Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F16/04—Acyclic compounds
  • C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F18/02—Esters of monocarboxylic acids
  • C08F18/04—Vinyl esters
  • C08F18/08—Vinyl acetate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
  • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/38—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
  • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
  • C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/38—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/30—Inorganic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
  • C08F4/34—Per-compounds with one peroxy-radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/12—Hydrolysis
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/28—Condensation with aldehydes or ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/19—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols

Definitions

• the present invention relates to a polyvinyl alcohol resin, a polyvinyl acetal resin, a method for producing a polyvinyl alcohol resin, and a method for producing a polyvinyl acetal resin.
• Polyvinyl alcohol resin obtained by saponifying polyvinyl acetate resin (hereinafter referred to as PVAc) is colorless and transparent and has strong mechanical properties, and is used in various applications.
• Polyvinyl acetal resin obtained by acetalizing PVA is colorless and transparent, and has higher mechanical strength than PVA.
• PVAc Polyvinyl alcohol resin
• PVB Polyvinyl acetal resin
• PVAc polyvinyl acetal resin
• it is necessary to increase the degree of polymerization of PVAc which is a raw material.
• PVAc obtained by a solution polymerization method is used. However, it is difficult to control the amount of heat generated by the solution polymerization method, and the upper limit of the weight-average molecular weight of the resulting resin is about 700,000.
• the molecular weight obtained using the above empirical formula is called the viscosity average molecular weight
• the viscosity average molecular weight is the average molecular weight obtained by the osmotic pressure method or the light scattering method, that is, the intermediate value of the values obtained by the number average molecular weight and the weight average molecular weight, respectively. show. This is because the value of the constant a takes an intermediate value between 0.5 and 1.
• Patent Document 1 states that PVA with an ultra-high degree of polymerization can be obtained by using a solution in which a polyvinyl ester polymer emulsion having a particle size of 5 ⁇ m or less is mixed with a predetermined amount of methanol. Further, in Patent Document 2, by using a specific solvent and setting the solvent composition and the polymerization temperature to predetermined conditions, a polyvinyl ester-based polymer having a limiting viscosity of 2.3 dl/g or more is produced. , and a method of saponifying this to obtain a polyvinyl alcohol resin with a high degree of polymerization.
• Patent Document 3 a vinyl ester monomer is subjected to photoemulsion polymerization at a low polymerization temperature of ⁇ 60° C. or higher and 10° C. or lower to prepare a polyvinyl ester with a high degree of polymerization having an intrinsic viscosity of 1.5 dl / g or more. is disclosed to obtain a polyvinyl alcohol resin with a high degree of polymerization by saponifying.
• At least one molecular end of the main chain is selected from the group consisting of a sulfone group, an alkylsulfonyl group, an aromatic sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, an amino group, and a hydroxyl group.
• It is a polyvinyl alcohol resin having at least one of the above, having a weight average molecular weight (Mw) of 1,000,000 or more, and having a water-soluble surfactant content of 0.02% by weight or less.
• the present disclosure (2) is the polyvinyl alcohol resin of the present disclosure (1) containing 0.0000001% by weight or more of the cationic surfactant.
• the present disclosure (3) is the polyvinyl alcohol of the present disclosure (1) or (2), wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 3.0 Resin.
• the present disclosure (4) is a polyvinyl alcohol resin in any combination with any one of the present disclosures (1) to (3) having a degree of saponification of 70 mol % or more and 99 mol % or less.
• (5) of the present disclosure is a polyvinyl alcohol resin in any combination with any of (1) to (4) of the present disclosure having a cloud point of 30° C. or higher.
• the present disclosure (6) is the present disclosure containing at least one selected from the group consisting of a dialkylamine compound having an alkyl group having 1 to 10 carbon atoms and a trialkylamine compound having an alkyl group having 1 to 10 carbon atoms
• (7) of the present disclosure is a polyvinyl acetal resin which is an acetalized product of the polyvinyl alcohol resin of any one of (1) to (6) of the present disclosure.
• This start (8) is an interlayer film for laminated glass containing the polyvinyl acetal resin of the present disclosure (7).
• This disclosure (9) is a binder composition comprising the polyvinyl acetal resin of this disclosure (7).
• the present disclosure (10) includes a polymerization step of adding a polymerization initiator to polymerize a vinyl ester to produce a polyvinyl ester, and a saponification catalyst to saponify the polyvinyl ester to produce a water-soluble polyvinyl alcohol resin.
• the polymerization initiator is at least selected from the group consisting of a sulfone group, an alkylsulfonyl group, an aromatic sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, an amino group and a hydroxyl group.
• 1 is a method for producing a polyvinyl alcohol resin.
• the present disclosure (11) is a method for producing a polyvinyl alcohol resin according to the present disclosure (10), wherein the amount of the water-soluble surfactant added in the polymerization step is 0.02 parts by weight or less per 100 parts by weight of the vinyl ester.
• the polymerization step is to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester by adding a polymerization initiator to an aqueous monomer solution containing vinyl ester and water, and
• the polyvinyl ester has an average particle size of 0.01 ⁇ m or more and 10 ⁇ m or less
• the saponification step includes saponifying the polyvinyl ester by directly adding a saponification catalyst to the aqueous emulsion polymerization slurry, and the saponification catalyst is (10) or (11) of the present disclosure, which is at least one selected from the group consisting of a dialkylamine compound having an alkyl group having 1 to 10 carbon atoms and a trialkylamine compound having an alkyl group having 1 to 10 carbon atoms.
• the polymerization step is to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester by adding a polymerization initiator to an aqueous monomer solution containing vinyl ester and water, and further, the aqueous emulsion polymerization slurry
• the present disclosure (10) or ( 11) is a method for producing a polyvinyl alcohol resin.
• the present disclosure (14) is the present disclosure (10) to (13), wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polyvinyl ester is 1.0 to 3.0
• a method for producing a polyvinyl alcohol resin in any combination with any of The present disclosure (15) is a polyvinyl acetal resin obtained by adding aldehyde to the polyvinyl alcohol resin obtained by the method for producing a polyvinyl alcohol resin according to any one of the present disclosure (10) to (14) to acetalize the polyvinyl alcohol resin. manufacturing method.
• the present invention will be described in detail below.
• an ultra-high molecular weight polyvinyl alcohol resin having a specific substituent at the molecular end and having a predetermined amount of water-soluble surfactant content relative to the weight of the entire resin is acetal
• the present inventors have found that a molded article having excellent strength can be obtained by reducing the amount of the resin, and a resin film having excellent transparency can be obtained, and have completed the present invention.
• the polyvinyl alcohol resin of the present invention is selected from the group consisting of a sulfone group, an alkylsulfonyl group, an aromatic sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, an amino group and a hydroxyl group at at least one molecular end of the main chain. have at least one
• the polyvinyl alcohol resin having the above-described substituent has a strong mechanical strength, and when the polyvinyl acetal resin obtained by acetalization is molded, a molded product having high strength and excellent transparency can be produced. can be done.
• the above polyvinyl alcohol resin may have the above functional group at at least one molecular end of the main chain. It may have a carboxyalkylamidine group such as a carboxyethylamidine group at the molecular end. In addition to the hydroxyl group, those having a hydroxyl group may also have a hydroxyalkylamino group such as a hydroxyethylamino group or a hydroxyalkylamide group such as a hydroxyethylamide group at the molecular end. Furthermore, the sulfone group may be a salt or an ester. Examples of the above salts include ammonium salts, sodium salts, potassium salts and the like.
• ester examples include esters having an aliphatic group having 1 to 12 carbon atoms and an aromatic group having 6 to 12 carbon atoms, and alkyl esters are more preferable.
• alkylsulfonyl group examples include sulfonyl groups having alkyl having 1 to 12 carbon atoms, and specific examples include methylsulfonyl, ethylsulfonyl, propylsulfonyl and the like.
• aromatic sulfonyl group examples include sulfonyl groups having an aromatic group having 12 or less carbon atoms, and specific examples include a phenylsulfonyl group.
• the sulphine group may be a salt or an ester.
• the above salts include ammonium salts, sodium salts, potassium salts and the like.
• the ester include esters having an aliphatic group having 1 to 12 carbon atoms and an aromatic group having 6 to 12 carbon atoms, and alkyl esters are more preferable.
• the amino group may be a monoamino group, diamino group or triamino group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms).
• the polyvinyl alcohol resin preferably has a sulfone group at the molecular end.
• the specific substituent at at least one molecular terminal of the main chain of the polyvinyl alcohol resin is preferably derived from a polymerization initiator.
• the polyvinyl alcohol resin of the present invention has a weight average molecular weight (Mw) of 1,000,000 or more.
• Mw weight average molecular weight
• the polyvinyl alcohol resin of the present invention preferably has a weight average molecular weight (Mw) of 1,500,000 or more, more preferably 2,000,000 or more, preferably 4,000,000 or less, and preferably 3,000,000 or less. more preferred.
• the polyvinyl alcohol resin of the present invention preferably has a number average molecular weight (Mn) of 500,000 or more, more preferably 1,000,000 or more, preferably 2,000,000 or less, and 1,500,000 or less. is more preferable.
• Mn number average molecular weight
• the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyvinyl alcohol resin of the present invention is preferably 1.0 or more, more preferably 1.5 or more. It is preferably 3.0 or less, more preferably 2.0 or less. By setting it as the said range, the toughness of resin can be improved more.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, measured by gel permeation chromatography (GPC), measuring polyvinyl ester before saponification by GPC, and polyvinyl alcohol resin. It can be obtained by measuring the polyvinyl ester obtained by re-esterification by the GPC method and by measuring the viscosity of the aqueous solution according to JIS K6726. For example, columns such as TSKgel (Tosoh Corporation), PLgel (AMR Corporation), KF-806, KF-807 (Shodex Corporation) and the like can be used with polystyrene as a standard.
• the degree of saponification of the polyvinyl alcohol resin of the present invention is preferably 70 mol % or more, and preferably 99.9 mol % or less. By setting it as the said range, the toughness of resin can be improved more. Moreover, when it is made into a polyvinyl alcohol resin film, both water resistance and gas barrier properties can be improved in a well-balanced manner.
• the degree of saponification is more preferably 80 mol% or more, still more preferably 85% or more, even more preferably 90 mol% or more, particularly preferably 92 mol% or more, particularly preferably 93 mol% or more, and 94 mol% or more.
• the degree of saponification can be measured according to JIS K6726.
• the degree of saponification indicates the ratio of units actually converted to vinyl alcohol units among units that can be converted to vinyl alcohol units by saponification.
• the degree of saponification can be appropriately adjusted by saponification conditions, that is, hydrolysis conditions.
• the polyvinyl alcohol resin of the present invention preferably has a cloud point of 30°C or higher. By setting it as the said range, the toughness of resin can be improved more.
• the cloud point is more preferably 35° C. or higher, still more preferably 40° C. or higher, and for example 90° C. or lower.
• the cloud point can be visually confirmed, and can also be measured by a haze meter, static light scattering method, or the like.
• the proportion of undissolved components is preferably 10% by weight or less, more preferably 1% by weight or less.
• the lower limit is not particularly limited, and is preferably 0% by weight.
• the proportion of the undissolved component can be measured by mesh filtration. For example, a resin aqueous solution with a concentration of 4% by weight is allowed to stand for 12 hours or more, the temperature is raised to 80 ° C., and then allowed to stand to lower the temperature to room temperature. Water and water-absorbed and swollen resin are separated, the separated resin is dried at 60° C.
• the degree of polymerization of the polyvinyl alcohol resin of the present invention is preferably 10,000 or more, and preferably 30,000 or less.
• the degree of polymerization of the polyvinyl alcohol resin for example, is obtained by measuring the polyvinyl acetate resin before saponification by gel permeation chromatography (GPC) or by measuring the viscosity of the aqueous solution in accordance with JIS K6726. be able to.
• the polyvinyl alcohol resin of the present invention has a water-soluble surfactant content of 0.02% by weight or less. That is, when the polyvinyl alcohol resin of the present invention contains a water-soluble surfactant and other components, the polyvinyl alcohol resin of the present invention can be said to be a polyvinyl alcohol resin composition containing the polyvinyl alcohol resin.
• the content of the water-soluble surfactant in the compatibility of the composition is 0.02% by weight or less. By setting it as the said range, it can be set as resin with high transparency.
• the content of the water-soluble surfactant is preferably 0.002% by weight or less.
• the lower limit is not particularly limited, and is preferably 0% by weight, more preferably 0.0005% by weight or more.
• the method for measuring the content of the water-soluble surfactant is not particularly limited, it can be measured, for example, by a method using liquid chromatography such as HPLC, or a method of extraction using methanol or the like.
• the water-soluble surfactant is preferably a surfactant having a solubility of 10 g/100 g or more in water at 25°C.
• the water-soluble surfactant is used as a dispersant added during emulsion polymerization.
• examples include anionic surfactants such as alkylsulfonates and polymeric surfactants such as polyalkylene glycol. mentioned.
• examples of the alkylsulfonate include sodium, potassium and ammonium salts of octylsulfonic acid, decylsulfonic acid, dodecylsulfonic acid and p-toluenesulfonic acid.
• the polyvinyl alcohol resin of the present invention When the polyvinyl alcohol resin of the present invention is made into a resin solution, even if the amount of the resin solution is very small, it becomes cloudy due to the content of the water-soluble surfactant. Further, since the polyvinyl alcohol resin of the present invention has a very high molecular weight, the resin solution becomes cloudy even if the solubility in the solvent is poor.
• the water-soluble surfactant is usually an anionic surfactant.
• the polyvinyl alcohol resin of the present invention may contain a cationic surfactant.
• a cationic surfactant By containing the above cationic surfactant, the resin can be made more excellent in transparency.
• the cationic surfactant is different from the water-soluble surfactant, and preferably has a solubility in water of 0.05 g/100 g or more at 25°C.
• cationic surfactant examples include amine salts such as quaternary ammonium salts, aliphatic amine salts, aromatic amine salts and heterocyclic amine salts, and phosphonium salts.
• quaternary ammonium salts include tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, hexyltrimethylammonium bromide, n-octyltrimethylammonium bromide, n-octyltrimethylammonium chloride, nonyltrimethyl Ammonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, tetrade
• amine salt examples include stearic acid dimethylaminopropylamide, n-octylammonium chloride, n-octylammonium bromide, dodecylamine hydrochloride, dodecyl ammonium bromide, octadecylamine hydrochloride and the like.
• Examples of the phosphonium salts include trans-2-butene-1,4-bis(triphenylphosphonium chloride), tributyl(cyanomethyl)phosphonium chloride, (2-carboxyethyl)triphenylphosphonium bromide, tributyldodecylphosphonium bromide, tributyl Hexadecylphosphonium bromide, tributyl-n-octylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium chloride, tetraphenylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium sulfate, tetrabutylphosphonium bromide, tetraphenylphosphonium chloride, tetraethylphosphonium bromide, tetra butylphosphonium chloride, tetra-n-octylphosphonium bromide, tetrae
• quaternary ammonium salts, amine salts and phosphonium salts are preferred, quaternary ammonium salts and amine salts are more preferred, 1-ethyl-3-methylimidazolium chloride, cetylpyridinium chloride, tetrabutylammonium bromide, tetra butylammonium chloride, hexyltrimethylammonium bromide, n-octyltrimethylammonium bromide, n-octyltrimethylammonium chloride, nonyltrimethylammonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyl trimethylammonium bromide, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, cet
• the content of the cationic surfactant in the polyvinyl alcohol resin of the present invention is preferably 0% by weight or more. By setting it as the said range, it can be set as resin with higher transparency.
• the content of the cationic surfactant is more preferably greater than 0% by weight, more preferably 0.0000001% by weight or more, and more preferably 0.0001% by weight or more. It is particularly preferably 0.002% by weight or less, more preferably 0.0015% by weight or less, and even more preferably 0.001% by weight or less.
• the content of the cationic surfactant can be measured by HPLC method or GC-MS method.
• the polyvinyl alcohol resin of the present invention contains at least one compound selected from the group consisting of a dialkylamine compound having an alkyl group of 1 to 10 carbon atoms and a trialkylamine compound having an alkyl group of 1 to 10 carbon atoms.
• a dialkylamine compound having an alkyl group of 1 to 10 carbon atoms and a trialkylamine compound having an alkyl group of 1 to 10 carbon atoms may be containing the above compound, the toughness of the resin can be further enhanced.
• dialkylamines having an alkyl group of 1 to 10 carbon atoms and trialkylamines of 1 to 10 carbon atoms are preferred.
• Dialkylamine compounds having an alkyl group having 1 to 10 carbon atoms include, for example, dimethylamine and diethylamine.
• Trialkylamines having an alkyl group of 1 to 10 carbon atoms include, for example, trimethylamine, triethylamine, tributylamine and the like.
• the content of the dialkylamine compound and the trialkylamine compound in the polyvinyl alcohol resin of the present invention is preferably 0.00001% by weight or more, more preferably 0.0001% by weight or more, and 0.1% by weight or more. % by weight or less is preferable, and 0.05% by weight or less is more preferable.
• the above content can be measured by HPLC method or GC-MS method.
• a polymerization step of adding a polymerization initiator having a specific substituent to polymerize a vinyl ester to produce a polyvinyl ester, and a saponification catalyst to add a polyvinyl A method having a saponification step of saponifying the ester is preferred. It has a polymerization step of adding a polymerization initiator to polymerize a vinyl ester to produce a polyvinyl ester, and a saponification step of adding a saponification catalyst to saponify the polyvinyl ester to produce a water-soluble polyvinyl alcohol resin.
• the polymerization initiator has at least one selected from the group consisting of a sulfone group, an alkylsulfonyl group, an aromatic sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group and a hydroxyl group. is also one of the present invention.
• a polymerization initiator is added to an aqueous monomer solution containing vinyl ester and water to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester.
• vinyl ester is not particularly limited, examples thereof include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, etc. Among them, vinyl acetate is preferable.
• the polyvinyl ester may be copolymerized with a vinyl-based monomer as long as the polymerization degree and saponification degree of the resulting polyvinyl alcohol resin are not affected.
• the vinyl-based monomer include ethylene, butadiene, 1,3-butadiene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, isoprene, acrylic acid ester, methacrylic acid ester, maleic acid, Higher fatty acid vinyl esters such as fumaric acid and itaconic acid, alkyl vinyl ethers, N-(2-dimethylaminoethyl) methacrylamides or quaternized products thereof, N-vinylimidazole or quaternized products thereof, N-vinylpyrrolidone, N -n-butoxymethylacrylamide, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, acrylonitrile, methacryl
• the polyvinyl ester preferably has a weight average molecular weight of 1,000,000 or more. Normally, it is very difficult to increase the degree of polymerization to about 1,000,000. Since the polymerized resin has a high Tg, the mobility of the molecular ends is poor and the probability of collision with radicals is very low. Therefore, it is usually difficult to obtain a high molecular weight polyvinyl ester having a weight average molecular weight of 1,000,000 or more. Normally, in emulsion polymerization, monomer polymerization proceeds in dispersant micelles, but in order to obtain a high-molecular-weight resin, it is necessary to form huge micelles.
• the resin contains a large amount of dispersant as a foreign substance, the transparency and strength of the resin are also low.
• the dispersant used in ordinary emulsion polymerization is not used.
• a water-soluble radical polymerization initiator having a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, and a hydroxyl group is used as a base point to initiate polymerization of a vinyl ester monomer dispersed in water, and each monomer domain collides. , dispersion polymerization is carried out at a low concentration so as not to coalesce.
• a polymer in which the size of each domain is uniform and the particle size is uniform can be obtained.
• the growth of molecules in the particles is the same, the molecular weight is very high, and a resin having a weight average molecular weight of 4,000,000 or more can be synthesized.
• the reason why the weight average molecular weight increases is that by polymerizing a water-soluble radical polymerization initiator having a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group, and a hydroxyl group at a low concentration, unevenness such as hydrogen abstraction is caused. This is because multiple polymers are less likely to grow within the domain because the polymerization reaction can be minimized.
• a water-soluble radical polymerization initiator having at least one selected from the group consisting of a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group and a hydroxyl group can be used.
• a high-molecular-weight polyvinyl ester can be produced without adding a large amount of a dispersant as in normal emulsion polymerization. .
• water-soluble radical polymerization initiator examples include 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2′-azobis[2-(2-imidazoline-2 -yl)propane]sulfatohydrate, 2,2′-azobis[2-(2-imidazolin-2-yl)propane] acid mixtures of imidazole azo compounds, 2,2′-azobis(2-methyl propionamidine) dihydrochloride, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate, 2,2′-azobis[2-methyl-N-(2-hydroxyethyl) ) propionamide], water-soluble azo compounds such as 4,4′-azobis-4-cyanovaleric acid, potassium persulfate (potassium peroxodisulfate), ammonium persulfate (ammonium peroxodisulfate), sodium persulfate
• acid mixtures of imidazole-based azo compounds, water-soluble azo compounds, and oxoacids are preferred.
• a polyvinyl ester having a weight average molecular weight within a predetermined range can be produced, but the weight average molecular weight of the polyvinyl ester may be adjusted by adding a chain transfer agent or a polymerization terminator.
• the chain transfer agent and polymerization terminator are not particularly limited, but sodium 3-mercapto-1-propanesulfonate, mercaptosuccinic acid, mercaptopropanediol, (allylsulfonyl)benzene, ethyl 2-mercaptoethanesulfinate, 3 - mercaptopropionamide and the like.
• At least one selected from the group consisting of a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group and a hydroxyl group is added to at least one molecular end of the main chain.
• Polyvinyl ester having one type and having a weight average molecular weight within a predetermined range can be produced.
• These water-soluble radical polymerization initiators may be used alone, or two or more of them may be used in combination.
• the amount of the water-soluble radical polymerization initiator added is preferably 0.03 to 0.2 parts by weight, more preferably 0.05 to 0.15 parts by weight, with respect to 100 parts by weight of the raw material monomer. preferable. By setting the amount to be added to 0.03 parts by weight or more, the reaction rate of the raw material monomer can be sufficiently increased. By setting the amount to be added to 0.2 parts by weight or less, the molecular weight of the polyvinyl ester can be sufficiently increased.
• the polyvinyl ester having at least one selected from a sulfone group, a sulfonyl group, a sulphine group, an imidazoline group, a carboxyl group, an amide group and a hydroxyl group at the molecular terminal ( ⁇ position) is low in water. It is possible to obtain a resin with a uniform particle size by dispersing it at a concentration. Furthermore, in general emulsion polymerization, 1 part by weight or more of a water-soluble surfactant is added to 100 parts by weight of raw material monomers. Less is better. However, it is difficult to polymerize a resin having a high molecular weight simply by reducing the water-soluble surfactant.
• the amount of the raw material monomer to be added is preferably 50 to 300 parts by weight per 1000 parts by weight of water. When the content is within the above range, aggregation during polymerization and adhesion of the resin to the reaction vessel can be prevented. Further, the addition amount of the raw material monomer is more preferably 70 to 200 parts by weight per 1000 parts by weight of water. By setting the amount within the above range, it is possible to reduce the amount of residual monomers and achieve uniform polymerization.
• a high-speed rotating mixer or the like is not required. After charging the monomer, it is only necessary to rotate the blade at 100 to 250 rpm to disperse the monomer in the water.
• the reaction temperature in the polymerization step is preferably 50° C. or higher and preferably 70° C. or lower. Since vinyl acetate, which is a vinyl ester monomer, has a high reaction heat, it is not preferable to react at a very high temperature. By setting the temperature to 50° C. or higher, radicals can be sufficiently generated and the reaction can proceed sufficiently. Moreover, by setting the temperature to 70° C. or lower, adhesion of scale to the reaction vessel can be suppressed, and poor polymerization can be prevented.
• a small amount of water-soluble surfactant may be added.
• the water-soluble surfactant is used as a dispersant to be added during emulsion polymerization, and includes those mentioned above.
• the amount of the water-soluble surfactant added is preferably 0 to 0.02 parts by weight, more preferably 0.002 to 0.01 parts by weight, per 100 parts by weight of the raw material monomer.
• a polymerization initiator is added to an aqueous monomer solution containing vinyl ester and water to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester, and a cationic surfactant is added to the aqueous emulsion polymerization slurry. It is preferable to have a recovery step of filtering the slurry to which the is added to recover the polyvinyl ester. Examples of the cationic surfactant include those described above.
• the amount of the cationic surfactant added is preferably 1 ⁇ 10 ⁇ 6 to 10000 ⁇ 10 ⁇ 6 parts by weight with respect to 100 parts by weight of the raw material monomer. By setting it as the said range, it can fully adsorb
• the average particle size of the polyvinyl ester in the aqueous emulsion polymerization slurry is preferably 0.001 ⁇ m or more, and preferably 50 ⁇ m or less. By setting it as the said range, the transparency of resin obtained can be improved more.
• the average particle size is more preferably 0.005 ⁇ m or more, still more preferably 0.01 ⁇ m or more, even more preferably 0.1 ⁇ m or more, more preferably 30 ⁇ m or less, and 10 ⁇ m It is more preferably 5 ⁇ m or less, particularly preferably 1 ⁇ m or less, particularly preferably 0.8 ⁇ m or less, and most preferably 0.5 ⁇ m or less.
• the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polyvinyl ester is preferably 1.0 or more and preferably 3.0 or less. By setting it as the said range, the transparency of resin obtained can be improved more.
• the above ratio is more preferably 1.5 or more, and more preferably 2.0 or less.
• Examples of the saponification step include a method of directly adding a saponification catalyst to the aqueous emulsion polymerization slurry obtained in the polymerization step, and a method of saponifying the polyvinyl ester recovered in the recovery step.
• the saponification catalyst examples include alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alcoholate, and sodium carbonate, and acid catalysts such as sulfuric acid, phosphoric acid, and hydrochloric acid.
• Alkaline catalysts are preferred, and sodium hydroxide is particularly preferred, since they can improve the properties.
• amines such as dialkylamine compounds and trialkylamine compounds as the saponification catalyst.
• the dialkylamine compounds include dialkylamine compounds having an alkyl group having 1 to 10 carbon atoms
• the trialkylamine compounds include trialkylamine compounds having an alkyl group having 1 to 10 carbon atoms. Specific examples include dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine and the like.
• the polyvinyl ester recovered in the recovery step it is preferable to add the polyvinyl ester to an organic solvent and further add a saponification catalyst.
• the saponification catalyst in the above method include alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alcoholate and sodium carbonate, and acid catalysts such as sulfuric acid, phosphoric acid and hydrochloric acid.
• alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alcoholate and sodium carbonate
• acid catalysts such as sulfuric acid, phosphoric acid and hydrochloric acid.
• an alkali catalyst is preferable, and sodium hydroxide is particularly preferable, because it can improve productivity.
• the amount of the saponification catalyst used is preferably 0.002 to 0.50, more preferably 0.003 to 0.30, in terms of molar ratio to the vinyl ester monomer unit of the vinyl ester copolymer. , 0.004 to 0.10 is particularly preferred.
• the saponification catalyst may be added all at once at the beginning of the saponification reaction, or may be partially added at the beginning of the saponification reaction and the rest may be additionally added during the saponification reaction. .
• the saponification reaction is preferably carried out at a temperature of 5-80°C, more preferably 20-70°C.
• the saponification reaction is preferably carried out for 5 minutes to 10 hours, more preferably 10 minutes to 5 hours.
• the saponification reaction can be carried out by either batch method or continuous method.
• the remaining catalyst may be neutralized, if desired.
• Usable neutralizing agents include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate.
• a step of washing the PVA resin may be provided if necessary.
• a solution containing a lower alcohol such as methanol as a main component and further containing water and/or an ester such as methyl acetate produced in the saponification step can be used.
• organic solvent examples include methanol, ethanol, propanol, butanol, tertiary butanol, isobutanol, isopropyl alcohol, n-propyl alcohol, hexanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, and the like.
• esters such as methyl acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, hydrocarbons such as toluene, xylene, cyclohexane, isooctane, isopentane, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketones such as ketones, cyclohexanone and diacetone alcohol; ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and 1,4-dioxane; and tetrahydrofuran, 2-pyrrolidone, NMP and DMF.
• a polymerization initiator is added to an aqueous monomer solution containing vinyl ester and water to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester, and the average particle size of polyvinyl ester in the aqueous emulsion polymerization slurry is is 0.01 ⁇ m or more and 0.5 ⁇ m or less
• the saponification step is to saponify the polyvinyl ester by directly adding a saponification catalyst to the aqueous emulsion polymerization slurry, and the saponification catalyst has 1 to 10 carbon atoms. and a trialkylamine compound having an alkyl group having 1 to 10 carbon atoms. .
• a polymerization initiator is added to an aqueous monomer solution containing vinyl ester and water to prepare an aqueous emulsion polymerization slurry containing polyvinyl ester.
• the method for producing a polyvinyl alcohol resin includes a recovery step of filtering the slurry to which the activator is added to recover the polyvinyl ester, and the saponification step includes saponifying the polyvinyl ester recovered in the recovery step. is one.
• the polyvinyl alcohol resin has an ultrahigh molecular weight, it can be preferably used for film applications and the like.
• the gas barrier property can be effectively improved, and a uniform film can be obtained.
• the film contains the polyvinyl alcohol resin. Moreover, the film may contain a surface tension modifier, an antifoaming agent, a surfactant, an antiseptic, a water-soluble plasticizer such as glycerin or polyethylene glycol, and the like, if necessary.
• the film may be a laminated film laminated on a support member.
• the material of the support member is not particularly limited, examples thereof include polyolefin resins, polyester resins, acrylic resins, and the like.
• the polyolefin resin include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer and the like.
• the polyester-based resin include polyethylene terephthalate and polyethylene naphthalate.
• the material of the support member is preferably not polyvinyl alcohol resin.
• the film may have a dichroic dye adsorbed on its surface.
• a dichroic dye adsorbed on its surface By having the above structure, it can be suitably used as a polarizing layer of a polarizing plate.
• the dichroic dyes include iodine and dichroic dyes such as azo dyes, anthraquinone dyes, and tetrazine dyes. Azo dyes are preferred from the viewpoint of the optical properties and durability of the polarizing plate.
• the azo dye include C.I. I. Direct Yellow 12, C.I. I. Direct Yellow 28, C.I. I. Direct Yellow 44, C.I. I. Direct Yellow 142, C.I. I. Direct Orange 26, C.I. I. Direct Orange 39, C.I. I.
• Direct Orange 71 C.I. I. Direct Orange 107, C.I. I. Direct Red 2, C.I. I. Direct Red 31, C.I. I. Direct Red 79, C.I. I. Direct Red 81, C.I. I. Direct Red 117, C.I. I. Direct Red 247, C.I. I. Direct Green 80, C.I. I. Direct Green 59, C.I. I. Direct Blue 71, C.I. I. Direct Blue 78, C.I. I. Direct Blue 168, C.I. I. Direct Blue 202, C.I. I. Direct Violet 9, C.I. I. Direct Violet 51, C.I. I. Direct Brown 106, C.I. I. Direct Brown 223 and the like.
• dyes produced by known methods include the method described in JP-A-3-12606 and the method described in JP-A-59-145255.
• the thickness of the film is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less. Within the above range, gas barrier properties can be further enhanced. Moreover, transparency can be made still higher. Furthermore, the drying time during production can be shortened to improve productivity.
• the lower limit of the thickness of the film is not particularly limited, and is, for example, 1 ⁇ m or more.
• the polyvinyl alcohol resin is suitably used for obtaining a packaging film or a stretched film having a thickness of 30 ⁇ m or less, and in particular, for obtaining a packaging film or a stretched film having a thickness of 20 ⁇ m or less.
• thin packaging films and stretching films having a thickness of 30 ⁇ m or less are likely to break during stretching due to air bubbles or liquid droplets.
• the polyvinyl alcohol resin even when obtaining a packaging film or a stretched film having a thickness of 30 ⁇ m or less, the inclusion of air bubbles and droplets in the film can be sufficiently suppressed during stretching. film breakage can be prevented.
• the thickness of the polarizing layer in the polarizing plate can be appropriately set according to the purpose and application of the LCD in which the polarizing plate is used, but is generally 5 ⁇ m or more. 80 ⁇ m or less.
• the polarizing layer made of stretched and dyed polyvinyl alcohol resin is vulnerable to heat and moisture, so it is preferable to provide a protective layer on the surface.
• the material of the protective layer is not particularly limited, examples thereof include cellulose resins such as triacetyl cellulose, polyester resins such as polyethylene naphthalate, cyclic polyolefin resins such as cycloolefin polymer, and acrylic resins.
• the method of forming a film using the polyvinyl alcohol resin is not particularly limited, and for example, a method of applying an aqueous polyvinyl alcohol resin solution and drying can be used.
• coating methods include solution casting method (casting method), roll coating method, spin coating method, screen coating method, fountain coating method, dipping method, and spray method.
• roll coating method include wire bar coating method, reverse coating method, gravure coating method and the like.
• drying method include a method of natural drying, a method of drying by heating at a temperature not higher than the glass transition temperature of the polyvinyl alcohol resin, and the like.
• composition of the polyvinyl alcohol resin aqueous solution is not particularly limited, and if necessary, surface tension modifiers, antifoaming agents, surfactants, preservatives, water-soluble plasticizers such as glycerin and polyethylene glycol, etc. may be added. good.
• the film may be provided in a state of being laminated on a support member. It is preferable that the supporting member can maintain the polyvinyl alcohol resin aqueous solution on the surface when the polyvinyl alcohol resin aqueous solution is applied and can support the obtained polyvinyl alcohol resin film.
• the material of the support member is not particularly limited, examples thereof include polyolefin resins, polyester resins, acrylic resins, and the like.
• the polyolefin resin include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer and the like.
• the polyester-based resin include polyethylene terephthalate and polyethylene naphthalate.
• the material of the support member is preferably not polyvinyl alcohol resin.
• the above film can be suitably used as a packaging film such as a water-soluble packaging film for packaging medicines such as agricultural chemicals, a stretching film, and the like.
• a polarizing plate can be produced by dyeing the film after stretching.
• the method for dyeing the film include a method in which the film is uniaxially stretched and a dichroic dye such as iodine is adsorbed and oriented.
• the polarizing layer is preferably a polarizing film obtained by stretching the film uniaxially about 2 to 8 times to adsorb and align the dichroic dye.
• a polyvinyl acetal resin can be obtained by adding an aldehyde to the polyvinyl alcohol resin in the presence of an acid catalyst to proceed with the acetalization reaction.
• a polyvinyl acetal resin, which is an acetalized product of the polyvinyl alcohol resin of the present invention, is also one aspect of the present invention.
• the degree of polymerization of the polyvinyl acetal resin is preferably 10,000 or more, and preferably 40,000 or less. By setting it as the said range, the intensity
• the degree of polymerization is more preferably 15,000 or more, and more preferably 25,000 or less.
• the degree of acetalization of the polyvinyl acetal resin is preferably 50 mol % or more, and preferably 80 mol % or less. By setting it as the said range, the solubility to a solvent can fully be improved. In addition, the compatibility with the plasticizer is sufficiently enhanced to facilitate molding of the polyvinyl acetal resin.
• the degree of acetalization is more preferably 60 mol % or more, and more preferably 75 mol % or less.
• the hydroxyl group content of the polyvinyl acetal resin is preferably 16 mol % or more, and preferably 50 mol % or less. When the content is within the above range, the dispersibility of the inorganic powder is improved when the ceramics dispersed sheet is produced, and the compatibility with the plasticizer can be enhanced.
• the amount of hydroxyl groups is more preferably 20 mol % or more, and more preferably 33 mol % or less.
• a method for producing a polyvinyl acetal resin in which an aldehyde is added to the polyvinyl alcohol resin obtained by the above method for producing a polyvinyl alcohol resin to acetalize the polyvinyl alcohol resin is also one aspect of the present invention.
• the polyvinyl alcohol resin of the present invention has an ultra-high molecular weight and is excellent in toughness and transparency. By acetalization, it is made into a polyvinyl acetal resin with an ultra-high molecular weight and excellent toughness and transparency. can be done.
• a known method can be used for the acetalization, and it is preferably carried out in a water solvent, in a mixed solvent of water and an organic solvent having compatibility with water, or in an organic solvent.
• an organic solvent compatible with water for example, an alcohol-based organic solvent can be used.
• the organic solvent include alcohol-based organic solvents, aromatic organic solvents, aliphatic ester-based solvents, ketone-based solvents, lower paraffin-based solvents, ether-based solvents, amide-based solvents, and amine-based solvents.
• the alcohol-based organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.
• Examples of the aromatic organic solvent include xylene, toluene, ethylbenzene, and methyl benzoate.
• Examples of the aliphatic ester solvent include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetoacetate, and ethyl acetoacetate.
• Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzophenone, and acetophenone.
• Examples of the lower paraffin solvents include hexane, pentane, octane, cyclohexane, and decane.
• Examples of the ether solvent include diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether and the like.
• Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethyltesetamide, N-methylpyrrolidone, acetanilide and the like.
• amine solvent examples include ammonia, trimethylamine, triethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, aniline, N-methylaniline, N,N-dimethylaniline and pyridine. These can be used alone, or two or more solvents can be used in combination. Among these, ethanol, n-propanol, isopropanol, and tetrahydrofuran are particularly preferred from the viewpoints of solubility in resins and ease of purification.
• the acetalization is preferably carried out in the presence of an acid catalyst.
• the acid catalyst is not particularly limited, and includes mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, carboxylic acids such as formic acid, acetic acid and propionic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and paratoluenesulfone. sulfonic acids such as acids.
• These acid catalysts may be used alone or in combination of two or more compounds. Among them, hydrochloric acid, nitric acid and sulfuric acid are preferred, and hydrochloric acid is particularly preferred.
• Aldehydes used in the acetalization include aldehydes having a chain aliphatic group, a cycloaliphatic group or an aromatic group having 1 to 10 carbon atoms. Conventionally known aldehydes can be used as these aldehydes.
• the aldehyde used in the acetalization reaction is not particularly limited, and examples thereof include aliphatic aldehydes and aromatic aldehydes.
• Examples of the aliphatic aldehyde include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, 2-ethylhexylaldehyde, n-heptylaldehyde, n- octylaldehyde, n-nonylaldehyde, n-decylaldehyde, amylaldehyde and the like.
• the aromatic aldehydes include benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, ⁇ -phenylpropionaldehyde and the like. These aldehydes may be used individually by 1 type, and may use 2 or more types together.
• aldehydes formaldehyde, acetaldehyde, butyraldehyde, 2-ethylhexylaldehyde, 2-ethylhexylaldehyde, etc., which are excellent in acetalization reactivity, bring about a sufficient internal plasticizing effect on the resin to be produced, and as a result impart good flexibility.
• n-nonylaldehyde is preferred. More preferred are formaldehyde, acetaldehyde, and butyraldehyde, since an adhesive composition having particularly excellent impact resistance and adhesiveness to metal can be obtained.
• the amount of the aldehyde to be added can be appropriately set according to the desired degree of acetalization of the polyvinyl acetal resin.
• the acetalization reaction is efficiently performed, and unreacted aldehyde It is also preferable because it is easy to remove.
• the holding time after the reaction is preferably 1.5 hours or longer, more preferably 2 hours or longer, although it depends on other conditions.
• the acetalization reaction can be allowed to proceed sufficiently by setting the holding time as described above.
• the holding temperature after the reaction is preferably 15° C. or higher, more preferably 20° C. or higher. By setting it as the said holding temperature, an acetalization reaction can fully be advanced.
• the polyvinyl acetal resin is excellent in toughness and transparency, and can be used for applications that take advantage of these properties.
• the polyvinyl acetal resin can be used as an interlayer film for laminated glass.
• An interlayer film for laminated glass containing the polyvinyl acetal resin is also one aspect of the present invention.
• the interlayer film for laminated glass can be obtained by forming the polyvinyl acetal resin and the plasticizer into a sheet by an extruder. Also, a laminated glass can be obtained by sandwiching the interlayer film for laminated glass between two glass plates and hot-pressing them. Since the polyvinyl acetal resin is excellent in toughness and transparency, even when it is used as an intermediate film having another resin layer for imparting characteristics to laminated glass, it can have sufficient strength. Also, the laminated glass can be thinner.
• the polyvinyl acetal resin can be suitably used in binder compositions such as binders for manufacturing laminated ceramic capacitors, binders for paints, and binders for secondary batteries.
• binder compositions such as binders for manufacturing laminated ceramic capacitors, binders for paints, and binders for secondary batteries.
• many multilayer ceramic capacitors are mounted in electronic devices such as smartphones, but miniaturization is required, and by using the polyvinyl acetal resin, ceramic sheets with higher strength can be obtained.
• the binder is thermally decomposed, and if there is a large amount of firing residue, the reliability of the capacitor is lowered.
• the polyvinyl acetal resin it is possible to reduce the amount of the binder to be added and reduce the baking residue.
• the present invention it is possible to provide an ultra-high molecular weight polyvinyl alcohol resin that can be acetalized to form a resin film having high strength and transparency. Moreover, the manufacturing method of polyvinyl acetal resin and polyvinyl alcohol resin, and the manufacturing method of polyvinyl acetal resin can be provided.
• Example 1 Preparation of polyvinyl acetate resin (PVAc)) (Polymerization process)
• PVAc polyvinyl acetate resin
• Example 2 Preparation of polyvinyl acetate resin (PVAc) (Polymerization process)
• a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath and a nitrogen gas inlet was prepared, and 900 parts by weight of water and 100 parts by weight of vinyl acetate (VAc) as a monomer were added to the 2 L separable flask. put in. Thereafter, the mixture was stirred with a stirring blade at 150 rpm to disperse the monomers in water to obtain a monomer mixture.
• VAc vinyl acetate
• a polymerization initiator solution was added to the monomer mixed solution to initiate polymerization, and 12 hours after the initiation of polymerization, the polymerization was terminated by cooling to room temperature to obtain a polyvinyl acetate resin (
• An aqueous solution (polymerization slurry) containing PVAc) was obtained. 2 g of the resulting aqueous solution was dried in an oven at 150° C., and the resin solid content was evaluated.
• the polymerization slurry was evaluated by a zetatizer, the polyvinyl acetate resin had an average particle size of 0.2 ⁇ m and a CV value of the particle size of 4%.
• polyvinyl alcohol resin (Preparation of polyvinyl alcohol resin (PVA))
• the resulting polyvinyl acetate resin was added to methanol (MeOH) as a solvent so as to have a concentration of 6% by weight.
• a methanol solution of sodium hydroxide was added so as to be mol/1 mol of resin, and saponified at 40°C. After that, it was washed with ethyl acetate and dried in a vacuum oven to obtain a polyvinyl alcohol resin (PVA).
• the degree of saponification was 87.7 mol % when measured according to JIS K6726. Moreover, when the clouding point was measured visually, the clouding point was 90° C. or higher.
• the ratio of undissolved components when added to water at a concentration of 4% by weight was measured by a filtration method
• the ratio of undissolved components was 0% by weight.
• the ratio of undissolved components was measured by the following method. First, an aqueous resin solution having a concentration of 4% by weight was allowed to stand still for 12 hours or more, the temperature was raised to 80° C., and then the temperature was lowered to normal temperature by allowing the solution to stand. After that, using a metal mesh (opening #100 mesh), the water and the resin that has absorbed water and swollen are separated, the separated resin is dried at 60 ° C. for 3 hours, and the metal mesh after drying is used.
• Weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated based on a calibration curve prepared using high molecular weight standard polystyrene EasiVial PS-H manufactured by GL Sciences as a standard substance.
• a polyvinyl acetal resin (PVB) was obtained.
• the weight-average molecular weight of the obtained polyvinyl acetal resin was measured by gel permeation chromatography using LF-804 (manufactured by SHOKO) as a column, in terms of polystyrene, and found to be 1.82 million.
• Example 2 to 10 Polyvinyl acetate resin and polyvinyl alcohol resin were obtained in the same manner as in Example 1 except that the water-soluble surfactant and the polymerization initiator were added so that the types and formulations shown in Table 1 were obtained.
• a polyvinyl acetal resin was obtained in the same manner as in Example 1, except that n-butyraldehyde was added so as to obtain a composition as shown in Table 3.
• the following water-soluble surfactants and polymerization initiators were used.
• VA-057 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Tetramethylammonium peroxodisulfate P-toluenesulfonic acid peroxide Peroxodisulfinic acid
• VA-61 2,2'-azobis[2-(2-imidazolin-2-yl)propane]
• V-50 2,2′-azobis(2-methylpropionamidine) dihydrochloride
• VA-086 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• Example 11 to 16 Vinyl acetate, water, a water-soluble surfactant, and a polymerization initiator were added so that the formulations as shown in Table 1 were obtained, and polyvinyl acetate resin (PVAc) was prepared in the same manner as in Example 1, except that the recovery step was not performed. ) was obtained (polymerization slurry).
• a polyvinyl alcohol resin was obtained in the same manner as in Example 1, except that the compound shown in Table 2 was added as a saponification catalyst to the obtained polymerization slurry.
• a polyvinyl acetal resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl alcohol resin was used.
• a saponification catalyst the following was used.
• Dialkylamine compound diethylamine
• Trialkylamine compound triethylamine: solubility in water at 25° C. 8 g/100 g
• Tributylamine solubility in water at 25° C. 0.3 g/100 g
• Example 17-23 A polyvinyl acetate resin was obtained in the same manner as in Example 1 except that vinyl acetate, water, a water-soluble surfactant, a polymerization initiator, and a cationic surfactant were added so as to have the formulation shown in Table 1. rice field.
• a polyvinyl alcohol resin was obtained in the same manner as in Example 1, except that the type of solvent and the blending amount of the saponification catalyst were changed.
• a polyvinyl acetal resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl alcohol resin was used.
• the following cationic surfactants were used.
• the mixture is cooled to 20° C. under a nitrogen atmosphere, and 0.03% hydrogen peroxide solution prepared with separately deaerated ion-exchanged water is uniformly dropped continuously at 12 parts/hr for polymerization. started. After 2 hours, when the polymerization rate reached 48%, the addition of the hydrogen peroxide solution was stopped, and 1.0 part of hydroquinone was added to stop the polymerization, thereby obtaining an aqueous solution (polymerization slurry) containing a polyvinyl acetate resin.
• the polymerization slurry was evaluated by a zetatizer, the polyvinyl acetate resin had an average particle size of 0.2 ⁇ m and a CV value of 20%.
• the obtained polymerization slurry was spray-dried to obtain a polyvinyl acetate resin composition.
• the obtained polyvinyl acetate resin dissolved in acetone and methanol. Moreover, the molecular weight of the obtained polyvinyl acetate resin was 1,000,000.
• a polyvinyl alcohol resin and a polyvinyl acetal resin were obtained in the same manner as in Example 1, except that the obtained polyvinyl acetate resin was used.
• Example 2 A 2 L separable flask equipped with a stirrer, condenser, thermometer, hot water bath and nitrogen gas inlet was prepared. A 2-L separable flask was charged with 900 parts by weight of water and 100 parts by weight of vinyl acetate as a monomer. Thereafter, 2.0 parts by weight of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, 12 parts by weight of sodium dodecylsulfonate was added as an emulsifier, and the reaction system was emulsified using a homogenizer.
• AIBN azobisisobutyronitrile
• aqueous solution (polymerization slurry) containing a polyvinyl acetate resin having an isobutyrolonitrile group at one molecular end of the main chain. 2 g of the obtained aqueous solution was dried in an oven at 150° C., and the solid resin content was evaluated.
• the polyvinyl acetate resin When the polymerization slurry was evaluated by a zetatizer, the polyvinyl acetate resin had an average particle size of 10 ⁇ m and a CV value of 40%.
• the resulting polymerized slurry was dehydrated using a filter cloth and dried for 18 hours in a vacuum dryer set at 27° C. to obtain a polyvinyl acetate resin.
• the obtained polyvinyl acetate resin dissolved in acetone and methanol.
• the molecular weight of the obtained polyvinyl acetate resin was 150,000.
• a polyvinyl alcohol resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl acetate resin was used.
• a polyvinyl acetal resin was obtained in the same manner as in Example 1 except that the obtained polyvinyl alcohol resin was used and the amounts of polyvinyl alcohol resin, water and aldehyde added were as shown in Table 3.
• a polyvinyl acetate resin was obtained in the same manner as in Example 1, except that the type and amount of the water-soluble surfactant were as shown in Table 1.
• a polyvinyl alcohol resin was obtained in the same manner as in Example 1 except that the type of solvent and the amount of saponification catalyst added were as shown in Table 2.
• a polyvinyl acetal resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl alcohol resin was used. The following water-soluble surfactants were used. ⁇ Water-soluble surfactant> Polycarboxylic acid: Demol P (Kao Corporation)
• a polymerization initiator solution was prepared by dissolving 1.2 parts by weight of ammonium persulfate (APS) as a polymerization initiator in 200 parts by weight of water. After removing dissolved oxygen by bubbling the emulsified monomer mixture for 20 minutes with nitrogen gas, the inside of the separable flask is replaced with nitrogen gas, and the water bath is heated to 60°C while stirring. Then, a polymerization initiator solution was added dropwise to initiate polymerization.
• APS ammonium persulfate
• aqueous solution (polymerization slurry) containing a polyvinyl acetate resin having a sulfonic acid group at one molecular end of the main chain.
• 2 g of the obtained aqueous solution was dried in an oven at 150° C., and the solid resin content was evaluated.
• the polymerization slurry was evaluated by a zetatizer, the polyvinyl acetate resin had an average particle size of 0.2 ⁇ m and a CV value of 20%.
• the resulting polymerized slurry was dehydrated using a filter cloth and dried for 18 hours in a vacuum dryer set at 27° C. to obtain a polyvinyl acetate resin.
• the obtained polyvinyl acetate resin dissolved in acetone and methanol.
• the molecular weight of the obtained polyvinyl acetate resin was 900,000.
• a polyvinyl alcohol resin was obtained in the same manner as in Example 1, except that the obtained polyvinyl acetate resin was used.
• a polyvinyl acetal resin was obtained in the same manner as in Example 1 except that the obtained polyvinyl alcohol resin was used and the amounts of polyvinyl alcohol resin, water and aldehyde added were as shown in Table 3.
• PVA film To 190 parts by weight of water, 10 parts by weight of the obtained polyvinyl alcohol resin, 40 parts by weight of glycerin as a plasticizer, and 0.4 parts by weight of polyether silicone (KF-642 manufactured by Shin-Etsu Chemical Co., Ltd.) as an antifoaming agent are added. Then, a polyvinyl alcohol resin aqueous solution was prepared. The obtained aqueous solution was coated on a release PET film to form a liquid coating, which was cast on a chromium plating drum heated to 80° C. and dried for 3 minutes to obtain a 40 ⁇ m PVA film.
• KF-642 manufactured by Shin-Etsu Chemical Co., Ltd.
• the film was cut into a size of 100 mm ⁇ 15 mm to prepare a measurement sample (PVA film).
• the resulting measurement sample was subjected to a tensile test in accordance with JIS K7113 at a temperature of 23° C., a humidity of 50%, and a peel speed of 100 mm /min. was measured.
• PVB resin sheet 10 parts by weight of the obtained polyvinyl acetal resin was added to 90 parts by weight of an ethanol/toluene mixed solvent (weight ratio: 1:1), and dissolved by stirring to obtain a resin sheet composition.
• a measurement sample is prepared by applying the obtained resin sheet composition on a release-treated PET film using a coater so that the thickness after drying becomes 20 ⁇ m, followed by heating and drying. did.
• the resulting measurement sample was stretched at a tensile speed of 20 mm/min using AUTOGRAPH (AGS-J, manufactured by Shimadzu Corporation) according to JIS K7113, and the breaking stress was measured.
• the strength was evaluated according to the standard. ⁇ : Breaking stress is 100 MPa or more ⁇ : Breaking stress is less than 100 MPa
• Interlayer film for laminated glass 100 parts by weight of the obtained polyvinyl acetal resin and 40 parts by weight of triethylene glycol-di-2-ethylbutyrate as a plasticizer are mixed, and the mixture is thoroughly melt-kneaded with a mixing roll and then molded with a press molding machine. Press molding was performed at 150° C. for 30 minutes to obtain a resin (interlayer film for laminated glass) having a thickness of 0.3 mm. The resulting resin film was sandwiched between two sheets of transparent float glass (30 cm long x 30 cm wide x 3 mm thick), placed in a rubber bag, degassed at a vacuum of 20 torr for 20 minutes, and then heated to 90°C. A laminated glass was obtained by transferring to an oven and vacuum pressing while holding for 30 minutes.
• the transparency of the obtained laminated glass was confirmed according to JIS R3205.
• the falling ball impact peeling property was confirmed in accordance with JIS R3205, the height of visible cracks was measured in the falling ball test, and the strength was evaluated according to the following criteria. ⁇ : 6.0 m or more ⁇ : less than 6.0 m
• the present invention it is possible to provide an ultra-high molecular weight polyvinyl alcohol resin that can be acetalized to form a resin film having high strength and transparency. Moreover, the manufacturing method of polyvinyl acetal resin and polyvinyl alcohol resin, and the manufacturing method of polyvinyl acetal resin can be provided.

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