WO2022230825A1 - ビニルアルコール系重合体、これを含む粉末、粉末の製造方法、コーティング剤、塗工物、塗工物の製造方法、乳化重合用安定剤、水性エマルジョン及び接着剤 - Google Patents

ビニルアルコール系重合体、これを含む粉末、粉末の製造方法、コーティング剤、塗工物、塗工物の製造方法、乳化重合用安定剤、水性エマルジョン及び接着剤 Download PDF

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WO2022230825A1
WO2022230825A1 PCT/JP2022/018771 JP2022018771W WO2022230825A1 WO 2022230825 A1 WO2022230825 A1 WO 2022230825A1 JP 2022018771 W JP2022018771 W JP 2022018771W WO 2022230825 A1 WO2022230825 A1 WO 2022230825A1
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Prior art keywords
mass
pva
powder
less
vinyl alcohol
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English (en)
French (fr)
Japanese (ja)
Inventor
美鈴 藤森
悠太 田岡
敦 直原
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to US18/288,570 priority Critical patent/US20240209128A1/en
Priority to JP2023517518A priority patent/JPWO2022230825A1/ja
Priority to EP22795738.8A priority patent/EP4332126A4/en
Priority to CN202280031698.6A priority patent/CN117279961A/zh
Publication of WO2022230825A1 publication Critical patent/WO2022230825A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C09D129/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C08J2331/00—Characterised by the use of 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, or carbonic acid, or of a haloformic acid
    • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2331/04—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
    • C08L2201/00—Properties
    • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C

Definitions

  • the present invention relates to a vinyl alcohol polymer, a powder containing the same, a method for producing the powder, a coating agent, a coated product, a method for producing the coated product, a stabilizer for emulsion polymerization, an aqueous emulsion, and an adhesive.
  • Vinyl alcohol polymer (hereinafter sometimes referred to as "PVA") is known as a water-soluble synthetic polymer, and is a stable polymer for paper processing, fiber processing, adhesives, emulsion polymerization and suspension polymerization. It is widely used for applications such as agents, inorganic binders, and films.
  • PVA containing structural units derived from carboxylic acid or derivatives thereof is known (see Patent Document 1).
  • Such PVA is used as a sizing agent for acidic paper containing aluminum sulfate, as a water-resistant coating film in combination with a cross-linking agent, as an adhesive, etc., by utilizing the reactivity of carboxylic acid.
  • Patent Document 2 describes a pressure-sensitive adhesive composition containing an alkyl-modified PVA having a specific viscosity range and a (meth)acrylic emulsion.
  • the present invention has been made to solve the above problems, and includes a PVA having good coatability, a powder containing such PVA, a method for producing this powder, a coating agent using the above PVA, and a coating.
  • An object of the present invention is to provide a method for manufacturing a product and a coated product.
  • Another object of the present invention is to provide an adhesive that causes less coating streaks and less liquid splattering during roll coating, and an emulsion polymerization stabilizer and aqueous emulsion capable of obtaining such an adhesive.
  • At least one selected from the group consisting of the above monomers having a carboxy group and derivatives thereof is at least one selected from the group consisting of ethylenically unsaturated dicarboxylic acids, monoesters, diesters and anhydrides thereof.
  • P is the viscosity average degree of polymerization.
  • g A is the degree of branching at an absolute molecular weight of 200,000.
  • g B is the degree of branching at an absolute molecular weight of 800,000.
  • a method for producing a powder wherein the content is 12% by mass or less; [12] The method for producing a powder according to [11], wherein the heat treatment temperature in step (3) is 110°C or higher and the heat treatment time is 1 hour or longer; [13] A coating agent comprising the PVA of any one of [1] to [7]; [14] A coated product obtained by applying the coating agent of [13] onto a substrate; [15] The coated product of [14], which is a heat-sensitive recording material; [16] The coated product of [14], which is a base paper for release paper; [17] The coated product of [14], which is greaseproof paper; [18] The coated product of [14], which is an inkjet recording material; [19] The coated article of [14], which is gas barrier paper or flavor barrier paper; [20] The coated product of [14], which is white paperboard; [21] A method for producing a coated product, comprising the step of applying the coating agent of [13] onto a substrate with a curtain coater; [22]
  • a PVA having good coatability a powder containing such PVA, a method for producing this powder, a coating agent using the PVA, a coated product, and a method for producing a coated product are provided. can do.
  • an adhesive that causes less coating streaks and less scattering of the coating liquid during roll coating, and an emulsion polymerization stabilizer and an aqueous emulsion capable of obtaining such an adhesive are provided. can provide.
  • FIG. 1 is a graph showing the relationship between absolute molecular weights and intrinsic viscosities ([ ⁇ ] branch and [ ⁇ ] linear ) of PVA-3 and PVA-17 in Examples.
  • FIG. 2 is a graph showing the relationship between the absolute molecular weight and branching degree (g m ) of PVA-3 in Examples.
  • FIG. 3 is a diagram for explaining a method for evaluating splattering (liquid splashing) in Examples.
  • the PVA (vinyl alcohol polymer) of the present invention is PVA containing a structural unit derived from at least one selected from the group consisting of monomers having a carboxy group and derivatives thereof, and having an absolute molecular weight of 200,000 or more.
  • the minimum branching degree in the range of 800,000 or less is 0.93 or less, and the insoluble content when 4 parts by mass of the PVA is added to 96 parts by mass of water and stirred at 60 ° C. for 1 hour is 0.1 ppm or more and less than 2000 ppm. be.
  • the PVA has good coatability when applied as an aqueous solution. Moreover, the coating agent containing the PVA suppresses the occurrence of defects even when the coating is performed at high speed, and is excellent in coatability. Although the reason why such an effect occurs is not clear, the following reason is presumed.
  • the degree of branching of a polymer is an index representing the degree of branching structure of a polymer in the range of 0 to 1, as will be described later in detail, and the smaller the value, the more the branching structure.
  • the PVA has a minimum branching degree of 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less, and has a sufficiently branched structure. The difference is a small value.
  • the normal stress is the stress generated in the direction perpendicular to the direction in which the shear is applied when rotational deformation is applied to the object to be measured, which is a viscoelastic fluid.
  • the PVA has a small amount of insoluble matter, which is one of the other factors that cause splattering and coating unevenness during coating.
  • the PVA has a sufficiently branched structure and a small amount of insoluble matter, so it is presumed that the coatability is good when the aqueous solution is applied.
  • the PVA of the present invention contains structural units derived from at least one selected from the group consisting of vinyl alcohol units and monomers having a carboxy group and derivatives thereof.
  • "at least one selected from the group consisting of monomers having a carboxy group and derivatives thereof” may be referred to as "monomer (a)".
  • the PVA is usually obtained by saponifying a vinyl ester polymer (copolymer of monomer (a) and vinyl ester) containing a structural unit derived from monomer (a).
  • Derivatives of a monomer having a carboxy group include esters and anhydrides of a monomer having a carboxy group.
  • a carboxy group (--COOH) may exist in the form of a salt (--COONa, etc.).
  • a structural unit derived from the monomer (a) may form a crosslinked structure and bond with other structural units.
  • Monomer (a) includes ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids and derivatives thereof.
  • ethylenically unsaturated monocarboxylic acids and derivatives thereof include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
  • ethylenically unsaturated dicarboxylic acids and their derivatives include ethylenically unsaturated dicarboxylic acids, their monoesters, their diesters, their anhydrides, and the like.
  • Ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.
  • Monoesters of ethylenically unsaturated dicarboxylic acids include monomethyl maleate, monoethyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl citraconate, monoethyl citraconate, monomethyl mesaconate, monoethyl mesaconate, monomethyl itaconate, itaconic acid.
  • Examples include monoalkyl unsaturated dicarboxylic acid esters such as monoethyl.
  • Diesters of ethylenically unsaturated dicarboxylic acids include dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl citraconate, diethyl citraconate, dimethyl mesaconate, diethyl mesaconate, dimethyl itaconate, diethyl itaconate.
  • dialkyl unsaturated dicarboxylic acid esters such as Examples of anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride and citraconic anhydride.
  • the monomer (a) is preferably an ethylenically unsaturated dicarboxylic acid, and its monoester, diester and anhydride, and maleic acid and monoalkyl maleate.
  • Esters, dialkyl maleates, maleic anhydride, fumaric acid, monoalkyl fumarate and dialkyl fumarate are more preferred, with monomethyl maleate, dimethyl maleate, maleic anhydride, monomethyl fumarate and dimethyl fumarate being particularly preferred.
  • 1 type(s) or 2 or more types can be used for a monomer (a).
  • the lower limit of the content (S) of the structural unit derived from the monomer (a) with respect to the total structural units of the PVA of the present invention is preferably 0.1 mol%, more preferably 0.5 mol%. 0 mol % is more preferred, and 1.5 mol % is particularly preferred.
  • the upper limit of the content (S) is preferably 15 mol%, more preferably 10 mol%, still more preferably 5 mol%, and even more preferably 3 mol% in some cases.
  • the above content (S) can be determined by 1 H-NMR analysis of the vinyl ester polymer before saponification of the PVA of the present invention.
  • the minimum degree of branching is 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less.
  • the degree of branching is an index representing the degree of branched structure of a polymer, and the degree of branching of a linear polymer, ie, a polymer having no branched structure, is set to 1, and the closer to 0, the more the branched structure.
  • the degree of branching is obtained for each absolute molecular weight in the range of 200,000 to 800,000. Then, the smallest degree of branching in the above range is set as the minimum degree of branching.
  • the absolute molecular weight of PVA when the absolute molecular weight of PVA is not distributed over the entire range of 200,000 or more and 800,000 or less, for example, when only PVA with an absolute molecular weight of 600,000 or less is included, the absolute molecular weight is 200,000 or more and 60,000.
  • the smallest degree of branching in the range of 10,000 or less is the minimum degree of branching. That is, the PVA of the present invention consisting of a plurality of molecules includes molecules having an absolute molecular weight within the range of 200,000 or more and 800,000 or less, and the absolute molecular weight is distributed over the entire range of 200,000 or more and 800,000 or less. It doesn't have to be.
  • the degree of branching gm at each absolute molecular weight of the PVA of the present invention is obtained from the following formulas (1) and (2).
  • g m ′ [ ⁇ ] branch /[ ⁇ ] linear (1)
  • gm gm ' (1/ ⁇ ) (2)
  • [ ⁇ ] branch is the intrinsic viscosity at the absolute molecular weight x (x is 200,000 or more and 800,000 or less) of the PVA (branched PVA) of the present invention having a branched structure. , values calculated from the light scattering detector and the viscosity detector.
  • [ ⁇ ] linear is the intrinsic viscosity of linear PVA at the above absolute molecular weight x, and is similarly a value calculated from a differential refractive index detector, a light scattering detector and a viscosity detector.
  • the linear PVA the viscosity of the 4% by mass aqueous solution is within ⁇ 20% of the PVA of the present invention to be measured, and the degree of saponification is within ⁇ 3 mol% of unmodified PVA (vinyl acetate homopolymer saponified product) is used.
  • the intrinsic viscosity at each absolute molecular weight of the PVA and linear PVA of the present invention can be measured by the method described in Examples.
  • the relationship between the intrinsic viscosity ratio g m ′ and the degree of branching g m represented by the above formula (1) is given by the above formula (2).
  • the minimum degree of branching is 0.93 or less, and a sufficient branched structure (crosslinking) is formed. Therefore, according to the PVA of the present invention, the difference in the first normal stress in the aqueous solution becomes small, and the scattering of the coating liquid and the coating unevenness during coating are reduced.
  • the upper limit of the minimum degree of branching is preferably 0.85, more preferably 0.6, and even more preferably 0.4, 0.25 or 0.18 in some cases.
  • the lower limit of the minimum degree of branching may be, for example, 0.01 or 0.05, preferably 0.15, and more preferably 0.20.
  • the branches in the PVA are formed by heat treatment, such as ester bonding between the carboxy group and the hydroxy group of the PVA. Therefore, the minimum degree of branching can be adjusted by heat treatment conditions such as heat treatment temperature and heat treatment time, content of structural units derived from the monomer (a), degree of saponification, and the like.
  • the PVA of the present invention includes PVA having an absolute molecular weight within the range of 200,000 or more and 800,000 or less.
  • the PVA of the present invention preferably contains PVA with an absolute molecular weight of 200,000 and PVA with an absolute molecular weight of 800,000, and the absolute molecular weight is distributed over the entire range of at least 200,000 to 800,000. is more preferable.
  • the upper limit of the viscosity-average degree of polymerization (P) of the PVA of the present invention may be, for example, 8,000, preferably 5,000, more preferably 4,000.
  • the lower limit of the viscosity-average degree of polymerization (P) may be, for example, 100 or 200, preferably 300, more preferably 400, and even more preferably 500 or 1,000.
  • the viscosity average degree of polymerization (P) is a value measured according to JIS K6726:1994. Specifically, it can be determined by the method described in the Examples.
  • the lower limit of the vinyl alcohol unit content relative to all structural units in the PVA of the present invention is preferably 35 mol%, more preferably 50 mol%, still more preferably 70 mol%, and even more preferably 80 mol% or 85 mol%. In some cases it is preferable.
  • the upper limit of the vinyl alcohol unit content is preferably 99.9 mol %, more preferably 99 mol %.
  • the lower limit of the saponification degree of the PVA of the present invention is preferably 65 mol%, more preferably 80 mol%, and even more preferably 85 mol%.
  • the upper limit of the degree of saponification may be 100 mol%, preferably 99 mol%, more preferably 95 mol%, and even more preferably 92 mol% in some cases.
  • the degree of saponification is a value measured by the method described in JIS K6726:1994.
  • the PVA of the present invention preferably satisfies the following formula (I). S ⁇ P>250 (I)
  • S is the content (mol%) of structural units derived from the monomer (a) with respect to all structural units.
  • P is the viscosity average degree of polymerization.
  • the extent of the effects of carboxylic acid modification (formation of a branched structure, etc.) and the extent of effects due to the degree of polymerization are balanced, and coatability and the like are further improved.
  • coating unevenness during coating tends to be more suppressed, and the strength of the resulting film tends to increase.
  • the lower limit of S ⁇ P is more preferably 300, and may be even more preferably 400, 500, 600 or 700.
  • the upper limit of S ⁇ P is preferably 4,000, more preferably 3,000, still more preferably 2,000, and even more preferably 1,500.
  • the PVA of the present invention preferably satisfies formula (ii), and more preferably satisfies formula (II).
  • formula (ii) 1.0 ⁇ g A /g B ⁇ 5.0
  • ii) 1.0 ⁇ g A /g B ⁇ 3.0
  • g A is the branching degree at an absolute molecular weight of 200,000 (the branching degree of PVA having an absolute molecular weight of 200,000 among the PVA of the present invention).
  • g B is the branching degree at an absolute molecular weight of 800,000 (the branching degree of PVA having an absolute molecular weight of 800,000 among the PVA of the present invention).
  • cross-linking proceeds by sufficient heat treatment, and PVA with a small minimum degree of branching is obtained.
  • PVA generally a component with a large molecular weight
  • the ratio g A /g B becomes large. From this point of view, the ratio g A /g B is more preferably less than 2.7.
  • the insoluble content is 0.1 ppm or more and less than 2000 ppm.
  • the insoluble content is preferably less than 1,750 ppm, more preferably less than 1,600 ppm. Since the insoluble matter is small in this way, coatability and the like can be improved.
  • the insoluble content may be 1 ppm or more, 10 ppm or more, or 100 ppm or more.
  • ppm is a mass standard, and the said insoluble content (ppm) shows the content rate of the insoluble content in PVA.
  • the insoluble matter can be obtained by the method described in the Examples.
  • the value of the ratio g A /g B and the content of the insoluble matter tend to increase as the proportion of PVA that is excessively heated and excessively crosslinked increases. Therefore, as will be described later, when heat-treating a saponified product of a vinyl ester polymer (copolymer), fine powder that is likely to be heated excessively is removed in advance, the heat treatment is performed while removing the fine powder, or the fine powder is removed after the heat treatment. can reduce the ratio g A /g B and the content of the insoluble matter.
  • the PVA of the present invention may contain structural units other than vinyl alcohol units, vinyl ester units, and structural units derived from the monomer (a).
  • monomers that give the other structural units include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene; N-methylacrylamide, N-ethylacrylamide, 2-acrylamido-2-methylpropane acrylamide derivatives such as sulfonic acid; methacrylamide derivatives such as N-methyl methacrylamide and N-ethyl methacrylamide; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether and n-butyl vinyl ether; ethylene glycol vinyl ether, hydroxy group-containing vinyl ethers such as 1,3-propanediol vinyl ether and 1,4-butanediol vinyl ether; allyl acetate; 3,4-
  • the upper limit of the content of the other structural units to the total structural units of the PVA of the present invention may be preferably 20 mol %, more preferably 10 mol %, 3 mol %, 1 mol % or 0.5 mol %. 1 mol % may be even more preferred.
  • the content of a structural unit derived from an ⁇ -olefin as another structural unit is high, foaming may easily occur when an aqueous solution is prepared. Therefore, by setting the content ratio of the other structural unit to the total structural units of the PVA to be equal to or less than the above upper limit, the coatability may be further improved.
  • the lower limit of the content of the other structural unit may be, for example, 0.1 mol % or 1 mol %.
  • the PVA of the present invention is relatively unaffected by pH, and is expected to exhibit good coatability even under acidic or alkaline conditions.
  • the powder of the present invention is powder containing the PVA of the present invention. Since the powder contains the PVA of the present invention, it has good coatability when dissolved in water and applied.
  • the PVA of the present invention is usually the main component.
  • a main component means a component with the largest content on a mass basis.
  • the lower limit of the content of the PVA of the present invention with respect to the non-volatile content of the powder of the present invention is preferably 50% by mass, more preferably 70% by mass, still more preferably 90% by mass, and even more preferably 99% by mass.
  • the upper limit of the content of the PVA of the present invention with respect to the non-volatile content of the powder of the present invention may be 100% by mass.
  • Non-volatile matter other than the PVA of the present invention that may be contained in the powder of the present invention includes PVA other than the PVA of the present invention, resins other than PVA, surfactants, additives such as plasticizers, and additives used during production Each compound etc. are mentioned.
  • the content of volatile matter in the powder of the present invention is usually 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less.
  • Volatile matter that can be contained in the powder of the present invention includes alcohol, water, and the like.
  • the powder of the invention may be the PVA powder of the invention.
  • the upper limit of the content of powder (fine powder) that passes through a 180 ⁇ m sieve is preferably 12% by mass, and may be more preferably 10% by mass, 8% by mass or 5% by mass.
  • the fine powder tends to be excessively heated by the heat treatment, and the cross-linking proceeds too much to become an insoluble matter. Therefore, by setting the content of the powder that passes through a sieve with a mesh size of 180 ⁇ m to the above upper limit or less, the insoluble matter is reduced, and the coatability and the like when used as an aqueous solution are improved.
  • the lower limit of the content of powder that passes through a sieve with an opening of 180 ⁇ m may be 0.1% by mass or 1% by mass.
  • the mesh size of the sieve conforms to the nominal mesh size W of JIS Z 8801-1-2006 (hereinafter the same).
  • the content of powder that passes through a sieve with an opening of 1.00 mm is 97% by mass or more, and the content of powder that passes through a sieve with an opening of 500 ⁇ m is 40% by mass or more. preferable.
  • the lower limit of the content of powder that passes through a sieve with an opening of 1.00 mm is more preferably 98% by mass, and even more preferably 99% by mass.
  • the upper limit of the content of powder that passes through a sieve with an opening of 1.00 mm may be 100% by mass or 99.9% by mass.
  • the upper limit of the content of powder that passes through a sieve with an opening of 500 ⁇ m may be 70% by mass or 60% by mass.
  • the particle size distribution of the powder of the present invention can be adjusted by sieving during the manufacturing process or after manufacturing.
  • the insoluble content is preferably 0.1 ppm or more and less than 2000 ppm.
  • the insoluble content is more preferably less than 1,750 ppm, even more preferably less than 1,600 ppm. Since the insoluble matter is small in this way, the coatability of the aqueous solution obtained from the powder of the present invention can be improved.
  • the insoluble content may be 1 ppm or more, 10 ppm or more, or 100 ppm or more.
  • the measurement of the insoluble content of the powder can be performed in the same manner as the measurement of the insoluble content of PVA.
  • the PVA and powders of the present invention can be used in a variety of applications similar to conventional PVA and powders thereof. Examples are given below, but are not limited thereto.
  • Vinyl chloride dispersant Applications dispersion stabilizers and dispersing aids for suspension polymerization of vinyl chloride and vinylidene chloride Metal corrosion inhibitor, brightener for zinc plating, antistatic agent
  • Adhesives, binders Uses Adhesives, adhesives, rewetting adhesives, various binders, additives for cement and mortar (4)
  • flocculant Applications flocculants for suspended solids and dissolved substances in water, metal flocculants (7)
  • Film applications water-soluble films, polarizing films, barrier films, films for packaging textiles, Seed curing sheet, vegetation sheet,
  • the PVA and powder of the present invention have good coatability when made into an aqueous solution. Therefore, it is particularly suitable for applications in which it is dissolved in water and applied.
  • Such uses include adhesives, films (film-forming solutions), and the like. That is, an aqueous solution containing the PVA of the present invention, an adhesive containing the PVA of the present invention, a film containing the PVA of the present invention, and the like are also preferred embodiments of the present invention.
  • the content of the PVA of the present invention in the aqueous solution, adhesive, film forming solution, etc. is, for example, 1% by mass or more and 30% by mass or less, may be 5% by mass or more and 20% by mass or less, or 10% by mass. or more.
  • the above aqueous solution, adhesive, film-forming solution, etc. may further contain components other than the PVA and water of the present invention. Examples of such other components include components contained in conventionally known adhesives, film-forming solutions, and the like.
  • the method for producing the PVA or powder of the present invention is not particularly limited, the following method is preferred. That is, the method for producing PVA or powder of the present invention is step (1) of obtaining a copolymer of the monomer (a) and a vinyl ester; Step (2) of obtaining a saponified product of the copolymer, and Step (3) of heat-treating the saponified product Prepare.
  • step (1) a copolymer of monomer (a) and vinyl ester is obtained.
  • monomer (a) examples and suitable examples of the monomer (a) are as described above.
  • vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and vinyl versatate. Among them, vinyl acetate is preferred.
  • Examples of polymerization methods include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these methods, a bulk polymerization method performed without a solvent and a solution polymerization method performed using a solvent such as alcohol are preferable, and a solution polymerization method performed in the presence of a lower alcohol is more preferable. As the lower alcohol, alcohols having 3 or less carbon atoms are preferable, methanol, ethanol, n-propanol and isopropanol are more preferable, and methanol is even more preferable. In performing a polymerization reaction by a bulk polymerization method or a solution polymerization method, either a batch system or a continuous system can be employed as the reaction system.
  • initiators used in the polymerization reaction examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy -2,4-dimethylvaleronitrile); and known initiators such as organic peroxide initiators such as benzoyl peroxide and n-propylperoxycarbonate.
  • organic peroxide initiators such as benzoyl peroxide and n-propylperoxycarbonate.
  • a copolymerizable monomer can be further copolymerized within a range that does not impair the gist of the present invention.
  • Specific examples of such other monomers are as described above as monomers that provide other structural units.
  • a chain transfer agent may coexist during copolymerization for the purpose of adjusting the degree of polymerization of the obtained PVA.
  • chain transfer agents include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone and cyclohexanone; mercaptans such as 2-hydroxyethanethiol and 3-mercaptopropionic acid; thiocarboxylic acids such as thioacetic acid.
  • the amount of the chain transfer agent to be added is determined according to the chain transfer constant of the chain transfer agent to be added and the desired degree of polymerization of PVA, but is generally 0.1 to 10% by mass based on the vinyl ester used. is preferred.
  • step (2) the copolymer (vinyl ester polymer) obtained in step (1) above is saponified in a solution using an alkali catalyst or an acid catalyst to obtain a saponified product.
  • an alcoholysis or hydrolysis reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as p-toluenesulfonic acid can be applied.
  • Solvents used in the saponification reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; and aromatic hydrocarbons such as benzene and toluene. These can be used alone or in combination of two or more. Among these, it is convenient and preferable to use methanol or a mixed solution of methanol and methyl acetate as a solvent and perform the saponification reaction in the presence of sodium hydroxide as a basic catalyst.
  • the saponification reaction can be carried out using a belt-type reactor, a kneader-type reactor, a tower-type reactor, or the like.
  • the temperature for saponification is not particularly limited, it is preferably 20° C. or higher and 60° C. or lower.
  • a gel-like product precipitates as the saponification progresses, it is preferable to pulverize the product and further proceed with the saponification. Thereafter, the resulting solution is neutralized to complete saponification and washed to obtain a saponified product.
  • the saponification method is not limited to the methods described above, and known methods can be employed.
  • step (3) the saponified product obtained through step (2) is heat-treated.
  • the heat treatment is preferably performed under an air atmosphere or a nitrogen atmosphere.
  • the heat treatment is preferably performed on a solid, more preferably powdery (particulate) saponified product.
  • the saponified product may be pre-dried, and the saponified product from which volatile matter has been removed to some extent may be subjected to heat treatment.
  • the heat treatment may be performed while stirring the saponified product.
  • the heat treatment can be performed using, for example, a cylindrical agitation dryer or the like.
  • the content of powder that passes through a 180 ⁇ m sieve in the saponified product at the end of step (3) is 12% by mass or less.
  • the upper limit of the content of powder that passes through this 180 ⁇ m sieve may preferably be 10% by mass, 8% by mass or 5% by mass.
  • the heat treatment may be divided into a plurality of times, and fines may be removed by sieving between each heat treatment. Further, fine powder may be removed after the heat treatment.
  • heat treatment is preferably performed at a heat treatment temperature of 110°C or higher and a heat treatment time of 1 hour or longer.
  • a sufficient cross-linking reaction occurs, and PVA with a minimum degree of branching of 0.93 or less can be efficiently obtained.
  • the lower limit of the heat treatment temperature may be 115°C or 120°C.
  • the upper limit of the heat treatment temperature may be 150°C, 140°C, 130°C, or 125°C.
  • the lower limit of the heat treatment time is preferably 2 hours, more preferably 3 hours, even more preferably 4 hours, and even more preferably 5 hours.
  • the upper limit of the heat treatment time may be 24 hours, 12 hours, or 8 hours.
  • step (2) a step of pulverizing the saponified product into particles, a step of sieving the particulate saponified product, and the like may be provided.
  • the coating agent of the invention contains the PVA of the invention.
  • the coating agent has good coatability, especially when the coating is performed at high speed.
  • the coating agent can exhibit good coatability even when it is applied at a coating speed of more than 800 m/min or 1,000 m/min or more using a curtain coater, for example.
  • the coating agent usually contains water as a solvent or dispersion medium.
  • the coating agent may contain organic solvents instead of or together with water as solvent or dispersion medium.
  • the upper limit of the content of the organic solvent is preferably 50 parts by mass, more preferably 30 parts by mass, and more preferably 10 parts by mass, 5 parts by mass, or 1 part by mass with respect to 100 parts by mass of water.
  • the lower limit of the content is preferably 0 parts by mass and more preferably 10 parts by mass with respect to 100 parts by mass of water.
  • the coating agent may be free of organic solvents.
  • organic solvents examples include alcohol solvents such as methanol and ethanol; ester solvents such as methyl acetate and ethyl acetate; ether solvents such as diethyl ether and 1,4 dioxane; ketone solvents such as acetone and diethyl ketone; Glycol solvents such as glycol and propylene glycol; glycol ether solvents such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether; glycol ester solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate;
  • the coating agent may further contain other ingredients.
  • other components include fillers, dispersants, water-soluble polymers, synthetic resin emulsions, plasticizers, pH adjusters, antifoaming agents, release agents, surfactants, and the like.
  • fillers include kaolin, clay, calcined clay, calcium carbonate, titanium oxide, diatomaceous earth, aluminum oxide, aluminum hydroxide, synthetic aluminum silicate, synthetic magnesium silicate, polystyrene fine particles, polyvinyl acetate fine particles, urea-formalin. Resin fine particles, precipitated silica, gel silica, silica synthesized by vapor phase method (hereinafter referred to as vapor phase silica), colloidal silica, colloidal alumina, pseudo-boehmite, talc, zeolite, alumina, zinc oxide, satin white , organic pigments, and the like.
  • vapor phase silica colloidal silica, colloidal alumina, pseudo-boehmite, talc, zeolite, alumina, zinc oxide, satin white , organic pigments, and the like.
  • Dispersants include, for example, sodium pyrophosphate, sodium hexametaphosphate, and sodium polyacrylate.
  • water-soluble polymers examples include PVA other than the PVA described above, vinyl alcohol-vinyl ester copolymer, polyacrylamide, polyacrylic acid, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl propyl cellulose, casein, oxidized starch, and the like. Starch etc. are mentioned.
  • Synthetic resin emulsions include emulsions such as styrene-butadiene copolymer, polyacrylate, polymethacrylate, vinyl acetate-ethylene copolymer, and vinyl acetate-acrylate copolymer.
  • the coating agent may contain these synthetic resins in the form of an emulsion.
  • plasticizers examples include glycols and glycerin.
  • pH adjusters examples include ammonia, caustic soda, sodium carbonate, phosphoric acid and the like.
  • the solid content concentration in the coating agent is not particularly limited, and can be appropriately adjusted according to the application, etc., but considering the coatability, etc., it is preferably 1% by mass or more and 65% by mass or less.
  • the upper limit of the solid content concentration may be 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, or 15% by mass.
  • the lower limit of the solid content concentration may be 3% by mass, 5% by mass, 10% by mass, 20% by mass, or 30% by mass.
  • the content of PVA in the solid content of the coating agent may be, for example, 0.1% by mass or more and 100% by mass or less.
  • the upper limit of the content may be 80% by mass, 50% by mass, 30% by mass or 10% by mass.
  • the lower limit of the content may be 1% by mass, 10% by mass, 30% by mass or 50% by mass.
  • the coated article of the present invention is obtained by applying the coating agent of the present invention onto a substrate.
  • the coated article usually has a base material and a PVA-containing layer laminated on the base material. Part or all of the PVA may impregnate the substrate.
  • the coated article has little coating unevenness.
  • the coated material can be suitably used for, for example, heat-sensitive recording materials, base paper for release paper, oil-resistant paper, inkjet recording materials, gas barrier paper, flavor barrier paper, white paperboard, and the like.
  • the coating agent may be applied only on one surface of the substrate, or both surfaces may be coated with the coating agent.
  • the base material of the coated material can be appropriately selected according to the application, and examples thereof include paper, cloth, wood board, and resin board.
  • the coated material may be coated paper whose substrate is paper.
  • Examples of the paper include board paper such as manila board, white board and liner; printing paper such as general high quality paper, medium quality paper and gravure paper.
  • Examples of cloth include nonwoven fabrics, woven fabrics, and knitted fabrics.
  • Examples of the wood board include a single board, plywood, laminated wood, and the like.
  • resin plates include vinyl chloride plates and acrylic plates.
  • the coating amount of the coating agent onto the substrate is not particularly limited, but is usually about 0.1 g/m 2 or more and 100 g/m 2 or less in terms of solid content per side of the substrate, and 1 g/m 2 It may be more than or equal to 40 g/m 2 or less.
  • a heat-sensitive recording material is a coated product obtained by applying the coating agent of the present invention onto a substrate.
  • the base material of the heat-sensitive recording material include the papers exemplified as the base material of the coated material, and among these, printing paper is preferable.
  • the basis weight of the base material of the heat-sensitive recording material is not particularly limited, but in consideration of handleability, etc., it is preferably 10 g/m 2 or more and 100 g/m 2 or less, and 35 g/m 2 or more and 80 g/m 2 or less. more preferred. In addition, basis weight means the mass per unit area.
  • the coating agent applied to the heat-sensitive recording material preferably contains a filler.
  • the solid content concentration of the coating agent applied to the heat-sensitive recording material can be appropriately adjusted, for example, within the range of 10% by mass or more and 65% by mass or less.
  • the base paper for release paper is a coated product obtained by applying the coating material of the present invention onto the base material of paper.
  • the coating agent forms a filling layer.
  • a release paper can be produced by forming a release layer with a silicone release agent on this filling layer. Since the base paper for release paper uses the coating agent, a highly uniform filler layer is formed.
  • Examples of the base paper for the base paper for release paper include the papers exemplified as the base paper for the coated product, and wood-free paper, medium-quality paper, alkaline paper, glassine paper, and semi-glassine paper are preferable, and semi-glassine paper is more preferable.
  • the adhesive constituting the adhesive layer a known adhesive can be used.
  • the basis weight of the base material of the base paper for the release paper is not particularly limited, it is preferably 10 g/m 2 or more and 120 g/m 2 or less, and more preferably 40 g/m 2 or more and 100 g, in consideration of the filling properties and handling properties of the release paper base paper. /m 2 or less is more preferable.
  • the solid content concentration of the coating agent applied to the base paper for release paper is preferably 1% by mass or more and 15% by mass or less, more preferably 2% by mass or more and 10% by mass or less.
  • Greaseproof paper is a coated product obtained by applying the coating material of the present invention onto the base material of paper.
  • the greaseproof paper can be suitably used as a packaging material for foods and the like.
  • Examples of the base material for the greaseproof paper include the papers exemplified as the base material for the coated product, and include fine paper, medium quality paper, unbleached kraft paper, bleached kraft paper, alkaline paper, glassine paper, semi-glassine paper, and cardboard.
  • Base paper for printing, base paper for white board, base paper for chipboard, etc. can be suitably used.
  • the basis weight of the base material of the greaseproof paper is not particularly limited, but considering the oil resistance etc., when using the greaseproof paper as wrapping paper, it is preferably 20 g/m 2 or more and 150 g/m 2 or less. When used, it is preferably 150 g/m 2 or more and 500 g/m 2 or less.
  • the inkjet recording material is a coated product obtained by applying the coating agent of the present invention onto a substrate.
  • the coating agent it is preferable to use the coating agent as a filler binder for the ink-receiving layer.
  • the coating agent preferably contains a filler.
  • the content of the filler is preferably 50 parts by mass or more and 300 parts by mass or less, more preferably 80 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass of PVA.
  • substrates for inkjet recording materials include papers exemplified as substrates for coated materials.
  • a gas barrier paper or a flavor barrier paper is a coated product having a paper as a base material and coating the coating material of the present invention on the base material. That is, the coating agent can also be used as a barrier agent.
  • the coating agent preferably contains a filler.
  • the content of the filler is preferably 3% by mass or more and 95% by mass or less, more preferably 5% by mass or more and 90% by mass or less, and even more preferably 10% by mass or more and 85% by mass or less, relative to the total solid content.
  • the coating agent preferably further contains a binder component other than PVA, such as a synthetic resin emulsion. PVA also functions as a binder component.
  • Base materials for the gas barrier paper or flavor barrier paper include the papers exemplified as the base material for the coated article.
  • the lower limit of the air resistance of the coated material which is gas barrier paper or flavor barrier paper, is preferably 500 seconds, more preferably 1,000 seconds. If the air resistance is high, it is suitable as gas barrier paper or flavor barrier paper because it has high gas and flavor barrier properties.
  • the upper limit of the air resistance may be, for example, 20,000 seconds, 10,000 seconds, 5,000 seconds, or 3,000 seconds. This air resistance is a value measured by the Oken test method described in JIS P 8117:2009.
  • This gas barrier paper or flavor barrier paper is preferably used after applying a coating formulation containing a barrier material and the like to adjust the air resistance to 100,000 seconds or more.
  • White paperboard is a coated product obtained by applying the coating material of the present invention onto the base material of the base material.
  • the coating agent contains a white filler (white pigment).
  • the content of the white filler (white pigment) is preferably 30% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, relative to the total solid content.
  • a known method can be employed as the method for producing the coated article of the present invention.
  • the method of applying the coating agent onto the substrate is not particularly limited, and known coaters such as curtain coaters, size press coaters, air knife coaters, blade coaters and roll coaters may be used.
  • the method using a curtain coater is preferable. That is, the method for producing a coated product of the present invention comprises a step of applying the coating agent onto a substrate using a curtain coater.
  • the coating speed in the production method may be, for example, 500 m/min or more and 2,000 m/min or less, 800 m/min or more and 1,600 m/min or less, or 900 m/min or more and 1,500 m/min. /min or less, or 1,000 m/min or more and 1,300 m/min or less.
  • the manufacturing method may include a step of drying after applying the coating agent. It may also include additional steps, such as a calendering step when the substrate is paper.
  • the emulsion polymerization stabilizer of the present invention contains the PVA of the present invention.
  • the stabilizer for emulsion polymerization may contain other components such as a surfactant as long as the effects of the present invention are not impaired.
  • surfactants include anionic surfactants such as alkylnaphthalene sulfonates and dialkylsulfosuccinic acids; cationic surfactants such as alkylamine salts and lauryltrimethylammonium chloride; polyoxyethylene alkyl ethers and polyoxyethylene alkyl Nonionic surfactants such as phenyl ether and sorbitan fatty acid ester; amphoteric surfactants such as alkylbetaine and amine oxide; vinyl alcohol polymers other than PVA of the present invention, and polymeric surfactants such as hydroxyethyl cellulose. be done.
  • anionic surfactants such as alkylnaphthalene sulfonates and dialkylsulfosuccinic acids
  • cationic surfactants such as alkylamine salts and lauryltrimethylammonium chloride
  • Nonionic surfactants such as phenyl ether
  • Components other than surfactants include buffers and polymerization degree modifiers.
  • buffering agents include acids such as acetic acid, hydrochloric acid, and sulfuric acid; bases such as ammonia, amine-charged soda, potassium hydroxide, and calcium hydroxide; and alkali carbonates, phosphates, acetates, and the like.
  • Mercaptans, alcohols and the like can be used as polymerization degree modifiers.
  • the lower limit of the content of the PVA of the present invention in the stabilizer for emulsion polymerization may be 10% by mass, 50% by mass, 70% by mass, 80% by mass, 90% by mass, 95% by mass, and 99% by mass. % or 99.5% by mass.
  • the upper limit of this content may be 100% by mass or 99.99% by mass.
  • the aqueous emulsion of the present invention contains the emulsion polymerization stabilizer and a polymer containing ethylenically unsaturated monomer units.
  • a polymer containing ethylenically unsaturated monomer units is usually contained as a dispersoid.
  • the aqueous emulsion usually contains water as a dispersion medium.
  • vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate
  • (meth)acrylic acid monomers such as acrylic acid and methacrylic acid
  • the polymer is a polymer containing monomer units derived from at least one selected from the group consisting of vinyl ester monomers, (meth)acrylate monomers, styrene monomers and diene monomers. is preferably Further, the total content of vinyl ester monomers, (meth)acrylic acid ester monomers, styrene monomers and diene monomers with respect to the total monomer units of the polymer is 70% by mass or more. It is preferably 75% by mass or more, and more preferably 75% by mass or more. Above all, it is particularly preferable that the polymer contains vinyl ester monomer units in an amount of 75% by mass or more based on the total monomer units.
  • a method for producing the aqueous emulsion of the present invention a method of emulsion polymerization of an ethylenically unsaturated monomer using a polymerization initiator in the presence of the stabilizer for emulsion polymerization is preferred.
  • the charging method or addition method when charging the stabilizer for emulsion polymerization into the polymerization vessel, there is no particular limitation on the charging method or addition method.
  • Examples include a method of adding the stabilizer for emulsion polymerization to the polymerization tank at once in the initial stage, a method of continuously adding the stabilizer during the polymerization, and the like.
  • a method of adding the emulsion polymerization stabilizer to the polymerization tank all at once at the initial stage is preferred.
  • the emulsion polymerization stabilizer it is preferable to add the emulsion polymerization stabilizer to cold water or preheated warm water, and then heat the mixture to 80° C. or more and 90° C. or less and stir the mixture in order to uniformly disperse the emulsion polymerization stabilizer.
  • the amount of the emulsion polymerization stabilizer added during emulsion polymerization is preferably 0.2 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the ethylenically unsaturated monomer.
  • the amount of the emulsion polymerization stabilizer added is more preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, and most preferably 4 parts by mass or more.
  • the amount of the stabilizer for emulsion polymerization is 80 parts by mass or less, the viscosity of the polymerization liquid does not become too high, and the polymerization proceeds uniformly, and the heat of polymerization is efficiently removed. There is a tendency.
  • the amount of emulsion polymerization stabilizer added is more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less.
  • a water-soluble single initiator or a water-soluble redox initiator that is commonly used for emulsion polymerization can be used. These initiators may be used individually by 1 type, and may use 2 or more types together. Among them, redox initiators are preferred.
  • Water-soluble single initiators include azo initiators, hydrogen peroxide, and peroxides such as persulfates (potassium, sodium, or ammonium salts).
  • azo initiators include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2 , 4-dimethylvaleronitrile) and the like.
  • a combination of an oxidizing agent and a reducing agent can be used as the redox initiator.
  • a peroxide is preferred as the oxidizing agent.
  • the reducing agent includes metal ions, reducing compounds, and the like. Combinations of oxidizing agents and reducing agents include combinations of peroxides and metal ions, combinations of peroxides and reducing compounds, and combinations of peroxides with metal ions and reducing compounds. be done.
  • peroxides examples include hydrogen peroxide, hydroxyperoxides such as cumene hydroxyperoxide and t-butyl hydroxyperoxide, persulfates (potassium, sodium or ammonium salts), t-butyl peracetate, peresters (peroxide t-butyl benzoate) and the like.
  • Metal ions include metal ions capable of undergoing electron transfer, such as Fe 2+ , Cr 2+ , V 2+ , Co 2+ , Ti 3+ , Cu + , and the like.
  • Reducing compounds include sodium bisulfite, sodium bicarbonate, tartaric acid, fructose, dextrose, sorbose, inositol, Rongalite, ascorbic acid.
  • one or more oxidizing agents selected from the group consisting of hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate, and selected from the group consisting of sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, Rongalit and ascorbic acid
  • a combination with one or more reducing agents is preferred, and a combination of hydrogen peroxide and one or more reducing agents selected from the group consisting of sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, Rongalit and ascorbic acid is more preferred.
  • alkali metal compounds, surfactants, buffers, polymerization degree modifiers, etc. may be used as appropriate within a range that does not impair the effects of the present invention.
  • Alkali metal compounds are not particularly limited, but include compounds containing sodium, potassium, rubidium, cesium, and the like.
  • the alkali metal compound may be an alkali metal ion itself or a compound containing an alkali metal.
  • Buffers include acids such as acetic acid, hydrochloric acid, and sulfuric acid; bases such as ammonia, amine-charged soda, potassium hydroxide, and calcium hydroxide; or alkali carbonates, phosphates, acetates, and the like. Mercaptans, alcohols and the like can be used as polymerization degree modifiers.
  • the emulsion polymerization temperature is not particularly limited, but is preferably about 20°C or higher and 85°C or lower, more preferably about 40°C or higher and 85°C or lower.
  • the aqueous emulsion of the present invention may contain conventionally known additives such as fillers such as titanium oxide, organic solvents such as toluene, plasticizers such as dibutyl phthalate, and film-forming aids such as glycol ethers. .
  • a so-called powder emulsion which is obtained by pulverizing an aqueous emulsion by spray drying or the like, can also be used.
  • An aqueous emulsion can be obtained by mixing the powder emulsion with water.
  • Such aqueous emulsions are suitably used in a wide range of applications such as various adhesives, paints, fiber processing agents, paper processing agents, inorganic binders, cement admixtures, and mortar primers.
  • the adhesive of the invention contains the aqueous emulsion of the invention.
  • the adhesive has the effect of reducing coating streaks and liquid splashing during roll coating.
  • the adhesive may be a water-based adhesive.
  • the adhesive of the present invention can also be made into an adhesive that is less prone to foaming and is less susceptible to pH by using, for example, PVA with a low content of the other structural units described above.
  • the lower limit of the PVA content in the adhesive of the present invention is preferably 0.1% by mass.
  • the lower limit of the PVA content is more preferably 1% by mass, still more preferably 3% by mass, particularly preferably 5% by mass, and most preferably 6% by mass.
  • the upper limit of the PVA content is preferably 50% by mass. When the content of PVA is 50% by mass or less, the viscosity of the adhesive becomes moderate, making it easy to handle.
  • the upper limit of the PVA content is more preferably 35% by mass, still more preferably 25% by mass, particularly preferably 18% by mass, and most preferably 13% by mass.
  • the mass ratio (A)/(B) of PVA (A) to polymer (B) containing ethylenically unsaturated monomer units is 2/98 to 80/20. is preferred.
  • the mass ratio (A)/(B) is 2/98 or more, the adhesive strength is improved.
  • the lower limit of the mass ratio (A)/(B) is more preferably 5/95, more preferably 8/92.
  • the mass ratio (A)/(B) is 80/20 or less, the water-resistant adhesion is good.
  • the upper limit of the mass ratio (A)/(B) is more preferably 70/30, still more preferably 60/40, and even more preferably 50/50.
  • the lower limit of the solid content in the adhesive of the present invention is preferably 10% by mass, more preferably 20% by mass, even more preferably 25% by mass, and even more preferably 30% by mass.
  • the upper limit of the solid content is preferably 60% by mass, more preferably 55% by mass, and even more preferably 50% by mass.
  • the solid content is 10% by mass or more, the viscosity stability of the adhesive tends to be excellent.
  • the solid content is 60% by mass or less, the open time tends to be long and the handleability tends to be excellent.
  • the adhesive may contain various additives within a range that does not impair the effects of the present invention.
  • additives include calcium carbonate, clay, kaolin, talc, inorganic particles such as titanium oxide, organic solvents (aromatic compounds such as toluene and xylene, alcohols, ketones, esters, halogen-containing solvents, etc.), cross-linking agent, plasticizer, suspending agent, thickener, fluidity improver, preservative, antifoaming agent, organic filler, wetting agent, coloring agent, binder, water retention agent, polyethylene oxide, antifungal agent, deodorant agents, fragrances, and the like.
  • organic solvents aromatic compounds such as toluene and xylene, alcohols, ketones, esters, halogen-containing solvents, etc.
  • cross-linking agent plasticizer, suspending agent, thickener, fluidity improver, preservative, antifoaming agent, organic filler, wetting agent, coloring agent, binder, water retention agent
  • Additives include metal salts of phosphoric acid compounds such as sodium polyphosphate and sodium hexametaphosphate; dispersants for inorganic substances such as water glass; polyacrylic acid and its salts; sodium alginate; Anionic polymer compounds such as polymers and metal salts thereof; surfactants such as ethylene oxide adducts of higher alcohols and nonionic surfactants such as copolymers of ethylene oxide and propylene oxide. Addition of these improves the fluidity of the adhesive.
  • one or more cross-linking agents selected from water-soluble metal compounds, colloidal inorganic substances, polyamidoamine epichlorohydrin adducts and glyoxal resins may be incorporated.
  • water-soluble metal compounds include aluminum chloride, aluminum nitrate, ammonium zirconium carbonate, and titanium lactate.
  • colloidal inorganic substances include colloidal silica and alumina sol.
  • Polyamidoamine-epichlorohydrin adducts include, for example, those obtained by adding epichlorohydrin to various polyamidoamines.
  • glyoxal-based resins include urea-glyoxal-based resins.
  • methylol group-containing compounds (resins), epoxy compounds (resins), aziridine group-containing compounds (resins), oxazoline group-containing compounds (resins), carbodiimide compounds, aldehyde compounds (resins), etc. It can also be used in combination with a cross-linking agent.
  • boric acid In order to improve adhesive strength, boric acid; borax; water-soluble boron compounds such as borate esters of polyhydric alcohols such as glycerin and ethylene glycol; sodium naphthalenesulfonate formalin condensate;
  • other additives such as starch, casein, gelatin, guar gum, gum arabic, sodium alginate and other natural sizing agents; carboxymethyl cellulose, oxidized starch, methyl cellulose and other processed natural sizing agents can also be added. These may be used individually by 1 type, and may use 2 or more types together.
  • the modification rate of PVA (the content of structural units derived from the monomer (a) in PVA) was obtained by a method using 1 H-NMR using a vinyl ester polymer that is a precursor of PVA.
  • the modification rate is obtained by the following procedure. That is, the vinyl ester polymer, which is the precursor of PVA, was sufficiently purified by reprecipitation three times or more using n-hexane/acetone as a solvent, and then the resulting purified product was dried at 70°C for one day. to prepare a sample for analysis. This sample is dissolved in CDCl 3 and measured at room temperature using 1 H-NMR.
  • the modification rate (content S of structural units derived from monomer (a)) can be calculated using the following formula.
  • S (mol%) ⁇ (number of protons in ⁇ /3)/(number of protons in ⁇ + (number of protons in ⁇ /3)) ⁇ ⁇ 100
  • hexafluoroisopropanol is used as a mobile phase, and gel permeation chromatography (GPC) is measured using a differential refractive index detector, a light scattering detector, and a viscosity detector.
  • the intrinsic viscosity for each absolute molecular weight of 200,000 or more and 800,000 or less of the linear PVA was obtained.
  • the straight-chain PVA used was unmodified PVA having a 4% by mass aqueous solution viscosity within ⁇ 20% of the PVA to be measured and a degree of saponification within ⁇ 3 mol%. Specific measurement conditions for GPC are shown below.
  • Solvent Hexafluoroisopropanol (containing sodium trifluoroacetate at a concentration of 20 mmol/L)
  • Flow rate 1.0 mL/min
  • Sample concentration 0.1 mass/vol%
  • Injection volume 100 ⁇ L
  • Intrinsic viscosity [ ⁇ ] of PVA to be measured for each measured absolute molecular weight The degree of branching gm for each absolute molecular weight was determined by the formulas (1) and (2).
  • FIG. 1 is a graph (Mark-Houwink plot) plotting the absolute molecular weight and intrinsic viscosity ([ ⁇ ] branch or [ ⁇ ] linear ) of PVA-3 to be measured and PVA-17, which is the corresponding linear PVA. be.
  • FIG. 2 is a graph plotting the degree of branching (g m ) for each absolute molecular weight of PVA-3 determined by the above formulas (1) and (2) based on the results shown in FIG. 1 above.
  • the particle size distribution of the PVA powder was measured by the dry sieving method described in JIS Z8815:1994. Using sieves with openings of 1.00 mm, 500 ⁇ m, and 180 ⁇ m, the ratio of the mass of the powder passing through the sieve with an opening of 1.00 mm to the mass of the PVA powder before sieving (content: mass%), The mass ratio (content: mass %) of powder that passed through a sieve with an opening of 500 ⁇ m and the mass ratio (content: mass %) of powder that passed through a sieve with an opening of 180 ⁇ m were determined. Incidentally, the above-mentioned opening complies with the nominal opening W of JIS Z8801-1-2006.
  • the filter was thoroughly washed with hot water at 30°C to remove the solution adhering to the filter, leaving only undissolved particles on the filter, and then the filter was dried in a heat dryer at 120°C for 1 hour.
  • the mass of the undissolved particles was calculated by comparing the mass of the filter after drying with the mass of the filter before being used for filtration.
  • the mass of the insoluble particles with respect to the PVA powder (12 g) used was defined as the insoluble content (ppm).
  • a PVA aqueous solution was prepared and the first normal stress difference of the PVA aqueous solution when shear was applied was measured.
  • the method for preparing the PVA aqueous solution is as follows. 90 parts by mass of water was added to 10 parts by mass of PVA, and the mixture was heated to 90°C with stirring and cooled after 1 hour. Flow curve measurements were performed using a rheometer to measure the first normal stress difference. In addition, the same non-denatured PVA used in the GPC measurement was selected as a standard non-denatured PVA. The first normal stress difference was similarly obtained for unmodified PVA. Specific measurement conditions for the first normal stress difference measurement are shown below.
  • Measuring device MCR rheometer 102 (manufactured by Antonpar) Jig: Parallel plate (diameter 25mm) Gap between plates: 0.05mm Shear rate range: 10 -2 to 10 5 s -1 Measurement temperature: 20°C
  • the ratio of the first normal stress difference of the reference unmodified PVA aqueous solution at a shear rate of 10 5 s ⁇ 1 to the first normal stress difference of the PVA aqueous solution to be measured (the reference unmodified PVA The normal stress difference/PVA of Example or Comparative Example) was calculated and evaluated according to the following criteria.
  • a PVA aqueous solution with a concentration of 5% by mass was prepared in the same procedure as above, and this was used as a coating liquid.
  • the coating liquid was applied to paper having a basis weight of 70 g/m 2 at a speed of 300 m/min.
  • the coated paper was dried in a hot air dryer at 100°C for 5 minutes.
  • the resulting coated paper was conditioned at 20° C. and 65% RH for 72 hours.
  • the coated paper after humidity conditioning was cut into a size of 1 cm long and 2 cm wide, and one drop of iodine aqueous solution of 1/200 normality was dropped, and the surface of the coated paper was observed.
  • the portion of the coated paper surface on which the coating liquid is applied is dyed bluish purple, and the portion on which the coating liquid is not applied is dyed reddish purple. Based on this difference, coating unevenness was evaluated according to the following criteria.
  • Air resistance of coated paper The air resistance of the coated paper produced at a speed of 1000 m/min in the evaluation of coating defects was measured by an Oken tester described in JIS P 8117:2009.
  • BH viscometer (BII viscometer” manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity at 30° C. and 2 rpm and the viscosity at 30° C. and 20 rpm.
  • liquid film streaks that occur on the roll 1 are reflected in the coating streaks on the coated product.
  • Example 1 (Production of PVA-1) 700 parts by mass of vinyl acetate and 1,050 parts by mass of methanol were charged into a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a comonomer dropping port, and a polymerization initiator addition port, and the system was stirred for 30 minutes while nitrogen bubbling was performed. was replaced with nitrogen. Monomethyl maleate was used as the monomer (a), and a methanol solution of monomethyl maleate (concentration 10%) was replaced with nitrogen by bubbling nitrogen gas.
  • Examples 2 to 10 and Comparative Examples 2 and 4 (Production of PVA-2 to PVA-10, PVA-12, and PVA-14) Polymerization conditions such as the amount of vinyl acetate and methanol used, the type and amount of monomer (a) used; saponification conditions such as the concentration of the vinyl ester polymer in saponification and the molar ratio of sodium hydroxide to vinyl acetate units; Each PVA of Examples 2 to 10 and Comparative Examples 2 and 4 (PVA-2 to PVA-10, Powders of PVA-12 and PVA-14) were obtained. The physical properties and evaluation results of these PVA are shown in Tables 2-4.
  • the solid content concentration at the time of stopping the polymerization was 9.0%, and the polymerization rate was 25%. Subsequently, unreacted monomers were removed at 30° C. under reduced pressure while occasionally adding methanol to obtain a methanol solution of a vinyl ester polymer (concentration: 25.3%). Next, 724.07 parts by mass of a methanol solution of a vinyl ester polymer prepared by further adding methanol to this methanol solution (150 parts by mass of the polymer in the solution) was added with a 10% methanol solution of sodium hydroxide. 97 parts by mass and water were added so that the water content in the system was 1%, and saponification was performed at 40 ° C.
  • each PVA of Examples 1 to 10 having a minimum branching degree of 0.93 or less and an insoluble content of less than 2000 ppm has suppressed splattering and coating unevenness, and the coating It can be seen that the properties are good.
  • the minimum degree of branching when the minimum degree of branching is 0.93 or less, it is evaluated as A to C, and when the minimum degree of branching is 0.50 or less, it is evaluated as A. It can be seen that when the minimum degree of branching is small, the first normal stress difference is sufficiently small compared to the standard unmodified PVA.
  • coating unevenness PVA-2, 3, 8-10 having a degree of polymerization of 500 or more, a minimum degree of branching of 0.85 or less, an insoluble content of less than 1,750 ppm, and a degree of saponification of 85 mol% or more , A, and it can be seen that coating unevenness is particularly reduced.
  • PVA-11 of Comparative Example 1 contained a large amount of fine powder, resulting in an increase in insoluble matter, causing scattering and uneven coating.
  • PVA-12 to 14 of Comparative Examples 2 to 4 do not have a sufficiently formed branched structure, or do not contain structural units derived from the monomer (a), and do not form branches even after heat treatment. And coating unevenness could not be suppressed.
  • Example 11 (Preparation of coating agent) 200 parts by mass of water was added to 350 parts by mass of calcium carbonate slurry ("Carbital 97" manufactured by Imerys Co., Ltd.: solid content 75% by mass). To this slurry, 100 parts by mass of a styrene-butadiene copolymer latex ("Styronal BN4606" manufactured by BASF, solid content: 50% by mass) was further added and stirred for 20 minutes to prepare a mixed slurry. Further, 90 parts by mass of water was added to 10 parts by mass of PVA-1, and the mixture was heated to 90° C. with stirring and cooled after 1 hour to prepare an aqueous PVA solution.
  • calcium carbonate slurry (“Carbital 97" manufactured by Imerys Co., Ltd.: solid content 75% by mass).
  • 100 parts by mass of a styrene-butadiene copolymer latex (“Styronal BN4606” manufactured by BASF, solid content: 50%
  • Example 11 having a viscosity of about 1000 cps at 20 ° C. and 60 rpm was applied. made.
  • the coating defect of the coating agent was evaluated and the air resistance of the obtained coated paper was measured. Table 5 shows the results.
  • Example 12 to 20 and Comparative Examples 5 to 8 (Preparation of coating agent) Coating agents of Examples 12 to 20 and Comparative Examples 5 to 8 were prepared using each PVA listed in Table 5 in place of PVA-1. Each coating agent obtained was evaluated for coating defects and the air resistance of the obtained coated paper was measured. Table 5 shows the results. In preparing the coating agent, the concentration of the PVA aqueous solution and the mixing ratio of the mixed slurry and the PVA aqueous solution are appropriately adjusted so that each PVA has a viscosity of about 1000 cps at 20° C. and 60 rpm. made.
  • each of the coating agents of Examples 11 to 20 had good coatability without any coating defects even at a coating speed of 1,000 m/min.
  • the coated papers (coated articles) obtained using the coating agents of Examples 11 to 20 had an air resistance exceeding 1,000 seconds and had high gas barrier properties.
  • Example 21 (Production of aqueous emulsion Em-1) 232 g of ion-exchanged water was introduced into a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet, and heated to 95°C. 27.2 g of PVA-1 was added and dissolved by stirring for 45 minutes. Additionally, 0.27 g of sodium acetate was added and mixed to dissolve. Next, after cooling the aqueous solution in which PVA-1 is dissolved and replacing with nitrogen, the temperature is raised to 85° C.
  • Example 21 The amount of PVA-1 added to 100 parts by mass of vinyl acetate during emulsion polymerization in Example 21 was 10 parts by mass.
  • Examples 22-29 and Comparative Examples 9-12 (Production of aqueous emulsions Em-2 to Em-14) Examples 22 to 29 and Comparative Examples 22 to 29 and Comparative Aqueous emulsions Em-2 to Em14 of Examples 9 to 12 were obtained.
  • each of the water-based adhesives of Examples 21 to 29 had less liquid splattering and less liquid film streaks during roll coating.
  • the PVA of the present invention can be used for various purposes such as coating agents, adhesives, and film raw materials.

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PCT/JP2022/018771 2021-04-27 2022-04-25 ビニルアルコール系重合体、これを含む粉末、粉末の製造方法、コーティング剤、塗工物、塗工物の製造方法、乳化重合用安定剤、水性エマルジョン及び接着剤 Ceased WO2022230825A1 (ja)

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US18/288,570 US20240209128A1 (en) 2021-04-27 2022-04-25 Vinyl alcohol polymer, powder containing same, method for producing powder, coating agent, coated article, method for producing coated article, stabilizer for emulsion polymerization, aqueous emulsion, and adhesive
JP2023517518A JPWO2022230825A1 (https=) 2021-04-27 2022-04-25
EP22795738.8A EP4332126A4 (en) 2021-04-27 2022-04-25 VINYL ALCOHOL-BASED POLYMER, POWDER CONTAINING SAME, PROCESS FOR PRODUCING THE POWDER, COATING AGENT, COATED PRODUCT, PROCESS FOR PRODUCING A COATED PRODUCT, STABILIZER FOR EMULSION POLYMERIZATION, AQUEOUS EMULSION, AND ADHESIVE AGENT
CN202280031698.6A CN117279961A (zh) 2021-04-27 2022-04-25 乙烯醇系聚合物、包含其的粉末、粉末的制造方法、涂布剂、涂布物、涂布物的制造方法、乳液聚合用稳定剂、水性乳液和粘接剂

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EP4332127A4 (en) * 2021-04-27 2025-05-14 Kuraray Co., Ltd. VINYL ALCOHOL POLYMER, POWDER COMPRISING IT, PROCESSES FOR PRODUCING IT, PAPER TREATMENT AGENT AND DISPERSANT FOR EMULSION POLYMERIZATION
WO2025127105A1 (ja) * 2023-12-13 2025-06-19 株式会社クラレ 農業用コーティング組成物及び被覆種子

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WO2025127105A1 (ja) * 2023-12-13 2025-06-19 株式会社クラレ 農業用コーティング組成物及び被覆種子

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