TW201116546A - Thickener comprising vinyl alcohol-based polymer - Google Patents

Abstract

The present invention relates to a thickener characterized by comprising vinyl alcohol-based polymer having polyoxyethylene group on side chain, wherein the vinyl alcohol-based polymer has a viscosity average degree of polymerization P of 200 to 5000, a degree of saponification of 20 to 99.99 mol% and a modifying amount of polyoxyethylene group S of 0.1 to 10 mol%. By which, provided is a thickener comprising vinyl alcohol-based polymer with high solubility to water or to solvent containing water and having high viscosity and high preservation stability.

Description

201116546 VI. Description of the Invention: [Technical Field] The present invention relates to a tackifier containing a polyoxyalkylene-modified polyvinyl alcohol-based polymer. More specifically, it relates to a tackifier which has a high solubility to water or an aqueous solvent, a high viscosity and an increase in temperature by a polyoxyalkylene-modified polyvinyl alcohol-based polymer. Less reduction in viscosity. [Prior Art] Polyvinyl alcohol-based polymers (hereinafter abbreviated as PVA) have excellent interfacial properties and strength properties as a small amount of crystalline water-soluble polymer, and are used in various adhesives, paper processing, fiber processing, and the like. In addition to stabilizers such as emulsions, it also plays an important role in raw materials such as PVA-based films and PVA-based fibers. On the one hand, we have also tried to control crystallinity or introduce sensory groups in order to pursue high functionality for improving specific performance, or so-called modified PVA has been developed in various ways. A hydrophobic group-modified PVA into which a long-chain alkyl group is introduced, which is known to have an association between hydrophobic groups by an interaction of a hydrophobic group in an aqueous solvent, exhibits a remarkable viscosity-increasing effect, and imparts a high viscosity. The solution. For example, Patent Document 1 discloses a tackifier which is a PVA high viscosity solution modified with a long-chain alkyl group which is a hydrophobic group, and which is used for a tackifier for an emulsion of vinyl acetate or the like. The more the alkyl group content in the PVA of the alkyl-modified PVA, the higher the viscosity of the resulting solution, but if it exceeds a certain amount, the water solubility of PVA is lowered. Therefore, it is extremely difficult to obtain a high viscosity solution using an alkyl modified PVA. Further, in the temperature range in which the alkyl-modified PVA solution does not reach room temperature, although 201116546 can impart a high-viscosity solution, the viscosity of the solution is lowered while the temperature of the solution rises, and when the temperature rises in the summer, the viscosity is not exhibited. The performance of the agent. Therefore, a PVA-based tackifier which is not affected by ambient temperature changes is expected. CITATION LIST Patent Literature Patent Literature 1 Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. PVA, which has high solubility to water or aqueous solvents' and is highly viscous and has less viscosity reduction due to changes in solution temperature. Means for Solving the Problems The above problems can be solved by providing a tackifier, which is characterized in that the tackifier contains a polyoxyalkylene-modified polyvinyl alcohol-based polymer (hereinafter referred to as POA-modified PVA). The modified PVA contains a polyoxyalkylene group (hereinafter abbreviated as POA group) represented by the following formula (1) in the side chain, and has a viscosity average degree of polymerization P of 200 to 5,000 and a degree of saponification of 20 to 99.99 mol%. The oxygen-modified alkyl group-modified amount S is from 0.1 to 1 mol. R1 " I -C-C-0 L η2 η c2h5

Jm π2το η R2 (I) (wherein R1 represents a hydrogen atom or a methyl group, r2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and 111 and n each represent a repeating unit number of an oxygen-deseneene unit, 201116546 ISmglO, 3^nS20). In the above case, the above tackifier is more preferably water or an aqueous solvent. The present invention further contains the above-mentioned tackifier, water and oil component 'with respect to 100 parts by weight of oil component', and also contains a tackifier composition containing the P0A modified pVA 〇.1 to 50 parts by weight. EFFECT OF THE INVENTION A small amount of a tackifier containing the POA-modified PVA of the present invention can be used in a small amount to obtain a large viscosity-increasing effect, and further, the viscosity is hardly lowered due to an increase in temperature. [Embodiment] The present invention is a POA-modified PVA contained in the tackifier of the present invention, which contains a POA group represented by the following formula (I) in the side chain. R1—pC—C-0.L Η2 Η where R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom or a hospital group having a carbon number of 1 to 8; m and ^ each represent the number of repeating units of the oxygen stretching unit, ISmSIO' 3$nS20. Here, a unit in which the number of repeating units is m is referred to as a unit 1', and a unit in which the number of repeating units is η is referred to as unit 2. The arrangement of the unit 1 and the unit 2 can be either a random shape or a block shape. The number of repeating units m of the unit 1 of the formula ) 必须 必须 must be KmS10, more preferably i$m2. 111 is 0 〒 2h5 cg-° η R2 (I) 201116546 case,疏水 疏水 The hydrophobicity of the A group is reduced, and the water solubility of the 改性 A modified PVA is lowered. Further, the number of repeating units η of the unit 2 must be 3SHS20, more preferably 5 S 18 'extra is 8 S 15 . In the case where η is less than 3, the interaction between the ruthenium groups is not revealed, and the viscosity of the ruthenium-modified PVA aqueous solution is low. On the one hand, in the case where η exceeds 20, the hydrophobicity of the fluorenyl group becomes high, and the water solubility of the POA-modified PVA is lowered. The Ρ A modified P VA contained in the tackifier of the present invention preferably contains a POA group represented by the above formula (I) in a side chain, and a method for producing the POA-modified PVA is not particularly limited, but It is preferred to carry out a method of copolymerizing an unsaturated monomer having a PO A group represented by the general formula (I) with a vinyl ester monomer, and saponifying the obtained POA modified vinyl ester copolymer. Here, the above copolymerization is preferably carried out in an alcohol solvent or without a solvent. The unsaturated monomer having a PO A group represented by the formula (I) is preferably an unsaturated monomer represented by the following formula (II). C2h5 ^+h2'h'°^R2 (5) R1

I I HC=C—X —-C-C-0 I Η, Η R3 2 wherein R1, R2, m, and η are the same as the above formula (I). R3 represents a hydrogen atom or a -COOM group, and Μ represents a hydrogen atom, an alkali metal or an ammonium group. R4 represents a hydrogen atom, a methyl group or a -CH2-COOM group, and is herein defined above. X represents -0-, -CH2-0-, -CO-, -(CH2)k-, -C0-0- or -CO-NR5-. Here, R5 means a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms, and k is a repeating unit number of a methylene unit, l$k$15. 201116546 The R2 aspect of the unsaturated monomer represented by the formula (II) is preferably a hydrogen atom, a methyl group or a butyl group, more preferably a hydrogen atom or a methyl group. Particularly preferably, R1 of the unsaturated monomer represented by the formula (II) is an argon atom or a methyl group, R2 is a hydrogen atom or a methyl group, and R3 is a hydrogen atom. For example, when R1 of the formula (π) is a hydrogen atom or a methyl group, R2 is a hydrogen atom, and R3 is a hydrogen atom, and the unsaturated monomer represented by the formula (π) is specifically mentioned, specifically, polyoxyethylene is exemplified. Polyoxybutylene monoacrylate, polyoxyethylene polyoxybutylene monomethacrylate, polyoxyethylene polyoxybutylene methacrylate, polyoxyethylene polyoxybutylene monomethacrylate , polyoxyethylene polyoxybutylene monoallyl ether, polyoxyethylene polyoxybutylene monomethyl propyl ether, polyoxyethylene polyoxybutylene monovinyl ether, polyoxypropylene polyoxybutylene Acrylate, polyoxypropylene polyoxybutylene monomethacrylate, polyoxypropylene polyoxybutylene butyl methacrylate, polyoxypropylene polyoxybutylene monomethyl propyl decanoate, polyoxypropylene The polyoxypropylene butyl butyl sulphonate, the polyoxypropylene propylene polyoxybutylene monomethyl allylic ether, the polyoxypropylene polyoxybutylene monovinyl ether and the like. Among them, polyoxyethylene polyoxybutylene monoamide decylamine, polyoxyethylene polyoxybutylene monomethacrylate decylamine, polyoxyethylene polyoxybutylene monovinyl ether, and polycondensation are preferably used. Oxyethylene polyoxybutylene butyl monomethacrylate decylamine, polyoxyethylene polyoxybutylene monovinyl ether ° The general formula (II) wherein R 2 is an alkyl group having 1 to 8 carbon atoms 'general formula (Π) In the case of the unsaturated monomer, it is exemplified that the oxime group of the terminal of the unsaturated monomer exemplified in the case where R 2 of the above formula (Π) is a hydrogen atom is substituted by an alkoxy group having 1 to 8 carbon atoms. Things. Among them, it is preferred to use an unsaturated monomer which is substituted with a methoxy group of polyoxyethylene polyoxybutylene monomethacrylate decylamine, polyoxyethylene polyoxybutylene monoethylene 201116546 ether end, and is particularly preferable. In order to use an unsaturated monomer in which an OH group at the terminal of polyoxyethylene polybutylene methacrylate oxime is substituted with a methoxy group, an unsaturated monomer having a P〇A group represented by the general formula (I) is carried out. The temperature to be used in the copolymerization with the ethyl ester monomer is preferably from 〇 to 200 ° C, more preferably from 30 to 140 ° C. In the case where the temperature at which copolymerization is carried out is low, it will be difficult to obtain a sufficient polymerization rate. Further, when the temperature at which the polymerization is carried out is higher than 20 (TC is high, it is difficult to obtain a POA-modified PVA having the POA-based modification amount prescribed by the present invention. The temperature used in the copolymerization is controlled at 〇 to 200 ° C. The method may be a method of obtaining a balance between heat generated by polymerization and heat release from the surface of the reactor by controlling the polymerization rate, or a method of controlling by using an external jacket of a suitable heat medium, or the like. However, in terms of safety, the latter method is preferred. The polymerization method used for copolymerization of the unsaturated monomer having the POA group represented by the general formula (I) and the vinyl ester monomer may be batchwise. (batch) Any of a polymerization method, a semi-batch polymerization, a continuous polymerization, and a semi-continuous polymerization. Any one of known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method may be used. A bulk polymerization method and a solution polymerization method in which no solvent or polymerization is carried out in an alcohol solvent, and in the case of producing a copolymer having a high degree of polymerization, an emulsion polymerization method is employed. In particular, methanol, ethanol, propanol, etc. may be used, but it is not limited thereto. These solvents may be used in combination of two or more kinds. The initiator used in the copolymerization may be appropriately used in accordance with the polymerization method. Select 201116546 to select a previously known azo initiator, a peroxide initiator, a redox initiator, etc. The azo initiator may, for example, be 2,2'-azobisisobutyronitrile, 2, 2'-azobis(2,4.dimethyl pentanenitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), etc. The agent may, for example, be a percarbonate compound such as diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate or diethoxyethylperoxydicarbonate; a perester compound such as oxy neodecanoate, α- cumenyl peroxy neodecanoate or tertiary butyl peroxy neodecanoate; acetamyl cyclohexylsulfonate peroxide; 2, 4 , 4-trimethylpentyl-2-peroxyphenoxyacetate, etc. Further, potassium persulfate, ammonium persulfate, hydrogen peroxide or the like may be combined as an initiator in the above initiator. The redox initiator may be a combination of the above-mentioned peroxide with a reducing agent such as sodium hydrogen sulfite, sodium hydrogencarbonate, tartaric acid, L-ascorbic acid or Rongalite. When copolymerizing an unsaturated monomer having a POA group represented by the formula (I) and a vinyl ester monomer, PVA coloring or the like due to decomposition of the vinyl ester monomer can be found, and therefore, in this case, the purpose is It is also possible to prevent the coloring, and it is also possible to add an antioxidant such as tartaric acid to the polymerization system to the vicinity of the vinyl ester monomer. The vinyl ester monomer may, for example, be vinyl formate or vinyl acetate. , Vinyl propionate, Vinyl butyrate, Vinyl isobutyrate, Trimethyl vinyl acetate, Tetraethylene carbonate, Vinyl hexanoate, Vinyl octoate, Vinyl laurate, Vinyl palmitate, Hard Vinyl fatty acid ester, vinyl oleate, vinyl benzoate, etc., of which vinyl acetate is most preferred. When the unsaturated monomer having a POA group represented by the formula (I) is copolymerized with the vinyl ester monomer 201116546, it is also possible to copolymerize other monomers within the range not impairing the gist of the present invention. The monomer which can be used may, for example, be an α-olefin such as ethylene, propylene, n-butene or isobutylene; acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate or n-butyl acrylate. Acrylates, isobutyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.; methacrylic acid and its salts; methyl methacrylate, A Ethyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate , methacrylates such as dodecyl methacrylate and octadecyl methacrylate; acrylamide; hydrazine-methacrylamide, hydrazine-ethyl acrylamide, hydrazine, hydrazine dimethyl propylene Indoleamine, diacetone acrylamide, acrylamidamine sulfonic acid and salts thereof, acrylamidamine dimethylamine and salts thereof or quaternary salts thereof, hydrazine-hydroxymethyl acrylamide and derivatives thereof Acrylamide derivative; methacrylamide; Ν-methylmethyl Acrylamide, Ν_ethylmethacrylamide, methacrylamide sulfonate and its salt, methacrylamidamine dimethylamine and its salt or its quaternary salt, Ν-hydroxyl a methacrylamide derivative such as methacrylamide and its derivatives; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl Vinyl ethers, tertiary butyl vinyl ethers, dodecyl vinyl ethers, stearyl vinyl ethers, vinyl ethers such as 2,3-diethyloxy-1-vinyloxypropane; acrylonitrile, methacryl Nitriles such as nitrile; halogenated vinyls such as vinyl chloride and fluorinated ethylene; vinyl halides such as vinylidene chloride and vinylidene fluoride; allyl acetate and 2,3-diethoxyoxy-bupropene Allyl compound such as oxypropane or allylic chloride; cis-10-201116546 unsaturated dicarboxylic acid such as butenedioic acid, itaconic acid or fumaric acid and salts thereof or ester thereof; ethylene trimethoxy An ethylene alkylene compound such as a decane or the like; an isopropenyl acetate or the like. Further, when the unsaturated monomer having a PO A group represented by the formula (I) is copolymerized with a vinyl ester monomer, the purpose is to adjust the polymerization degree of the obtained copolymer, etc., without departing from the gist of the present invention. Even if it is copolymerized in the presence of a chain transfer agent, the chain transfer agent may, for example, be an aldehyde such as acetaldehyde or propionaldehyde; a ketone such as acetone or methyl ethyl ketone; or a thiol such as 2-hydroxyethane thiol. A phosphinate such as a halogenated hydrocarbon such as trichloroethylene or perchloroethylene; or a phosphinate such as sodium phosphinate monohydrate. Among them, aldehydes and ketones are preferably used. The amount of the chain transfer agent to be added is determined by the chain shift constant of the chain transfer agent to be added and the degree of polymerization of the intended vinyl ester polymer, but is generally from 1 to 10% by weight based on the vinyl ester monomer. Preferably, in the saponification reaction of the ruthenium-modified vinyl ester copolymer, a previously known alkaline catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acid such as ruthenium-toluenesulfonic acid can be used. The alcohol is decomposed by the catalyst and even hydrolyzed. The solvent to be used in the reaction may, for example, be an alcohol such as methanol or ethanol; an ester such as methyl acetate or ethyl acetate; a ketone such as acetone or methyl ethyl ketone; or an aromatic hydrocarbon such as benzene or toluene; These may be used alone or in combination of two or more. Among them, the methanol or methanol/methyl acetate mixed solution is preferably used as a solvent, and the sodium hydroxide is used for the saponification reaction of the catalyst. The bismuth-modified PVA contained in the tackifier of the present invention must have a thiol-modified amount S of from 0.1 to 10 mol%. When the thiol-modified amount S exceeds 10 mol%, the ratio of the hydrophobic group contained in each molecule of the yttrium-modified PVA becomes higher, and the solubility of the PVA to the aqueous solvent is lowered. On the one hand, the 改性 基 A-based modification amount S is less than 〇·1 mol%, and the p 〇a-modified PVA is excellent in water solubility, and the number of POA units contained in the PVA is small, based on POA-modified physical properties. Can't show up. The POA group modification amount S is expressed by the molar fraction of the POA group for the main chain methylene group of PVA. The lower limit of the POA group modification amount S is preferably 〇.2 mol% or more. The upper limit of the 改性 基 A group modification amount S is preferably less than 2 mol%, more preferably 1.5 mol% or less. The POA-based modification amount S of the POA-modified PVA can be determined by proton NMR of a POA-modified vinyl ester-based copolymer which is a precursor of the POA-modified PVA. Specifically, the POA-modified vinyl ester-based copolymer was reprecipitated and purified three times or more with n-hexane/acetone, and then dried under reduced pressure at 50 ° C for 2 days to prepare a POA-modified vinyl ester for analysis. A sample of a copolymer. This sample was dissolved in CDC13 and measured at room temperature using a 500 MHz proton NMR (JEOL GX·500). Using the following formula, the peak 値α (4.7 to 5.2 ppm) from the main chain methine of the vinyl ester copolymer and the peak 値β (0·8 to 1.0 ppm) from the terminal methyl group of the unit 2, The POA-based modification amount S was calculated. Further, in the formula, η represents the number of repeating units of the unit 2. S (mole%)={(proton number of β/3η)/(number of protons of α+(number of protons of β/3η))}χ100 POA modified PVA viscosity average degree of polymerization Ρ system JIS-K67 26 Determination. Namely, the PVA was further saponified and purified, and then obtained by the following formula 'from the ultimate viscosity [η] measured in water at 30 °C. Further, the viscosity average degree of polymerization is simply referred to as the degree of polymerization. Ρ = ([η] χ 1 0 3 / 8.2 9 ) (1/0 62 ) -12- 201116546 The tackifier of the present invention contains a POA-modified PVA having a polymerization degree of 200 to 5,000. When the degree of polymerization exceeds 5,000, the productivity of the POA-modified PVA is lowered, which is not practical. Moreover, when the degree of polymerization is less than 200, the tackifying effect of the tackifier containing POA-modified PVA is lowered, and it is not practical. The degree of saponification of the POA-modified PVA must be 20 to 99.99 mol%, preferably 4 0 to 9 9.9 mol%. When the degree of saponification is less than 20% by mole, the hydrophobic group-based interaction of the POA-modified PVA causes a decrease in the viscosity-increasing effect, and if the degree of saponification exceeds 99.99 mol%, the production of the POA-modified PVA becomes Difficult, it is not practical. Further, the degree of saponification of the above POA-modified PVA is obtained by the measurement of JIS-K6726. The content of the POA group represented by the formula (I) is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and particularly preferably 15 parts by weight or less. When the content of the POA group exceeds 50 parts by weight, the hydrophobicity of the PVA becomes high, and the solubility in an aqueous solvent is lowered. The lower limit of the content is preferably 2 · 5 parts by weight or more. Here, the content of the POA group represented by the formula (I) is represented by the weight fraction (weight fraction) of the POA group represented by the formula (I) in terms of 1 part by weight of the PVA main chain, and the above POA is used. The basis weight S, the number of repeating units m of the unit 1, the number of repeating units η of the unit 2, and the saponification degree of the POA-modified PVA are calculated. Even if the aforementioned P0A-based modification amount S is the same, the content of the POA group in the POA-modified PVA becomes larger as the degree of roadway changes to iSi or as m or η becomes larger. When the viscosity of the 4% by weight aqueous solution of the ΡA modified P VA contained in the tackifier of the present invention was measured by a BL type viscometer at a rotor rotation rate of 6 rpm, the viscosity ηι and 40 ° C in 2 〇t The ratio of the viscosity η2 in the η2/ηι' -13- 201116546 is preferably 0·8 or more. The viscosity is preferably 1 or more than τ^/η 1 , and more preferably 丨5 or more, and particularly preferably 2·0 or more. When the viscosity ratio η 2 /η ! is less than 〇 8 , the interaction between the Ρ Α Α groups is small, and the physical properties modified by ρ 〇 a cannot be revealed. Further, the Ρ 〇 A modified VA VA contained in the tackifier of the present invention has a viscosity of 4% by weight of an unmodified PVA having a similar polymerization degree measured at 20 t and a rotor rotation rate of 6 rpm, and is set to η 3 . When the viscosity ratio η "" is preferably greater than 1.2, more preferably greater than 1.5, and even more preferably greater than 2 〇, particularly preferably greater than 5.0. Here, the unmodified PVA having a similar degree of polymerization means having ΡΟΑ The unmodified PVA of the degree of polymerization of the modified PVA in the range of 95.95 times to ι_05 times » The tackifier of the present invention contains the above Ρ Ο Α modified Ρ V Α. The tackifier of the present invention can be used in the resin powder In the state of use, it may be used as it is, or it may be mixed with water or an aqueous solvent as a liquid tackifier. Here, the aqueous solvent is composed of a solvent other than water and water, and is used for coatings, adhesives, and the like. In the case of the aqueous emulsion, a liquid tackifier is preferably used. When a liquid tackifier is used, the solvent other than the water contained in the aqueous solvent may be exemplified by an alcohol solvent such as methanol or ethanol; Ester, ethyl acetate and other ester solvents; diethyl ether, 1, 4 - Dioxane, methyl 赛路苏, 赛路苏, butyl 赛路苏, MTBE (methyl tertiary butyl ether), butyl carbitol and other ether solvents; ketones such as acetone and diethyl ketone Solvent; ethylene glycol solvent such as ethylene glycol, propylene glycol, diethylene glycol or triethylene glycol; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether 'propylene glycol monomethyl ether, 3 · methoxy _3_methyl-丨-butanol and other glycol ether solvent; ethylene glycol monomethyl ether acetate, PM A (propylene glycol mono-14· 201116546 methyl ether acetate), diethylene glycol monobutyl a glycol ester solvent such as ether acetate or diethylene glycol monoethyl ether acetate, but is not limited thereto. When a liquid tackifier is used, the amount of the above-mentioned P A modified PVA is relatively 100 parts by weight of the solvent 'preferably 1 to 7 parts by weight, more preferably 10 to 40 parts by weight. The liquid tackifier can be heated by adding the above POA-modified PVA to water or an aqueous solvent. When the liquid tackifier is prepared, various plasticizers, various surfactants, various antifoaming agents, and ultraviolet light absorbers can be formulated without impairing the effects of the present invention. Further, it is also possible to mix various well-known PVA, starch, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose in the same manner as not to impair the effects of the present invention. And other water-soluble polymer such as hydroxypropylmethylcellulose. The amount of the other water-soluble polymer is preferably 50 parts by weight or less based on 100 parts by weight of the POA-modified PVA. Other examples of the tackifier-containing composition can be obtained by mixing the above-mentioned tackifier, water and oil of the present invention in the same manner as above. Examples of the above-mentioned tackifier-containing composition can be exemplified by water. A polyacrylate dispersion, an olefinic unsaturated monomer alone or a copolymer aqueous dispersion, an aqueous polyvinyl acetate dispersion, an aqueous polyurethane dispersion, an aqueous polyester dispersion, etc. An aqueous dispersion. The content of the POA-modified PVA in the composition is preferably from 0.1 to 50 parts by weight, more preferably from 0.3 to 5.0 parts by weight, per part by weight of the oil component. In addition to the above-mentioned Ρ Ο A modified VA VA tackifier, in addition to being able to obtain a very large viscosity-increasing effect at low use, the viscosity drop with the temperature rise is lower -15-201116546, so even in summer, the temperature rises. In the case of the situation, it can also exert a stable viscosity-increasing performance. Therefore, it is suitable for use as an adhesion promoter in aqueous solutions and aqueous emulsions such as paints, paints, cements, concretes, paper coatings, bonding materials, adhesives, cosmetics, and the like. EXAMPLES The present invention will be described in detail by way of examples and comparative examples. In the following examples and comparative examples, "parts" and "%" mean the basis of weight unless otherwise stated. The PVA obtained in the following production examples was evaluated according to the following method. [Saponification degree of PVA] The degree of saponification of PVA was determined by the method described in JIS-K6726. [Solubility of PVA] 4 g of POA-modified PVA was added to 96 g of distilled water at room temperature, and the mixture was stirred for 30 minutes. The obtained POA-modified PVA aqueous solution was heated to 9 (TC), stirred for 1 hour as usual, cooled to room temperature, and filtered using a metal mesh of 10 mm 5 mm 0. After filtration, the metal mesh was dried at 105 ° C for 3 hours. After cooling to room temperature in a desiccator, the weight is measured, and the weight of the metal mesh is increased before and after filtration. The weight of the metal mesh added after filtration is taken as a(g) ' Further, in the formula for calculating the insoluble component, the purity (%) is obtained by the following formula: Purity (%) = [POA modified PVA dried at 3 ° C for 3 hours) Weight (g) / weight of POA modified PVA before drying (g)] xl00 Insoluble content (%) = a (g) / 4 (g) xl00 / purity (%) χ 100 -16- 201116546 According to the following criteria, The insoluble component calculated according to the above formula is determined. A: the insoluble component is less than 0.01% B: the insoluble component is 0. 0% or more and less than 0.1% C: the insoluble component is 0.1% or more and less than 0.5% D: No The dissolved component is 0.5% or more and less than 1.0%. E: the insoluble component is 1.0% or more [the viscosity of the PVA aqueous solution]. The PVA aqueous solution having a concentration of 4% is prepared. The viscosity at a temperature of 20 ° C or 40 ° C was measured using a BL type viscometer at a rotor rotation rate of 6 rpm. [Etylene-vinyl acetate copolymer emulsion adhesion test] Ethylene-vinyl acetate copolymer emulsion (Kuraray shares) 2 parts of PVA aqueous solution of 4% concentration (1.5 parts of solid content of PVA relative to 100 parts of emulsion solid content) and 2.4 parts of water were added to 100 parts of OM-4200NT and 55% by weight of the company. 45% mixed solution of PVA and emulsion, using a BL type viscometer, measuring the viscosity at 20 ° C at the rotor rotation rate pm [Storage stability test of ethylene-vinyl acetate copolymer emulsion] will be used The solution of the adhesion test was stored in a dryer at 50 °C. 'The number of turns separating the emulsion layer from the water layer was observed and judged on the following basis. A : 30 days or more B: 1 5 to 30 C: 7 to 15th D: 3rd to 7th E: 3rd to 17th - 201116546 <Manufacturing method of PVA> Manufacturing Example 1 (Production of PVA1) A mixer, a reflux cooling tube, a nitrogen introduction tube, and a comon monomer are provided. a 3L reactor with a mouth and an initiator addition port, filled with vinyl acetate 75 0 g, 250 g of methanol, and 3.3 g of an unsaturated monomer (monomer A) having a POA group, and nitrogen substitution was carried out for 30 minutes while performing nitrogen foaming. Further, an unsaturated monomer having a PO A group was prepared ( The monomer A) was dissolved in methanol to obtain a comonomer solution having a concentration of 20%, and was subjected to nitrogen substitution by foaming of nitrogen as a delay solution. The temperature of the reactor was started, and when the internal temperature was 60 ° C, 0.25 g of 2,2'-azobisisobutyronitrile (AIBN) was added to initiate polymerization. The delayed solution was dropped, and while the monomer composition (ratio of vinyl acetate to monomer A) in the polymerization solution was constant, the mixture was polymerized at 60 ° C for 3 hours, and then cooled, and the polymerization was stopped. The total amount of the comonomer solution added until the polymerization was stopped was 75 ml. Further, the solid content concentration at the time of stopping the polymerization was 24.4%. Then, at the temperature of 30 ° C and under reduced pressure, methanol was added frequently, and the unreacted vinyl acetate monomer was removed to obtain a methanol solution of POA-modified polyvinyl acetate (POA-modified PVAc) (concentration 35). %). Further, methanol was added thereto, and 55.6 g of an alkali solution (1% by mol of methanol solution of sodium hydroxide) was added to 453.4 g of a methanol solution of POA-modified PVAc (POA-modified PVAClOO.Og in solution). Saponification was carried out (POA-modified PVAc concentration of the saponification solution was 20%, and molar ratio of sodium hydroxide to the vinyl acetate unit in the POA-modified PVAc was 0.1 mol%). After the addition of the alkali solution, a gel was formed at about 1 minute, so it was pulverized in the pulverizer, left at 40 ° C for 1 hour, and then saponified, and then added with methyl acetate 500 00g to neutralize -18- 201116546 Residual alkali. After confirming that the neutralization was completed using a phenolphthalein indicator, it was filtered off to obtain a white solid, and methanol (20 g) was added thereto, and the mixture was allowed to stand at room temperature for 3 hours, and washed. After the above washing operation was repeated three times, the mixture was centrifuged and dehydrated, and the obtained white solid was allowed to stand at 65 ° C for 2 days in a dryer to obtain P〇 A modified PVA (PVAl). The degree of polymerization of PVA1 was 1 760, the degree of saponification was 98.7 mol%, and the amount of modification of POA group was 0.4 mol%. Production Examples 2 to 28 (manufacturing of PVA 2 to 28) In addition to changing the loading amount of vinyl acetate and methanol, the polymerization conditions such as the type (Table 2) or the amount of the unsaturated monomer having a POA group used in the polymerization, The saponification conditions of the concentration of the POA-modified PVAc and the molar ratio of the sodium hydroxide to the vinyl acetate unit at the time of saponification were as shown in Table 1 and Table 2, and various POA modifications were carried out in the same manner as in Production Example 1. PVA (PVA2 to 28). Production Example 29 (Production of PVA 29) In a 3 L reactor equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and an initiator addition port, 700 g of vinyl acetate and 300 g of methanol were charged, and nitrogen foaming was carried out while Nitrogen substitution was carried out in the system for 30 minutes. The temperature of the reactor was started. When the internal temperature was 6 (TC, 0.25 g of 2,2'-azobisisobutyronitrile (AIBN) was added, and polymerization was started. After 6 (TC was polymerized for 3 hours, it was cooled) to stop the polymerization. When the polymerization was stopped, the solid content concentration was 17.0%. Then, methanol was added to the unreacted vinyl acetate monomer while adding methanol at a reduced pressure at 30 ° C to obtain a polyvinyl acetate (PVAc) methanol solution. (concentration of 30%). Further, methanol was added thereto, and 55.8 g of an alkali solution was added to 54.4 g of the prepared PVAc methanol solution (PVACl 20.0 g in the solution)-19-201116546 (sodium hydroxide) L〇% methanol solution), saponification (the PVAc concentration of the saponification solution is 20%, and the molar ratio of sodium hydroxide to the vinyl acetate unit in PVAc is 0.1 mol%). After the addition of the alkali solution, it is formed about 1 minute later. After the gel was pulverized, the mixture was pulverized at 40 ° C for 1 hour, and after saponification, 500 g of methyl acetate was added to neutralize the remaining alkali. The phenolphthalein indicator was used to confirm that the neutralization was completed. , filtered off to obtain a white solid, which was added with 2000 g of methanol at room temperature. After standing for 3 hours, it was washed. After the above washing operation was repeated three times, it was centrifuged and dehydrated, and the obtained white solid was allowed to stand at 65 ° C for 2 days in a dryer to obtain an unmodified PVA (PVA29). The polymerization degree was 1700, and the degree of saponification was 98.5 mol%. Production Examples 30 to 34 (manufacture of PVA 30 to 34) In addition to the loading amount of ethylene glycol and methanol, the concentration of PVAc at the time of saponification, and the ethyl acetate unit The saponification conditions such as the molar ratio of sodium hydroxide were changed as shown in Table 1, and the other unmodified PVA (PVA 30 to 34) was produced in the same manner as in Production Example 29. Production Example 35 (PVA35) Manufacture) In a 6L reactor equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a co-monomer dropping port, and an initiator addition port, 2400 g of ethylene carbonate, 600 g of methanol, and 1 to 16 hexa-1 of 6.6 were charged. g, while performing nitrogen foaming, nitrogen substitution was carried out in the system for 30 minutes. The temperature of the reactor was started, and when the internal temperature was 60 ° C, 2,2'-azobisisobutyronitrile (AIBN) 2_8 g was added. The polymerization was started. After polymerization at 60 ° C for 2 hours, it was cooled to 'stop the polymerization. The polymerization stopped. The solid content concentration was 32.5%. Then, methanol was frequently added at 30 ° C under reduced pressure, and the unreacted ethylene glycol monomer was removed by -20-201116546 to obtain an alkyl-modified polyacetate. A solution of the ester (alkyl-modified PVAc) in methanol (concentration: 35%). Further, methanol was added thereto, and 453.4 g of a methanol solution of the modified alkyl-modified PVAc (alkyl modified PVAclOO.Og in the solution) was added. Add 55.6g of alkali solution (10% methanol solution of sodium hydroxide) to saponification (alkylation modified PVAc concentration of saponification solution 20%, sodium hydroxide of ethylene acetate unit in alkyl modified PVAc) The molar ratio is 0.1 mol%). When the alkali solution was added, the gel was formed at about 1 minute, so it was pulverized in a pulverizer, left at 40 ° C for 1 hour, and then saponified, and then 500 mM of methyl acetate was added to neutralize the remaining alkali. . Using a phenolphthalein indicator, it was confirmed that after completion of neutralization, it was filtered off to obtain a white solid, and 200 g of methanol was added thereto, and the mixture was allowed to stand at room temperature for 3 hours and washed. After the above washing operation was repeated three times, it was centrifugally dehydrated, and the obtained white solid was placed in a 65 ° C dryer for 2 days to obtain an alkyl-modified PVA (PVA35). The degree of polymerization of PVA35 was 1720, the degree of saponification was 98.6 mol%, and the amount of alkyl modification was 〇·3 mol%. The manufacturing conditions of PVA1 to 35 are shown in Tables 1 and 2. -21- 201116546 [Table 1] POA Modified PVA Charge D Saponification conditions Manufacturing Example No. Vinyl acetate (g) Methanol (g) Unsaturated monomer unsaturated monomer polymerization rate (%) PVAc concentration sodium hydroxide Ear ratio 2) Type (g) (%) (% by mole) Manufacturing Example 1 PVA1 750 250 A 17.6 35 20 0.1000 Manufacturing Example 2 PVA2 400 600 A 13 50 20 0.1000 Manufacturing Example 3 PVA3 550 450 A 11.7 30 20 0.1000 Manufacture Example 4 PVA4 900 100 A 21.5 35 20 0.1000 Production Example 5 PVA5 950 50 A 14.8 20 20 0.1000 Manufacturing Example 6 PVA6 100 900 A 4.5 80 20 0.1000 Manufacturing Example 7 PVA7 1000 0 A 8 5 20 0.1000 Manufacturing Example 8 PVA8 550 450 A 11.8 30 20 0.0075 Production Example 9 PVA9 550 450 A 11.8 30 20 0.0020 Manufacturing Example 10 PVA10 550 450 A 11.8 30 20 0.0010 Manufacturing Example VA PVA11 750 250 A 9.9 40 20 0.1000 Manufacturing Example 12 PVA12 750 250 A 4.9 40 20 0.1000 Manufacturing Example 13 PVA13 750 250 A 3.9 40 20 0.1000 Manufacturing Example 14 PVA14 750 250 C 97.4 40 20 0.1000 Manufacturing Example 15 PVA15 750 250 C 235 40 20 0.1000 Manufacturing Example 16 PVA16 750 250 B 7.4 40 20 0.1000 Manufacturing Example 17 PVA17 750 250 C 6.1 40 20 0.1000 Example 18 PYA18 750 250 D 4.9 40 20 0.1000 Manufacturing Example 19 PVA19 750 250 E 3.7 40 20 0.1000 Manufacturing Example 20 PVA20 750 250 F 11.2 40 20 0.1000 Manufacturing Example 21 PVA21 750 250 G 13.5 40 20 0.1000 Manufacturing Example 22 PVA22 750 250 H 14.8 40 20 0.1000 Production Example 23 PVA23 750 250 I 32 40 20 0.1000 Manufacturing Example 24 PVA24 750 250 J 78 40 20 0.1000 Manufacturing Example 25 PVA25 750 250 K 14.9 40 20 0.1000 Manufacturing Example 26 PVA26 750 250 L 7.4 40 20 0.1000 Manufacture Example 27 PVA27 750 250 M 9.9 40 20 0.1000 Manufacturing Example 28 PVA28 750 250 N 11.2 40 20 0.1000 Manufacturing Example 29 PVA29 700 300 - - 25 20 0.1000 Manufacturing Example 30 PVA30 550 450 - - 40 20 0.1000 Manufacturing Example 31 PVA31 350 650 - - 40 20 0.1000 Production Example 32 PVA32 800 200 20 15 0.1000 Production Example 33 PVA33 950 50 - - 5 10 0.1000 Production Example 34 PVA34 980 20 - - 2 5 0.1000 Production Example 35 PVA35 2400 600 1-hexadecene 16.6 32.5 20 0.1000 -22- 201116546 1) In all the production examples, the polymerization initiator used 2,2'-azobisisobutyronitrile (AIBN) 0.25 g 2) POA modified PVAc sodium hydroxide for vinyl acetate units (NaOH) Mohr's ratio [Table 2] Monomer R1 R2 R3 R4 X mn A -H -H -H -ch3 -CO-NH- 2 13 B -H -H -H -ch3 -CO-NH- 2 9 C - H -H -H -ch3 -CO-NH- 2 6 D -H -H -H -ch3 -CO-NH- 2 4 E -H -H -H -ch3 -CO-NH- 2 2 F -H - H -H -ch3 -CO-NH- 2 16 G -H -H -H -ch3 -CO-NH- 2 19 Η -H -H -H -ch3 -CO-NH- 2 21 I -H -H - H -H -0- 2 10 ' J -H -H -H -CH2-COONa -CO-NH- 2 12 K -H -H -COONa -H· -CO-NH- 2 13 L -H -H - H -ch3 -CO-NH- 20 0 Μ -ch3 -H -H -ch3 -CO-NH- 20 0 NM -H -H -ch3 -CO-NH- 0 17 Examples 1 to 19 and Comparative Example 1 to The results of the above evaluations of PVA1 to 35 are shown in Tables 3 and 4. -23- 201116546

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c J 201116546 [inch] £m test result storage stability test (50 Q 1 QI Ο < Q Ω < QQQQQQQ 20 °C medium viscosity (mPa _ s) § 1 ο 1 1450 1 130 1320 300 250 沄Evaluation results of 400 500 600 1300 PVA Ph JI - 11 Amoy, S comparison & 1 1 Comparative Example 10 1 Comparative Example 10 Comparative Example 10 Comparative Example 10 Comparative Example 10 Comparative Example 10 1 1 1 1 1 1 Comparative Example 10 Viscosity Than?? l/ 1 1 1—» 1 (Ν 1 225.0 OS ο q 160.7 1 1 1 1 • 1 232.1 Viscosity ratio ηι/η \ 00 〇1 On Ο 1 卜d inch (Ν οο ο 00 d (Ν Ν Ν 1 1 1 1 1 1 d 40°C Medium viscosity 7? 2 (mPa · s) 00 1 00 (Ν 1 in cs 15000 rs tN <N 9800 • 1 1 1 1 1 800 20°C medium viscosity...3) (mPa * s) 〇1 1 6300 νο <Ν 4500 ΟΟ fS Ui (N cn 420 6500 &行< ώ < ω < D << Q 1 1 1 1 1 1 < polymerization result monomer Content (parts by weight) 10.0 CN 68.0 〇(N 00 〇\ 卜 11.2 1 1 1 1 1 1 1 Saponification degree (Mo [_ ear%) 98.6 00 98.5 00 ο 98.6 98.8 98.5 98.5 98.5 98.5 98.4 98.6 98.5 98.6 98.4 98.6 POA base modification halo s (mo %) inch d to d 0.08 2 (N d (Ν Ο to ο d ο 1 1 1 1 1 1 0.34) Viscosity average polymerization Cu m 1040 1720 1680 1720 1700 1700 1700 1700 1700 1000 500 2400 3500 4800 1720 POA Modified PVA PVA6 PVA10 PVA13 PVA15 PVA19 j PVA22 PVA26 PVA27 1 PVA28 PVA29 PVA30 PVA31 PVA32 PVA33 PVA34 PVA35 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 -^- ¥#1 袋¥+(inch& 赃glmOI 匡镒qq < s. Bd-ooool 脉经虼露露SM line (e 201116546 The POA-modified PVA contained in the tackifier of the present invention is excellent in solubility, and further has high viscosity compared to the equivalent unmodified PVA having a polymerization degree. Further, it has a characteristic that the viscosity of the aqueous solution at 40 ° C is high as compared with the viscosity of the aqueous solution at 20 ° C. Therefore, it has excellent performance in the viscosity-increasing effect and storage stability of the emulsion. Further, even when compared with the polyethylene oxide-modified PVA (Comparative Example 7) and the polypropylene oxide-modified PVA (Comparative Example 8), it had a remarkable viscosity-increasing effect. However, in the case of m = 0, even if η is in the range of 3Sn$20, the water solubility of the obtained cerium-modified PVA is low, and it can be confirmed as an insoluble component in the aqueous solution (Comparative Example 9). Further, the alkyl-modified PVA produced using 1-hexadecene has a certain degree of viscosity-increasing effect, and has low storage stability, and the separation of the aqueous solution can be confirmed (Comparative Example 16). As shown in the examples, the tackifier of the present invention provides high viscosity and high storage stability by using P 〇 A modified PVA. Therefore, it is suitable as a tackifier for various emulsions, paints, and the like. [Simple description of the diagram] None. [Main component symbol description] None. -26-

Claims (1)

201116546 VII. Patent application scope: 1. A tackifier which contains a polyoxyalkylene-modified polyethene alcohol polymer. The modified polyethyl alcohol polymer has the following general formula in the side chain. The polyoxyalkylene group (I) has a viscosity average degree of polymerization P of 200 to 5,000 and a degree of saponification of 20 to 99.99 mol%. The polyoxyalkylene group-modified amount s is 〇.1 to 1 〇 mol % ' m I- I ο 11 RICH I 2 CH c2h5c—c a οK Η R2 (I) (wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; m, η each Indicates the number of repeating units of the oxygen-deionized unit, ISmSIO, 3SnS20). 2. The tackifier of claim 1 further comprising water or a water-containing solvent. 3. A tackifier-containing composition comprising a tackifier, water and oil component as described in the scope of the claims of the patent, relative to 100 parts by weight of the oil, the polyoxyalkylene-modified polyvinyl alcohol-based polymerization The substance contains 0.1 to 50 parts by weight. -27- 201116546 IV. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: