用いたことを除いて、実施例１と同様の方法を用いて、実施例５のロール状ペーパー用接着剤を得た。
実施例６
(B-3)の替わりに(B-2)を用いたことを除いて、実施例１と同様の方法を用いて、実施例６のロール状ペーパー用接着剤を得た。
実施例７
(B-3)の替わりに(B-5)を用いたことを除いて、実施例１と同様の方法を用いて、実施例７のロール状ペーパー用接着剤を得た。
Example 5
Using the same method as in Example 1 except that (B-1) was used in place of (B-3), an adhesive for roll paper of Example 5 was obtained.
Example 6
Using the same method as in Example 1 except that (B-2) was used in place of (B-3), an adhesive for roll paper of Example 6 was obtained.
Example 7
Using the same method as in Example 1 except that (B-5) was used instead of (B-3), an adhesive for roll paper of Example 7 was obtained.
実施例８
(B-3)の替わりに(B-4)を用いたことを除いて、実施例１と同様の方法を用いて、実施例８のロール状ペーパー用接着剤を得た。
実施例９
(B-3)の替わりに(B-7)を用いたことを除いて、実施例１と同様の方法を用いて、実施例９のロール状ペーパー用接着剤を得た。
実施例１０
(C-1)の替わりに(C-2)を用いたことを除いて、実施例１と同様の方法を用いて、実施例１０のロール状ペーパー用接着剤を得た。
Example 8
Using the same method as in Example 1 except that (B-4) was used instead of (B-3), an adhesive for roll paper of Example 8 was obtained.
Example 9
Using the same method as in Example 1 except that (B-7) was used instead of (B-3), an adhesive for roll paper of Example 9 was obtained.
Example 10
Using the same method as in Example 1, except that (C-2) was used in place of (C-1), an adhesive for roll-shaped paper of Example 10 was obtained.
実施例１１
(C-1)の替わりに(C-3)を用いたことを除いて、実施例１と同様の方法を用いて、実施例１１のロール状ペーパー用接着剤を得た。
実施例１２
(C-1)の替わりに(C-4)を用いたことを除いて、実施例１と同様の方法を用いて、実施例１２のロール状ペーパー用接着剤を得た。
実施例１３
(C-1)の替わりに(C-2)を用いたことを除いて、実施例２と同様の方法を用いて、実施例１３のロール状ペーパー用接着剤を得た。
Example 11
Using the same method as in Example 1 except that (C-3) was used in place of (C-1), an adhesive for roll paper of Example 11 was obtained.
Example 12
Using the same method as in Example 1 except that (C-4) was used instead of (C-1), an adhesive for roll paper of Example 12 was obtained.
Example 13
Using the same method as in Example 2, except that (C-2) was used in place of (C-1), an adhesive for roll-shaped paper of Example 13 was obtained.
実施例１４
(C-1)の替わりに(C-3)を用いたことを除いて、実施例２と同様の方法を用いて、実施例１４のロール状ペーパー用接着剤を得た。
実施例１５
(C-1)の替わりに(C-4)を用いたことを除いて、実施例２と同様の方法を用いて、実施例１５のロール状ペーパー用接着剤を得た。
実施例１６
(A-1)の量を４４部から７０部に、(C-1)の量を５０部から２６．８部に、（B-3)の量６部から３．２部に変更したことを除いて、実施例１と同様の方法を用いて、実施例１６のロール状ペーパー用接着剤を得た。
Example 14
A roll paper adhesive of Example 14 was obtained in the same manner as in Example 2 except that (C-3) was used instead of (C-1).
Example 15
Using the same method as in Example 2 except that (C-4) was used in place of (C-1), an adhesive for roll paper of Example 15 was obtained.
Example 16
The amount of (A-1) was changed from 44 parts to 70 parts, the amount of (C-1) was changed from 50 parts to 26.8 parts, and the amount of (B-3) was changed from 6 parts to 3.2 parts. A roll paper adhesive of Example 16 was obtained using the same method as in Example 1 except for.
実施例１７
(A-1)の量を４４部から３０部、(C-1)の量を５０部から６４部に変更したことを除いて、実施例１と同様の方法を用いて、実施例１７のロール状ペーパー用接着剤を得た。
実施例１〜１７のロール状ペーパー用接着剤１４１部(消泡剤１部含む)の組成を表１にまとめた。
Example 17
Using the same method as in Example 1, except that the amount of (A-1) was changed from 44 parts to 30 parts and the amount of (C-1) was changed from 50 parts to 64 parts, Example 17 An adhesive for roll paper was obtained.
Table 1 summarizes the composition of 141 parts (including 1 part of an antifoaming agent) of roll paper adhesives of Examples 1-17.
比較例１〜９のロール状ペーパー用接着剤を以下に示される処方および配合条件で製造した。
比較例１
攪拌装置を備えたフラスコに、水４０部、(A-1)を５０部、(C-1)を５０部添加し、６０℃に加熱して１時間攪拌し、混合液１４０部を得た。混合液に（Ｂ）粘性調整剤を添加しないで、室温（２３℃）に冷却し、その後、（D-1）１部を添加し、３０分間攪拌して、比較例１のロール状ペーパー用接着剤を得た。
The adhesive for roll-shaped paper of Comparative Examples 1-9 was manufactured by the prescription and compounding conditions shown below.
Comparative Example 1
To a flask equipped with a stirrer, 40 parts of water, 50 parts of (A-1) and 50 parts of (C-1) were added and heated to 60 ° C. and stirred for 1 hour to obtain 140 parts of a mixed solution. . Cool to room temperature (23 ° C.) without adding (B) viscosity modifier to the mixture, then add 1 part of (D-1) and stir for 30 minutes for the roll paper of Comparative Example 1 An adhesive was obtained.
比較例２
(A-1)５０部の替わりに(A-2)６７部を加え、水の添加量を４０部から２５部に変更したことを除いて、比較例１と同様の方法を用いて、比較例２のロール状ペーパー用接着剤を得た。
比較例３
(A-1)の替わりに（A'-3)を用いたことを除いて、比較例１と同様の方法を用いて、比較例３のロール状ペーパー用接着剤を得た。
比較例４
(A-1)の替わりに（A'-3)を用いたことを除いて、実施例１と同様の方法を用いて、比較例４のロール状ペーパー用接着剤を得た。
Comparative Example 2
(A-1) Instead of 50 parts, (A-2) 67 parts were added, and the amount of water was changed from 40 parts to 25 parts. The adhesive for roll paper of Example 2 was obtained.
Comparative Example 3
A roll paper adhesive of Comparative Example 3 was obtained in the same manner as in Comparative Example 1, except that (A'-3) was used instead of (A-1).
Comparative Example 4
A roll paper adhesive of Comparative Example 4 was obtained in the same manner as in Example 1 except that (A'-3) was used instead of (A-1).
比較例５
(A-1)の替わりに（A'-3)を用いたことを除いて、実施例３と同様の方法を用いて、比較例５のロール状ペーパー用接着剤を得た。
比較例６
(A-1)の替わりに（A'-4)を用い、水の添加量を４０部から８８０部に変更したことを除いて、実施例１と同様の方法を用いて、比較例６のロール状ペーパー用接着剤を得た。４０部の水を用いても、(A'-4)は、十分に溶解しなかったので、水の添加量を増やして、粘度を調節した。
比較例７
(A-1)の替わりに（A'-5)を用い、水の添加量を４０部から８８０部に変更したことを除いて、実施例１と同様の方法を用いて、比較例７のロール状ペーパー用接着剤を得た。比較例６と同様に水の添加量を増やして、粘度を調節した。
Comparative Example 5
A roll paper adhesive of Comparative Example 5 was obtained in the same manner as in Example 3 except that (A'-3) was used instead of (A-1).
Comparative Example 6
(A'-4) was used instead of (A-1), and the same method as in Example 1 was used except that the amount of water added was changed from 40 parts to 880 parts. An adhesive for roll paper was obtained. Even when 40 parts of water was used, (A'-4) did not dissolve sufficiently, so the amount of water added was increased to adjust the viscosity.
Comparative Example 7
(A'-5) was used instead of (A-1), and the same method as in Example 1 was used except that the amount of water added was changed from 40 parts to 880 parts. An adhesive for roll paper was obtained. As in Comparative Example 6, the amount of water added was increased to adjust the viscosity.
比較例８
(A-1)の替わりに(B-8)を用い、水の添加量を４０部から４４０部に変更したことを除いて、実施例１と同様の方法を用いて、比較例８のロール状ペーパー用接着剤を得た。比較例６と同様に水の添加量を増やして粘度を調節した。
比較例９
攪拌装置を備えたフラスコに、水40部、(A-1)を79部、(B-3)を21部添加し、60℃に加熱して１時間攪拌し、混合物を得た。混合物を室温に冷却し、(D-1)１部を添加後、30分間攪拌して、比較例９のロール状ペーパー用接着剤を得た。
比較例１〜９のロール状ペーパー用接着剤（消泡剤１部含む）の組成を表２にまとめた。
Comparative Example 8
The roll of Comparative Example 8 was used in the same manner as in Example 1 except that (B-8) was used instead of (A-1) and the amount of water added was changed from 40 parts to 440 parts. An adhesive for paper was obtained. As in Comparative Example 6, the viscosity was adjusted by increasing the amount of water added.
Comparative Example 9
40 parts of water, 79 parts of (A-1) and 21 parts of (B-3) were added to a flask equipped with a stirrer, heated to 60 ° C. and stirred for 1 hour to obtain a mixture. The mixture was cooled to room temperature, 1 part of (D-1) was added, and the mixture was stirred for 30 minutes to obtain an adhesive for roll paper of Comparative Example 9.
Table 2 shows the compositions of the adhesives for roll paper of Comparative Examples 1 to 9 (including 1 part of antifoaming agent).
実施例および比較例のロール状ペーパー用接着剤について、評価試験を実施した。試験方法及び評価基準を以下に記載する。 An evaluation test was conducted on the adhesives for roll-shaped paper of Examples and Comparative Examples. Test methods and evaluation criteria are described below.
〈剥離性試験〉
実施例及び比較例のロール状ペーパー用接着剤の各々を、バーコーターNO.40（日本コーティングテスター株式会社）を用いて、市販のトイレットロール用紙管原紙に塗工（塗工量：７０〜８０ｇ／ｍ２Wet）し、この紙管を市販の２プライ−トイレットロール状ペーパー紙に張り合わせた。室温（２３℃）で、２４時間乾燥後、接着剤の剥離性を評価した。
（評価基準）
〇：ペーパーが破れないで、紙管から容易に剥がれる
△：ペーパーが紙管から剥がれるときに、わずかに破れる
×：ペーパーが紙管から剥がれるときに、破れる
<Peelability test>
Each of the adhesives for roll paper of Examples and Comparative Examples was coated on a commercial toilet roll paper tube base paper using a bar coater No. 40 (Nippon Coating Tester Co., Ltd.) (Coating amount: 70 to 80 g). / M 2 Wet), and the paper tube was laminated to a commercially available two-ply toilet roll paper. After drying at room temperature (23 ° C.) for 24 hours, the peelability of the adhesive was evaluated.
(Evaluation criteria)
○: The paper does not tear and easily peels off from the paper tube. △: It tears slightly when the paper peels off from the paper tube. ×: It tears when the paper peels off from the paper tube.
〈初期接着性試験〉
実施例及び比較例で製造したロール状ペーパー用接着剤の各々を、市販の２プライ−トイレットロール状ペーパー紙に、薄塗り塗工条件及び厚塗り塗工で塗工した。各塗工条件で塗工した接着剤について、塗工直後に、室温で、タックレベルを指蝕試験によって評価した。
薄塗り塗工条件：バーコーターNO.6（日本コーティングテスター株式会社）を用いて、塗工量：１３〜１４ｇ／ｍ２Wetで塗工した。
厚塗り塗工条件：バーコーターNO.70（日本コーティングテスター株式会社）を用いて、塗工量１３０〜１４０ｇ／ｍ２Wetで塗工した。
（評価基準）
◎：非常にタックが強い
〇：タックが強い
△：ややタックがある
×：全くタックがない
<Initial adhesion test>
Each of the adhesives for roll-shaped paper manufactured by the Example and the comparative example was apply | coated to the commercially available 2-ply-toilet roll-shaped paper paper by thin coating conditions and thick coating. About the adhesive agent coated on each coating condition, the tack level was evaluated by the finger-corrosion test at room temperature immediately after coating.
Thin coating conditions: Bar coater No. 6 (Nippon Coating Tester Co., Ltd.) was used, and the coating amount was 13 to 14 g / m 2 Wet.
Thick coating conditions: Coating was performed at a coating amount of 130 to 140 g / m 2 Wet using a bar coater No. 70 (Nippon Coating Tester Co., Ltd.).
(Evaluation criteria)
◎: Very strong tack 〇: Strong tack △: Slightly tack ×: No tack at all
〈べたつき試験〉
実施例及び比較例で製造したロール状ペーパー用接着剤の各々を、バーコーターNO.70（日本コーティングテスター株式会社）を用いて、紙管原紙に塗工（塗工量１３０〜１４０ｇ／ｍ２Wet）し、この紙管を２プライ−トイレットロール状ペーパー紙と貼りあわせた。室温（２３℃）で２４時間放置後、紙管と２プライ−トイレットロール状ペーパー紙とを剥がした後、接着剤が塗工された面のタックレベルを指蝕試験によって評価した。
（評価基準）
◎：全くべたつきがない
〇：ほとんどべたつきがない
△：ややべたつきがある
×：べたつきがある
<Stickness test>
Each of the adhesives for rolled paper produced in Examples and Comparative Examples is coated on a paper tube base paper using a bar coater No. 70 (Nippon Coating Tester Co., Ltd.) (coating amount 130 to 140 g / m 2). Wet), and this paper tube was bonded to 2-ply-toilet roll paper. After leaving at room temperature (23 ° C.) for 24 hours, the paper tube and the 2-ply-toilet roll paper were peeled off, and then the tack level of the surface coated with the adhesive was evaluated by a finger-corrosion test.
(Evaluation criteria)
◎: No stickiness ◯: Little stickiness △: Some stickiness ×: Stickiness
実施例１〜１７及び比較例１〜９のロール状ペーパー用接着剤の剥離性試験、初期接着性試験、べたつき試験の評価結果を、下記表３及び４にまとめた。 Tables 3 and 4 below show the evaluation results of the peelability test, the initial adhesion test, and the stickiness test of the adhesives for roll paper of Examples 1 to 17 and Comparative Examples 1 to 9.
表１及び３に示されるように、実施例１〜１７の接着剤は、剥離性及び初期接着性に優れ、べたつきも生じなかった。これらの性能をバランス良く維持する接着剤は、ロール状ペーパー用接着剤、特にピックアップ剤として有効である。
比較例１〜９の接着剤は、表２及び４に示されるように、剥離性、初期接着性、べたつきのいずれかに問題がある。
As shown in Tables 1 and 3, the adhesives of Examples 1 to 17 were excellent in peelability and initial adhesiveness, and did not cause stickiness. An adhesive that maintains these performances in a well-balanced manner is effective as an adhesive for rolled paper, particularly as a pickup agent.
As shown in Tables 2 and 4, the adhesives of Comparative Examples 1 to 9 have problems in any of peelability, initial adhesiveness, and stickiness.
比較例１〜３の接着剤は、成分（Ｂ）を含まないので、初期接着性が低下している。比較例４〜８の接着剤は、グルコース成分である（Ａ−１）又は（Ａ−２）を含まないので、実施例の接着剤と比較すると、剥離性に劣る。比較例４及び５は、糖類として（Ａ’−３）デキストリンを含むが、グルコースを含まないので、剥離性が低下している。比較例６〜７は、糖類として（Ａ’−４）カルボキシメチルセルロースや（Ａ’−５）メチルセルロースを含むが、グルコースを含まず、更に剥離性や初期接着性が低下している。比較例８は、ポリビニルアルコールを含むが、糖類を全く含まず、剥離性や初期接着性に乏しい。比較例９は、成分（Ｃ）を含まないので、べたつきを生じる。 Since the adhesives of Comparative Examples 1 to 3 do not contain the component (B), the initial adhesiveness is lowered. Since the adhesives of Comparative Examples 4 to 8 do not contain (A-1) or (A-2) which is a glucose component, they are inferior in peelability as compared with the adhesives of Examples. Comparative Examples 4 and 5 contain (A′-3) dextrin as a saccharide, but do not contain glucose, so that the peelability is reduced. Comparative Examples 6 to 7 contain (A′-4) carboxymethyl cellulose and (A′-5) methyl cellulose as saccharides, but do not contain glucose, and the peelability and initial adhesiveness are further reduced. Although the comparative example 8 contains polyvinyl alcohol, it does not contain saccharides at all and has poor peelability and initial adhesiveness. Since Comparative Example 9 does not contain the component (C), stickiness is generated.
これらの結果から、ロール状ペーパー用接着剤として優れた性能を持つために、３成分（（Ａ）〜（Ｃ））を必須成分とすることが明らかとなった。 From these results, it became clear that the three components ((A) to (C)) are essential components in order to have excellent performance as an adhesive for rolled paper.
本発明は、ロール状ペーパー用接着剤、及びそのロール状ペーパーが塗布されたロール状ペーパーを提供できる。本発明に係るロール状ペーパーは、特にピックアップ剤として有用である。 The present invention can provide an adhesive for roll-shaped paper and a roll-shaped paper coated with the roll-shaped paper. The roll paper according to the present invention is particularly useful as a pickup agent.
Claims (6)
（Ａ）糖類はグルコースを含み、
（Ｂ）粘性調整剤は、重量平均分子量２０，０００〜４，０００，０００の水性高分子を含み、
重量平均分子量２０，０００〜４，０００，０００の水性高分子は、重量平均分子量２５，０００〜４００，０００のビニルピロリドン系重合体及び／又は重量平均分子量３００，０００〜３，５００，０００のアルキレンオキシド系重合体であり、
（Ａ）〜（Ｃ）の総重量１００重量部に対し、（Ａ）糖類は、固形分として１０〜９０重量部が配合され、（Ｂ）粘性調整剤は、固形分として１〜１０重量部が配合される
ことを特徴とするロール状ペーパー用接着剤。 An adhesive for rolled paper containing (A) a saccharide, (B) a viscosity modifier and (C) a glycol and / or triol having a weight average molecular weight of less than 20,000,
(A) the saccharide contains glucose;
(B) The viscosity modifier includes an aqueous polymer having a weight average molecular weight of 20,000 to 4,000,000,
An aqueous polymer having a weight average molecular weight of 20,000 to 4,000,000 is a vinylpyrrolidone polymer having a weight average molecular weight of 25,000 to 400,000 and / or a weight average molecular weight of 300,000 to 3,500,000. Ri alkylene oxide polymer der,
10 to 90 parts by weight of (A) saccharide is blended as a solid content, and (B) the viscosity modifier is 1 to 10 parts by weight as a solid content with respect to a total weight of 100 parts by weight of (A) to (C). An adhesive for rolled paper, characterized in that is formulated .
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010078560A JP5871452B2 (en) | 2010-03-30 | 2010-03-30 | Adhesive for roll paper and roll paper |
| PCT/US2011/028992 WO2011126707A2 (en) | 2010-03-30 | 2011-03-18 | Article and an adhesive for a roll-shaped paper |
| EP11766368A EP2553031A2 (en) | 2010-03-30 | 2011-03-18 | Article and an adhesive for a roll-shaped paper |
| CN2011800172680A CN102892853A (en) | 2010-03-30 | 2011-03-18 | An article and an adhesive for a roll-shaped paper |
| US13/613,394 US20130011671A1 (en) | 2010-03-30 | 2012-09-13 | Article and an adhesive for a roll-shaped paper |
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| JP2010078560A JP5871452B2 (en) | 2010-03-30 | 2010-03-30 | Adhesive for roll paper and roll paper |
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| JP5871452B2 true JP5871452B2 (en) | 2016-03-01 |
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| JP6077795B2 (en) * | 2012-08-29 | 2017-02-08 | 大王製紙株式会社 | Kitchen paper roll manufacturing method |
| JP5938079B2 (en) | 2014-09-30 | 2016-06-22 | 大王製紙株式会社 | Manufacturing method of ply adhesive paste and sanitary thin paper |
| DE102015226578A1 (en) | 2015-12-22 | 2017-06-22 | Tesa Se | Process for the preparation of colorless and aging-stable polyacrylate-based pressure-sensitive adhesives |
| PL3436087T3 (en) * | 2016-04-01 | 2020-08-10 | Essity Operations France | Coreless roll of absorbent sheet and method for manufacturing the same |
| US10213066B2 (en) | 2016-04-01 | 2019-02-26 | Essity Operations France | Coreless roll of absorbent sheet and method for manufacturing the same |
| RU2751637C1 (en) | 2017-09-29 | 2021-07-15 | Эссити Хайджин Энд Хелт Актиеболаг | Coreless reel of an absorbent sheet and method for manufacture thereof |
| US20200277737A1 (en) * | 2017-09-29 | 2020-09-03 | Essity Hygiene And Health Aktiebolag | Coreless roll of absorbent sheet and method for manufacturing the same |
| FI3688225T3 (en) * | 2017-09-29 | 2023-01-13 | Coreless roll of absorbent sheet and method for manufacturing the same | |
| JP7289637B2 (en) * | 2018-11-27 | 2023-06-12 | ヘンケルジャパン株式会社 | Water-based adhesive |
| JP7288807B2 (en) * | 2019-06-03 | 2023-06-08 | 株式会社Ｄｎｐファインケミカル | Water-based temporary fixing adhesive and method for manufacturing various members or parts using the water-based temporary fixing adhesive |
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| US7915338B2 (en) * | 2005-12-28 | 2011-03-29 | 3M Innovative Properties Company | Adhesive with alkanoate blend |
| CN101418196A (en) * | 2007-10-24 | 2009-04-29 | 天津大学 | Pressure sensitive viscous composite using rice flour as raw material and use thereof |
| JP5348932B2 (en) * | 2008-04-23 | 2013-11-20 | ヘンケルジャパン株式会社 | Label adhesive |
-
2010
- 2010-03-30 JP JP2010078560A patent/JP5871452B2/en active Active
-
2011
- 2011-03-18 CN CN2011800172680A patent/CN102892853A/en active Pending
- 2011-03-18 EP EP11766368A patent/EP2553031A2/en not_active Withdrawn
- 2011-03-18 WO PCT/US2011/028992 patent/WO2011126707A2/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011126707A2 (en) | 2011-10-13 |
| JP2011206369A (en) | 2011-10-20 |
| EP2553031A2 (en) | 2013-02-06 |
| CN102892853A (en) | 2013-01-23 |
| WO2011126707A3 (en) | 2012-01-26 |
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