WO2019020156A1 - Copolymères d'alcool vinylique hydrophobes et solubles dans l'eau froide - Google Patents

Copolymères d'alcool vinylique hydrophobes et solubles dans l'eau froide Download PDF

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Publication number
WO2019020156A1
WO2019020156A1 PCT/EP2017/068589 EP2017068589W WO2019020156A1 WO 2019020156 A1 WO2019020156 A1 WO 2019020156A1 EP 2017068589 W EP2017068589 W EP 2017068589W WO 2019020156 A1 WO2019020156 A1 WO 2019020156A1
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Prior art keywords
vinyl alcohol
mol
alcohol copolymers
vinyl
monomer units
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PCT/EP2017/068589
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German (de)
English (en)
Inventor
Abdulmajid Hashemzadeh
Udo EISLEBEN
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Wacker Chemie Ag
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Priority to PCT/EP2017/068589 priority Critical patent/WO2019020156A1/fr
Publication of WO2019020156A1 publication Critical patent/WO2019020156A1/fr

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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
    • 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
    • C08F216/02—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
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to vinyl alcohol copolymers and processes for their preparation and their use.
  • Polymers stabilized with protective colloids are mainly used in the form of their aqueous dispersions or water-redispersible polymer powders (dispersion powders) in many applications, for example as coating agents or adhesives, for a wide variety of substrates, for example as cementitious tile adhesives.
  • Dispersion powders are polymer powders which are obtainable by spray-drying the corresponding aqueous polymer dispersions.
  • Water-redispersible polymer powders are generally obtained by drying the corresponding aqueous polymer dispersions in the presence of a drying aid (generally a protective colloid) and, if appropriate, antiblocking agents and, if appropriate, further additives.
  • the drying process prevents the polymer particles from irreversibly sticking because the polymer particles are enveloped by the protective colloid particles.
  • this protective colloid matrix which dissolves again when the polymer powder is dispersed in water, causes the polymer particles to be present again with the particle size of the starting dispersion in the aqueous redispersion (TIZ fraberichte, 1985, Vol. 109 (9), 698).
  • protective colloids generally polyvinyl alcohols are used, for example in the process which in the
  • WO 2013/017491 AI is described.
  • the use of polyvinyl alcohol is desirable because, in comparison to systems which are stabilized by low molecular weight compounds (emulsifiers), it itself contributes to the strength (for example adhesion values in the tile adhesive).
  • emulsifiers low molecular weight compounds
  • problems can arise in the production and use of polyvinyl alcohol. polymerized polymers occur, in particular if the polyvinyl alcohol has a higher degree of saponification.
  • EP 1020493 A1 describes the use of a partially acetalized, water-soluble polyvinyl alcohol as a drying aid in the preparation of a water-redispersible polymer powder by spray-drying the corresponding polymer dispersion.
  • WO 2012/159848 Al fully hydrolyzed vinyl acetate
  • Isopropenyl acetate copolymers are used as a protective colloid for stabilizing an aqueous polymer dispersion and as a drying aid for drying an aqueous polymer dispersion.
  • EP 477900 A2 describes disperse powder compositions with polyvinyl alcohol, which still contain fully hydrolyzed vinyl acetate-1-methylvinyl acetate copolymers in order to improve the properties of building materials modified therewith.
  • Fully hydrolyzed or partially hydrolyzed copolymers of vinyl acetate and 1-alkylvinyl esters are known from EP 1180528 B1, which optionally also contain monomer units derived from vinyl esters of alpha-branched carboxylic acids.
  • WO 99/16794 Al describes the preparation of stabilized with protective colloid, aqueous polymer dispersions, being used as protective colloids teilverseifte copolymers of vinyl acetate and vinyl esters of alpha-branched carboxylic acids having 9 to 11 carbon atoms.
  • EP 1400557 Al describes the use of a vinyl alcohol copolymer with 1 to 12 mol% of ethylene units as a drying aid in the production of dispersion powders.
  • EP 1420033 B1 uses partially hydrolysed vinyl acetate-ethylene copolymers as a protective colloid in the preparation of a copolymer dispersion and as a drying aid in the spray-drying of aqueous polymer dispersions.
  • WO 2010/091766 A1 a copolymer of 11 mol% vinyl sulfonate, 45 mol%, is used in Example 3. Vinyl acetate, 33 mol% VeovalO and 11 mol% of vinyl alcohol used as a dispersant in a pigment preparation.
  • the object of the invention was to provide vinyl alcohol copolymers which have a hydrophobic character and which, even at a high degree of hydrolysis (degree of saponification), still have good storage stability (viscosity stability) and good solubility in water.
  • the invention provides vinyl alcohol copolymers with a) from 80 to 99 mol%, preferably from 85 to 97 mol% of vinyl alcohol monomer units,
  • Preferred vinyl esters of unbranched or branched alkylcarboxylic acids having 3 to 18 carbon atoms are vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate and vinyl esters of ⁇ -branched monocarboxylic acids having 5 to 13 carbon atoms, for example, vinyl pivalate, VeoVa9 R , VeoVal0 R or VeoVall R (trade name Hexion).
  • Particularly preferred are the vinyl esters of ⁇ -branched monocarboxylic acids having 9 to 10 carbon atoms (VeoVa9 R and VeoVal0 R ).
  • suitable ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and its anhydride, monoesters of fumaric acid or maleic acid, such as the ethyl and isopropyl esters or unsaturated fatty acids having 7 to 25
  • Carbon atoms as well as the salts of said carboxylic acids. Preference is given to acrylic and methacrylic acid, maleic acid (anhydride) and crotonic acid, and the salts of the carboxylic acids mentioned.
  • R 4 is Ci- to C 4 alkylene, and the salts of said acids.
  • Suitable monomers with quaternary ammonium groups as monomers c) are diallyldimethylammonium chloride (DADMAC), diallyl diethylammonium chloride (DADEAC), (3-methacryloxy) ropyltrimethylammonium chloride (MPTAC), (3-methacryloxy) ethyltrimethylammonium chloride (METAC), (3 Methacrylamido) ropyltrimethylammonium chloride (MAPTAC).
  • DADMAC diallyldimethylammonium chloride
  • DADEAC diallyl diethylammonium chloride
  • MPTAC (3-methacryloxy) ropyltrimethylammonium chloride
  • METAC (3-methacryloxy) ethyltrimethylammonium chloride
  • MATAC 3 Methacrylamido) ropyltrimethylammonium chloride
  • Suitable monomers having a phosphoric acid radical are vinylphosphonic acid and dimethyl vinylphosphonate, phosphoalkylmethacrylates such as phosphoethyl methacrylate and phosphopropyl methacrylate.
  • the most preferred monomers c) are vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and salts thereof.
  • reactive monomers from the group of ethylenically unsaturated monomers with alkoxysilane group or epoxy group or amine group or amide group can be copolymerized.
  • the vinyl alcohol copolymers can be prepared in a known manner by means of radical polymerization of vinyl acetate with the comonomers mentioned below b) and c) and subsequent hydrolysis of the resulting vinyl acetate copolymers.
  • Suitable solvents are, for example, methanol, ethanol, propanol, isopropanol and an ethanol-isopropanol mixture.
  • the polymerization is carried out under reflux at a temperature of 35 ° C to 100 ° C.
  • the radical initiation takes place by adding common initiators.
  • common initiators are percarbons such as cyclohexyl peroxydicarbonate, peresters such as t-butyl per neodecanoate or t-butyl peroxypivalate, peroxide initiators such as t-butyl hydroperoxide, diacyl peroxides such as dilauroyl peroxide, and azo initiators such as azobisisobutyronitrile (AIBN), 2,2 "azobis (AIBN).
  • AIBN azobisisobutyronitrile
  • AIBN 2,2 "azobis (AIBN).
  • the monomers can be initially introduced in total, be metered in in their entirety, or be charged in portions, and the remainder added after the initiation of the polymerization.
  • the initiator is preferably initially introduced and the remaining portion each to Siert.
  • the adjustment of the molecular weight can be carried out in a manner known to the skilled worker by polymerization in the presence of molecular weight regulators.
  • the saponification (transesterification, hydrolysis) of the vinyl acetate copolymer takes place in a manner known per se, for example by the kneader process or in a stirred tank, preferably in the alkaline phase with the addition of base.
  • the vinyl acetate copolymer is in alcoholic solution with monohydric aliphatic alcohols having 1 to 4 carbon atoms or mixtures thereof as a solvent. Particularly preferred are methanol and an ethanol / isopropanol mixture.
  • the content of vinyl acetate copolymer in the solution is 20 to 85 wt .-%, preferably 30 to 80 wt .-%.
  • alkaline catalysts are, for example, the hydroxides, alkoxides and carbonates of alkali or alkaline earth metals. Preference is given to sodium hydroxide.
  • the alkaline catalysts are preferably used in alcoholic solution. Most preferred is a methanolic solution of NaOH.
  • the amounts of alkaline catalyst used are generally 0.2 to 20.0 wt .-%, based on the vinyl acetate copolymer.
  • the hydrolysis is generally carried out at temperatures of 40 ° C to 90 ° C, preferably 50 ° C to 85 ° C, generally in a stirred tank. By adding the catalyst solution, saponification is initiated. Upon reaching the desired degree of hydrolysis, the hydrolysis is stopped. Preferably, the ester formed in the transesterification is distilled off during the Versei- tion reaction. In the preferred alkaline-catalyzed hydrolysis, the termination takes place by addition of acidic reagents, such as carboxylic acids or mineral acids, preferably acetic acid.
  • the solvent is distilled off, for example by means of steam stripping and the vinyl alcohol copolymer dissolved in water.
  • the vinyl alcohol Copolymer can also be separated by precipitation or drying of the liquid phase and isolated as a solid.
  • the vinyl alcohol copolymers according to the invention are suitable as protective colloids, dispersants, drying aids and for use in coating compositions, preferably for paper coating in paper coating formulations. Also preferred is their use as a protective colloid in the preparation of aqueous polymer dispersions and their use as a drying aid in drying, in particular spray drying, of aqueous polymer dispersions.
  • Vinyl ester of versatic acid R 10 (VeoVa R 10) 177 g
  • An initiator solution of 125 g of PPV in 1880 g of methanol was added within 240 minutes.
  • a monomer mixture 1 with 999 g of VeoVa R 10 and 18661 g of vinyl acetate was metered in with a metering time of 180 minutes.
  • the monomer solution 2, 1319 g of a 25% aqueous solution of vinyl sulfonate was metered in with a metering time of 195 minutes.
  • the reactor was locked, the pressure in the reactor increased to 0.2 bar and post-polymerized at 100 ° C for one hour. Thereafter, the polymer solution was cooled to 30 ° C and diluted with methanol to a 31 wt .-% solution. The polymer solution was coated without stirring with 38440 g of methanol and then a mixture of 775 g of methanol and 657 g of 46% sodium hydroxide solution was added and stirred. After two hours, the solution was neutralized with 342 g of acetic acid (99.8%). Subsequently, methanol and by-products were removed by steam stripping. After stripping, the vinyl alcohol copolymer was taken up in water and diluted to a 20% by weight solution.
  • Example 2 the procedure was as in Example 1, with the difference that the monomers vinyl acetate (VAc), VeoVa 10 and vinyl sulfonate (VS) in the monomer mixture 1 and the monomer solution 2 in such Quantities were added so that in each case the total amounts indicated in Table 1 were obtained.
  • the monomer c) used was DADMAC (diallyldimethylammonium chloride) and in example 6 as monomer c) AMPS (2-acrylamido-2-methylpropanesulfonic acid) instead of vinylsulfonate.
  • no vinylsulfonic acid was used. Table 1:
  • Viscosity Stability Testing The 20% by Weight Aqueous Solutions of the Vinyl Alcohol
  • Copolymers of Examples 1, 2, 3 and 5 and Comparative Example 4 were each stored for 1 day (ld) and 14 days (14d) at 23 ° C. After these storage times, the Brookfield viscosity was determined in each case. The determination of the Brookfield viscosities of the aqueous solutions was carried out with a
  • Table 2 shows in each case the composition of the vinyl alcohol copolymers from the examples and the comparative example. The proportions in the copolymer are in each case given in mol% and were determined by means of 1H NMR spectroscopy and elemental analysis (sulfur or nitrogen). Table 2:
  • VK Viscosity
  • the vinyl alcohol copolymers of the examples according to the invention show a very good viscosity stability over the entire period of 14 days. Testing the Redispersibility of the Films of the Vinyl Alcohol Copolymers
  • the vinyl alcohol copolymers were stabilized with an aqueous polyvinyl alcohol-stabilized (polyvinyl alcohol: Höppler viscosity 5 mPa.s, degree of hydrolysis 88 mol%) ethylene-vinyl acetate copolymer dispersion having a glass transition temperature Tg of -7 ° C and a solids content of 53 wt .-%, in an amount of 10 wt.%, Based on the total dry weight, blended.
  • polyvinyl alcohol-stabilized polyvinyl alcohol: Höppler viscosity 5 mPa.s, degree of hydrolysis 88 mol
  • ethylene-vinyl acetate copolymer dispersion having a glass transition temperature Tg of -7 ° C and a solids content of 53 wt .-%, in an amount of 10 wt.%, Based on the total dry weight, blended.
  • 0.2 mm thick films were produced from the mixtures on glass plates and these were dried at room temperature for 24 hours and then dried at 105 ° C. for 15 minutes.
  • a drop of water was applied at room temperature with a pipette to a homogeneous point of the film to be tested, and rubbed after 60 seconds exposure time of the water droplets with the fingertip at the same point until the glass plate at this Was film-free, the film fell into pieces of film or was completely preserved.
  • the redispersibility of the polymer films was evaluated by the following evaluation scheme:
  • Grade 1 Film can be readily redispersed by light rubbing or redispersed already on its own;
  • Grade 3 Film can only be redispersed by vigorous rubbing to form pieces of film

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des copolymères d'alcool vinylique contenant a) 80 à 99 % en moles de motifs monomères d'alcool vinylique, b) 0,5 à 10 % en moles de motifs monomères qui sont dérivés d'esters vinyliques d'acides alkylcarboxyliques ramifiés ou non ramifiés possédant de 3 à 18 atomes de carbone, c) 0,5 à 10 % en moles de motifs monomères qui sont dérivés de monomères éthyléniquement insaturés présentant un ou plusieurs groupes fonctionnels choisis dans le groupe constitué par le radical acide carboxylique, le radical acide sulfonique, le radical amine quaternisé, le radical acide phosphorique, ainsi que leurs sels, et d) 0 à 5 % en moles de motifs monomères d'acétate de vinyle, les pourcentages en moles s'additionnant pour donner un total de 100 % en moles.
PCT/EP2017/068589 2017-07-24 2017-07-24 Copolymères d'alcool vinylique hydrophobes et solubles dans l'eau froide WO2019020156A1 (fr)

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PCT/EP2017/068589 WO2019020156A1 (fr) 2017-07-24 2017-07-24 Copolymères d'alcool vinylique hydrophobes et solubles dans l'eau froide

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023137185A1 (fr) * 2022-01-14 2023-07-20 Sekisui Specialty Chemicals America, Llc Résine d'alcool polyvinylique modifiée à solubilité améliorée dans des mélanges d'alcools

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56139510A (en) * 1980-03-31 1981-10-31 Kuraray Co Ltd Water-repelling copolymer
JPS6344768B2 (fr) * 1981-06-19 1988-09-06 Kuraray Co
EP0477900A2 (fr) 1990-09-27 1992-04-01 Wacker-Chemie Gmbh Composition d'une poudre fluente
JPH1087937A (ja) * 1996-09-18 1998-04-07 Kuraray Co Ltd セメント混和剤
WO1999016794A1 (fr) 1997-09-26 1999-04-08 Wacker-Chemie Gmbh Procede de preparation de polymeres stabilises par colloides protecteurs
EP1020493A1 (fr) 1999-01-15 2000-07-19 Clariant GmbH Poudre de dispersion contenant de l'alcool polyvinylique partiellement acétalisée soluble dans l'eau, procédé pour sa préparation et son utilisation
EP1253157A1 (fr) * 2001-04-26 2002-10-30 Wacker-Chemie GmbH Utilisation de polymères d'alcool vinylique éthérifiés comme agents épaississants
EP1180528B1 (fr) 2000-08-17 2002-11-06 Wacker-Chemie GmbH Usage d'un copolymère d'alcool vinylique comme agent épaississant
EP1400557A1 (fr) 2002-09-17 2004-03-24 Kuraray Co., Ltd. Poudre de résine synthétique redispersable
EP1420033B1 (fr) 2002-11-14 2004-08-25 Wacker Polymer Systems GmbH & Co. KG Dispersions aqueuses de polymères stabilisés par un colloide protecteur et poudres redispersables dans l'eau
EP1908798A1 (fr) * 2005-07-13 2008-04-09 Kuraray Co., Ltd. Dispersion liquide aqueuse, procede pour produire celle-ci, une composition, un adhesif et un materiau de revetement
EP2016105A1 (fr) * 2006-05-02 2009-01-21 Celanese International Corporation Films d'alcool polyvinylique ayant une résistance améliorée aux produits chimiques oxydants
WO2010091766A1 (fr) 2009-02-12 2010-08-19 Clariant International Ltd Préparations de pigment solide facilement dispersibles
WO2012159848A1 (fr) 2011-05-24 2012-11-29 Wacker Chemie Ag Procédé de production de polymères stabilisés par des colloïdes protecteurs
WO2013017491A1 (fr) 2011-08-01 2013-02-07 Wacker Chemie Ag Procédé de préparation de poudres en dispersion
JP2017115019A (ja) * 2015-12-24 2017-06-29 関西ペイント株式会社 顔料ペースト及び塗工材

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56139510A (en) * 1980-03-31 1981-10-31 Kuraray Co Ltd Water-repelling copolymer
JPS6344768B2 (fr) * 1981-06-19 1988-09-06 Kuraray Co
EP0477900A2 (fr) 1990-09-27 1992-04-01 Wacker-Chemie Gmbh Composition d'une poudre fluente
JPH1087937A (ja) * 1996-09-18 1998-04-07 Kuraray Co Ltd セメント混和剤
WO1999016794A1 (fr) 1997-09-26 1999-04-08 Wacker-Chemie Gmbh Procede de preparation de polymeres stabilises par colloides protecteurs
EP1020493A1 (fr) 1999-01-15 2000-07-19 Clariant GmbH Poudre de dispersion contenant de l'alcool polyvinylique partiellement acétalisée soluble dans l'eau, procédé pour sa préparation et son utilisation
EP1180528B1 (fr) 2000-08-17 2002-11-06 Wacker-Chemie GmbH Usage d'un copolymère d'alcool vinylique comme agent épaississant
EP1253157A1 (fr) * 2001-04-26 2002-10-30 Wacker-Chemie GmbH Utilisation de polymères d'alcool vinylique éthérifiés comme agents épaississants
EP1400557A1 (fr) 2002-09-17 2004-03-24 Kuraray Co., Ltd. Poudre de résine synthétique redispersable
EP1420033B1 (fr) 2002-11-14 2004-08-25 Wacker Polymer Systems GmbH & Co. KG Dispersions aqueuses de polymères stabilisés par un colloide protecteur et poudres redispersables dans l'eau
EP1908798A1 (fr) * 2005-07-13 2008-04-09 Kuraray Co., Ltd. Dispersion liquide aqueuse, procede pour produire celle-ci, une composition, un adhesif et un materiau de revetement
EP2016105A1 (fr) * 2006-05-02 2009-01-21 Celanese International Corporation Films d'alcool polyvinylique ayant une résistance améliorée aux produits chimiques oxydants
WO2010091766A1 (fr) 2009-02-12 2010-08-19 Clariant International Ltd Préparations de pigment solide facilement dispersibles
WO2012159848A1 (fr) 2011-05-24 2012-11-29 Wacker Chemie Ag Procédé de production de polymères stabilisés par des colloïdes protecteurs
WO2013017491A1 (fr) 2011-08-01 2013-02-07 Wacker Chemie Ag Procédé de préparation de poudres en dispersion
JP2017115019A (ja) * 2015-12-24 2017-06-29 関西ペイント株式会社 顔料ペースト及び塗工材

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TIZ-FACHBERICHTE, vol. 109, no. 9, 1985, pages 698

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023137185A1 (fr) * 2022-01-14 2023-07-20 Sekisui Specialty Chemicals America, Llc Résine d'alcool polyvinylique modifiée à solubilité améliorée dans des mélanges d'alcools

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