WO2012070311A1 - Composition adhésive et son procédé de fabrication - Google Patents

Composition adhésive et son procédé de fabrication Download PDF

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Publication number
WO2012070311A1
WO2012070311A1 PCT/JP2011/072571 JP2011072571W WO2012070311A1 WO 2012070311 A1 WO2012070311 A1 WO 2012070311A1 JP 2011072571 W JP2011072571 W JP 2011072571W WO 2012070311 A1 WO2012070311 A1 WO 2012070311A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
emulsion
vinyl acetate
monomer
containing copolymerizable
Prior art date
Application number
PCT/JP2011/072571
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English (en)
Japanese (ja)
Inventor
慎一 大河原
和也 溝田
Original Assignee
昭和電工株式会社
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Publication date
Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to JP2012545645A priority Critical patent/JP5920986B2/ja
Publication of WO2012070311A1 publication Critical patent/WO2012070311A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09J2431/00—Presence of polyvinyl acetate

Definitions

  • the present invention relates to an adhesive composition, and particularly to an adhesive composition useful as an adhesive for plywood and wood that requires water resistance, and a method for producing the same.
  • a vinyl acetate resin emulsion using polyvinyl alcohol as a protective colloid is mainly used for paper tube and paper industry bonding due to its excellent adhesive strength and good workability such as roll suitability and mild odor. Widely used in adhesives and adhesives for wood.
  • the vinyl acetate resin emulsion has the disadvantage that the water resistance is low because the resin itself is hydrophilic and the protective colloid is water-soluble. Therefore, various methods have been studied for the purpose of improving the water resistance of the vinyl acetate resin emulsion.
  • Patent Document 1 mainly discloses a vinyl acetate-acrylic acid resin emulsion obtained by emulsion polymerization of vinyl acetate and acrylic acid in the presence of polyvinyl alcohol modified with an ⁇ -olefin having 4 or less carbon atoms.
  • a resin composition as a component has been proposed.
  • Patent Document 2 discloses a vinyl ester monomer of a fatty acid having 4 or less carbon atoms such as vinyl acetate and a carboxyl group such as acrylic acid in the presence of polyvinyl alcohol modified with an ⁇ -olefin having 4 or less carbon atoms.
  • An aqueous emulsion composition is proposed in which an aluminum compound is added to an aqueous emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer and a vinyl ester monomer of a fatty acid having 5 or more carbon atoms such as vinyl versatate.
  • an aluminum compound is added to an aqueous emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer and a vinyl ester monomer of a fatty acid having 5 or more carbon atoms such as vinyl versatate.
  • Patent Document 1 has a problem that water resistance and hot water resistance are insufficient.
  • the water-based emulsion composition of Patent Document 2 has good water resistance due to the addition of an aluminum compound, it has a problem of insufficient storage stability at high temperatures and coloring over time.
  • the present invention solves the above-mentioned problems of the prior art, has an excellent water resistance and hot water resistance, does not color with time, and is excellent in storage stability at high temperatures.
  • the purpose is to provide.
  • the present invention is an adhesive composition obtained by emulsion polymerization of a vinyl acetate monomer and an acetoacetoxy group-containing copolymerizable monomer using ethylene-modified polyvinyl alcohol as a protective colloid.
  • an environment-friendly adhesive composition that has excellent water resistance and hot water resistance, does not color with time, and has excellent storage stability at high temperatures.
  • the adhesive composition according to the present invention is mainly composed of a copolymer emulsion of a vinyl acetate monomer having ethylene-modified polyvinyl alcohol as a protective colloid and an acetoacetoxy group-containing copolymerizable monomer.
  • Examples of the acetoacetoxy group-containing copolymerizable monomer used in the present invention include allyl acetoacetate, vinyl acetoacetate, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, 2-acetoacetoxypropyl acrylate, 2- (Meth) acrylic acid acetoacetate ester of alkylene glycol such as acetoacetoxypropyl methacrylate, 2-cyanoacetoacetoxyethyl methacrylate, etc.
  • Crotonic acid acetoacetate of alkylene glycol such as 2-acetoacetoxyethyl crotonate, 2-acetoacetoxypropyl crotonate Esters, N- (acetoacetoxymethyl) acrylamide, N- (acetoacetoxymethyl) methacrylamide, N- (acetoacetoxyethyl) acrylic , N-alkylol (meth) acrylamide acetoacetate such as N- (acetoacetoxyethyl) methacrylamide and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl Acetacetylates of ethylenically unsaturated monomers having hydroxyl groups such as methacrylate, 1,4-butylene glycol monoacrylate, 1,4-butylene glycol monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide, hydroxys
  • acetoacetoxy group-containing copolymerizable monomers may be used alone or in combination of two or more.
  • 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate are preferable because they are inexpensive and easily available.
  • the use ratio of the vinyl acetate monomer and the acetoacetoxy group-containing copolymerizable monomer is preferably 90% by weight to 99.5% by weight of the vinyl acetate monomer, more preferably 95% by weight to 99% by weight,
  • the acetoacetoxy group-containing copolymerizable monomer is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight.
  • the proportion of the acetoacetoxy group-containing copolymerizable monomer is less than 0.5% by weight, it becomes difficult to obtain a resin emulsion excellent in water resistance and hot water resistance. Is not preferred because emulsion polymerization is less likely to proceed and the stability of the resulting resin emulsion tends to decrease.
  • the adhesive composition according to the present invention can be produced by a known emulsion polymerization method using ethylene-modified polyvinyl alcohol as a protective colloid.
  • ethylene-modified polyvinyl alcohol as a protective colloid.
  • the copolymerization reactivity between the vinyl acetate monomer and the acetoacetoxy group-containing copolymerizable monomer is low, the vinyl acetate monomer and the acetoacetoxy group-containing copolymerizable monomer are added immediately after the start of the polymerization reaction. If dripped simultaneously, it is easy to gel.
  • emulsion particles pre-reaction of vinyl acetate monomer in the presence of ethylene-modified polyvinyl alcohol form seed particles.
  • the seed particles are preferably emulsion-polymerized with an acetoacetoxy group-containing copolymerizable monomer.
  • the polymerization reaction is initiated by a known polymerization initiator.
  • Typical polymerization initiators include red peroxide polymerization initiators such as potassium persulfate, ammonium persulfate, hydrogen peroxide-tartaric acid, hydrogen peroxide-ascorbic acid, and organic peroxides such as benzoyl peroxide and cumene hydroperoxide. And azo compounds such as azobisisobutylnitrile.
  • the temperature at the time of polymerization varies depending on the polymerization initiator used, but is usually 60 ° C. to 90 ° C.
  • the reaction time is not particularly limited and may be appropriately adjusted according to the blending amount of each component, the reaction temperature, and the like.
  • the ethylene-modified polyvinyl alcohol used in the emulsion polymerization may be a saponified copolymer of ethylene and a vinyl ester such as vinyl acetate, vinyl formate, or vinyl propionate. Registered trademark) series and the like.
  • ethylene-modified polyvinyl alcohols having different degrees of ethylene modification, saponification, polymerization, etc. it is possible to adjust the viscosity, graft ratio, adhesion to the substrate, cohesion and the like.
  • the ethylene-modified polyvinyl alcohol as the protective colloid is preferably 5 to 20 parts by weight, more preferably 10 parts by weight with respect to 100 parts by weight as a total of the vinyl acetate monomer and the acetoacetoxy group-containing copolymerizable monomer. Used in a proportion of 15 to 15 parts by weight.
  • a surfactant may be appropriately used as long as the effects of the present invention are not impaired.
  • various additives can be mix
  • Additives include cellulose derivatives such as polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose and starch, natural and synthetic water-soluble polymers such as casein and polyacrylamide, dibutyl phthalate, dioctiphthalate, texanol, DBE (Dibasic ester) Plasticizers and film forming aids such as rosin, terpene resin and other tackifiers, pigments such as titanium oxide, inorganic substances such as calcium carbonate and clay, various antifoaming agents, preservatives and the like are appropriately used.
  • Example 1 Into a 1 liter separable flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, Exebar (registered trademark) HR-3010 (manufactured by Kuraray Co., Ltd., saponification degree: 99.3 mol%, polymerization degree) 1000) 25 g, Exeval (registered trademark) RS-1717 (manufactured by Kuraray Co., Ltd., degree of saponification 93.0 mol%, degree of polymerization 1700) and water 420 g were charged, the temperature was raised to 90 ° C. or higher, and ethylene-modified polyvinyl alcohol was added. Dissolved.
  • Exebar registered trademark
  • HR-3010 manufactured by Kuraray Co., Ltd., saponification degree: 99.3 mol%, polymerization degree
  • Exeval (registered trademark) RS-1717 manufactured by Kuraray Co., Ltd., degree of saponification 93.0 mol%
  • AAEM 2-acetoacetoxyethyl methacrylate
  • the external temperature was controlled so that the temperature inside the separable flask during emulsion copolymerization was 75 ° C to 85 ° C. After completion of dropping, the mixture was kept at 75 ° C. to 85 ° C. for 1 hour, then cooled to 30 ° C. or less, and 25 g of texanol was added to obtain a resin emulsion of Example 1.
  • the obtained resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.0% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13960 mPa ⁇ s.
  • Example 2 A resin emulsion of Example 2 was obtained by performing the same operation as in Example 1 except that the amount of AAEM added was changed to 22.5 g.
  • the resulting resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.9% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13800 mPa ⁇ s. Met.
  • Example 3 A resin emulsion of Example 3 was obtained in the same manner as in Example 1, except that 2-acetoacetoxyethyl methacrylate (AAEM) was changed to 2-acetoacetoxyethyl acrylate.
  • the obtained resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.0% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13500 mPa ⁇ s. Met.
  • Example 4 Except that 2-acetoacetoxyethyl methacrylate (AAEM) was changed to 2-acetoacetoxyethyl acrylate and the addition amount was changed to 22.5 g, the same operation as in Example 1 was performed, and the resin emulsion of Example 4 was obtained. Obtained.
  • the resulting resin emulsion had a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.7 wt%, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13900 mPa ⁇ s. Met.
  • Example 1 Except not adding AAEM, operation similar to Example 1 was performed and the resin emulsion of the comparative example 1 was obtained.
  • the obtained resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 49.0% by weight, and a viscosity (BH viscometer, 10 rotations, 23 ° C.) of 13000 mPa ⁇ s. Met.
  • ⁇ Comparative Example 2> Except for using 50 g of Kuraray Poval PVA 117 (manufactured by Kuraray Co., Ltd., degree of saponification of 98.5 mol%, degree of polymerization of 1700) instead of ethylene-modified polyvinyl alcohol, the same as in Example 1 The operation was carried out to obtain a resin emulsion of Comparative Example 2.
  • the obtained resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 48.7% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 14000 mPa ⁇ s. Met.
  • Comparative Example 3 A resin emulsion of Comparative Example 3 was obtained in the same manner as in Example 1 except that 12 g of acrylic acid was used instead of AAEM. The resulting resin emulsion has a solid content concentration (the solid content when dried at 105 ° C. for 1 hour) of 50.0% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13000 mPa ⁇ s. Met.
  • BH viscometer 10 revolutions, 23 ° C.
  • the resulting resin emulsion has a solid content concentration (solid content when dried at 105 ° C. for 1 hour) of 48.5% by weight, and a viscosity (BH viscometer, 10 revolutions, 23 ° C.) of 13500 mPa ⁇ s. Met.
  • a test piece of 75 mm ⁇ 75 mm was immersed in boiling water for 4 hours, then dried at 60 ° C. for 20 hours, further immersed in boiling water for 4 hours, and then dried at 60 ° C. for 3 hours.
  • the case where the length of the part where the side surface does not peel is 50 mm or more is evaluated as ⁇ , and even when one of the four samples is the length of the part where the side surface does not peel is less than 50 mm It was evaluated.
  • the resin emulsions of Examples 1 to 4 passed the JAS1 immersion peeling test had excellent compressive shear strength after repeated immersion in normal and hot water, and storage stability at high temperatures. It was very good. Further, gelation did not occur during the polymerization, and the polymerization stability was good. From the above, it can be said that the adhesive composition of the present invention is useful as an adhesive for plywood / woodwork.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Cette composition adhésive est obtenue par polymérisation en émulsion d'un monomère acétate de vinyle en présence d'un alcool polyvinylique modifié par l'éthylène afin de former des particules d'ensemencement, puis par polymérisation en émulsion d'un monomère copolymérisable à teneur en acétoacétoxy avec les particules d'ensemencement. En tant que monomère copolymérisable à teneur en acétoacétoxy, on préfère utiliser l'ester (méth)acrylique et acétoacétique d'un alkylène glycol. Cette composition adhésive est une composition adhésive respectueuse de l'environnement qui a une excellente résistance à l'eau et une excellente résistance à l'eau chaude, ne prend pas de couleur avec le temps et a une excellente stabilité au stockage aux températures élevées.
PCT/JP2011/072571 2010-11-24 2011-09-30 Composition adhésive et son procédé de fabrication WO2012070311A1 (fr)

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JP2012545645A JP5920986B2 (ja) 2010-11-24 2011-09-30 接着剤組成物の製造方法

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JP2010-261474 2010-11-24

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016060159A1 (fr) * 2014-10-14 2016-04-21 アイカ工業株式会社 Adhésif aqueux
CN109207070A (zh) * 2018-11-07 2019-01-15 温雄权 一种高耐水性的丙烯酸酯胶黏剂及其制备方法
JP6810307B1 (ja) * 2019-07-08 2021-01-06 株式会社クラレ 紙ストロー用水性接着剤及びそれを用いた紙ストロー
WO2021006234A1 (fr) * 2019-07-08 2021-01-14 株式会社クラレ Adhésif à base d'eau pour paille de papier, et paille de papier l'utilisant

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05287248A (ja) * 1992-04-10 1993-11-02 Sumitomo Chem Co Ltd 接着剤
JPH11172216A (ja) * 1997-12-12 1999-06-29 Shoei Kagaku Kogyo Kk 水系接着剤組成物
JP2000282004A (ja) * 1999-03-29 2000-10-10 Aica Kogyo Co Ltd 接着剤
JP2001123138A (ja) * 1999-10-26 2001-05-08 Konishi Co Ltd 合成樹脂エマルジョン型接着剤
JP2002256161A (ja) * 2001-02-27 2002-09-11 Unitika Chem Co Ltd 合成樹脂エマルジョン組成物
JP2002285119A (ja) * 2001-03-22 2002-10-03 Chuo Rika Kogyo Corp 酢酸ビニル系重合体エマルジョン接着剤
JP2003160764A (ja) * 2001-11-26 2003-06-06 Oji Paper Co Ltd 感圧接着シート

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05287248A (ja) * 1992-04-10 1993-11-02 Sumitomo Chem Co Ltd 接着剤
JPH11172216A (ja) * 1997-12-12 1999-06-29 Shoei Kagaku Kogyo Kk 水系接着剤組成物
JP2000282004A (ja) * 1999-03-29 2000-10-10 Aica Kogyo Co Ltd 接着剤
JP2001123138A (ja) * 1999-10-26 2001-05-08 Konishi Co Ltd 合成樹脂エマルジョン型接着剤
JP2002256161A (ja) * 2001-02-27 2002-09-11 Unitika Chem Co Ltd 合成樹脂エマルジョン組成物
JP2002285119A (ja) * 2001-03-22 2002-10-03 Chuo Rika Kogyo Corp 酢酸ビニル系重合体エマルジョン接着剤
JP2003160764A (ja) * 2001-11-26 2003-06-06 Oji Paper Co Ltd 感圧接着シート

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016060159A1 (fr) * 2014-10-14 2016-04-21 アイカ工業株式会社 Adhésif aqueux
CN106471084A (zh) * 2014-10-14 2017-03-01 爱克工业株式会社 水性粘接剂
CN109207070A (zh) * 2018-11-07 2019-01-15 温雄权 一种高耐水性的丙烯酸酯胶黏剂及其制备方法
JP6810307B1 (ja) * 2019-07-08 2021-01-06 株式会社クラレ 紙ストロー用水性接着剤及びそれを用いた紙ストロー
WO2021006234A1 (fr) * 2019-07-08 2021-01-14 株式会社クラレ Adhésif à base d'eau pour paille de papier, et paille de papier l'utilisant
CN114341303A (zh) * 2019-07-08 2022-04-12 株式会社可乐丽 纸吸管用水性粘接剂和使用其的纸吸管
CN114341303B (zh) * 2019-07-08 2023-08-18 株式会社可乐丽 纸吸管用水性粘接剂和使用其的纸吸管

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JP5920986B2 (ja) 2016-05-24

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