TWI335921B - - Google Patents

Description

1335921 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) The present invention relates to sterol and its manufacture [Prior Art] Conventional polyethylene strength, etc., aqueous agents, fiber-coated films, and the like. Therefore, use. Based on the use of a higher degree of saponification liquid, the water temperature rises, the fluidity becomes completely lost, and the polyethyl polyvinyl alcohol which is used to solve the ester copolymerization of the ester is high, but the polyvinyl alcohol B In the step of diol bonding, butadiene ester poly(polyvinyl acetate), the technical field is related to a method. The enol system utilizes a soluble specializing agent and various low-temperature winters which are used in addition to special occasions, and it is a major problem in the extreme. Rapid coating or seeding · 埽 埽 | | Introduced with high modification but using vinyl acetate 酉 之 之 之 之 之 之 对 对 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇Butadiene has the 1,2-B 2 publication). This is quite good. Very good, the above 1,2-form, the tendency to introduce a vinyl butyrate carbonate monomer, the bond has a 1,2~ethylene glycol bond, and its film forming properties Membrane property, oil resistance, used as an emulsifier, a suspending agent, an interfacial activity agent, a paper processing agent, an adhesive, and a thinner aqueous solution, which is usually used as an aqueous solution to dissolve the water when it is dissolved in water. Y. The solution of the aqueous solution in the case of the viscosity of the aqueous solution. The case of the carboxylate monomer obtained by carboxylation of the carboxylate monomer 20 02 - 241433 adhesion properties and the like for the aforementioned various substances (for example, 7 mol% Butadiene vinegar, the solubility of unreacted B solvent in the saponification or the introduction of the paste

2066-6499-PF(N3).ptd $5 page 1335921 V. Description of the invention (2) The manufacturing steps such as saponification of a solvent source generally used in the industry are limited by the amount of modification. Further, when the diol is derivatized by hydrolysis of the butadiene carbonate by saltiness, there is still a problem that it is necessary to treat by-products such as dimethyl carbonate mixed in the solvent recovery system. SUMMARY OF THE INVENTION As a result of intensive research on the above-mentioned subject, it was found that a bond obtained by saponifying a copolymer of a vinyl ester monomer and a compound represented by the following formula (1) has 1, 2 - The ethylene glycol-bonded polyethylene glycol is characterized in that the above-mentioned problems can be solved, and the water solubility and shelf stability of the polyvinyl alcohol can be greatly improved, and the present invention can be completed. H R1

I I c=c I I H R2 -CH-CH2 (1)

I I 〇 〇

II R3 R4 [wherein R 1 is hydrogen or alkyl; R 2 may have a single bond or a carbon atom of the alkyl group; the R 3 and R 4 are each independently 'hydrogen or R 5 — C 0 — wherein Further, in the present invention, the polyvinyl alcohol (partially saponified product) having a degree of saponification of less than 0.90 mol% is insoluble in the thermal history of the polyvinyl alcohol (partially saponified product). It can be solved by using the compound represented by the above formula (1).

2066-6499-PF(N3).ptd Page 6 1335921 V. INSTRUCTION DESCRIPTION (3) That is, the present invention relates to a copolymer of an ethyl styrene monomer and a compound represented by the formula (1) A polyvinyl alcohol obtained by saponification and having a 1,2-ethylene glycol bond in a branched chain is applied. Further, the present invention relates to a process for producing a polyvinyl alcohol having a 1,2-ethylene glycol bond in a branched chain, characterized by a copolymer of a vinyl ester monomer and a compound represented by the formula (1) Saponification is applied. The degree of saponification is preferably 0.99 mol% or more or less than 9 9 mm mol%. The copolymerization ratio of the compound represented by the formula (1) is preferably 11 to 40% by mole. [Embodiment] The present invention relates to a polyvinyl alcohol having a 1,2-ethylene glycol bond in a branched chain. The polyvinyl alcohol of the present invention is obtained by saponifying a copolymer of a vinyl ester monomer and a compound represented by the following formula (1). HR1

I I c=c I I H R2 -CH-CH2 (1)

I I 〇 〇

II R3 R4 wherein R1 is hydrogen or alkyl, preferably decyl, ethyl or butyl; R2 may have a single bond or an alkyl group, preferably a methyl, ethyl or butyl group. An alkylene group; R3 and R4 are each independently hydrogen or R5 - C0 - (wherein, R5

2066-6499-PF(N3).ptd Page 7 1335921 V. Description of the invention (4) is an alkyl group, preferably a methyl group, a propyl group, a butyl group, a hexyl group or an octyl group) as the formula (1) The compound to be represented includes 3,4-dihydroxy-1-butene, 3,4-bisdecyloxy-1-butene, 3-decyloxy-4-hydroxy-1-butene, 4-decyloxy-3-hydroxy-1-butene, 3,4-dioxaoxy-2-mercapto-1-butene, 4,5-dihydroxy-1-pentene, 4, 5 - Dimethoxy-1-pentene, 4,5-dihydroxy-3-methyl-1-pentene, 4,5-bis-decyloxy-3-mercapto-1-pentene, 5, 6 - Dihydroxy-1-hexene, 5,6-bisdecyloxy-1-hexene, and the like. Particularly, in view of excellent copolymerization reactivity and industrial processing, it is preferred to use 3,4-bis-decyloxy-1-butene, and 3,4-bis-decyloxy-1-butene. Among the olefins, 3,4-diethyloxy-1-butene is more preferred. Further, 3,4-dihydroxy-1-butene is commercially available from Eastman Chemical Ltd. or ACROS ORGANICS. Examples of the vinyl ester monomer include vinyl phthalate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, tridecyl vinyl acetate, and vinyl phthalate. Ester, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl acid ester, viny 1 ester of versatic acid, and the like. In particular, from the economical point of view, it is preferred to use vinyl acetate. Further, in the present invention, in addition to the above-mentioned copolymerization component, other monomers, for example, 〜5 to 10% by mole, may be copolymerized as long as the object of the present invention is not impaired. Examples of the other monomer include, for example, a rare hydrocarbon such as ethylene, propylene, isobutylene, hydrazine: octane, α-dilute, and α-octadecene; acrylic acid or methyl group; Acrylic acid, crotonic acid, maleic acid, maleic anhydride,

2066-6499-PF(N3).ptd Page 8 1335921 V. Description of invention (5) Unsaturated acids such as itaconic acid or salts thereof; mono or dialkyl groups; acrylonitrile, methacrylonitrile, etc. a nitrile; a decylamine such as diacetone acrylamide, acrylamide or methacrylamide; an olefin sulfonic acid such as ethylenesulfonic acid, allylsulfonic acid or methallylsulfonic acid or a salt thereof ; alkyl vinyl ethers; dimercaptopropyl vinyl fluorenone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride, polyethylene oxide (mercapto) allyl ether, polypropylene oxide (曱Polyalkylene oxide (meth)allyl ether such as allyl ether; polyalkylene oxide (methyl) such as polyethylene oxide (meth) acrylate or polypropylene oxide (meth) acrylate Acrylate; polyalkylene oxide (meth) acrylamide such as polyethylene oxide (meth) acrylamide, polypropylene oxide (meth) acrylamide; polyethylene oxide [1- (fluorenyl) acrylamido-1,1-dimethylpropyl]ester, polyethylene oxide vinyl ether, polypropylene oxide vinyl ether, polyethylene oxide allylamine, polypropylene oxide Propylamine, polyethylene oxide vinylamine, polypropylene oxide vinylamine, and the like. Further, N-propylene decyl fluorenyl fluorenyltrimethylammonium hydride, acrylamidoethyltrimethylammonium hydride, N-acrylamidopropyltrimethylammonium chloride, 2-propene Oxyethyltrimethylammonium chloride, 2-mercaptopropenyloxyethyltrimethylammonium chloride, 2-hydroxy-3-mercaptopropenylhydroxypropyltrimethylammonium chloride, allyl Trimethylammonium chloride, decylallyl tridecyl ammonium hydride, 3-butenyl trimethylammonium hydride, dimethyl diallyl ammonium chloride, diethyl diallyl A cationic group-containing monomer such as ammonium chloride or the like, an ethylidene group-containing monomer or the like. The polymerization method as the copolymerization of the vinyl ester monomer and the compound represented by the formula (1) (even other monomers) is not particularly limited.

2066-6499-PF(N3).ptd Page 9 1335921 V. Description of Invention (6) A conventional method such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, or emulsion polymerization may be employed, but usually a solution is applied. polymerization. The method of adding the monomer component at the time of copolymerization is not particularly limited, and any method such as batch addition, batch addition, continuous addition, or the like can be employed. The compound represented by the formula (1) is uniformly distributed in the molecular chain of the polyvinyl ester polymer, the reactivity with the crosslinking agent is improved, and the melting point of the polyvinyl alcohol is lowered. Liquid polymerization is preferred, and a polymerization method based on the HANNA method is preferred. The solvent to be used for the copolymerization is usually a lower alcohol such as methanol, ethanol, isopropanol, propanol or butanol, or a ketone such as acetone or methyl ethyl fluorenone. In particular, decyl alcohol is preferred in the industry. The amount of the solvent to be used is the degree of polymerization of the copolymer to be used, and the chain transfer constant of the solvent can be appropriately selected. For example, when the solvent is methanol, S (solvent) / Μ (monomer) = 0. A range of 0 1 to 1 0 (weight ratio), preferably 0. 0 5 to 3 (weight ratio) is selected. A polymerization catalyst is used for the copolymerization, and examples of the polymerization catalyst include a conventional radical polymerization catalyst such as azobisisobutyronitrile, acetonitrile, benzoquinone peroxide, and laurel peroxide; or A low-temperature living radical polymerization catalyst such as azobis decyl valeronitrile or azobisphosphonium decyl valeronitrile. The amount of the polymerization catalyst used is not determined depending on the type of the catalyst, but may be arbitrarily selected depending on the polymerization rate. For example, when using azobisisobutyronitrile or ruthenium oxyhydroxide, it is more preferably 0. 02~0. 15 mol% more than the vinyl ester monomer. good.

2066-6499-PF(N3).ptd Page 10 13359821 5 invention description (7) and 'e+ force of copolymerization reaction is set to 4 〇t: ~boiling point ^, the temperature is based on the solvent used or In the present invention, '' is better at the Vth. The rate is not particularly limited, and the copolymerization ratio can be determined by the copolymerization ratio of the compound represented by the formula (1). The coupling of the 1,2_glycol bond described later is carried out by dissolving the obtained copolymer in the obtained copolymer to a saponification, a catalyst or an acid catalyst. Among the = or 3 water alcohols, a base-catalyzed propanol, a third butanol or the like is used. Among them, the diols may be exemplified by the fact that the concentration of decyl alcohol and ethanol is particularly good based on the viscosity of the system. Copolymerization in alcohols 10~6. The range of % by weight. As an appropriate choice, it is usually selected such as potassium hydroxide H2; = use of (iv) a chemical, such as lithium alkali metal hydroxide sodium alkoxide, potassium decoxide, methic acid, nitric acid, metaphorite Acid, Buddha stone test catalyst; stone waste acid 'salt agent. The amount of the saponification catalyst used in the acid catalyzed by the ion exchange resin is appropriately selected, and the saponification degree or the like is appropriately selected, and the saponification method is usually used in comparison with the vinyl ester monomer and the first (丨). However, when using the catalyst, the total amount of 1 mole is 〇. 30 30 millimoles, and the compound represented by it is appropriate. It is preferably 2 to 丨7 mmol. The reaction temperature of the saponification reaction is not particularly high. (: preferably, 2〇~5 (TC is better. The poem is limited to 'but 1〇, 6〇) the polyvinyl alcohol of the present invention, which is characterized by the ester moiety of the vinyl ester monomer and a compound represented by the term "borrowing" at the time of specialization

2066-6499-PF(N3).ptd第11页

1335921, and the oxy group of the invention (8) is simultaneously converted into a hydroxyl group, so that by-products such as dimethyl discate which is disadvantageous in the case of using butadiene carbonate are not produced.

In the present invention, the average degree of polymerization of the polyvinyl alcohol (measured according to J J S K6726) is preferably from 150 to 4,000 (more preferably from 300 to 2,600, more preferably from 500 to 2,200). If the average degree of polymerization is less than 丨5〇, the mechanical strength is reduced when used for film applications and the like; if the average degree of polymerization exceeds 4〇〇〇, it is difficult to introduce a large amount of 1,2-ethylidene linkage. . Further, the degree of saponification of the polyvinyl alcohol is preferably 60 mol% or more, 7 mol% or more, 80 mol% or more, more preferably 9 mol% or more. When the degree of saponification is less than 60% by mole, there is a tendency for water solubility to decrease. Divided into: J '(1) hair 2 / saponification degree, the rate of change of the vinegar part of the ethyl ester monomer to the base group (/the saponification reaction of the methoxy group of the ear complex) The rate of change is expressed (in the case of 匕 匕 - 从 从 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Different use, some changes, agent), inkjet processing agent (adhesive = for the purpose; into = 9 layers 9 two = each two two - oxidized stone 黏 sticky in the agricultural market or detergent, etc. Bucket / ° slaves, and the application of 99. 〇 Mo Er% or more, but thin 膣 或 or, the packaging material, although the degree of change in the 'shows a unique effect of the solution two almost no change over time and, It is ideal for polyethylene I;:guide::]. It is particularly limited, but the amount of ethylene glycol bond with 〇1=2 is not pleasing to the ear/family good, 〇_5~25ml %更mi 2066-6499-PF(N3).ptd Page 12 1335921 V. Description of invention (9) Good, 1~20 mol% is better. If the introduction amount is less than 〇. 1 mol% ' Use a cross-linking agent, etc. The reactivity with the crosslinking agent is low, and the viscosity stability when the aqueous solution is formulated is reduced. Moreover, when the aqueous solution is used as a high-speed coating, the coating property is also reduced; if more than 40 In the case of mol%, the degree of polymerization of polyvinyl alcohol tends to be too low. In particular, in the present invention, even when a large amount of 7 mol% or more of 1,2-ethylene glycol bond amount is introduced as described above, There is no hindrance to the industrial implementation, and it can be easily manufactured, and the introduction of the polyethylene into the drenched, even the crystallinity is lowered, and it is easy to become water-soluble, and it is obvious that the stability of the aqueous solution of the polyvinyl alcohol is also It is quite excellent, the polyvinyl alcohol aqueous solution is low-foaming, and the film obtained from the polyvinyl alcohol is not reduced in water solubility even in an alkaline environment for a long period of time, and has these characteristics. It is quite useful in the use of water-soluble packaging materials, etc. On the other hand, since the 1,2-ethylene glycol bond has a primary hydroxyl group, the amount of introduction can be greatly increased, so it is used for aqueous ethylene. In the case of the use of an aminophthalic acid ester adhesive, etc., the adhesive strength can be greatly improved, and it is quite useful for adhesive bonding of woodwork, particularly for coniferous laminates, etc., and with colloidal cerium oxide or hazy cerium oxide. The interaction of cerium oxide is also high, and it is also applicable to a gloss layer for inkjet. Further, since the polyvinyl alcohol of the present invention has a high degree of saponification with a degree of saponification of about 9 mmol/〇, the melting point is low. An olefin-based resin such as an ethylene-vinyl acetate copolymer (a vinyl acetate content of about 40% by weight) is blended with a compatibilizing agent (an acid anhydride-modified various olefin-based resin such as maleic anhydride). In case, it can be easily melt blended 'for example for ethylene one

2066-6499-PF(N3).ptd Page 13 1335921 V. Description of the Invention (ίο) A vinyl acetate copolymer obtained by blending about 20% by weight of the polyvinyl alcohol of the present invention It is also very useful for agricultural films such as vinyl film which have the same thermal insulation properties. The polyvinyl alcohol of the present invention having a 1,2-ethylene glycol bond in the branch has a high crystallinity even if the degree of saponification is high, and the dissolution rate to water is fast, and it is excellent even in the stability of the aqueous solution. The effect 'more' is due to the presence of a hydroxyl group as a primary alcohol, so it is an isocyanate-based compound, polyamine amine epichlorohydrin, glyoxal, melamine resin, hydroxydecyl melamine, hydroxydecyl bisphenol S, dihydroxy The reactivity of the crosslinking agent such as guanyl urea is also quite high. The isocyanate-based compound is useful for having two or more isocyanate groups in the molecule, and examples thereof include anthraquinone diisocyanate (TDI), hydrogenated TDI, and trimethylolpropane-TDI adduct (for example). , "Desmodur L" manufactured by Bayer Material Science AG, triphenyldecane triisocyanate, bismuth diphenyl isocyanate (MDI), hydrogenated MDI, polymeric MDI, hexamethylene diisocyanate, benzodiazepine diisocyanate 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like. Other examples include a prepolymer having an isocyanate group in which a terminal group polymerized with an excess of polyisocyanate in advance in a polyalcohol. As the compounding ratio of the isocyanate compound, the molar ratio (NC0/0H) of the isocyanate group to the hydroxyl group is preferably 0.1 to 2. Moreover, it does not thicken even under high shear at high speed coatings and has good coating properties. Further, even in the case of butyraldehyde or acetalization, a butyral resin having high reactivity with an aldehyde and high flexibility can be obtained. The polyvinyl alcohol of the present invention can be used for various purposes, for a part

2066-6499-PF(N3).ptd Page 14 1335921 V. The use of the invention (11) is as described above, and the following specific examples include the following. (1) Adhesives for various building materials, such as adhesives for adhesives such as wood, paper, aluminum foil, and plastics, adhesives, rewetting agents, non-woven adhesives, gypsum board or fiberboard, and various powder granulation bonding Agents, additives for cement or plaster, hot melt adhesives, pressure sensitive adhesives, adhesives for anionic coatings, and the like. (2) There are easily water-soluble films for the packaging of molded fibers, films (especially pesticides, detergents, washing clothes, additives for civil engineering, fungicides, dyes, pigments, etc.): as the degree of saponification of polyvinyl alcohol, 6 5 mol% or more is preferred), original polarizing film (original polarizing film) (as 1,2-ethylene glycol bond amount, 0.2 to 2 mol % is preferred, as the degree of polymerization ' 2 0 0 0 The above preferred), sheet, pipe, pipeline, leakproof film, temporary film, chemical bearing race, water soluble fiber, etc. (3) There are cleaning coating agents for coated paper, pigment coating agents for paper, adhesives for paper, adhesives for fiber products, warp pastes, fiber processing agents, leather modifiers, coatings, antifogging agents, Metal corrosion inhibitor, gloss agent for galvanizing, antistatic agent, conductive agent, temporary coating, etc. (4) Emulsifiers for ethylenically unsaturated compounds, butyl disulfide compounds, various emulsified monomers for emulsion polymerization, hydrophobic resins such as polyolefin 'polyester resins, epoxy resins, and alkanes , post-emulsifier such as asphalt, and the like.

2066-6499-PF(N3).ptd Page 15 1335921 V. Description of invention (12) (5) Pigment dispersion stabilizers for suspension coatings, inks, water-based dyes, adhesives, etc., vinyl chloride, partial ethylene A dispersion stabilizer for suspension polymerization of various vinyl compounds such as styrene, (fluorenyl) acrylate or vinyl acetate. (6) Antistatic agent for hydrophobic resin for hydrophobic resin, hydrophilic agent, composite fiber, film (especially for heat preservation in agricultural film applications), and other molded products Additives, etc. (7) There are thickeners for various aqueous solutions or emulsions, and the like. (8) There are coagulants for suspended solids and dissolved substances in the flocculant, water filters for pulp and slurry, and the like. (9) There are soil conditioners (10) sensitizers, sensitized electrons, and sensitized anti-surname resins. (1 1) Other ion exchange resins, such as ion exchange membranes, chelating exchange resins, and the like. Among the above, the usefulness of the use of (1) to (5) in particular is particularly expected. Further, it is preferable to use a plasticizer for various applications, and as the plasticizer, a polyvalent alcohol having 3 to 6 valence (glycerin, trimethylolpropane, diglycerin, or the like) may be mentioned. Five erythritol, mixed xylene, arabinose, ribulose, sorbitol, etc.), various epoxides (ethylene oxide,

^ϋ

2066-6499-PF(N3).ptd Page 16 1335921 V. Description of Invention (13) Propylene oxide, a mixed adduct of ethylene oxide and propylene oxide, etc.). EXAMPLES Hereinafter, the present invention will be specifically described with respect to the present invention, but the present invention is not limited to the following examples. In addition, "parts" and "%" mean the basis of weight unless otherwise specified. Example 1: In a reaction vessel equipped with a reflux condenser, a dropping funnel, and a stirrer, 1300 g of vinyl acetate, 650 g of decyl alcohol, and 3,4-diethyl decyloxy-1-butene 78. lg (3) were placed. Mol%), azobisisobutyronitrile, 〇6 mol% (relative to the vinyl acetate charged), and the temperature was raised under a nitrogen stream while stirring to carry out polymerization. Thereafter, at a time when the polymerization rate of vinyl acetate reached 87.5 %, 50 ppm of m-dinitrobenzene (relative to the vinyl acetate charged) was added as a polymerization inhibitor to complete the polymerization. Next, the unreacted vinyl acetate monomer was removed from the system by a method of feeding sterol vapor to obtain a decyl alcohol solution of the copolymer. Next, the solution was diluted with decyl alcohol to adjust the concentration to 40%, and placed in a kneader while maintaining the solution temperature at 40 ° C, relative to the vinyl acetate and 3,4 - double B in the copolymer. The total amount of decyloxy-1 -butene was added to a 2% methanol solution of sodium hydroxide at a ratio of 8 mmol% to carry out saponification. As the saponification proceeds, the saponified product precipitates, and when it is in the form of granules, it is filtered off, washed with decyl alcohol, and dried in a hot air dryer to obtain polyvinyl alcohol.

2066-6499-PF(N3).ptd Page 17 1335921 V. Description of Invention (14) In the production of the above polyvinyl alcohol, the waste liquid after the saponification is completed by GC-MS ("Nylon Corporation" "597N GC/ MSD" system), using the following conditions to check for the presence or absence of by-products. [column condition] Column: HP - WAX (cross-linked polyethylene glycol) capillary column column temperature: fixed 4 〇 °c X 5 minutes, temperature rise at 10 °C / minute, stand still 240 °C x 10 minutes Injection inlet temperature: 2 4 0 T: Carrier gas: 氦 pipe column flow rate: 1. 〇m 1 / min [MS part condition] Instrument: agilent company "59 73MSD" system mass range : 10 -600 threshold :20 scan /sec. :2.54 As a result, no decyl carbonate was detected. Further, as a salt, it was not detected except for sodium acetate. The degree of saponification of the obtained polyvinyl alcohol (I) is 99% when analyzed by the alkali consumption required for the hydrolysis of residual vinyl vinegar and residual 3,4-diethoxymethoxy 4-butene. 5 mol%, and the average degree of polymerization was 87 时 when analyzed according to JIS K 672 6. Moreover, the viscosity of the aqueous solution of the polyvinyl alcohol is 8.6 mPa-s (20 ° C) when measured by a Heppler falling ball viscometer, and the introduction amount of the 1,2-glycol bond is 1 H - NMR (internal standard material · tetramethyl decane, solvent: d6 - DMs 〇) plus

1359摩尔%。 When the measurement and calculation, it is 3.1 mol%. Further, in the NMR measurement, "AVANCE DPX40 0" manufactured by Bruker Japan CO., Ltd. was used. ΓΗ — NMR 〕 (Refer to Figure 1) 1. 2~1_ 5ppm : Aachen matrix 1. 8ppm: Sub- 曱 曱 (caused by variant) 3. 5 ppm · First-order sulfhydryl-based fluorene matrix 3. 82~3. 84ppm: Sub-base matrix 4.13~4.6ppm: ^S 4.25ppm: diol via base and, in the saponification process, polyvinyl alcohol (II) [partial saponification (by partial saponification) The degree of saponification is 8 4 _ 2 mole % )]. The 1 H-NMR (solvent: d6 - DMSO ) chart of the polyvinyl alcohol (11) is shown below. [*H-NMR] (Refer to Fig. 2) 1. 36~1. 8ppm: Azolla matrix 1.93~1. 95ppm: 曱 matrix 3.5ppm: - grade sulfhydryl-based hydrazine substrate 3.8ppm : 曱 曱 曱 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 . (Solubility) The obtained polyvinyl alcohol was dried at 150 ° C for 3 hours, and adjusted.

2066-6499-PF(N3).ptd Page 19 1335921 V. INSTRUCTIONS (16) After the transition is 1 0 /»water/cold solution, the aqueous solution was filtered and residued with a mesh of 400 mesh. The amount is evaluated as follows. The results of the evaluation are as shown in Table 1, 〇 、, and the residual amount is less than 0. 0 0 5 % The filtration residual is 0. 00 5% or more and 0. 01% or less The filtration residual amount exceeds 〇. 〇 1 % Example 2 : In a reaction vessel equipped with a reflux condenser, a dropping funnel, and a stirrer, 13 gram of vinyl acetate, 19 0 g of decyl alcohol, and 3,4 bis ethoxy-1-butene (8) 60.52 ( 2 28 mol %), adding azobisisobutyronitrile 〇. 06 mol% (stomach phase ^ for vinyl acetate placed), while stirring, the temperature was raised under a nitrogen stream, and polymerization was started at 6 7 . At the same time, a solution of 5.4% f of 3,4-diethoxymethoxy-1-butene was added dropwise, and a polymerization rate of 85.3% was added to add 16 ml. # π > "When the polymerization rate of vinyl acetate is 85.3%, the polymerization is completed" Next, the unreacted vinyl acetate monomer is removed from the system by the method of introducing methanol vapor. The methanol solution of the copolymer is obtained. Next, the solution is diluted with methanol to adjust the concentration to 4% by weight, and placed in a kneader, the solution temperature is maintained at 4 〇t, and the ratio of acetic acid in the copolymer is relative to The total amount of vinyl ester and 3, 4-diethyloxy-ruthenium and butyl was added to a 2% methanol solution of sodium hydroxide at a ratio of 9 mmol% to carry out saponification. The precipitate was filtered off at the time of being granulated, washed with methanol, and dried by hot air to obtain polyvinyl alcohol. ^ ^

2066-6499-PF(N3).ptd Page 20 1335921 V. Description of Invention (17) In the production of the above polyvinyl alcohol, 'when the waste liquid after saponification is completed, it is examined by the same method as in the first embodiment' No dimethyl carbonate was detected. - the degree of saponification of the obtained polyethylidene alcohol (I) is analyzed by the amount of residual acetic acid and the amount of consumption required for the hydrolysis of 3,4-diethyloxy _ 1 _ The analysis was carried out for the analysis of the average polymerization degree of 9 9 6 X X 依 I卩κ. Moreover, the viscosity of the poly-B=:^^^ liquid is 18.7 mPa.s (20C) when measured by a Heplello ball viscometer, and the introduction amount of the 1'2 ethyl alcohol linkage With! The h-nmr internal standard substance: tetramethyl decane, solvent: d6 _DMS 〇) was measured and calculated to be 3.2 mol%. Further, in the saponification process, polyvinyl alcohol (Π) (partially saponified product (4% 〇 mol%)) was obtained by picking up a sample. The same evaluation as in Example 1 was carried out for the obtained polyvinyl alcohol (I) and (?). The evaluation results are shown in Table 1. Example 3: In a reaction chamber containing a reflux condenser, a dropping funnel, and a stirrer, an acetic acid was placed (A) l〇〇0g, methanol 5〇g, 3,4_cone ° °oxy - Bu Ding (6 mol%) 'Add azobisisobutanide. .〇3: Wide (relative to the vinyl acetate monomer placed), the temperature of one, hi, hexa/flow is stirred to carry out the polymerization. The polymerization was completed by adding a polymerization inhibitor to the enthalpy of ethylene oxide = 2% nitrogen. Next, a method of alcohol: gas was used to obtain an unreacted vinyl acetate monomer outside the system to obtain a methanol solution of the copolymer. The second step is to dilute the solution with methanol and adjust to a concentrated kneader. While keeping the branching ~' and placing it while maintaining the temperature of the solution at 40t, the side is relative to the copolymer 1359921. 5. The acetic acid in the invention (18) The vinyl ester and 3,4~bis acetophenone in a 2% methanol solution of sodium oxide are hydrogenated in a total amount of 8 mM of butene. As the saponification progresses, the hi-forms are precipitated: the polyvinyl alcohol which is subjected to the soaping is filtered off, and the methanol is removed to form an unstreak. The raw medium is dried and dried to obtain a polyethylene glycol. The saponified morphogen ester of polyvinyl alcohol (丨) obtained by a hot air dryer and the water=炻丄 of 3,4-diethoxydecyl butene are analyzed by residual acetic acid B. The ear %, the average kilogram of alkali consumption required for the analysis of 6726, is mo. And =, 乂 ^ 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据 依据: In the measurement, it is 18.6 (internal standard substance: tetramethyl decane, and the V content is determined by iH-NMR (see Figure 3) and 6 (10)-DMSO). Polyethylene oxime is obtained by picking up a sample. Further, in the saponified material (degree of recombination: 87.8 mol%)]. For the oxime (II) [partially chemically and (11), the same evaluation as in Example 1 was carried out, and the cited polyethylene glycol (I) was shown. D. The evaluation results are as follows: Example 4: In a reflux condenser, a dropping funnel, a reaction vessel of 1-100% of vinyl acetate and 5 〇g of methanol was placed. %) 'Addition of azobisisobutyl 3,4-diethoxycarbonyl to the vinyl acetate monomer to be placed), while searching for 〇6 耳% (phase increasing temperature for polymerization) The vinyl acetate is finished at the point of nitrogen flow, and the polymerization inhibitor is added to complete the polymerization. The time of the combination of ~~ is 70%, by steaming with methanol.

2066-6499-PF(N3).ptd Page 22 1335921 V. INSTRUCTION DESCRIPTION (19) Method of Gas The unreacted ethyl acetate monomer is in a methanol solution of the copolymer. /, the external removal is followed by 'diluting the solution with alcohol to adjust to the kneader while maintaining the solution temperature at 4 (rc, - 40% and placing the vinyl acetate and 3, 4- double B 2 」 相对 相对 相对 相对 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物 共聚物It is filtered, washed with decyl alcohol and dried into granules, and dried to obtain a polyethylene glycol. The degree of saponification of polyvinyl alcohol (I) obtained by hot air dryer, enester And the hydrolysis of 3, 4-diethoxymethoxy-1 -butene = the residual acetic acid B. When the analysis is carried out, it is 99.2 mol%, and the average consumption is 6726 for the analysis. Then, it is 9 〇〇. And, $ & degree, according to the viscosity of J IS K liquid using the Hepler falling ball type " plus ^, B, 4% water soluble mPa · s (20. (: The timing of the 1,2-glycol bond is 9.5 (internal standard substance: tetramethyl decane, solvent: quantity is 1 Η - NMR is determined and calculated as 14 · 9 mol%. And, in the interest ~ DMS 0), the sample was picked and obtained to obtain polyvinyl alcohol (丨)) [in the process of partialization [by 87.8 mol%)]. For the obtained poly B1 sulphuric acid alcohol 4 (saponification degree line was evaluated in the same manner as in Example 1. The evaluation results are as shown in I) and (II) in Comparative Example 1: Table. In addition to using the stone mountain represented by the following formula (2) In addition to 3, 4-diethyloxy-1-butene, quenching the S-butadiene ester to obtain a branch with a 1,2-ethylene glycol bond Sterol and comment

Page 23 1335921 V. Description of invention (20) Estimate. Further, the waste liquid after the saponification was completed was examined in the same manner as in Example 1, and a large amount of dinonyl carbonate was detected, and it was necessary to hydrolyze diphenyl carbonate in the step of solvent recovery. of. Η Η

I I c=c I I H CH-CH2 (2)

I I 〇 〇

The degree of saponification of the polyvinyl alcohol (I) obtained by \ / c II 〇 is 9 9 _ 5 mol % when analyzed by the alkali consumption required for the hydrolysis of the residual vinyl acetate monomer, and the average polymerization is carried out. The degree is 1 2 2 0 when analyzed according to J IS K 67 26. Further, the viscosity of the 4% aqueous solution of the polyvinyl alcohol is measured by a Hepler falling ball viscometer: 15.1 m P a . s (20 ° C), 1, 2 - ethylene glycol bond摩尔%。 When the amount is 1 NMR NMR (internal standard: tetramethyl decane, solvent: d6 - DMSO) and calculated to be 2. 8 mol%. Further, in the saponification process, polyvinyl alcohol (II) [partial saponified product (degree of saponification 8 1 · 9 mol%)] was obtained by picking up a sample. The same evaluation as in Example 1 was carried out for the obtained polyvinyl alcohols (I) and (11). The evaluation results are shown in Table 1. Comparative Example 2: Satisfy S/M = 0.05 [S: sterol (50 g), M: vinyl acetate

2066-6499-PF(N3).ptd Page 24 1335921 V. Description of invention (21) (lOOOOg), polymerization rate 70%], except that 2〇5g (15. 5 mol%) of carbonic acid was placed In the same manner as in Comparative Example t, except for the enester, an attempt was made to obtain a polyvinyl alcohol having a branched chain having 15 mol% of hydrazine and 2 ethylene glycol. Although a copolymer is obtained, after the completion of the polymerization, if methanol is added and the remaining unreacted vinyl acetate is removed, the polymer is precipitated in the decyl alcohol. When the copolymer was saponified, it was confirmed that the copolymer was precipitated in a decyl alcohol solvent, forcing uneven saponification. On the other hand, the saponification waste liquid was examined in the same manner as in Example 1 to detect a large amount of dimethyl carbonate, and the solvent recovery step _ $ # ψ ' was necessary. ^ The degree of polymethyl hydrazine (1) obtained by the step of hydrolyzing m-methyl s hydrazine, and the molar consumption of the residual olefinic monomer to carry out the molar % 'average polymerization Degree is based on JIS κ 6 7 26 for 9 Oxygen 5 720. And the viscosity of the 4% aqueous solution of the polyvinyl alcohol is 7.5 (P λ. The amount of introduction of 1 2-glycol bond is determined by 1 Η NMR (internal trait, 隹 '1 栎 quasi-substance: tetramethoate, solvent: d6-DMS0) and calculated as 15 % soil. Moreover, in the saponification process, 'by picking out the sample, (1) part of the compound (the degree of recombination 85. Moer & enol acupoints). For the polyglycol (1) and πη The evaluation results of the same evaluation as in Example 1 are shown in Table 1.

2066-6499-PF(N3).ptd Page 25 1335921 V. Description of invention (22) Table 1

Solubility Polyvinyl Alcohol (I) (II) Example 1 〇〇 Example 2 〇〇 Example 3 〇〇 Example 4 〇〇 Comparative Example 1 Δ X Comparative Example 2 Δ X Example 5 : Using Example 1 The obtained polyvinyl alcohols (I) and (II) were prepared by the following methods to prepare a two-liquid type adhesive. [Preparation of two-liquid type adhesive] The following main components (solid content: 43.5% of an aqueous emulsion) and a curing agent (polyvalent isocyanate compound) were prepared. (main agent) 15% aqueous solution of polyvinyl alcohol (I) or (II) 40 parts solid content 50% styrene-butadiene copolymer ("DL6 12" manufactured by Asahi Kasei Co., Ltd.) emulsion 35 parts Calcium carbonate 20 parts water 5 parts (hardener) MD I (NCO base content 6. 71 X 10-3 mol/g) 9. 72 parts

2066-6499-PF(N3).ptd Page 26 1335921

1335921 V. INSTRUCTION OF THE INVENTION (24) In the same manner as in Example i except that saponification was carried out (1 0 0 0 g), two kinds of polyvinyl alcohol were obtained. The degree of saponification of the obtained polyvinyl alcohol is 99% 丨 mol % [polyvinyl alcohol (I)] and 88. 2 mol% [polyvinyl alcohol (II)], and the degree of polymerization was 12 Å when analyzed according to JIS K 6726. The same evaluation as in Example 5 was carried out using the obtained polyvinyl alcohol. The evaluation results are shown in Table 2. The second table la 匕 person: γτ»τ· initial adhesion strength durable bonding strength after 5 minutes 10 minutes later Example 1 194/210 41/51 53/58 119/123 Example 2 215/222 50/53 63 /65 127/131 Example 3 245/270 52/62 63/72 137/141 Example 4 295/310 83/91 96/101 175/210 Comparative Example 3 130/180 21/27 29/36 51/54 Example 9: Using the polyvinyl alcohol (I) obtained in Example 1, a film was produced in the following manner, and the cold water solubility, alkali resistance, and chemical resistance of the obtained film were evaluated in the following manner. The results of the assessment are shown in Table 3. (Production of a film) A 15% aqueous solution of polyvinyl alcohol (I) was prepared, and 10 parts of glycerin was added to 100 parts of polyvinyl alcohol (I), and flow molding was carried out at 70 ° C in a hot roll.

2066-6499-PF(N3).ptd Page 28 1335921, invention description (25) A film having a thickness of 50 m was obtained. (Cold Water Solubility) The above film (3 cm X 3 Cm ) was immersed in 1 Torr. The water l〇ml was measured for the time until it was completely dissolved until it was completely dissolved. (Testability) The bag of 10 cm X 1 5 cm prepared by heat-sealing the above film, u sodium sodium sulphate was placed under the condition of 40 tx 85% RH for half a year, and 3 cm X 3 cm was collected from the bag. The membrane was soaked in 1 ml of water of 15 and measured for the time until it was completely dissolved until it was completely dissolved. (drug resistance)

The same evaluation as described above (alkaline resistance) was carried out except that sodium carbonate was used instead of sodium carbonate. Example 1 0 to 1 2, Comparative Example 4: Polyvinyl alcohol (I) obtained by using Example 2 (Example 1 〇) to Example 4 (Example 丨 2) and Comparative Example 3 (Comparative Example 4) The same evaluation as in Example 9 was carried out. The results of the assessment are shown in Table 3. Further, in the evaluation of any of Comparative Examples 4', the film was only expanded without being dissolved.

1335921 V. INSTRUCTIONS (26) Table 3 Cold water solubility (seconds) Alkali resistance (seconds) Chemical resistance (seconds) Example 9 30 39 35 Example 1〇27 31 33 Example 11 20 21 24 Example 12 12 16 18 Comparative Example ί 4 Expansion only expansion only expansion Industrial availability: The branched chain of the invention has a 1,2-ethylene glycol bonded polyvinyl alcohol characterized by a para-vinyl ester monomer And the compound represented by the formula (1) is obtained by copolymerization, so that at the time of production, diterpene carbonate or the like is not produced, and the step of recovering the liquid in the saponified waste liquid does not require carbonic acid. The removal step of the oxime ester, and since the introduction amount of the 1,3-glycol bond does not impair the solubility of the copolymer (paste) before saponification to the saponification solution (methanol), it is industrially It can be produced in a very useful manner, and even if the obtained polyvinyl alcohol (especially a partial saponified product) is subjected to a heat history, no water-insoluble matter or the like is generated. Therefore, various uses of the conventional polyvinyl alcohol are useful in terms of workability and product quality, and particularly useful for adhesives, related molded articles, related coating agents, related emulsifiers, and related suspending agents, particularly The use of water-soluble packaging materials such as alkali detergent packaging or woodworking bonding, especially for the use of adhesives such as conifer plywood, is quite useful.

2066-6499-PF(N3).ptd Page 30 1335921 Simple illustration of the diagram [Simplified illustration]

Fig. 1 is a 1 Η-NMR chart of the polyvinyl alcohol (I) obtained in Example 1. Fig. 2 is a 1 Η NMR chart of the polyvinyl alcohol (Π) obtained in Example 1.

Fig. 3 is a 1 Η-NMR chart of the polyvinyl alcohol (I) obtained in Example 3. [Main component symbol description]

Ml *»»,

2066-6499-PF(N3).ptd第31页

Claims (1)

1 Case No. 93l2F>j^9R VI. Patent application range: 1 year W month, -|a Amendment: ί, Κ A polyvinyl alcohol, which is a vinyl ester monomer and a compound represented by the following formula (1) The copolymer is subjected to saponification, and the polyvinyl alcohol having a branched L'2-glycol bond and having a degree of saponification of 6 〇 mol% or more; Η圮II c=c IIH R2 -ch-ch2 ( i) II 0 0 II R3 R4 where 'R1 is a nitrogen or a burnt group; R2 may have a single bond or a carbon number of the alkyl group, and the R3 and R4 are each independently hydrogen or R5 - C0 - (wherein R5 is an alkyl group). 2. The polyvinyl alcohol according to claim 1, wherein the polyvinyl alcohol is used as a packaging material, and the degree of saponification is 9 9. 〇 mol% or more. 3. The polyvinyl alcohol according to claim 1, wherein the polyvinyl alcohol has an aqueous vinyl urethane adhesive, a paper processing agent, and a cerium oxide binder for inkjet printing. 0摩尔的。 The arbitrarily - the degree of use is less than 99. 0 mole%. 4. The polyvinyl alcohol according to claim 1, wherein the copolymerization ratio of the compound represented by the formula (1) is 〇. The branched chain has a polyethylene glycol which is characterized by a saponification of the copolymer of the compound represented by the formula of the vinyl acetonate and the formula (1). 6. The manufacturer of polyvinyl alcohol as described in claim 5 2305-6499X1-PFl(N3).ptc Page 32 1335921 Amendment _ Saponification degree 9 9 . 0 Mo 曰 Case No. 93125325 6. Patent application method, in which the polyvinyl alcohol is used for packaging materials. 7. The method for producing a polyvinyl alcohol according to claim 5, wherein the polyvinyl alcohol has an aqueous vinyl urethane adhesive, a paper processing agent, and a dioxide for inkjet printing.摩尔%。 The saponification degree is less than 99.0%. 8. The method for producing a polyvinyl alcohol according to the invention of claim 5, wherein the copolymerization ratio of the compound represented by the formula (1) is 0.1 to 40 mol%. 2305-6499Xl-PFl(N3).ptc第33页