TW201038693A - Aqueous adhesive - Google Patents

Abstract

Provided is an aqueous adhesive which contains polyoxyalkylene modified vinyl alcohol-based polymer in aqueous phase. The vinyl alcohol-based polymer has polyoxyalkylene represented as following formula (I) on side chain, has a viscosity average polymerization degree of 200-3000, a saponification degree of 80-99.99 mole%, and polyoxyalkylene modification of 0.1-10 mole%. Thereby, it is able to provide an aqueous adhesive which has high initial adhesion of the important property in use, quick production, and excellent storage stability (viscosity stability, precipitation stability). (Wherein, R1 represents H atom or methyl; R2 represents H atom or alkyl with C1-C8. m and n represent separately repeat unit number of oxyalkylene unit, 1 ≤ m ≤ 10, 3 ≤ n ≤ 20.)

Description

201038693 VI. Description of the Invention: [Technical Field] The present invention relates to an aqueous binder containing a vinyl alcohol polymer having a specific functional group in an aqueous phase. [Prior Art] The aqueous adhesive has been treated with natural pastes such as starch, casein, gelatin, Guar gum, gum arabic, sodium alginate, etc.; CMC, oxidized starch, methyl cellulose, etc. Acrylate emulsion, polyvinyl acetate emulsion, synthetic resin emulsion such as ethylene/vinyl acetate copolymer emulsion; rubber latex such as SBR latex; and vinyl alcohol polymer (hereinafter sometimes abbreviated as "PVA") The main component is widely used alone or in combination. However, in addition to the lack of adhesion, lack of viscosity stability or spoilage of the adhesive solution, natural pastes or processed pastes are also difficult to continue to produce a paste of a certain quality for a long period of time. On the other hand, emulsions or latexes have excellent adhesion, but they have many problems such as lack of mechanical stability and serious surface crust. Q On the other hand, PVA-based water-based adhesives are inexpensive and have excellent adhesion, and are used in the following of cardboard, followed by corrugated paper, followed by paper, followed by Japanese paper paste and wallpaper, etc. The emulsion blender is used in woodworking, fiber processing, paper, and the like. Such PV A-based aqueous adhesives are widely used and are recommended as balanced adhesives. However, even in the case of the PVA-based aqueous binder, in recent years, progress has been made in the rapid coating of an aqueous binder which is aimed at reducing the cost or improving productivity, and to improve the handleability (stabilization of the coating amount, viscosity stability, sedimentation stability) Sexuality, etc.) The requirement for improving the efficiency of the work as an aqueous binder is increased by -4-201038693. For the improvement of the above-mentioned requirements, an adhesive containing PVA' clay and a water-soluble boron compound as a main component is proposed in Japanese Patent Laid-Open Publication No. Sho 62_1 95070 (Patent Document 1). Such an adhesive can improve rapid adhesion and initial adhesion. It has been widely used in industries such as corrugated paper. However, due to the fear of affecting the environment, there has been a tendency to restrict the use of boric acid in recent years, so there is a strong demand for substitutes. Moreover, there are many attempts to improve the initial adhesion by using a compound of a crosslinking agent of PVA (such as urea-formaldehyde tree 0, etc.), but substantially the safety of the compound used as a crosslinking agent is problematic. There are many cases where the viscosity stability of the composition is also problematic. Japanese Patent Publication No. 2004-239085 (Patent Document 2) proposes that an adhesive containing a specific metal salt has improved rapid coating properties and initial adhesion, but there is a problem in solution stability, which is not sufficiently satisfactory in the industry. Further, as disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei No. 1 1 - 02 1 5 30 (Patent Document 3), it is proposed that (A) a modified polyvinyl alcohol containing 1 to 20 mol% of an ethylene unit, (B) starch, and (C) a sugar Although the agent has improved adhesion, water resistance, and storage stability, it is insufficient for quick coating properties, heat resistance, and creep resistance. Further, JP-A-2001-164219 (Patent Document 4) proposes a vinyl alcohol-based polymer having (a) a molecular weight of 1.8 to 3.5 mol% 1,2-ethylene glycol bonded and having a degree of saponification of 90 mol% or more. And (b) the inorganic chelating agent is an adhesive of an essential component, and although the viscosity stability, the rapid coating property, and the initial adhesion are improved, there is a problem that the inorganic chelating agent settles during long-term storage.

Japanese Laid-Open Patent Publication No. SHO-59-158 (No. 5) proposes a method for producing a modified PVA 201038693, which comprises saponifying a copolymer containing an alkyloxy group-containing unsaturated monomer and vinyl acetate. The oxygen-extended alkyl group used in the production of the unsaturated PVA, for example, the number of repeating units is from 1 to 50

Polyoxyethylene, polyoxypropylene, polyoxybutenyl and the like. Further, an adhesive is also described in various applications exemplified by the modified PVA. Further, the above aqueous binder is used in combination with various aqueous emulsions for the purpose of improving adhesion to various adherends or increasing the concentration of solid components to enhance initial adhesion, but even this is not possible. Fully solve the above problems. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 04-239085 [Patent Document 3] Japanese Patent Publication No. Hei No. Hei 04-239085 [Patent Document 3] JP-A No. 1 1 - 〇2 1 5 3 0 [Patent Document 4] [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei 59- No. 55-55408. SUMMARY OF THE INVENTION [The present invention has been made to solve the problems of the prior art described above, and has an important performance as an aqueous adhesive. It is an initial adhesive, and it can be produced quickly, and it is intended to preserve an aqueous adhesive excellent in stability (viscosity stability, sedimentation stability). [Means for Solving the Problem] The inventors of the present invention have produced an industrial scale on the basis of the characteristics of an aqueous binder which does not impair "high safety" and "softness to the environment", and then 201038693 Ο 'capable of rapid production' and The results of careful study of the aqueous binders which are excellent in stability (viscosity stability and sedimentation stability) have been found to contain polyoxyalkylene-modified vinyl alcohol-based polymers in the aqueous phase (hereinafter sometimes abbreviated as yttrium-modified PVA). An aqueous binder, that is, the vinyl alcohol-based polymer contains, in its branch, a polyoxyalkylene group represented by the following general formula (I) (hereinafter sometimes abbreviated as hydrazine), and the vinyl alcohol-based polymer The average degree of polymerization of the viscosity is 200 to 3 000, the degree of saponification is 80 to 99.99 mol%, and the polyoxyalkylene modification amount is 〇.1 to 1 mol% of the aqueous binder is suitable for the target aqueous binder The present invention has been completed. C2h5 C-C-O- h2 h (I) R2 R1

I -〇一〇η2 η where 'R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; m and η respectively represent the number of repeating units of the oxygen-and-tropanene unit, ISm $10, 3SnS20 . Here, the unit indicated by the repeating unit m is referred to as unit 1, and the unit represented by the repeating unit η is referred to as unit 2. The configuration state of unit 1 and unit 2 can be either random or block. The polyoxyalkylene-modified vinyl alcohol-based polymer is preferably obtained by saponification by copolymerizing a polymer monomer having a polyoxyalkylene group represented by the following general formula (II) with a vinyl ester. R4 HC=C—X R3 ~C~C~〇· Η. Η -R2 (H) wherein R1 is a hydrogen atom or a methyl group, and R2 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; m and η Respectively indicate the number of repeating units of the oxygen-deionized unit, ISm 201038693 $10, 3SnS20; R3 is a hydrogen atom or a COOM group, Μ is a hydrogen atom, an alkali metal or an ammonium group; R4 is a hydrogen atom, a methyl group or a —CH 2 —COOM group , Μ is as defined above; X is a 0-, a CHa-〇-, - (CH2)k-, -CO-, - C0-0- or -CO-NR5-, R5 is a hydrogen atom or a carbon number of 1 ~ a saturated alkyl group of 4, k represents the number of repeating units of the methylene unit, 15.

The above polyoxyalkylene-modified vinyl alcohol-based polymer is obtained by copolymerizing a polymer monomer having a polyoxyalkylene group represented by the following general formula (III) with a vinyl ester and then saponifying to obtain a better R4 R5 II h2c. = c—c—n——ο R1 Icco h2 h C—C—O R 2 H 2 H jn (ΠΙ) where R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; m and η respectively represent the number of repeating units of the oxyalkylene unit, ISm €10,3SnS20; R4 is a hydrogen atom, a methyl group or a —CH 2 —C00M group, Q Μ is a hydrogen atom, an alkali metal or an ammonium group; and R 5 is a hydrogen atom. Or a saturated alkyl group having a carbon number of 1 to 4. The aqueous adhesive of the present invention preferably has a (co)polymerized emulsion comprising at least one monomer selected from the group consisting of an ethylenically unsaturated monomer and a diene monomer, and further contains an inorganic or organic hydrazine. Filling is also good. Further, the adhesive for paper or woodworking is a suitable embodiment of the aqueous adhesive of the present invention. [Effect of the invention] When the aqueous adhesive of the present invention is compared with the prior aqueous adhesive, the initial adhesion is high due to 201038693. Ability to produce quickly. Further, the aqueous binder of the present invention is excellent in storage stability when compared with the prior aqueous binder. [Embodiment] Hereinafter, the present invention will be described in detail. The present invention is an aqueous binder containing P 〇A modified PVA in an aqueous phase, the pVa having a POA group represented by the above general formula (I) in its branch, and the average degree of polymerization of the PVA is 200 〜 3 000, the degree of saponification is 80 to 99.99 mol%, and the amount of polyoxyalkylene modification is 〇"~1 0 mol%. In the present invention, the number of repeating units m of the unit 1 of the POA group in which the pVA is contained in the aqueous phase of the aqueous binder is required to be 3SnS20. When m and η are within this range, the aqueous binder can exhibit excellent adhesion, especially initial adhesion. m is preferably 2 or more. m is preferably 5 or less, and 3 or less is preferred. η is more preferably 5 or more and more preferably 8 or more. η is preferably 1 or less, more preferably 15 or less. In the case of a PVA having a fluorenyl group represented by the above formula (I), the amount of thiol modification of the chain should be 〇.1~1〇mol%, and ο.η~8 mol% is better. 0.2 to 6 mol% is better. When the thiol modification amount is less than 0.1 mol%, the aqueous binder containing the cerium-modified PVA in the aqueous phase of the present invention cannot exhibit the target initial adhesion. On the other hand, when it exceeds 1% by mole, the hydrophobicity of the ruthenium-modified PV oxime increases, which may cause a decrease in storage stability or water solubility, which is not preferable. The amount of the POA-based modification is expressed by the molar fraction of the poa group relative to the PVA main chain methylene group. The POA-based modification amount of the POA-modified PVA, for example, the PVA-modified POA-modified polyvinyl ester, and the specific example may be a polyvinyl acetate modified by p0A (hereinafter, polyvinyl acetate is abbreviated as PVAc). 201038693 Proton NMR was obtained. Specifically, the POA-modified PVAc was sufficiently subjected to re-sedimentation purification with n-hexane/acetone three times or more, and then dried at 50 ° C under reduced pressure for 2 days to prepare a P0A-modified PVAc for analysis. After dissolving the PVAc in CDCh, it was measured at room temperature using a 500 MHz proton NMR UEOL GX-500). From the peak of the methylene group of the vinyl ester main chain 値ct (4.7~5.2ppm) and the peak of the methyl group from the end of the unit 2 (0.8~l.Oppm), the modified amount of the POA group is calculated by the following formula . ^ S (mole%) = {(/3 proton number / 3η) / [α proton number + (cold Ο proton number / 3η)]} χ 100 η is the number of repeating units of unit 2. Further, in the present invention, the sulfhydryl group content in the yttrium-modified PVA is preferably from 2.0 to 50 parts by weight, and when it is within this range, the initial adhesion property of the aqueous adhesive of the present invention is particularly good. Here, the content of the sulfhydryl group is represented by weight percent (% by weight) based on 100 parts by weight of the PVA main chain. The thiol content is calculated by using the thiol-modified amount S, the number of repeating units m of the unit 1, the number of repeating units η of the unit 2, and the degree of saponification of the cerium-modified PVA. Even if the Ρ 基 A group modification amount S is equal, the POA group content in the POA-modified PVA becomes large as the degree of saponification increases or as m or η increases. The PVA having a mercapto group represented by the above general formula (I) in the branched chain has a viscosity average degree of polymerization of 200 to 3000' and preferably 250 to 2800, more preferably 300 to 2,600. Here, the viscosity average degree of polymerization was measured in accordance with ns - Κ6726. That is, the Ρ Ο A modified Ρ V A is further saponified and refined, and then obtained by the following formula from the intrinsic viscosity [??] measured in water at 30 °C. -10- 201038693 ?= ([η ]xl 0 3 / 8.2 9 ) (1/0 6 2) Further, the viscosity average degree of polymerization is sometimes referred to as the degree of polymerization. When the degree of polymerization is less than 200, the aqueous adhesive containing the PVA does not exhibit sufficient initial adhesion. Further, when the degree of polymerization is more than 3,000, the storage stability of the aqueous binder is deteriorated, which is not preferable. In the case of a PVA having a sulfhydryl group represented by the above general formula (I), the degree of roadway must be 80 to 99.99 mol%, and preferably 83 to 99.5 mol%, preferably 85 to 99 mol%. . When the degree of saponification is less than 80, since the PVA loses water solubility, storage stability sometimes causes problems, and there is a problem that the initial adhesion is reduced. On the other hand, when the degree of saponification exceeds 99.99 mol%, the storage stability may be deteriorated. The PVA having a mercapto group represented by the above general formula (I) in the branched chain can be produced by various methods. Although it can be produced by reacting a compound having a functional group (for example, a carboxyl group, an isocyanate group, or the like) reactive with a hydroxyl group represented by the general formula (I) and a hydroxyl group of PV oxime with PVA, it is generally industrially The unsaturated monomer (macromonomer, high molecular monomer) containing a ruthenium POA group is copolymerized with a vinyl ester and then obtained by saponification. Here, the polymer monomer containing a POA group is preferably represented by the above formula (II). When R1 of the general formula (II) is a hydrogen atom, R2 is a hydrogen atom, and R3 is a hydrogen atom, specific examples of the polymer monomer represented by the general formula (II) include, for example, polyoxyethylene polyoxybutylene-acrylic acid. Ester, polyoxyethylene polyoxybutylene monomethacrylate, polyoxyethylene polyoxybutylene propylene amide, polyoxyethylene polyoxybutylene monomethacrylamide, polyoxyethylene polyoxybutylene propylene Ether, poly 201038693 oxyethylene polyoxybutylene monomethacryl ether, polyoxyethylene polyoxybutylene ether, and the like. Among them, polyoxyethylene polyoxybutylene-propylene amide, ethylene polyoxybutylene monomethacrylamide, polyoxyethylene polyoxybutylene monoether is more suitable, and polyoxyethylene polyoxybutylene Monomethyl propylamine, polyoxyethylene polyoxybutylene monovinyl ether is particularly suitable for use. When R2 of the general formula (II) is an alkyl group having 1 to 8 carbon atoms, specifically, when R1 of the above formula (II) is a hydrogen atom and R2 is a hydrogen atom, it is a hydrogen atom. The alkoxy group having a terminal OH group number of 1 to 8 of the polymer monomer is substituted. Among them, a polymer monomer substituted with polyoxyethylene polyoxybutylene-acrylamide and polyoxyethylene polyoxybutylene monovinyl ether terminal OH methoxy is suitable for use, and polyoxyethylene butene is used. High monomers in which the terminal OH group of methacrylamide is substituted with a methoxy group are particularly suitable for use. Further, in the case where the POA PVA contained in the aqueous phase of the aqueous binder of the present invention is obtained by saponification of the polymer monomer represented by the above formula (II) and the vinyl ester terpene polymer, considering the copolymerizability, X is used. -co - The above-mentioned polymer monomer represented by the general formula (III) is more preferable. The polymer monomer represented by the above general formula (III) is an ethylene polyoxybutylene-acrylamide and a terminal OH group thereof, and a polyoxyethylene polyoxybutylene is obtained by a methoxy group. The methacrylamide and its OH group are represented by a methoxy-substituted unsaturated monomer. When the POA-modified PVA used in the present invention is produced, a polymer monomer having a PO A group and a vinyl ester-based mono-ethylene polyoxyethylene olefin oxime may be used in an alcohol-based or solvent-free manner, and R3 may be passed through a carbon methyl group. The co-NR5 polyoxygenated terminal agent modified by polyoxyl molecules is in the form of -12- Ο 201038693, and the obtained fluorene-modified vinyl ester copolymer is preferably added. When a polymer having a PO A group and a vinyl ester system are copolymerized, the temperature is preferably from 0 to 200 ° C, and when the temperature at 30 to 14 (TC ) is less than 0 ° C is not sufficient. When the polymerization rate is higher than 200 ° C, it is difficult to obtain a POA-modified PVA having a modified amount of 2 POA groups. The method for controlling the temperature is 0 to 200 ° C, for example, Control the polymerization to generate heat and balance the heat dissipation of the surface of the reactor. ί The method of controlling the external jacket of the appropriate heat transfer medium, etc., but the latter method is better. The polymer sheet with Ρ0Α base When the body and the vinyl ester monomer are introduced, the polymerization method may be any one of batch polymerization, semi-batch polymerization, and semi-continuous polymerization. The polymerization method may use an overall poly-solution polymerization method, a suspension polymerization method, or an emulsion polymerization method. A conventional method such as a method in which polymerization is carried out in a solvent-free or in an alcohol-based solvent, and a solution polymerization method is preferably used, and an emulsion polymerization method is used in the case of producing a high polymerization degree. Can use methanol, propanol However, the solvent is not limited to these types. Further, these solvents may be used in a mixture of two types. The initiator for copolymerization may be an azo initiator or a peroxide initiator according to the polymerization method. Redox 3, etc. Azo initiators such as 2,2'-azobis(isobutyronitrile), 2,2'bis(2,4-dimethylvaleronitrile), 2,2'-azo Double (4-methoxy-saponified body is good. Progress. Also, invented: when taken: degree to make poly:, use safety: line copolymerization, continuous ί legal, Ϊ method. 丨 polymerization method: The polymer is ethanol, species or conventionally known; initiator - azo 2,4 -di-13- 201038693 methylvaleronitrile, etc.; peroxide-based initiator such as diisopropyl peroxydicarbonate Peroxydicarbonate compounds such as ester, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, tertiary butyl peroxy neodecanoate, α-decyl peroxy neodecanoate, Perester compound such as tertiary butyl peroxydecanoate, acetyl cyclohexyl sulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate (2,4 ,4 - trimethyl - pent Yl - 2 -peroxyphenoxy acetate), etc. Further, potassium sulfamate, ammonium persulfate, 0 hydrogen peroxide, etc. may be combined with the above initiator to form a starter. Further, the redox initiator is as described above. A combination of an oxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogencarbonate, tartar, L-ascorbic acid, or white powder (also known as white block, Rongalit), and a polymer monomer having a P〇A group. When the vinyl ester monomer is copolymerized at a high temperature, PVA is colored by the decomposition of the vinyl ester monomer, and at this time, 1 to 100 ppm (relative to the vinyl ester) is added to the polymerization reaction system for the purpose of preventing coloration. Antioxidants such as tartaric acid are also not available. Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, versatic acid, vinegar, and caproic acid. Ethyl acetonate, vinyl octanoate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate, etc., of which vinyl acetate is preferred. When a polymer monomer having a POA group is copolymerized with a vinyl ester monomer, it may be copolymerized with another monomer within a range not impairing the scope of the present invention -14-201038693. Examples of the monomer which can be used include α-olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and butyl acrylate. Acrylates, isobutyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.; methacrylic acid and its salts; methyl methacrylate, methyl Ethyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butyl methacrylate, 2-hexyl methacrylate , methacrylates such as lauryl methacrylate and octadecyl methacrylate; acrylamide; Ν-methacrylamide, Ν-ethyl acrylamide, hydrazine, hydrazine-dimethyl Acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid and salts thereof, acrylamidopropyldimethylamine and salts thereof or quaternary salts thereof, hydrazine-hydroxymethyl acrylamide and derivatives thereof Ethylene decylamine derivative: methacrylamide; Ν-甲Methyl acrylamide, hydrazine-ethyl methacrylamide, methacrylamide propylene sulfonic acid and salts thereof, methacrylamide propyl hydrazine methylamine and salts thereof or quaternary salts thereof, hydrazine a methacrylamide derivative such as hydroxymethylmethacrylamide or a derivative thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, Vinyl ethers such as isobutyl vinyl ether, tertiary butyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; halogenated vinyls such as vinyl chloride and vinyl fluoride a vinylidene halide such as vinylidene chloride or vinylidene fluoride; an allyl compound such as allyl acetate or chloropropene; an unsaturated dicarboxylic acid such as maleic acid, itaconic acid or fumaric acid; And its salt or its ester; ethylene-15-201038693 vinyl decane compound such as trimethoxy decane; isopropenyl acetate and the like. Further, when a polymer monomer having a POA group is copolymerized with a vinyl ester monomer, the copolymerization degree of the copolymer is adjusted, and the copolymerization is carried out in the presence of a chain shifting agent without impairing the gist of the present invention. can. Examples of the chain shifting agent include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; thiols such as 2-hydroxyethanethiol; and halogenated hydrocarbons such as trichloroethane and hexachloroethane; Aldehydes and ketones are more suitable for use. The amount of the chain shifting agent to be added may be determined in accordance with the chain shift constant of the chain extender and the polymerization degree of the target vinyl ester polymer, and is usually 0.1 to 10% by weight based on the vinyl ester monomer. The saponification reaction of the POA-modified vinyl ester copolymer can be carried out by using an alkali catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an alcohol decomposition reaction or hydrolysis using an acid catalyst such as p-toluenesulfonic acid. reaction. Solvents which can be used in the reaction, such as alcohols such as methanol and ethanol, esters such as methyl acetate and ethyl acetate, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene and toluene, etc., may be used alone or Two or more types are used in combination. Among them, a saponification reaction using a mixed solution of methanol or methanol/methyl acetate as a solvent and using sodium hydroxide as a catalyst is simple and preferable. The POA-modified PVA contained in the aqueous adhesive of the present invention can be re-modified with a POA-modified PVA by a conventional method while maintaining the water solubility without impairing the gist of the present invention. . Such a POA-modified PVA is obtained by, for example, modifying a POA-modified PVA with an aldehyde such as butyraldehyde or modifying it with diketene. -16- 201038693 The aqueous adhesive of the present invention 'is basically contained in the aqueous phase containing the above-mentioned POA-modified PV A, but may be contained for the purpose of improving the adhesion to various substrates or increasing the solid content to reduce the drying load. A (co)polymerized emulsion composed of one or more monomers selected from the group consisting of an ethylenically unsaturated monomer and a diene monomer. As the emulsion, a vinyl acetate emulsion (vinyl acetate polymer, vinyl acetate-ethylene copolymer, vinyl acetate-terpene ethylene carbonate copolymer, vinyl acetate di(meth)acrylate copolymer, etc.) can be used. , (meth) propylene acrylate emulsion, styrene emulsion, butadiene emulsion (styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, etc.). In this case, a water-soluble cellulose such as a vinyl alcohol polymer or hydroxyethyl cellulose, various surfactants, or the like can be used as the dispersion stabilizer of the emulsion. Among them, a vinyl acetate emulsion or a (meth) acrylate emulsion using a vinyl alcohol polymer as a dispersion stabilizer is preferred from the viewpoint of initial adhesion and storage stability of the aqueous binder of the present invention. The emulsion is usually used in an amount of 500 parts by weight or less and preferably 300 parts by weight or less, more preferably 250 parts by weight or less, based on 100 parts by weight of the P? A-modified PVA. Further, the aqueous adhesive of the present invention may contain an inorganic or organic enamel charge for the purpose of reducing the dry load or increasing the strength and hardness of the formed back layer. Inorganic strontium is filled with clay such as kaolin, Helestone, pyrophyllite or sericite, heavy, light or surface treated calcium carbonate, aluminum hydroxide, alumina, gypsum, talc, titanium oxide and the like. The organic system is filled with starch, oxidized starch, wheat flour, wood flour, and the like. Among them, various clays and various starches are suitable for use. These bismuth fillers are based on the solid content -17-201038693, and are preferably used in an amount of 1000 parts by weight, preferably 500 parts by weight or less, more preferably 400 parts by weight or less, based on 100 parts by weight of the POA-modified PVA in the aqueous adhesive. When the cerium charge is more than 100 parts by weight, problems such as sputum filling and sedimentation may occur during storage. The aqueous adhesive of the present invention may be added to various additives without impairing the effects of the present invention. These additives are metal salts of phosphoric acid compounds such as sodium polyphosphate and sodium hexametaphosphate or inorganic dispersants such as water glass, polyacrylic acid and its salts, sodium alginate, and α-olefin-maleic anhydride copolymer. Anionic polymer compound and its metal salt, ethylene oxide adduct of higher alcohol, nonionic surfactant such as copolymer of ethylene oxide and propylene oxide, carboxymethyl cellulose, methyl fiber , sodium alginate, polyethylene oxide, various antifoaming agents, preservatives, fungicides, coloring pigments, deodorants, perfumes, etc. The method of preparing the aqueous adhesive of the present invention is not particularly limited. For example, pre-mixing Ρ0Α modified PVA and other additives such as strontium filling, and then putting it into the water while stirring, or sequentially adding various additives, strontium filling, Ρ0Α modified PVA to the surface while stirring, preparing the slurry, heating and dissolving, etc. method. In this case, the heating method may be a heating method in which steam is directly blown into the slurry, or an arbitrary heating method such as a jacket heating method. This modulation can be done in batch or continuous mode. The aqueous adhesive agent of the present invention has high initial adhesion, can be produced quickly, and is excellent in storage stability (viscosity stability, sedimentation stability). Therefore, this aqueous adhesive is suitable for use with corrugated paper, paper bags, cartons, paper tubes, walls -18-

201038693 Paper adhesives for the manufacture or use of paper, etc., followed by wood and fiber, wood and paper, wood and plastic woodworking, can also be used for fabrics such as cloth and non-woven fabrics, concrete such as water, aluminum foil, etc. The use of sticky objects. However, the use of the present invention is not limited thereto. The viscosity of the aqueous adhesive of the present invention can be determined according to the application, for example, when the coating property is fast, the viscosity at the bonding temperature is 100 to 100 mPa·s. The POA-modified PVA contained in the present invention can be expected to form a pseudo-association by a particularly hydrophobic interaction in water, and therefore the initial adhesion is an important characteristic of increasing the concentration. Further, the POA-modified PVA has a temperature-sensitizing viscosity which is caused by an increase in hydrophobic interaction due to the POA-based temperature. Since the viscosity is usually lowered due to an increase in temperature, the stability of sedimentation stability of another enthalpy is improved. "Embodiment" Hereinafter, the present invention will be described more specifically by way of examples, but any limitation of Ma et al. In addition, "%" and "parts" in the examples are "%" and "parts by weight" unless otherwise stated. [Production of yttrium-modified PVA] Production Example 1 (manufacturing PVA1) A 3L-capacity reaction apparatus equipped with a mixer, a reflux cooling tube, a nitrogen gas conduit, a port, and a polymerization initiator addition port, and wood, I-agent β, mud The shape and the water content of the product can be arbitrarily selected. The use of a large amount of water in the form of a crucible is followed by a large increase in the viscosity of the crucible. The dehydration is thought to be able to suppress the stability, and the invention is not indicated by the fact that "the heavy comonomer is added dropwise to the ethyl acetate 19-201038693 enester 750g, 250 g of methanol and 1 7.6 g of a polymer monomer (monomer A) having a POA group, and introducing a nitrogen gas bubble for 30 minutes to replace the environment in the reactor with nitrogen gas, and further preparing a polymer monomer having a P〇A group (monomer) A) The comonomer solution dissolved in methanol at a concentration of 20% is used as a retardation solution, and is replaced by a nitrogen gas bubble into a nitrogen atmosphere. After the reactor starts to heat up, 2,2'-azobis is added when the internal temperature reaches 60 °C. The polymerization was started at 0.25 g of isobutyronitrile (AIBN). At this time, a delayed solution was added dropwise so that the monomer composition (ratio of vinyl acetate to monomer A) in the polymerization solution was a certain ratio, and polymerization was carried out at 60 ° C. After a few hours, the enthalpy was cooled to stop the polymerization. The total amount of the comonomer solution added until the polymerization was stopped was 75 ml, and the solid concentration at the time of stopping the polymerization was 24.4%. Then, it was occasionally added at 30 ° C under reduced pressure. Methanol to remove unreacted A methanol solution of P0A modified PVAc (concentration: 35%) was obtained from the vinyl acetate monomer. A POA modified PVAc methanol solution was prepared by adding POA to the POA modified PVAc methanol solution to prepare 453.4 g of POA modified solution. PVAc 100.0g), adding an alkaline solution (1% methanol solution of sodium hydroxide) 5 5.6 g for saponification (POA modified PVAc concentration of saponified solution 20%, relative to ethyl acetate acetate unit in POA modified PVAc In other words, sodium hydroxide is more than 〇. 丨 mol%). A gel is formed about 1 minute after the addition of the alkaline 'solution', and the gel is pulverized by a pulverizer at 40°. C was allowed to stand for 1 hour, and saponification was continued, and 500 g of methyl acetate was added to neutralize the remaining alkaline solution. It was confirmed by filtration with a phenolphthalein indicator that the white solid was filtered after completion of neutralization, and 2000 g of methanol was added thereto, and the mixture was left to stand at room temperature for 3 hours. After the above washing operation was repeated 3 times, the white solid obtained by centrifugal deliquoring was placed in a dryer at 65 ° C for 2 days to obtain POA modified -20- 201038693 乂 乂 ( ( ( ( 八 八 八 八 八 八 八 八 八 八The degree of polymerization was 17 60, the degree of saponification was 98.7 mol%, and the amount of modification of the POA group (S) was 0.4 mol%. Production Examples 2 to 22 (Production of PVA 2 to 22) Polymerization of the amount of vinyl acetate and methanol, polymerization of a polymer (unsaturated) monomer type (second table) having a PO A group, and addition amount, etc. The conditions, the POA-modified PVAc concentration at the time of saponification, and the saponification conditions such as the molar ratio of sodium hydroxide to the vinyl acetate unit in the P0A-modified PVAc are changed as shown in Tables 1 and 2, and other manufacturing examples 1 Various P0A modified PVAs (PVA 2 22 22) were produced in the same manner. Production Example 23 (Production of PVA 23) A 3 L-capacity reactor equipped with a stirrer, a reflux cooling tube, a nitrogen gas conduit, a comonomer dropping port, and a polymerization initiator addition port was added, and 700 g of vinyl acetate and 300 g of methanol were introduced to introduce a nitrogen gas bubble. The environment in the reactor was replaced with nitrogen for 30 minutes. After the reactor began to heat up, when the internal temperature reached 60 ° C, 2,2'-azobis(isobutyronitrile) (6 16 ^ 1) 0.25 £ was added to start the polymerization, and the polymerization was carried out at Q 60 ° C for 3 hours. To stop the aggregation. The solid content concentration at the time of stopping the polymerization was 17.0%. Next, methanol was occasionally added at 30 ° C under reduced pressure to remove unreacted vinyl acetate monomer to obtain a polyvinyl acetate (PVAc) methanol solution (concentration: 30%). Adding 5004.1 g of polyvinyl acetate (PVAc) methanol solution to a polyvinyl acetate (PVAc) methanol solution and adding methanol to this solution (containing PVAc 120.0 g in solution), adding an alkaline solution (10% methanol solution of sodium hydroxide) 55.8 g was subjected to saponification (the PVAc concentration of the saponification solution was 20%, and the sodium hydroxide molar ratio was 0.1 with respect to the vinyl acetate unit in PVAc). -21- 201038693 A gel was formed about 1 minute after the addition of the alkaline solution, and the gel was pulverized in a pulverizer, and left at 40 ° C for 1 hour to continue saponification, and then 500 g of methyl acetate was added for neutralization. A residual alkaline solution. Using a phenolphthalein indicator, it was confirmed that the white solid was filtered after completion of neutralization, and 2000 g of methanol was added thereto, and the mixture was allowed to stand at room temperature for 3 hours. After the above washing operation was repeated 3 times, the white solid obtained by centrifugal deliquoring was placed in a 651 drier for 2 days to obtain a modified PVA (PVA23)-PVA23 having a degree of polymerization of 1,700 and a degree of saponification of 98.5 mol%. Examples 24 to 26 (manufacturing PVA 24 to 26) In addition to the addition amount of vinyl acetate and methanol, the PVAc concentration at the time of saponification, and the vinyl acetate unit in PVAc, the saponification conditions such as sodium hydroxide molar ratio were changed to Various unmodified PVAs (PVAs 24 to 26) were produced in the same manner as in Production Example 23 except as shown in Table 1.

-22- 201038693

Synthesis result POA group content (heavy halo) 10.0 Ο ο oo 10.0 od V-) oo vr> oo CO in Η 33.2 49.4 VO oi Saponification degree (mole %) 98.7 98.7 ι 98.9 98.9 98.6 oo cK oo 99.7 wn 98.9 98.5 98.2 98.0 98.4 P0A base modification amount S (mole%) inch · 々· inch. 乂CN 0.08 OJ viscosity average degree of polymerization P 1760 Ό 2450 3500 1030 1 1030 1030 1750 1720 1730 1680 1700 #: NaOH ° Moerbi Ear %) 0.1000 0.1000 0.1000 0.1000 0.1000 0.0750 0.2000 0.0060 0.1000 Country 0.1000 0.1000 0.1000 ίΐρ PVAc Concentration (%) Polymerization Condition Polymerization Rate (%) CO cn R so ο ooo Initial Charge Unsaturated Monomer | cn 21.5 oo OO oq oo r '^H as 〇< ON CO 70.7 170.6 On C! cn CO cn CO cn CO cn CO CO cn inch inch B CN cs CN CN cs 04 <N (M cs OJ CN CS -1 type <<<<<<<<<<<<<<<<<<<<<<><<><<><<><<><<>><<>>> \ as 8 r—( o wn vn 承tn 〇 v〇 oo JO PVA PVA1 PVA2 j 1 PVA3 PVA4 PVA5 PVA6 PVA7 PVA8 1 PVA9 ! PVA10 PVA11 PVA12 PVA13 Manufacturing Example No. Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 - 1 Manufacturing Example 5 J Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Manufacturing Example 9 Manufacturing Example 10 Manufacturing Example 11 Manufacturing Example 12 Manufacturing Example 13 201038693 οο ο i〇VO CO (N vn 1 1 1 1 Ό 〇ς 5 Os 98.6 98.8 v〇od 〇s ^7Ί cn od ON 98.4 od σ\ οό OS v〇od <J \ 98.5 98.6 CN Οί ο CN <N CN <N CN (-η 1 1 ι ι 1680 1720 ι 1700 1 1700 1700 1680 1720 1680 2400 "1700 8 2400 3500 0.1000 0.1000 ι 0.1000 1 0.1000 I 0.1000 | (U000 0.1000 0.1000 I 0.2000 I 0.1000 0.1000 1 0.1000 0.1000 00 V-» 〇ο ο 〇v〇CO vn CO oo § ννη cn 〇〇cn 4 < CM CO OO ON . Wear I 1 1 1 〇\ οα π • CO cn 〇CS CO 〇OJ CN o oj CS cs CN Ο Q w 〇t—t 1 1 1 1 Ο »〇CM o vr> cs This cs 〇CN o CN om ΓΊ o cs § o CO Ό ο cs 卜 o folk - r- 〇vn 〇so cn 8 OO ON PVA14 i PVA15 PVA16 PVA17 PVA18 | PVA19 PVA20 PVA21 PVA22 [PVA23 PVA24 PVA25 PVA26 Manufacturing Example 15 Manufacturing Example 16 Manufacturing Example Π Manufacturing Example 18 Manufacturing Example 19 Manufacturing Example 20 Manufacturing Example 21 Manufacturing Example 22 Manufacturing Example 23 Manufacturing Example 24 Manufacturing Example 25 Manufacturing Example 26 ^wM-NIRn^^K )^i[fi(H〇£)rE:gA3>Jffii_fr3VAd#l^v〇d(I):ii 201038693 [Table 2] Monomer R1 R2 R3 R4 X mn A -Η -Η -Η -ch3 - CO-NH- 2 13 B -Η -Η -Η -ch3 -CO-NH- 2 4 C -Η -Η -Η -ch3 -CO-NH- 2 2 D -Η -Η -Η -ch3 -CO- NH- 2 19 E Η -Η -Η -ch3 -CO-NH- 2 21 F ΛττΤ ΙΙΙΙΙ -Η -Η -ch3 -CO-NH- 0 13 G -Η -Η -Η -ch3 -CO-NH- 12 13 Η -Η -Η -Η -H -0- 2 10 I -Η -Η -Η -CH2-COONa -CO-NH- 2 12 J -Η -Η -COONa -H -CO-NH- 2 13 K -ch3 -ch3 -Η -H -O-CH plant 24 0 In the examples and comparative examples, various PVA-modified aqueous binders were used and evaluated by the following method. ^ [Storage Stability] The state of the aqueous adhesive solution was observed at 70 ° C for 7 days, and the following indicators were used to evaluate the state changes before and after storage. 〇: No separation, sedimentation, no viscosity change. △: It is possible to determine some slight separation and sedimentation, but there is fluidity. X: It can be determined that there is separation and sedimentation. Or no liquidity. [Initial adhesion] The initial adhesion was measured under the following conditions using an initial test machine manufactured by JT Corporation. -25- 201038693 Condition: Kraft/kraft paper bonding speed 〇.5m/sec Shear speed 300mm/sec Open time 1 second Adhesive time 2 seconds Maintenance time 1 second, 3 seconds, 5 seconds, 10 seconds Next area Immx25mmx8 points (count 2cm2)

^ Temperature and Humidity 20 ° C, 65% RH 实施 Example 1 PVA was added at room temperature 1 100 parts were mixed with ion-exchanged water 769 and heated to 95 ° C over 1 hour. The mixture was cooled to room temperature by maintaining 2 small portions at 95 ° C to obtain a 13% PVA1 solution. In this way, the evaluation of preservation stability and initial adhesion according to the above method is shown in Table 3. Example 2 to 1 2, Comparative Examples 1 to 1 4 In the same manner as in Example 1, except that PVA1 of Example 1 was replaced by 26 obtained in Production Examples 2 to 26, an adhesive such as an adhesive was prepared in the same manner as above. The method is to preserve the stability and initial price. The results are shown in Table 3. Example 1 3 A glass polymerization vessel equipped with a reflux cooling tube, a dropping funnel, a thermometer, and a nitrogen anchor type stirring blade was charged, and 32 parts of PVA23 obtained in Example 23 of ion exchange water was charged, and the fraction was dissolved at 95 ° C. After stirring, stir the adhesive, . The result is as follows: PVA2~. Use this qualitative evaluation portal, 450 copies and . Next, -26- 201038693 After cooling the aqueous solution of PVA23 and replacing it with nitrogen, 40 parts of vinyl acetate was charged with stirring at 14 rpm, and the redox initiator of hydrogen peroxide/tartaric acid was heated to 60 °C. The polymerization starts in the presence. After the initiation of the polymerization for 15 minutes, 360 parts of vinyl acetate was continuously added over 3 hours to complete the polymerization. The initiator used was 30 g of 1% hydrogen peroxide water and 10 g of a 5% aqueous solution of tartaric acid. The solid concentration of the obtained PVAc emulsion was 46.8%. 100 parts of a 13% aqueous solution of PVA1 obtained in Example 1 and 27.7 parts of a PVAc emulsion were mixed to prepare an adhesive (solid content: 20.3%: solids of PVA1 and PVAc in a weight ratio of 100:100). Using this adhesive, the evaluation of the preservation stability and the initial adhesion was carried out in accordance with the above method. The results are shown in Table 4. Comparative Example 1 5 The same procedure as in Example 13 was carried out in the same manner as in Example 13 except that the PVA1 aqueous solution of Example 13 was replaced with the PVA23 7 under solution obtained in Comparative Example 11 to prepare an adhesive (solid content: 20.3%, PVA23 and PVAc). The solid component weight ratio is 100: 00). Using this adhesive, the evaluation of storage stability and initial adhesion was carried out in accordance with the above method. The results are as shown in Table 4. Example 1 4 Adding clay (Huber-900, kaolin clay, average particle diameter 0.6 μm, manufactured by HUBER Co., Ltd.) to 26 parts of a 13% aqueous solution of PVA1 prepared in Example 1, stirring was carried out to sufficiently disperse the clay to form Agent (solid component 31.0%, weight ratio of PVA1 to clay solid content is 100: 200). Using this adhesive, the evaluation of preservation stability and initial adhesion was carried out in accordance with the above method -27-201038693. The results are shown in Table 4. Comparative Example 16 A clay was prepared in the same manner as in Example 14 except that the PVA1 aqueous solution of Example 14 was replaced with the PVA23 aqueous solution prepared in Comparative Example 11, and the solid content was 31.0%, and the solid content ratio of PVA23 to clay was For 100: 200). Using this adhesive, the evaluation of preservation stability and initial adhesion was carried out in accordance with the above method. The results are shown in Table 4. A Example 1 5 Adding clay (Huber-900, kaolin clay, average particle diameter 0.6 m, manufactured by HUBER) 26 parts of 100 parts of PVA1 aqueous solution prepared in Example 1, stirring to fully disperse the clay and then adding 27.7 parts of the PVAc emulsion prepared in the mixed example 13 was prepared into an adhesive (solid content 33.8%: solid content ratio of PVA1 to PVAc and clay was 1〇〇: 1〇〇: 200). Using this adhesive, the evaluation of storage stability and initial adhesion was carried out in accordance with the above method. The results are shown in Table 4. 〇Comparative Example 1 7 In addition to the aqueous solution of PV A 1 of Example 15 was replaced with the aqueous solution of PVA23 prepared in Comparative Example 11, the same method as in Example 15 was used to add clay and PVAc emulsion to prepare an adhesive (solid component 33.8). %: The weight ratio of PVA23 to PVAc and clay is 1 00:1 00: 200). Using this adhesive, the evaluation of preservation stability and initial adhesion was carried out in accordance with the above method. The results are shown in Table 4. Example 1 6 , 1 7 -28 - 201038693 In addition to the clay of Example 15, respectively, calcium carbonate (Example 16, Whiton P-30, heavy carbonic acid, average particle diameter of 1.75 / zm, manufactured by Shiraishi Kogyo Co., Ltd.) and An adhesive was prepared in the same manner as in Example 15 except that the oxidized starch (Example 17, MS-3800, manufactured by Nippon Food Processing Co., Ltd.) was replaced. Evaluation of preservation stability and initial adhesion was carried out by the above method using this adhesive agent. The results are shown in Table 4. Example 1 8 ^ A glass polymerization vessel equipped with a reflux cooling tube, a dropping funnel, a thermometer, and a nitrogen introduction port was charged, and 500 parts of ion-exchanged water and a polyvinyl alcohol having a thiol group at the end (M - 205: polymerization) were charged. Degree 550, degree of saponification 88.2 mol%, manufactured by KURAREY Co., Ltd.) 28 parts 'dissolved at 95 °C. Next, 20 g of methyl methacrylate and 20 g of n-butyl acrylate were added, and after heating with nitrogen, the temperature was raised to 65 ° C, and polymerization was started by adding 1% of a 1% potassium persulfate aqueous solution, and methyl methacrylate 1 was continuously added over 2 hours. 80 g and n-butyl acrylate 1 80 g. The polymerization was carried out in 4 hours to obtain an emulsion of methyl methacrylate/n-butyl acrylate copolymer (ACR) having a solid concentration of 〇 45.1%' viscosity of 28 00 mPa. Adding clay (Huber-900: kaolin clay, average particle diameter 0.6/zm, manufactured by HUBER) 26 parts of 100 parts of PVA1 aqueous solution prepared in Example 1, stirring to fully disperse the clay, then adding and mixing ACR emulsion 28.2 The mixture was prepared into an adhesive (solid content 33.7%: weight ratio of solid content of PVA1 to ACR and clay was 100:100:200). Using this adhesive, the evaluation of storage stability and initial adhesion was carried out in accordance with the above method. The results are shown in Table 4. -29-201038693 Example 1 9 In addition to the methyl methacrylate/n-butyl acrylate copolymer (ACR) emulsion of Example 18, an ethylene-vinyl acetate copolymer (VAE) emulsion (OM-4200NT, solid content) In the same manner as in Example 丨8, the adhesive was prepared in the same manner as in Example 丨8 (concentration: 55.0%, manufactured by KURAREY Co., Ltd.) (solid content: 34.8%: weight ratio of solid content of PVA1 to VAE and clay was 100:1 00:200 ). Using this adhesive, the evaluation of preservation stability and initial adhesion was carried out in accordance with the above method. The results are shown in Table 4. Example 20 The methyl methacrylate/n-butyl acrylate copolymer (ACR) emulsion of Example 18 was used as a styrene-butadiene ester copolymer (SBR) emulsion (Narustar SR-107, solid content concentration 48.0%). In addition to the substitution of 27.1 parts by Japan A&L Co., Ltd., the same procedure as in Example 19 was used to prepare an adhesive (solid content 34.0%: solid content ratio of PVA1 to SBR and clay was 100:100:200). Using this adhesive, the evaluation of preservation stability and initial adhesion was carried out in accordance with the above method. The results are shown in Table 4. -30- 201038693 [Table 3]

❹ water) bio-adhesive property PVA solid content preservation stability initial adhesion (g/cm) (pressure-bonding time) (%) 1 second 3 seconds 5 seconds 10 seconds Example 1 PVA1 13.0 〇 15 70 280 500 Example 2 PVA2 13.0 〇10 60 250 450 Example 3 PVA3 13.0 〇12 70 250 450 Comparative Example 1 PVA4 13.0 Δ 5 30 150 300 Comparative Example 2 PVA5 13.0 〇0 10 60 100 Example 4 PVA6 13.0 〇10 60 230 430 Example 5 PVA7 13.0 〇13 70 270 480 Comparative Example 3 PVA8 13.0 〇0 20 80 180 Example 6 PVA9 13.0 〇10 70 260 480 Comparative Example 4 PVA10 13.0 〇5 20 100 200 Example 7 PVA11 13.0 〇10 60 200 390 Comparative Example 5 PVA12 13.0 Δ 7 25 90 230 Example 8 PVA13 13.0 〇9 60 200 380 Example 9 PVA14 13.0 〇12 70 270 490 Comparative Example 6 PVA15 13.0 〇0 10 80 170 Comparative Example 7 PVA16 13.0 Δ 5 30 140 200 Comparative Example 8 PVA17 13.0 〇8 50 170 350 Comparative Example 9 PVA18 13.0 〇6 25 170 280 Example 10 PVA19 13.0 〇10 60 270 340 Example 11 PVA20 13.0 〇10 60 250 330 Example 12 PVA21 13.0 〇10 70 250 360 Comparative Example 10 PVA22 13.0 〇0 10 50 140 Comparative Example 11 PVA23 13.0 〇5 40 150 280 Comparative Example 12 PVA24 13.0 〇0 10 40 180 Comparative Example 13 PVA25 13.0 〇7 30 150 270 Comparative Example 14 PVA26 13.0 〇7 30 130 280 -31- 201038693 [第4 Table] Aqueous Adhesive Performance Composition Solid Content Preservation Stability Initial Adhesion (g/cm) PVA Emulsion 塡Materials placed after 7曰 (compression time) (parts) (parts) (parts) (%) 1 second 3 seconds 5 seconds 10 seconds Example 13 PVA1 100 PVAc 100 — — 20.3 〇 20 120 370 540 Comparative Example 15 PVA23 100 PVAc 100 — — 20.3 Δ 15 90 250 340 Example 14 PVA1 100 — — Clay 200 31.0 〇 25 170 400 570 Comparative Example 16 PVA23 100 - Clay 200 31.0 X 15 110 280 380 Example 15 PVA1 100 PVAc 100 Clay 200 33.8 〇 25 120 430 650 Comparative Example 17 PVA23 100 PVAc 100 Clay 200 33,8 Δ 15 120 350 420 Example 16 PVA1 100 PVAc 100 Calcium carbonate 200 33.8 〇25 110 420 630 Example Π PVA1 100 PVAc 100 Oxidation powder 200 33.8 〇25 100 400 600 Example 18 PVA1 100 ACR 100 Clay 200 33.7 〇20 100 380 600 Implementation 19 PVA1 100 VAE 100 Clay 200 34.8 〇25 130 430 660 Example 20 PVA1 100 SBR 100 Clay 200 34.0 〇20 100 370 570 〇 Note: (parts) based on solid content; Clay: Huber-900, kaolin clay ( Average particle size 0.6 "m, manufactured by HUBER; Calcium carbonate: Whiton P-30, heavy calcium carbonate (average particle size 1.75 / / m, manufactured by Shiraishi Kogyo Co., Ltd.); Oxidized starch: MS-3 8 0 0 (Japan Food Processing Co., Ltd.). -32- 201038693 As shown in the examples, the aqueous adhesive of the present invention is suitable for use in corrugated paper because of its high initial adhesion, rapid production, and excellent storage stability (viscosity stability, sedimentation stability). , paper binders for paper bags, cartons, paper tubes, wallpapers, etc., and adhesives for woodworking, wood and fiber, wood and paper, wood and plastic. In addition, it can also be used for the use of fabrics such as cloth and non-woven fabrics, cement moldings such as concrete, various plastics, aluminum foils, etc. as an adherend, and the industrial price is 极^. [Simple description of the diagram] None. [Main component symbol description] None. 〇 -33-

Claims (1)

201038693 VII. Patent application scope: 1. An aqueous adhesive containing a polyoxyalkylene-modified vinyl alcohol polymer in an aqueous phase, the vinyl alcohol polymer having the following general formula (I) in its branch The polyoxyalkylene group is represented, and the vinyl alcohol polymer has a viscosity average degree of polymerization of 200 to 3000, a degree of saponification of 80 to 99.99 mol%, and a polyoxyalkylene group modified amount of 〇. 1 to 1 〇 Moer%; ψ C2H5 4^2 alternative. 4^民1 one. In the formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a carbon number of 1 to 8; m and η represent the number of repeating units of the oxygen-and-tropane unit, respectively, ISm '1〇, 3 S n $ 20). 2. The aqueous adhesive according to claim 1, wherein the polyoxyalkylene-modified vinyl alcohol-based polymer is a polymer monomer having an oxygen-extended alkyl group represented by the following general formula (II) It is prepared by saponification after copolymerization with vinyl ester; R1 C2H5 Η〇=〇一X一[-〇-〇-〇-(--[~C—C~〇-4rR2 (K) I 1 h2 h Jm 1 h2 h Jn (wherein R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a fluorenyl group having a carbon number of 1 to 8; m and n respectively represent the number of repeating units of the oxygen-deseneene unit, Sl〇, 3Sn guest 20 R3 is a hydrogen atom or a COOM group, hydrazine is a hydrogen atom, an alkali metal or an ammonium group; R4 is a hydrogen atom, a methyl group or a -CH2-COOM group Μ is as defined above; X is -〇-, -CH2- 〇 —, —(CH2)k -34 - 201038693 —, —co—, —c〇—〇—or —CO—NR5—, R5 is a hydrogen atom or a saturated alkyl group having a carbon number of 1 to 4, and k represents a methylene group. The number of repeating units of the unit, 1 S kS 15). 3 · The aqueous adhesive according to item 2 of the patent application, wherein the polyoxy-extension-based modified vinyl alcohol-based polymer is represented by the following general formula (ΠΙ) Polyoxygen The alkyl group polymer monomer and the vinyl ester are copolymerized and then saponified to obtain ο R4丨iII C2 Η >=o R51N OJ 11 RICH iH2 C-H2 R2 R Chinese formula or sub-hydrogen is sub-raw gas For the 2 R η and m-alkane number of carbon or IP complexes, the mono-alkene extension of the oxygen is shown in the table. m <= <= η R sub > the original hydrogen alkane is Μ or 饱A5, R sub-primary ammonium hydroxide is or is a base of gold base hydrogen 4 M i ο 1 C number I carbon H2 or sub-genogen C's single agent is a single unit of olefinic and water body and 1 full任不液中乳类烯聚3乙共~ Since the selection of the first structure, the inclusion of the body, the Fan, the single step, the specialization, and the application of the seed, the splicing of the agent. It is a system or a 3 system in the machine. Use 3 ~ work 1 wood or use the fan paper as a special agent, please apply for the same as -35- 201038693 IV. Designated representative map: (1) The representative representative of the case is: No. (2) A brief description of the symbol of the representative figure: te 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: