WO2023190884A1 - 水溶液、コーティング剤、接着剤、紙加工剤、乳化重合用分散剤、水性エマルジョン、積層体及び水性エマルジョンの製造方法 - Google Patents

水溶液、コーティング剤、接着剤、紙加工剤、乳化重合用分散剤、水性エマルジョン、積層体及び水性エマルジョンの製造方法 Download PDF

Info

Publication number
WO2023190884A1
WO2023190884A1 PCT/JP2023/013207 JP2023013207W WO2023190884A1 WO 2023190884 A1 WO2023190884 A1 WO 2023190884A1 JP 2023013207 W JP2023013207 W JP 2023013207W WO 2023190884 A1 WO2023190884 A1 WO 2023190884A1
Authority
WO
WIPO (PCT)
Prior art keywords
pva
aqueous solution
mass
group
dispersant
Prior art date
Application number
PCT/JP2023/013207
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
美鈴 藤森
依理子 今岡
Original Assignee
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Priority to CN202380031467.XA priority Critical patent/CN118974109A/zh
Priority to DE112023001013.7T priority patent/DE112023001013T5/de
Priority to JP2024512807A priority patent/JPWO2023190884A1/ja
Publication of WO2023190884A1 publication Critical patent/WO2023190884A1/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/52—Natural or synthetic resins or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C08F116/00—Homopolymers 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
    • C08F116/02—Homopolymers 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
    • C08F116/04—Acyclic compounds
    • C08F116/06—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
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate

Definitions

  • the present invention relates to an aqueous solution, a coating agent, an adhesive, a paper processing agent, a dispersant for emulsion polymerization, an aqueous emulsion, a laminate, and a method for producing an aqueous emulsion.
  • Vinyl alcohol polymer (hereinafter also referred to as "PVA") is known as a water-soluble synthetic polymer, and in addition to being used as a raw material for fibers and films, it is also used as a paper processing agent, fiber processing agent, and inorganic material. It is widely used as a binder, adhesive, stabilizer for emulsion polymerization and suspension polymerization, etc.
  • coating agents based on PVA are used as paper processing agents. By coating paper with PVA, which has excellent film-forming properties, it is possible to impart barrier properties against gas and oil resistance.
  • Release paper base paper is usually manufactured by coating the surface of a cellulose base material with PVA.
  • a release paper is obtained by forming a release layer (silicone layer) on the surface of this release paper base paper.
  • PVA in release paper plays the role of a filler that suppresses the penetration of expensive silicone and platinum into the base material.
  • Patent Document 1 describes a cellulose base material coated with PVA in which double bonds have been introduced into the side chains through an acetalization reaction.
  • the acetalization reaction is carried out in water under acidic conditions, and a basic compound is added to perform a neutralization treatment.
  • this reaction solution is used as a coating agent, the solution stability of the coating agent is low due to a large amount of salt generated by the neutralization treatment.
  • Patent Document 2 describes a release base paper in which a base material is coated with a coating agent containing PVA in which a double bond is introduced into the side chain by an esterification reaction.
  • the pyridine used in the esterification reaction may remain in the PVA and act as a catalyst poison, inhibiting the silicone curing reaction of the release layer.
  • Patent Document 3 describes a peeling method in which a coating agent containing PVA having a double bond in a side chain, which is obtained by esterifying PVA with a carboxylic acid having an unsaturated double bond or a salt thereof, is applied to a base material.
  • the original paper is listed.
  • this coating agent is applied to the release base paper, it has excellent sealing properties for the silicone on the release base paper, accelerates the curing of the silicone in the release layer, and improves the adhesion between the base material and the release layer. has been done.
  • the PVA having a double bond in the side chain described in Patent Document 3 also contains components that are insoluble in water, the coating property is insufficient when used as a coating liquid.
  • adhesives containing PVA as a main component are inexpensive and have excellent adhesive properties, and are used for bonding paperboard, corrugated paper, paper tubes, sliding doors, wallpaper, wood, etc. Furthermore, adhesives made by mixing various emulsions and PVA are used as adhesives for woodworking, textile processing, paper, and the like. As described above, adhesives containing PVA (PVA-based water-based adhesives) are used in a wide range of applications. However, even in PVA-based water-based adhesives, in order to respond to the recent trend toward high-speed coating, it has been proposed to use various modified PVAs for the purpose of improving adhesive properties including initial adhesion.
  • Patent Document 4 describes alkyl-modified PVA.
  • a PVA-based water-based adhesive using this modified PVA is said to have excellent initial adhesion, water-resistant adhesion, and storage stability of the adhesive.
  • the water-resistant adhesion of adhesives using such modified PVA is insufficient.
  • Patent Document 5 describes aldehyde-modified PVA. Adhesives containing this modified PVA are said to be excellent in initial adhesive strength, normal adhesive strength, durable adhesive strength, and storage stability of the main agent. However, even in adhesives using such modified PVA, there is room for improvement in initial adhesive strength, and the effects when no curing agent is used are not disclosed.
  • PVA is also known as a protective colloid for emulsion polymerization of vinyl ester monomers typified by vinyl acetate.
  • Aqueous emulsions obtained by emulsion polymerization using PVA as a dispersant for emulsion polymerization are widely used in the fields of various adhesives, paint bases, various binders for impregnated paper and nonwoven products, and various coating agents. There is.
  • Aqueous emulsions synthesized using PVA as a dispersant for emulsion polymerization have (a) excellent adhesion to substrates without migration of low-molecular components, and (b) easy viscosity adjustment and good coating properties. It has good suitability for coating applications.
  • the monomers that can usually be used are limited to vinyl acetate and vinyl chloride, which have high radical reactivity, and there are problems with conventional aqueous emulsions that use only surfactants as dispersion stabilizers. In comparison, improvements are expected in terms of insufficient physical properties such as water resistance, oil resistance, mechanical stability, and freeze-thaw stability.
  • Patent Document 6 describes a technique for improving dispersibility by introducing a sulfone group into PVA, which is a dispersant.
  • PVA is often physically adsorbed to the polymer in the emulsion, and physical properties such as polymerization stability and mechanical stability may be insufficient.
  • Patent Document 7 discloses that a polymer of ethylenically unsaturated monomers such as acrylic monomers, styrene monomers, and diene monomers is dispersed using PVA containing diacetone acrylamide units as a dispersant. Aqueous emulsions are described. Although such PVA has excellent polymerization stability and mechanical stability, it is necessary to add a crosslinking agent separately in order to exhibit required physical properties such as water resistance and oil resistance.
  • Patent Document 8 describes the use of a polyvinyl alcohol polymer having a mercapto group at the molecular end as a dispersant for emulsion polymerization.
  • PVA polyvinyl alcohol polymer having a mercapto group at the molecular end
  • PVA is synthesized by chain transfer polymerization, and a mixture of PVA with mercapto groups and PVA without mercapto groups is obtained, so the degree of polymerization and the rate of introduction of mercapto groups, etc.
  • the present invention provides that an aqueous solution containing a vinyl alcohol polymer or a coated paper produced using the aqueous solution has storage stability, coatability, air permeation resistance, silicone curability, release layer and base material.
  • the primary objective is to provide an aqueous solution that has excellent adhesion, initial adhesion, and water-resistant adhesion, and coating agents, adhesives, and paper processing agents containing such an aqueous solution.
  • the present invention provides a dispersant for emulsion polymerization that is capable of synthesizing an aqueous emulsion that has excellent mechanical stability, produces little aggregates, and can produce coated paper and the like that have excellent oil resistance.
  • a second object of the present invention is to provide an aqueous emulsion containing such a dispersant for emulsion polymerization, a method for producing the same, and a laminate.
  • aqueous solution containing a vinyl alcohol polymer having a carbonyl group, a formyl group, and an alkenyl group in the same or different molecules [2] The aqueous solution of [1], wherein the vinyl alcohol polymer has a structure represented by the following formula (1) containing the carbonyl group; In formula (1), m is an integer from 1 to 11. [3] An aqueous solution containing a vinyl alcohol polymer having a group represented by the following formula (2) at the end of the polymer chain; In formula (2), R 1 is an alkenyl group.
  • R 1 is an alkenyl group.
  • Emulsion [24] A laminate comprising a base material and a layer formed from the aqueous emulsion of [22] or [23]; [25] The laminate of [24], wherein the base material is paper. [26] A laminate comprising a base material and a layer containing the emulsion polymerization dispersant according to any one of [13] to [21]; [27] At least one monomer selected from the group consisting of ethylenically unsaturated monomers and diene monomers in the presence of the emulsion polymerization dispersant according to any one of [13] to [21].
  • a method for producing an aqueous emulsion including a step of emulsion polymerization; [28]
  • the ethylenically unsaturated monomer is at least one monomer selected from the group consisting of styrene monomers, acrylic ester monomers, and methacrylic ester monomers, [27] ] Method for producing an aqueous emulsion; This is achieved by providing
  • the aqueous solution of the present invention or coated paper produced using the aqueous solution has storage stability, coatability, air permeation resistance, silicone curability, adhesion between the release layer and the base material, initial adhesion, and Excellent water-resistant adhesion. Therefore, the aqueous solution is suitably used for coating agents, adhesives, paper processing agents, and the like.
  • the dispersant for emulsion polymerization of the present invention is an aqueous emulsion with excellent mechanical stability and little generation of aggregates, and is capable of synthesizing an aqueous emulsion that can produce coated paper etc. with excellent oil resistance. can. Therefore, the obtained aqueous emulsion is suitably used for various adhesives, paints, various binders, admixtures, coating agents, laminates, etc.
  • the aqueous solution according to the first aspect of the present invention contains a vinyl alcohol polymer (PVA) having a carbonyl group, a formyl group, and an alkenyl group in the same or different molecules, and water.
  • PVA vinyl alcohol polymer
  • the aqueous solution itself or coated paper produced using the aqueous solution has storage stability, coating properties, air permeation resistance, silicone curability, adhesion between the release layer and the base material, initial adhesion, and water resistance. Excellent adhesion.
  • the aqueous solution may contain a solvent other than water, such as an organic solvent.
  • the proportion of water in the solvent in the aqueous solution is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and 95% by mass or more based on the total amount of the solvent. In some cases, it is even more preferable. Further, the proportion of water in the solvent in the aqueous solution may be 100% by mass or less, or 99% by mass or less. Further, it is preferable that the solvent in the aqueous solution consists essentially of water.
  • the concentration of the PVA contained in the aqueous solution for example, 0.5% by mass is preferred, 1% by mass is more preferred, 2% by mass is still more preferred, and even more preferably 4% by mass. be.
  • the upper limit of the concentration of the PVA contained in the aqueous solution but for example, 30% by mass is preferable, 25% by mass is more preferable, and 20% by weight may be even more preferable.
  • the upper limit of the insoluble content in the aqueous solution is preferably 1000 ppm, more preferably 500 ppm, even more preferably 200 ppm, even more preferably 100 ppm, particularly preferably 70 ppm, more particularly preferably 50 ppm, and even more particularly preferably 10 ppm.
  • the lower limit of the insoluble content in the aqueous solution is preferably 0 ppm, and may be 1 ppm. This undissolved portion may be an undissolved portion of PVA.
  • the insoluble content in the aqueous solution is the mass ratio of the component remaining dissolved in the aqueous solution to the total amount of PVA contained in the aqueous solution, and is specifically measured by the following method.
  • the aqueous solution is passed through a metal filter with an opening of 63 ⁇ m, and the filter is further washed with warm water at 90° C. to obtain solids that remain undissolved in the aqueous solution.
  • the ratio of the mass of undissolved solids to the mass of PVA contained in the aqueous solution before filtration is calculated, and this is defined as the undissolved content in the aqueous solution.
  • the aqueous solution may contain other solutes than the PVA.
  • Other solutes include water-soluble resins other than the PVA, surfactants, salts, and the like.
  • the lower limit of the content of PVA with respect to all solutes contained in the aqueous solution is preferably 70% by mass, more preferably 80% by mass, even more preferably 90% by mass, 95% by mass, 99% by mass, or 99.9% by mass. In some cases, mass % is even more preferable.
  • the upper limit of the content of PVA with respect to all solutes contained in the aqueous solution may be 100% by mass, 99.9% by mass, 99% by mass, or 95% by mass.
  • the aqueous solution is suitable for coating agents, adhesives, paper processing agents, etc.
  • the method for producing the aqueous solution is not particularly limited. For example, it can be obtained by dissolving solid PVA in a solvent such as water.
  • PVA contained in the aqueous solution according to the first embodiment of the present invention has a carbonyl group, a formyl group, and an alkenyl group in the same or different molecules.
  • the case where the PVA is used as a dispersant for emulsion polymerization will also be explained.
  • the PVA does not need to contain all of the carbonyl group, formyl group, and alkenyl group in one molecule.
  • the PVA may be, for example, a mixture of PVA (a) having two groups out of a carbonyl group, a formyl group, and an alkenyl group, and PVA (b) having the remaining one group.
  • both PVA (a) and PVA (b) may have one or more of a carbonyl group, a formyl group, and an alkenyl group.
  • the PVA may be a mixture of three or more types of PVA.
  • the PVA is a polymer having vinyl alcohol units as structural units.
  • the PVA is obtained by polymerizing a vinyl ester in the presence of an aliphatic unsaturated aldehyde and saponifying the obtained vinyl ester polymer, as will be described in detail later.
  • the lower limit of the degree of saponification of the PVA is not particularly limited, but may be, for example, 20 mol%, 30 mol%, or 40 mol%.
  • the lower limit of the degree of saponification of the PVA is preferably 65 mol%, more preferably 70 mol%, even more preferably 75 mol%, and even more preferably 80 mol%.
  • the lower limit of the degree of saponification of the PVA may be even more preferably 82 mol%, 90 mol%, or 92 mol%.
  • the degree of saponification of PVA is equal to or higher than the above lower limit, the solubility of the PVA in water is improved, the uniformity of the film surface coated with the aqueous solution is improved, the filling property of silicone is improved, and Adhesive strength is further increased.
  • the upper limit of the degree of saponification of the PVA is not particularly limited and may be 100 mol%, but for example, 99.99 mol% is preferable, 99.5 mol% is more preferable, and 99 mol% is still more preferable. In some cases.
  • the upper limit of the degree of saponification may be even more preferably 98 mol% or 96 mol%.
  • the degree of saponification of the PVA is less than or equal to the upper limit, the production of PVA becomes easy.
  • the degree of saponification of the PVA is within the above range, when the PVA is used as a dispersant for emulsion polymerization, the surfactant performance is optimized, and various performances of the resulting aqueous emulsion ( It has fewer coarse particles, has excellent storage stability, has appropriate water resistance, etc.).
  • the degree of saponification is a value measured by the method described in JIS K6726:1994.
  • the PVA preferably has a structure represented by the following formula (1) containing a carbonyl group.
  • m is an integer from 1 to 11.
  • m is preferably an integer from 2 to 9, and may preferably be an integer from 3 to 7.
  • the content of carbonyl groups relative to the total content of vinyl alcohol units and vinyl ester units in the PVA is not particularly limited, but the lower limit is, for example, preferably 0.001 mol%, more preferably 0.005 mol%, 0. .008 mol% is more preferred, and 0.01 mol%, 0.03 mol% or 0.05 mol% may be even more preferred.
  • the upper limit of the carbonyl group content in the PVA is preferably 5 mol%, more preferably 3 mol%, even more preferably 1 mol%, and even more preferably 0.3 mol% or 0.1 mol%. There is also.
  • the upper limit of the carbonyl group content in the PVA may be 0.05 mol% when the PVA is used as a dispersant for emulsion polymerization.
  • various performances are improved when the aqueous solution is used, for example, as a coating agent or adhesive.
  • various performances when the PVA is used as a dispersant for emulsion polymerization are also improved.
  • the content of the carbonyl group is a value determined by the method described in Examples described later.
  • the content of formyl groups relative to the total content of vinyl alcohol units and vinyl ester units in the PVA is not particularly limited, but the lower limit is preferably, for example, 0.01 mol%, more preferably 0.03 mol%, 0. .05 mol% is more preferred, and 0.07 mol% or 0.1 mol% may be even more preferred.
  • the upper limit of the formyl group content in the PVA is, for example, preferably 5 mol%, more preferably 3 mol%, even more preferably 2 mol%, and 1 mol%, 0.8 mol% or 0.5 mol%. In some cases, it may be even more preferable.
  • the formyl group content in the PVA is within the above range, various performances are improved when the aqueous solution is used as a coating agent, adhesive, etc., for example. Further, when the content of formyl groups in the PVA is within the above range, various performances when the PVA is used as a dispersant for emulsion polymerization are also improved.
  • the content of the formyl group is a value determined by the method described in Examples described later.
  • the alkenyl group that the PVA has is a monovalent group obtained by removing any one hydrogen atom from an alkene.
  • the number of carbon atoms in the alkenyl group is preferably 2 to 13, more preferably 3 to 12, even more preferably 4 to 11, and even more preferably 5 to 9.
  • the alkenyl group may be linear or have a branched structure, but is preferably linear.
  • the alkenyl group is located at the end of the polymer chain.
  • the alkenyl group that the PVA has preferably has a carbon-carbon double bond at the end (tip). That is, the PVA preferably has a vinyl group at the end (tip).
  • the alkenyl group that the PVA has is more preferably a group represented by the following formula (5).
  • n is an integer from 1 to 11. n is preferably an integer of 2 to 9, more preferably an integer of 3 to 7.
  • the content of alkenyl groups relative to the total content of vinyl alcohol units and vinyl ester units in the PVA is not particularly limited, but the lower limit is, for example, preferably 0.005 mol%, more preferably 0.01 mol%, 0. .02 mol% is more preferred, and 0.003 mol% or 0.04 mol% may be even more preferred.
  • the upper limit of the alkenyl group content in the PVA is, for example, preferably 5 mol%, more preferably 3 mol%, even more preferably 1 mol%, 0.5 mol%, 0.3 mol%, or 0.2 mol%. % may be even more preferable.
  • the content of alkenyl groups in the PVA is within the above range, various performances are improved when the aqueous solution is used as a coating agent, adhesive, etc., for example. Further, when the content of alkenyl groups in the PVA is within the above range, various performances when the PVA is used as a dispersant for emulsion polymerization are also improved.
  • the content of the alkenyl group is a value determined by the method described in the Examples below.
  • the preferred content range of vinyl groups relative to the total content of vinyl alcohol units and vinyl ester units in the PVA is the same as the preferred content range of alkenyl groups.
  • the PVA preferably has a terminal group derived from an aliphatic unsaturated aldehyde or a structural unit derived from an aliphatic unsaturated aldehyde.
  • the number of carbon atoms in the aliphatic unsaturated aldehyde is preferably 3 to 14, more preferably 4 to 12, and even more preferably 6 to 10.
  • the aliphatic unsaturated aldehyde preferably has a carbon-carbon double bond, and more preferably has a carbon-carbon double bond at the terminal (tip). That is, the aliphatic unsaturated aldehyde preferably contains a vinyl group.
  • the aliphatic unsaturated aldehyde having a carbon-carbon double bond is an alkenyl group having a methylene group at the end on the carbonyl group side, that is, a group represented by R-CH 2 - (R is an alkenyl group). Preference is given to aliphatic unsaturated aldehydes having .
  • the aliphatic unsaturated aldehyde is preferably an aliphatic unsaturated aldehyde other than ⁇ , ⁇ -unsaturated aldehyde.
  • the aliphatic unsaturated aldehyde is preferably a compound represented by the following formula (6).
  • p is an integer from 1 to 11. p is preferably an integer of 2 to 9, more preferably an integer of 3 to 7.
  • the aliphatic unsaturated aldehydes include 2-propenal, 3-butenal, 4-pentenal, 5-hexenal, 3-methyl-5-hexanal, 6-heptenal, 6-octenal, 7-octenal, 7-methyl-7 -octenal, 3,7-dimethyl-7-octenal, 8-nonenal, 9-decenal, 10-undecenal, 11-dodecenal and the like.
  • Examples of the terminal group derived from an aliphatic unsaturated aldehyde that the PVA preferably has include a group represented by the following formula (2).
  • R 1 is an alkenyl group.
  • the number of carbon atoms in the alkenyl group represented by R 1 in formula (2) is preferably 2 to 13, more preferably 3 to 12, even more preferably 4 to 11, and even more preferably 5 to 9.
  • the alkenyl group represented by R 1 may be linear or have a branched structure, but is preferably linear.
  • the alkenyl group represented by R 1 is preferably a group having a methylene group at the end on the carbonyl group side (a group represented by R-CH 2 - (R is an alkenyl group)); A group having a carbon-carbon double bond is more preferable, and a group represented by the above formula (5) may be even more preferable.
  • the terminal group represented by formula (2) is usually formed when an aliphatic unsaturated aldehyde acts as a chain transfer agent.
  • the structural unit derived from an aliphatic unsaturated aldehyde that the PVA preferably has includes a structural unit represented by the following formula (3) or (4).
  • R 2 to R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • q is an integer from 1 to 11.
  • r is an integer from 1 to 11.
  • R 2 to R 4 in formula (3) are preferably hydrogen atoms.
  • q is preferably an integer of 2 to 9, more preferably an integer of 3 to 7.
  • the structural unit represented by formula (3) is usually formed when an aliphatic unsaturated aldehyde acts as a monomer and is introduced into a polymer chain.
  • R 5 to R 7 in formula (4) are preferably hydrogen atoms.
  • r is preferably an integer of 2 to 9, more preferably an integer of 3 to 7.
  • the structural unit represented by formula (4) is usually formed when the formyl group in the structural unit represented by formula (3) further acts as a chain transfer agent.
  • the PVA has tertiary carbon atoms (carbon atoms directly bonded to three carbon atoms). Further, the PVA preferably has a structural unit containing a tertiary carbon atom. In such a case, that is, when the PVA has a branched structure, various performances are improved when the aqueous solution is used, for example, as a coating agent or adhesive. Moreover, when the PVA has a branched structure, various performances are also improved when the PVA is used as a dispersant for emulsion polymerization. For example, when the PVA has a structural unit represented by the above formula (3) or (4) and R 2 to R 7 are hydrogen atoms, the PVA has a tertiary carbon atom.
  • the PVA may have structural units other than the structural units derived from vinyl esters (vinyl alcohol units and vinyl ester units) and the structural units derived from aliphatic unsaturated aldehydes.
  • Monomers providing other structural units include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene; acrylic acid, methacrylic acid; acrylic acid esters such as methyl acrylate and ethyl acrylate; ; Methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; Acrylamide derivatives such as N-methylacrylamide, N-ethylacrylamide, and 2-acrylamido-2-methylpropanesulfonic acid; N-methylmethacrylamide, N-ethylmethacrylamide Methacrylamide derivatives such as maleic acid; maleic esters such as monomethyl maleate and dimethyl maleate; fumaric acid; fumaric acid esters such as monomethyl fuma
  • the proportion of the other structural units in all structural units in the PVA may be preferably 20 mol% or less, more preferably less than 20 mol%, 10 mol% or less, 5 mol% or 1 mol%. may be even more preferable. On the other hand, the proportion of the other structural units may be, for example, 0.1 mol% or more, or 1 mol% or more.
  • the proportion of ethylene units in all structural units in the PVA may be preferably less than 20 mol%, and may be more preferably 10 mol% or less, 5 mol% or 1 mol%. On the other hand, the proportion of the ethylene units may be, for example, 0 mol% or more, or 1 mol% or more.
  • the lower limit of the viscosity average degree of polymerization of the PVA is not particularly limited, and may be, for example, 50 or 100, but is preferably 200, more preferably 300, even more preferably 400, and even more preferably 500.
  • the viscosity average degree of polymerization is at least the above-mentioned lower limit, the protective colloid properties are enhanced, and various performances are enhanced when the PVA is used, for example, as a dispersant for emulsion polymerization.
  • the viscosity average degree of polymerization of the PVA is 1,000 or more. There is also.
  • the upper limit of this viscosity average degree of polymerization is not particularly limited, but is preferably, for example, 5,000, more preferably 3,000, and even more preferably 2,000 or 1,500. Further, in cases where the PVA is used as a dispersant for suspension polymerization, the upper limit of the viscosity average degree of polymerization may be 1,000. When the viscosity average degree of polymerization is below the upper limit, the surface active performance is increased, and various performances when used as a dispersant for emulsion polymerization, for example, are improved.
  • the viscosity average degree of polymerization is a value measured according to JIS K6726:1994.
  • the water-insoluble content of the PVA is preferably 1000 ppm or less.
  • the upper limit of this water-insoluble content is preferably 500 ppm, more preferably 200 ppm, and even more preferably 100 ppm, 70 ppm, 50 ppm, or 10 ppm.
  • the lower limit of the water-insoluble content of PVA may be 0 ppm or 1 ppm.
  • the water-insoluble content is the mass ratio of components that remain dissolved after PVA is added to water at a concentration of 5% by mass and stirred at 90°C for 60 minutes. Specifically, it is measured by the following method. be done.
  • a 500 mL flask equipped with a stirrer and a reflux condenser is prepared in a water bath set at 20° C.
  • 285 g of distilled water is poured into the flask, and stirring is started at 300 rpm.
  • the temperature of the water bath is raised to 90° C. over 30 minutes to dissolve PVA and obtain a PVA solution.
  • dissolution is continued with stirring at 300 rpm for an additional 60 minutes.
  • undissolved and residual PVA solids (hereinafter sometimes referred to as "insoluble solids” or “insoluble particles”) are filtered through a metal filter with an opening of 63 ⁇ m.
  • the filter is washed with warm water at 90°C to remove the PVA solution adhering to the filter, leaving only undissolved solids on the filter, and then the filter is dried in a heated dryer at 120°C for 1 hour.
  • the mass of the filter after drying is compared with the mass of the filter before being used for filtration, and the mass of the undissolved solids is calculated.
  • the ratio of the mass of the undissolved solid to the mass of PVA (15 g) initially added to the water is defined as the water-insoluble content.
  • the isolated PVA may contain trace components such as sodium atoms (Na).
  • Na sodium atoms
  • sodium atoms may interact with PVA in the form of sodium ions, or may be mixed with PVA in the form of sodium salts.
  • products containing such trace components may also be simply referred to as PVA.
  • the upper limit of the Na content in PVA is preferably 8% by mass, more preferably 5% by mass, even more preferably 1% by mass, even more preferably 0.6% by mass, and particularly preferably 0.3% by mass.
  • the lower limit of the Na content in PVA is not particularly limited, and may be 0% by mass, 0.01% by mass, or 0.1% by mass.
  • the sodium Na content in PVA is measured by the method described in Examples described later.
  • the aqueous solution may contain sodium atoms.
  • the sodium atom may be present in the form of a sodium ion or a sodium salt.
  • the upper limit of the sodium atom (Na) content relative to the solid content in the aqueous solution is preferably 8% by mass, more preferably 5% by mass, even more preferably 1% by mass, and 0.6% by mass. It is even more preferable that the amount is 0.3% by mass, and in some cases it is particularly preferable that the amount is 0.3% by mass.
  • the lower limit of the Na content relative to the solid content is not particularly limited, and may be 0% by mass, 0.01% by mass, or 0.1% by mass.
  • the aqueous solution according to the second embodiment of the present invention contains PVA having a group represented by the following formula (2) at the end of a polymer chain and water.
  • the aqueous solution itself or coated paper produced using the aqueous solution has storage stability, coating properties, air permeation resistance, silicone curability, adhesion between the release layer and the base material, initial adhesion, and water resistance. Excellent adhesion.
  • preferred forms such as the concentration of PVA, the amount of insoluble matter, other components, and uses are the same as those of the aqueous solution according to the first embodiment of the present invention. .
  • R 1 in formula (2) is an alkenyl group.
  • the specific form and preferred form of the group (terminal group) represented by the formula (2) are as described above.
  • the group represented by the formula (2) forms a polymer chain when the vinyl ester is polymerized in the presence of an aliphatic unsaturated aldehyde and the aliphatic unsaturated aldehyde acts as a chain transfer agent.
  • introduced at the end of the The PVA may consist of only one type of PVA, or may be a mixture of two or more types of PVA.
  • the specific form and preferred form of PVA contained in the aqueous solution according to the second embodiment of the present invention do not necessarily require "having a carbonyl group, a formyl group, and an alkenyl group in the same or different molecules."
  • the specific form and preferred form of PVA contained in the aqueous solution according to the first embodiment of the present invention described above are the same.
  • the PVA of the present disclosure is produced by a step of polymerizing a vinyl ester in the presence of an aliphatic unsaturated aldehyde (step A) and a step of saponifying the obtained vinyl ester polymer (step B).
  • step A vinyl ester is polymerized in the presence of an aliphatic unsaturated aldehyde to obtain a vinyl ester polymer.
  • methods for polymerizing vinyl esters include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these methods, bulk polymerization without a solvent and solution polymerization using a solvent such as alcohol are preferred.
  • the alcohol is preferably an alcohol having 3 or less carbon atoms, more preferably methanol, ethanol, n-propanol and isopropanol, and even more preferably methanol.
  • a batch method or a continuous method can be adopted as the reaction method.
  • There is no particular restriction on the polymerization temperature during the polymerization reaction but a range of 5°C or higher and 200°C or lower is suitable.
  • vinyl ester examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like. Among them, vinyl acetate is preferred.
  • polymerization initiator used in the polymerization reaction examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4- Known polymerization initiators such as azo initiators such as methoxy-2,4-dimethylvaleronitrile; organic peroxide initiators such as benzoyl peroxide, n-propyl peroxycarbonate, and diisopropyl peroxydicarbonate are used. Can be mentioned.
  • the amount of the polymerization initiator used is preferably, for example, 0.01 to 5% by mass based on the vinyl ester used.
  • aliphatic unsaturated aldehyde present during the polymerization of vinyl ester are as described above.
  • One type or two or more types of aliphatic unsaturated aldehydes can be used.
  • the amount of the aliphatic unsaturated aldehyde used is preferably 0.1 to 10% by mass based on the vinyl ester, for example.
  • chain transfer agents other than the aliphatic unsaturated aldehyde may be present.
  • chain transfer agents include aliphatic saturated aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, 1-pentanal, 1-hexanal, 1-octanal, 1-nonanal, and 1-decanal; ketones such as acetone and methyl ethyl ketone; Examples include mercaptans such as -hydroxyethanethiol and 3-mercaptopropionic acid; thiocarboxylic acids such as thioacetic acid; and halogenated hydrocarbons such as trichloroethylene and perchlorethylene.
  • copolymerizable monomers When polymerizing the vinyl ester, further copolymerizable monomers can be copolymerized within a range that does not impair the spirit of the present invention.
  • copolymerizable monomers include those mentioned above as monomers providing other structural units.
  • step B the vinyl ester polymer obtained in step A is saponified, for example, in an alcohol solution using an alkali catalyst or an acid catalyst to obtain PVA.
  • an alkali catalyst or an acid catalyst for example, conventionally known basic catalysts such as sodium hydroxide, potassium hydroxide, sodium methoxide, etc., or acidic catalysts such as p-toluenesulfonic acid are used. Hydrolysis reaction can be applied.
  • Examples of the solvent 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 perform the saponification reaction in the presence of sodium hydroxide, which is a basic catalyst, using methanol or a mixed solution of methanol and methyl acetate as a solvent. Saponification can be carried out using a belt reactor, kneader reactor, tower reactor, or the like.
  • the manufacturing method further includes, as steps after step B, a step of washing the resin solid material containing PVA, a step of drying the resin solid material containing PVA, a step of heat treating the resin solid material containing PVA, etc. Good too.
  • One embodiment of the present invention is a coating agent containing the aqueous solution described above.
  • the aqueous solution contained in the coating agent may be the aqueous solution according to the first form described above, the aqueous solution according to the second form, or both.
  • the coating agent may be a coating agent for paper base materials or film base materials, or a coating agent used when manufacturing release paper or release films.
  • the coating agent may contain an organic solvent, and may contain water-insoluble organic particles, inorganic particles, etc.
  • concentration of PVA contained in the coating agent for example, 1% by mass is preferred, 2% by mass is more preferred, and 4% by mass may be even more preferred.
  • concentration of PVA contained in the coating agent for example, 30% by mass is preferable, and 25% by weight may be more preferable.
  • the upper limit of the insoluble content in the coating agent is preferably 1,000 ppm, more preferably 500 ppm, even more preferably 200 ppm, even more preferably 100 ppm, particularly preferably 70 ppm, more particularly preferably 50 ppm, and even more particularly preferably 10 ppm.
  • the lower limit of the insoluble content in the coating agent is preferably 0 ppm, and may be 1 ppm. Note that the insoluble content in the coating agent is the mass ratio of the component remaining dissolved in the coating agent to the total amount of PVA contained in the coating agent, and is specifically measured by the following method.
  • the coating agent is passed through a metal filter with an opening of 63 ⁇ m, and the filter is further washed with warm water at 90°C to obtain the solids remaining undissolved in the coating agent, and to remove the PVA contained in the coating agent before filtration.
  • the ratio of the mass of undissolved solids to the mass is calculated, and this is taken as the undissolved content in the coating agent.
  • the method for producing the coating agent is not particularly limited.
  • a coating agent can be obtained by dissolving PVA particles in a solvent such as water.
  • the coating agent may contain other components other than the above-mentioned PVA and solvent as long as the effects of the present invention are not impaired.
  • Other ingredients include water-based dispersible resins such as SBR, NBR, polyvinyl acetate, ethylene vinyl acetate copolymer, poly(meth)acrylic ester, and polyvinyl chloride; wheat, corn, rice, potato, cane, and tapioca.
  • the coating agent may contain a pigment to the extent that the effects of the present invention are not impaired.
  • pigments include inorganic pigments (clay, kaolin, aluminum hydroxide, calcium carbonate, talc, etc.) and organic pigments (plastic pigments, etc.) that are generally used in the field of coated paper manufacturing.
  • the content of these pigment components in the coating liquid is preferably 50% by mass or less.
  • the substrate to which the coating agent of the present invention is applied is not particularly limited, and examples thereof include paper, film, and the like. Among these, the substrate to which the coating agent of the present invention is applied is preferably paper.
  • Paper processing agent containing the aqueous solution described above.
  • the paper processing agent can be used, for example, by coating it on paper as a base material.
  • this form of paper processing agent is an example of a coating agent.
  • the paper processing agent can also be used as a paper adhesive or the like.
  • the paper used for the base material may be made from chemical pulp such as hardwood kraft pulp or softwood kraft pulp, or mechanical pulp such as GP (ground wood pulp), RGP (refiner ground pulp), or TMP (thermomechanical pulp). Any known paper or synthetic paper can be used.
  • wood-free paper, medium-quality paper, alkaline paper, glassine paper, semi-glassine paper, etc. can be used, and paperboard and white paperboard used for cardboard, building materials, white balls, chipboard, etc. etc. can also be used.
  • the paper may contain papermaking auxiliary chemicals such as organic or inorganic pigments, paper strength enhancers, sizing agents, and retention improvers. Further, the paper may be subjected to various surface treatments.
  • a preferred embodiment of the present invention is a release paper base paper obtained by coating paper with the paper processing agent.
  • the coating agent plays the role of a filler.
  • the release paper base paper obtained by applying the coating agent to paper has a sealing layer formed on the base material.
  • the method for producing the release paper base paper is not particularly limited, a method including a step of applying a coating agent to a base material and a step of drying the base material after coating is preferred. The paper mentioned above can be used.
  • Coating of the paper finishing agent of the present invention can be carried out using general coated paper equipment, such as a blade coater, air knife coater, transfer roll coater, rod metaling size press coater, curtain coater, wire bar coater, etc.
  • the coating liquid can be applied to the paper base material in one layer or in multiple layers using an on-machine coater or an off-machine coater equipped with a coating device such as a coater.
  • various heating drying methods such as hot air heating, gas heater heating, infrared heater heating, etc. can be appropriately employed.
  • the coating amount is preferably 0.3 to 5.0 g/m 2 in terms of dry mass. When the coating amount is 0.3 g/m 2 or more, the sealing effect of silicone is improved.
  • the coating amount is more preferably 0.5 g/m 2 or more. On the other hand, when the coating amount is 5.0 g/m 2 or less, the reduction in surface area due to the sealing layer can be suppressed, and the adhesion with the silicone layer can be further improved.
  • the coating amount is more preferably 3.0 g/m 2 or less.
  • the air permeability measured using an Oken smoothness air permeability tester according to JIS P8117:2009 can be used.
  • the air permeability is preferably 1,000 sec or more, more preferably 5,000 sec or more, even more preferably 10,000 sec or more, and particularly preferably 50,000 sec or more.
  • the sealing effect is better. Note that the smaller the value of air permeability (seconds; sec), the higher the air permeation rate.
  • a paper finishing agent may be dried after being applied and smoothing treatment may be performed as long as the effect is not impaired.
  • smoothing treatment a super calender, a gross calender, a multi-nip calender, a soft calender, a belt nip calender, etc. are suitably employed.
  • a release paper comprising the above-mentioned release paper base paper and a release layer formed on the surface of the release paper base paper is also a preferred embodiment of the present invention.
  • the release layer contains an addition type silicone and platinum, and contains 0.001 parts by mass or more and 0.05 parts by mass or less of platinum based on 100 parts by mass of the addition type silicone.
  • the content of platinum is preferably 0.002 parts by mass or more, and more preferably 0.004 parts by mass or more.
  • the amount of platinum blended is preferably 0.03 parts by mass or less, and more preferably 0.02 parts by mass or less.
  • Addition-type silicones are organopolysiloxanes containing at least two carbon-carbon double bonds in one molecule that are reactive with SiH groups, and organohydrogen polysiloxanes containing at least two SiH groups in one molecule. may be obtained by a hydrosilylation reaction in the presence of a platinum catalyst.
  • Organopolysiloxanes containing at least two carbon-carbon double bonds in one molecule that are reactive with SiH groups include vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, hexenyl groups, etc.
  • the organopolysiloxane contains at least two carbon-carbon double bonds in one molecule.
  • the organopolysiloxane is exemplified by one in which the main chain is a repeating unit of diorganosiloxane and the terminal end is a triorganosiloxane structure, and may have a branched or cyclic structure.
  • organo group bonded to silicon at the terminal or in the repeating unit examples include a methyl group, an ethyl group, and a phenyl group.
  • a specific example is methylphenylpolysiloxane having vinyl groups at both ends.
  • An organohydrogenpolysiloxane containing at least two SiH groups in one molecule is an organopolysiloxane containing two or more SiH groups at the terminal and/or in the repeating structure.
  • the organopolysiloxane is exemplified by one in which the main chain is a repeating unit of diorganosiloxane and the terminal end is a triorganosiloxane structure, and may have a branched or cyclic structure.
  • Examples of the organo group bonded to silicon at the terminal or in the repeating unit include a methyl group, ethyl group, octyl group, and phenyl group, in which two or more of these groups are substituted with hydrogen.
  • the addition-type silicone is appropriately selected from solvent-type, solvent-free type, and emulsion-type, but solvent-free addition-type silicone is preferably employed from the viewpoint of environmental load reduction and coatability. These silicones do not necessarily need to be used alone, and two or more types can be mixed and used as necessary.
  • a platinum catalyst is usually used to cure silicone, but the type of platinum catalyst used in the present invention is not particularly limited. Those that cure addition type silicone through a hydrosilylation reaction are preferably used. Platinum catalysts do not necessarily need to be used alone, and two or more types can be used in combination as necessary. The blended amount of platinum can be determined by quantifying platinum in the platinum catalyst using an ICP emission spectrometer or the like.
  • the release layer of the release paper may also contain other components other than addition-type silicone and platinum to the extent that the effects of the present invention are not impaired.
  • the amount of other components to be blended is usually 30 parts by mass or less based on 100 parts by mass of the total amount of the release layer.
  • Other components include, for example, viscosity modifiers, adhesion improvers, antifoaming agents, plasticizers, waterproofing agents, preservatives, antioxidants, penetrants, surfactants, inorganic pigments, organic pigments, fillers, Examples include starch and its derivatives, cellulose and its derivatives, sugars, latex, and the like.
  • the method for producing the release paper is not particularly limited, but after applying a coating agent onto the base material and forming a sealing layer, the amount of platinum blended in the release layer is 0.001 to 0.000 parts by weight based on 100 parts by mass of the addition type silicone.
  • a method is adopted in which a coating solution containing a platinum catalyst prepared to have a concentration of 0.5 parts by mass is applied onto the sealing layer to form a release layer.
  • the coating amount of the platinum catalyst-containing coating solution that forms the release layer is not particularly limited, but from the viewpoint of better release properties, the solid content is preferably 0.1 to 5 g/m 2 .
  • the coating amount is more preferably 0.3 g/m 2 or more in terms of solid content.
  • the coating amount is within the above range, the adhesion between the sealing layer and the release layer containing addition type silicone and platinum is improved.
  • the coating amount is more preferably 3 g/m 2 or less in terms of solid content.
  • Various coating methods can be used, but blade coaters, air knife coaters, bar coaters, etc. are suitable.
  • One embodiment of the present invention is an adhesive containing the aqueous solution described above.
  • the adhesive may also contain other additives and the like.
  • the concentration range of PVA contained in the adhesive is not particularly limited, but from the viewpoint of applicability, adhesiveness, strength of the bonded part, water resistance, etc., it is preferably, for example, 0.5% by mass or more and 30% by mass or less, and 1% by mass or less. More preferably % by mass or more and 20% by mass or less.
  • the adhesive according to a preferred embodiment of the present invention has excellent initial adhesive properties. Although the mechanism is not clear, the alkenyl group of PVA in the adhesive acts more effectively as a hydrophobic group, forming a pseudo-association in water due to hydrophobic group interaction, increasing the viscosity and reducing the initial adhesive strength. It is thought that this may occur. However, the adhesive of the present invention is not limited to one that exhibits this mechanism.
  • the adhesive can contain a polymer in an emulsion state and a filler.
  • the adhesive may contain other additives.
  • Other additives include metal salts of phosphoric acid compounds such as sodium polyphosphate and sodium hexametaphosphate, and inorganic dispersants such as water glass; polyacrylic acid and its salts, sodium alginate, and ⁇ -olefin maleic anhydride.
  • Anionic polymer compounds such as copolymers and their metal salts; nonionic surfactants such as polyethylene oxide, ethylene oxide adducts of higher alcohols, copolymers of ethylene oxide and propylene oxide; carboxymethyl cellulose, methyl cellulose, etc.
  • Cellulose derivatives; other examples include antifoaming agents, preservatives, antifungal agents, coloring pigments, deodorants, fragrances, and the like.
  • the adhesive By containing a polymer in an emulsion state, the adhesive can improve adhesiveness and reduce the load during drying due to increased solid content.
  • the polymer contained in the emulsion state (hereinafter also referred to as a polymer emulsion) is not particularly limited, but at least one type of monomer selected from the group consisting of ethylenically unsaturated monomers and diene monomers. Polymers (including copolymers) obtained from polymers are preferred.
  • ethylenically unsaturated monomer examples include olefins such as ethylene, propylene, and isoptylene, vinyl esters such as vinyl acetate, (meth)acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, and styrene. can be mentioned.
  • examples of the diene monomer include butadiene, isoprene, chloroprene, and the like.
  • polymer emulsions include vinyl acetate polymer, vinyl acetate-ethylene copolymer, vinyl acetate-vinyl versatate copolymer, vinyl acetate-(meth)acrylate copolymer, etc.
  • vinyl acetate emulsions such as methyl methacrylate/n-butyl acrylate copolymers; styrene emulsions; styrene-butadiene copolymers, methyl methacrylate-butadiene copolymers, etc.
  • examples include butadiene emulsions.
  • vinyl acetate-based emulsion particles or (meth)acrylic acid ester-based emulsion particles are preferred from the viewpoint of the initial adhesion and storage stability of the adhesive.
  • the stability of the emulsion state can be improved.
  • a dispersion stabilizer vinyl alcohol polymers, water-soluble cellulose derivatives such as hydroxyethyl cellulose, various surfactants, etc. can be used, and vinyl alcohol polymers are preferred among them.
  • the upper limit of the content of these emulsions is not particularly limited, but for example, it is usually preferably 1,000 parts by mass or less, and 700 parts by mass based on solid content based on 100 parts by mass of PVA. The following is more preferable, and 500 parts by mass or less is even more preferable.
  • the lower limit of the content is not particularly limited, but for example, it can be used in an amount of 100 parts by mass or more.
  • the adhesive can reduce the load during drying due to an increase in solid content, and improve the strength and hardness after bonding.
  • fillers examples include clays such as kaolinite, halosilane, pyroferrite, and sericite, and inorganic fillers such as heavy, light, or surface-treated calcium carbonate, aluminum hydroxide, aluminum oxide, gypsum, talc, and titanium oxide.
  • inorganic fillers such as heavy, light, or surface-treated calcium carbonate, aluminum hydroxide, aluminum oxide, gypsum, talc, and titanium oxide.
  • organic fillers such as starch, oxidized starch, wheat flour, and wood flour.
  • various clays and various starches can be suitably used.
  • the upper limit of the filler content is not particularly limited, but for example, based on solid content, it is preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, 400 parts by mass or less and 50 parts by mass or more. may be even more preferable.
  • the content of the filler is within the above range, sedimentation of the filler during storage is suppressed, and storage stability tends to be improved.
  • the method for preparing the adhesive is not particularly limited, and any known method can be used.
  • a slurry liquid can be prepared by adding a mixture of PVA and other additives such as fillers into water while stirring, or by sequentially adding various additives, fillers, and PVA into water while stirring. After that, a method such as heating and dissolving can be mentioned.
  • a heating method at this time a known heating method such as a heating method in which steam is directly blown into the slurry liquid or an indirect heating method using a jacket can be adopted. This preparation may be carried out either batchwise or continuously.
  • the adhesive according to a preferred embodiment of the present invention has excellent storage stability such as viscosity stability and sedimentation stability in addition to water solubility and initial adhesiveness. Further, by adjusting the amount of PVA contained, the water resistance after adhesion can also be improved. Therefore, the adhesive is a paper adhesive used in the production or use of corrugated paper, paper bags, paper boxes, paper tubes, wallpaper, etc. Suitable for use as a woodworking adhesive. It can also be used to adhere to fibers such as cloth and non-woven fabrics, cement molded products such as concrete, various plastics, aluminum foil, etc. Note that the uses of the adhesive of the present invention are not limited to these.
  • the viscosity of the adhesive can be arbitrarily selected depending on the application.
  • the viscosity at the bonding temperature is preferably B-type viscosity of 100 to 10,000 mPa ⁇ s.
  • the dispersant for emulsion polymerization according to the first aspect of the present invention is a dispersant for emulsion polymerization that contains PVA having a carbonyl group, a formyl group, and an alkenyl group in the same or different molecules.
  • the dispersant for emulsion polymerization contains ethylenically unsaturated monomers, especially olefin monomers, vinyl ester monomers, (meth)acrylic acid ester monomers, acrylamide monomers, and styrene monomers. It can be suitably used as a dispersant for emulsion polymerization of at least one monomer selected from monomers, diene monomers, and halogenated vinyl monomers. The dispersant for emulsion polymerization can also be used as a dispersant for emulsion polymerization of diene monomers.
  • PVA used in the dispersant for emulsion polymerization of this embodiment are the same as the specific form and preferred form of PVA contained in the aqueous solution according to the first embodiment of the present invention described above.
  • the method for producing PVA is also as described above.
  • the dispersant for emulsion polymerization may consist only of the PVA, or may further contain other components. Other components include conventionally known dispersants for emulsion polymerization and the like.
  • the lower limit of the content of PVA in the dispersant for emulsion polymerization is preferably 70% by mass, more preferably 80% by mass, even more preferably 90% by mass, and more preferably 95% by mass, 99% by mass or 99.9% by mass. In some cases, it may be even more preferable.
  • the upper limit of the content of PVA in the dispersant for emulsion polymerization may be 100% by mass, 99.9% by mass, 99% by mass, or 95% by mass.
  • the dispersant for emulsion polymerization according to the second embodiment of the present invention is a dispersant for emulsion polymerization that contains PVA having a group represented by the following formula (2) at the end of the polymer chain.
  • R 1 is an alkenyl group.
  • the specific form and preferred form of the group (terminal group) represented by the formula (2) are as described above.
  • the group represented by the formula (2) forms a polymer chain when the vinyl ester is polymerized in the presence of an aliphatic unsaturated aldehyde and the aliphatic unsaturated aldehyde acts as a chain transfer agent.
  • introduced at the end of the The PVA may consist of only one type of PVA, or may be a mixture of two or more types of PVA.
  • the specific form and preferred form used for the dispersant for emulsion polymerization of this form are based on the above-mentioned form, except that it does not necessarily "have a carbonyl group, a formyl group, and an alkenyl group in the same or different molecules."
  • the specific form and preferred form of PVA contained in the aqueous solution according to the first embodiment of the invention are the same.
  • the method for producing PVA is also as described above.
  • the uses, components, etc. of the dispersant for emulsion polymerization according to the second embodiment of the present invention are the same as those of the dispersant for emulsion polymerization according to the first embodiment of the present invention.
  • One embodiment of the present invention provides an aqueous polymer containing a structural unit derived from at least one selected from the group consisting of an ethylenically unsaturated monomer and a diene monomer, and the dispersant for emulsion polymerization. It is an emulsion.
  • a polymer containing a structural unit derived from at least one selected from the group consisting of ethylenically unsaturated monomers and diene monomers is a dispersoid of an aqueous emulsion.
  • the dispersion medium of the aqueous emulsion contains water.
  • the dispersion medium of the aqueous emulsion may be water.
  • the aqueous emulsion may further contain components other than the polymer and dispersion medium.
  • the pH of the aqueous emulsion is preferably 5 or more and 6 or less from the viewpoint of stability.
  • the aqueous emulsion may contain a dispersion stabilizer other than the above-mentioned dispersant for emulsion polymerization.
  • Surfactants are preferably used as the dispersion stabilizer.
  • the surfactant is not particularly limited, and includes, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and polymeric compounds having surface activity (polymeric surfactants). ) can be used.
  • anionic surfactants include alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyldiphenyl ether sulfonates, naphthalene sulfonic acid-formalin condensates, polyoxyethylene alkyl ether sulfate salts, and polyoxyethylene alkyl phenyl ether sulfates. Examples include ester salts. Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts such as lauryltrimethylammonium chloride, and distearyldimethylammonium chloride.
  • nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, polyethylene glycol fatty acid ester, polyoxyethylene alkyl amine, etc. .
  • amphoteric surfactants include alkyl betaines, amine oxides, and imidazolium betaines.
  • the polymeric surfactant may be one having a hydrophilic group and a hydrophobic group in the molecule, such as various carboxylic acid type polymeric surfactants, oxyethylene-oxypropylene block polymer (Pluronic (registered trademark) type surfactant), PVA other than the above-mentioned PVA, and cellulose derivatives such as hydroxyethyl cellulose.
  • various carboxylic acid type polymeric surfactants such as oxyethylene-oxypropylene block polymer (Pluronic (registered trademark) type surfactant), PVA other than the above-mentioned PVA, and cellulose derivatives such as hydroxyethyl cellulose.
  • dialkyl sulfosuccinate, alkyldiphenyl ether sulfonate polyoxyethylene alkyl ether sulfate
  • lauryl trimethyl ammonium chloride polyoxyethylene alkyl ether
  • polyoxyethylene alkyl phenyl ether polyoxyethylene alkyl phenyl ether
  • other PVA hydroxyethyl cellulose
  • Examples of one or more monomers selected from ethylenically unsaturated monomers and diene monomers include olefinic monomers such as ethylene, propylene, and isobutylene; vinyl chloride, vinyl fluoride, vinylidene chloride, Halogenated olefin monomers such as vinylidene fluoride; Vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate; (meth)acrylic acid, methyl (meth)acrylate, ( (meth)acrylic acid ester monomers such as ethyl meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc.
  • olefinic monomers such as ethylene, propylene, and isobutylene
  • vinyl chloride vinyl fluoride, vinylidene chloride, Halogenated
  • (meth)acrylic acid dimethylaminoethyl, and their quaternized products (meth)acrylamide, N-methylol(meth)acrylamide, N,N-dimethyl(meth)acrylamide, (meth)acrylamide-2-methylpropanesulfone (meth)acrylamide monomers such as acids and their sodium salts; styrene monomers such as styrene, ⁇ -methylstyrene, p-styrenesulfonic acid and their sodium and potassium salts; butadiene, isoprene, chloroprene, etc. Diene monomers such as N-vinylpyrrolidone and the like.
  • (meth)acrylic means acrylic and methacryl.
  • ethylenically unsaturated monomers and diene monomers from the group consisting of vinyl ester monomers, (meth)acrylate monomers, styrene monomers, and diene monomers. At least one selected type is preferred.
  • a (meth)acrylic acid ester monomer a styrene monomer, and a mixture of two or more of these monomers. It may contain a monomer as a minor component (for example, 0 to 40% by mass).
  • the monomers constituting the (meth)acrylic acid ester polymer include acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms, methacrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms, or these. Mixtures are more preferred.
  • One embodiment of the present invention includes a step of emulsion polymerizing at least one monomer selected from the group consisting of ethylenically unsaturated monomers and diene monomers in the presence of the emulsion polymerization dispersant.
  • a method for producing an aqueous emulsion including: The aqueous emulsion thus obtained has a low content of aggregates containing coarse particles and has excellent mechanical stability.
  • the dispersant for emulsion polymerization when the dispersant for emulsion polymerization is charged into the polymerization system, there are no particular restrictions on the method of charging or adding. Examples include a method in which the dispersant for emulsion polymerization is added to the polymerization system all at once at the initial stage, and a method in which it is added continuously during the polymerization. Among these, from the viewpoint of increasing the grafting rate of PVA to the emulsion dispersoid, a method in which a dispersant for emulsion polymerization is initially added to the polymerization system all at once is preferred.
  • the amount of the dispersant for emulsion polymerization used during emulsion polymerization is preferably 100 parts by mass of at least one monomer selected from the group consisting of ethylenically unsaturated monomers and diene monomers. It may be 0.2 to 40 parts by weight, more preferably 0.3 to 20 parts by weight, even more preferably 0.5 to 15 parts by weight.
  • amount of the dispersant for emulsion polymerization within the above range, aggregation of dispersoid particles in the aqueous emulsion is further suppressed, polymerization stability is improved, and the viscosity of the polymerization system is suppressed from becoming too high. Polymerization can proceed more uniformly, and the heat of polymerization tends to be removed better.
  • a water-soluble single initiator or a water-soluble redox initiator commonly used in emulsion polymerization is used as the polymerization initiator.
  • sole initiators include hydrogen peroxide, persulfates (potassium, sodium or ammonium salts), and the like.
  • the redox initiator include a combination of a peroxide and a metal ion, and a combination of a peroxide, a metal ion, and a reducing substance.
  • the peroxides include hydrogen peroxide, hydroxy peroxides such as cumene hydroxy peroxide and t-butyl hydroxy peroxide, persulfates (potassium, sodium or ammonium salts), t-butyl peracetate, peracid esters ( t-butyl perbenzoate).
  • the metal ions include metal ions that can undergo one-electron transfer, such as Fe 2+ , Cr 2+ , V 2+ , Co 2+ , Ti 3+ , and Cu + .
  • the reducing substance include sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, Rongalit, 1-ethyl-ascorbic acid, and ascorbic acid.
  • the dispersion medium in emulsion polymerization is preferably an aqueous medium containing water as a main component.
  • the aqueous medium containing water as a main component may contain a water-soluble organic solvent (alcohols, ketones, etc.) that is soluble in water in any proportion.
  • the term "aqueous medium containing water as a main component" refers to a dispersion medium containing 50% by mass or more of water. From the viewpoint of cost and environmental impact, the dispersion medium is preferably an aqueous medium containing 90% by mass or more of water, and more preferably water.
  • auxiliary agents conventionally used in emulsion polymerization such as liquid regulators, monohydric or polyhydric alcohols, plasticizers, and antifoaming agents, may be used during or after the polymerization.
  • One embodiment of the present invention is a laminate comprising a base material and a layer formed from the aqueous emulsion.
  • the layer formed from the aqueous emulsion may be a layer formed by drying the aqueous emulsion.
  • the laminate may include a base material and a layer formed from a coating agent containing the aqueous emulsion.
  • Another embodiment of the present invention is a laminate including a base material and a layer containing the emulsion polymerization dispersant.
  • the layer formed from the aqueous emulsion described above is an example of a layer containing a dispersant for emulsion polymerization.
  • a preferred embodiment of the laminate is a coated paper in which a coating agent containing the aqueous emulsion is applied to paper as a base material.
  • the coating agent may be the aqueous emulsion described above.
  • As the base paper used for the coated paper chemical pulp such as hardwood kraft pulp and softwood kraft pulp, mechanical pulp such as GP (ground wood pulp), RGP (refiner ground pulp), TMP (thermomechanical pulp), etc.
  • GP ground wood pulp
  • RGP refiner ground pulp
  • TMP thermomechanical pulp
  • the paper may include wood-free paper, medium-quality paper, alkaline paper, glassine paper, semi-glassine paper, paperboard, white paperboard, etc. used for cardboard, building materials, manila balls, white balls, chipboards, etc. Can be used.
  • the basis weight of the front paper is not particularly limited and may be adjusted depending on the use, but it is usually 10 to 500 g/m 2 or less, preferably 40 to 200 g/m 2 .
  • the paper used for the coated paper may contain organic or inorganic pigments and papermaking auxiliary chemicals such as paper strength enhancers, sizing agents, and retention improvers. Further, the paper used for the coated paper may be subjected to various surface treatments.
  • the coating amount of the coating agent can be arbitrarily selected depending on the properties of the paper to be coated, but it is usually preferably about 0.1 to 30 g/m 2 in terms of solid content.
  • the coating agent may be applied to the surface of the paper, or may be impregnated into the paper. In the former case, the coating agent may be applied to one side or both sides of the paper.
  • Methods for applying the coating agent to paper include transfer methods such as a shim sizer and gate roll coater, and impregnation methods such as a size press.
  • the transfer method is preferable since the coating layer is more easily formed.
  • the coating agent tends to form a film, even when the impregnation method is adopted, the penetration of the coating agent into the inside of the paper is suppressed, and a coating layer is efficiently formed near the surface. Therefore, the amount of coating is reduced, drying becomes easier, and costs are reduced.
  • the temperature of the coating agent during application is usually room temperature to 100°C.
  • the paper coated with the coating agent solution can be dried by a known method, such as hot air, infrared rays, a heating cylinder, or a combination thereof.
  • the drying temperature is usually room temperature to 120°C.
  • Barrier properties can be further improved by subjecting the dried coated paper to humidity control and calender treatment.
  • the calendering conditions are usually a roll temperature of room temperature to 100°C and a roll linear pressure of 20 to 300 kg/cm.
  • the coated paper may have a layer other than a layer formed from an aqueous emulsion or a layer containing a dispersant for emulsion polymerization.
  • Coated paper is also used as special paper such as release base paper, oil-resistant paper, thermal paper, ink-jet paper, pressure-sensitive paper, gas barrier paper, and other barrier papers, and among them, it is suitably used as release base paper and oil-resistant paper.
  • the peak of CH connected to OH groups appears at 3.8 to 4.0 ppm (integral value [M]), and the peak of CH connected to OAc groups appears at 4.2 to 4.0 ppm. Appears at .6 ppm (integral value [N]). Furthermore, the peak of the methylene group adjacent to the formyl group and carbonyl group appears at 2.3 to 2.5 ppm (integral value [O]). Furthermore, the peak of protons constituting the formyl group appears at 9.5 to 10.0 ppm (integral value [P]).
  • Carbonyl group content (mol%) [ ⁇ ([O]/2)-[P] ⁇ /([M]+[N])] ⁇ 100
  • the peak of CH to which an OH group is connected appears at 3.8 to 4.0 ppm (integral value [M]), and the peak to CH to which an OAc group is connected appears at 4.2 to 4. Appears at .6 ppm (integral value [N]).
  • alkenyl groups in PVA was determined from the following formula as a value for structural units derived from vinyl alcohol monomers (vinyl alcohol units and vinyl ester units).
  • Alkenyl group content (mol%) ⁇ [Q]/([M]+[N]) ⁇ 100
  • the peak of CH connected to OH groups appears at 3.8 to 4.0 ppm (integral value [M]), and the peak of CH connected to OAc groups appears at 4.2 to 4.0 ppm. Appears at .6 ppm (integral value [N]).
  • the peak of protons constituting the formyl group appears at 9.5 to 10.0 ppm (integral value [P]).
  • the Na content was measured by atomic absorption measurement as follows. After carbonizing 1.0 parts by mass of PVA at 650°C, 2.0 parts by mass of hydrochloric acid was added and heated at 150°C for 3 minutes. It was dissolved in ion-exchanged water to create a 50 mL aqueous solution. The atomic absorption of the aqueous solution was measured, and the Na content was calculated using a separately prepared calibration curve.
  • the water-insoluble content of PVA was measured as follows. A 500 mL flask equipped with a stirrer and a reflux condenser was prepared in a water bath set at 20° C., 285 g of distilled water was put into the flask, and stirring was started at 300 rpm. 15 g of PVA particles were weighed and gradually introduced into the flask. After adding the entire amount (15 g) of PVA particles, the temperature of the water bath was raised to 90° C. over 30 minutes to dissolve the PVA particles, thereby obtaining a PVA solution. After the temperature of the water bath reached 90° C., dissolution was continued with stirring at 300 rpm for an additional 60 minutes.
  • the solid content concentration at the time of termination of polymerization was 39.7% by mass, and the polymerization rate was 40%. Subsequently, unreacted monomers were removed at 30° C. under reduced pressure while occasionally adding methanol to obtain a methanol solution (concentration 35.2% by mass) of a vinyl ester polymer. Next, 116.8 parts by mass of a methanol solution of a vinyl ester polymer prepared by further adding methanol to this methanol solution (30 parts by mass of the polymer in the solution) was added with 2 parts of a 10% by mass methanol solution of sodium hydroxide. .1 part by mass and 1.2 parts by mass of ion-exchanged water were added, and saponification was carried out at 40°C.
  • the solid content concentration at the time of termination of polymerization was 26.7% by mass, and the polymerization rate was 30%. Subsequently, unreacted monomers were removed at 30° C. under reduced pressure while occasionally adding methanol to obtain a methanol solution (concentration 30.2% by mass) of a vinyl ester polymer. Next, 117.7 parts by mass of a methanol solution of a vinyl ester polymer prepared by further adding methanol to this methanol solution (30 parts by mass of the polymer in the solution) was added with 1 part by mass of a 10% by mass methanol solution of sodium hydroxide. .3 parts by mass and 1.2 parts by mass of ion-exchanged water were added, and saponification was carried out at 40°C.
  • Example A1 (Preparation of aqueous solution) PVA-A1 obtained in Production Example A1 was poured into stirring water, heated to 95°C, and dissolved in water to give a concentration of 6% by mass (1560 parts by mass of water per 100 parts by mass of PVA). An aqueous solution was prepared.
  • a release paper base paper was prepared in the following manner.
  • the stability of the coating agent (aqueous solution), coating unevenness of the release paper base paper, air permeability (air permeation resistance), silicone curability, and adhesion of the release layer were evaluated using the following methods. The results are shown in Table 3.
  • Aqueous solution stability The state of the aqueous solution after being left at 40° C. for 7 days was observed, and the change in state before and after storage was evaluated using the following index. If it was A to B, it was judged that the storage stability was excellent. A: No separation or sedimentation B: Slight separation or sedimentation, but fluidity C: Separation or sedimentation observed. or no liquidity
  • the coating agent was applied to glassine paper with an air permeability of 100 sec using a wire bar so that the coating amount was about 0.7 g/m 2 in terms of dry mass. After coating, coated paper was obtained by drying at 100° C. for 5 minutes. The obtained coated paper was treated twice in a supercalender at 70° C. and 400 kg/cm 2 to obtain a release paper base paper.
  • the air permeability of the release paper base paper was measured using an Oken type smoothness air permeability tester according to JIS P8117, and evaluated using the following index. If it was A to B, it was judged that the resistance to air permeation was excellent. A: 50,000 seconds or more B: 1,000 seconds or more and less than 50,000 seconds C: Less than 1,000 seconds
  • the time it takes for the silicone to harden refers to the time (seconds) required until the silicone layer does not peel off at all when the silicone layer is strongly rubbed with a finger 10 times at predetermined time intervals. If it was A to B, it was judged that the silicone curability was excellent. A: Less than 60 seconds B: 60 seconds or more and less than 120 seconds C: 120 seconds or more
  • the silicone layer was rubbed strongly with a finger. As a result, the silicone layer did not peel off. After standing for another week under the same conditions, the silicone layer was rubbed vigorously with a finger. As a result, the silicone layer did not peel off.
  • B After being left for one week at 40° C. and 90% RH, the silicone layer was strongly rubbed with a finger. As a result, the silicone layer did not peel off. However, under the same conditions, after being left for another week, the silicone layer peeled off when rubbed forcefully with a finger.
  • C After being left for one week at 40° C. and 90% RH, the silicone layer was rubbed strongly with a finger. As a result, the silicone layer peeled off.
  • Examples A2 to A6, Comparative Examples A1 to A4 An aqueous solution (coating agent) was prepared and a release paper base paper was prepared in the same manner as in Example A1 except that the type of PVA was changed as shown in Table 3.
  • the aqueous solution stability of the obtained aqueous solution (coating agent), coating unevenness of the release paper base paper, air permeability, silicone curability and adhesion were evaluated in the same manner as in Example A1. The results are shown in Table 3.
  • coating agents containing aqueous solutions of vinyl alcohol polymers having carbonyl groups, formyl groups, and alkenyl groups in the same or different molecules have excellent aqueous solution stability and It can be seen that there are few manufacturing irregularities. Furthermore, it can be seen that the obtained release paper base paper has high air permeability, good silicone curability, and good adhesion of the release layer (Examples A1 to A6).
  • the carbonyl group content of PVA is 0.05 mol% or more
  • the alkenyl group content is 0.04 mol% or more
  • the formyl group content is 0.1 mol% or more
  • silicone curability and peelability The layer adhesion was particularly excellent (Examples A1 to A3, A5, and A6).
  • Example A7 (Preparation of adhesive) PVA-A1 obtained in Production Example A1 was poured into stirring water, heated to 95°C, and dissolved in the water to form an aqueous solution with a concentration of 15% by mass (567 parts by mass of water per 100 parts by mass of PVA). was prepared and used as an adhesive. Initial adhesion and water-resistant adhesion were evaluated using the following methods.
  • Examples A8 to A12, Comparative Examples A5 and A6 An adhesive was produced in the same manner as in Example A7, except that the type of PVA was changed to the contents shown in Table 4. The initial adhesion and water-resistant adhesion of the resulting adhesive were evaluated in the same manner as in Example A7. The results are shown in Table 4.
  • adhesives containing aqueous solutions of vinyl alcohol polymers having carbonyl, formyl, and alkenyl groups in the same or different molecules had good initial adhesion and water-resistant adhesion.
  • the saponification degree of PVA is 75 mol% or more
  • the carbonyl group content is 0.05 mol% or more
  • the alkenyl group content is 0.04 mol% or more
  • the formyl group content is 0.1 mol%.
  • the water-resistant adhesion was particularly excellent (Examples A7, A8, A11, A12).
  • the solid content concentration at the time of termination of polymerization was 44.3% by mass, and the polymerization rate was 45%. Subsequently, unreacted monomers were removed at 30° C. under reduced pressure while occasionally adding methanol to obtain a methanol solution (concentration 38.2% by mass) of a vinyl ester polymer. Next, 191.3 parts by mass of a methanol solution of a vinyl ester polymer prepared by further adding methanol to this methanol solution (60 parts by mass of the polymer in the solution) was added with 6 parts by mass of a 5% by mass methanol solution of sodium hydroxide. .8 parts by mass and 1.84 parts by mass of ion-exchanged water were added, and saponification was carried out at 40°C.
  • methanol was used during polymerization, aldehyde (a) was not used, polymerization conditions such as the amount of vinyl acetate charged, the concentration of vinyl ester polymer during saponification, and water relative to vinyl acetate units. It was produced in the same manner as in the production of PVA-B1, except that the saponification conditions such as the molar ratio of sodium oxide were changed as shown in Table 5.
  • PVA-B9 methanol was used during polymerization, aldehyde (a) was not used, a chain transfer agent (b) was used, polymerization conditions such as the amount of vinyl acetate charged, and vinyl ester type during saponification.
  • Example B1 (Production of Em-1)
  • 22 g of an ammonium persulfate aqueous solution with a concentration of 5% by mass and 6.1 g of a sodium hydrogen carbonate aqueous solution with a concentration of 1% by mass were added.
  • the aqueous emulsion was used as a coating agent, and this coating agent was applied by hand to PPC (Plain Paper Copier) paper (high quality paper) having a basis weight of 70 gsm using a wire bar. Next, using a cylinder type rotary dryer, drying was performed at 105° C. for 5 minutes to produce coated paper.
  • This coated paper is a laminate including PPC paper as a base material and a layer containing an aqueous emulsion.
  • the coating amount of the coating agent in terms of solid content was 5.0 gsm (one side).
  • the resulting coated paper was conditioned at 20° C. and 65% RH for 72 hours.
  • the oil resistance of the coated paper after humidity conditioning was evaluated by the following KIT test. The results are shown in Table 7.
  • Example B2 Manufacture of Em-2
  • An aqueous emulsion (Em-2) and coated paper were prepared and evaluated in the same manner as in Example B1, except that the mass ratio of methyl methacrylate and 2-ethylhexyl acrylate was changed as shown in Table 7. The results are shown in Table 7.
  • Example B3 Manufacture of Em-3) An aqueous emulsion (Em-3) and coated paper were prepared in the same manner as in Example B1, except that methyl methacrylate, 2-ethylhexyl acrylate, and styrene were used as monomers in the mass ratios listed in Table 7. ,evaluated. The results are shown in Table 7.
  • Examples B4 to B8, Comparative Examples B1 to B3 (Production of Em-4 to Em-11) As shown in Table 7, aqueous emulsions (Em-4 to Em-11) were prepared in the same manner as in Example B1, except that PVA-B2 to PVA-B9 were used instead of PVA in Example B1 (PVA-B1). And each coated paper was produced and evaluated. The results are shown in Table 7.
  • aqueous emulsions obtained using dispersants containing vinyl alcohol polymers having carbonyl groups, formyl groups, and alkenyl groups in the same or different molecules are free from the formation of aggregates. It also had excellent mechanical stability. Furthermore, coated papers produced using these aqueous emulsions as coating agents also had excellent oil resistance.
  • the aqueous solution containing PVA of the present invention is suitable for coating agents, adhesives, paper processing agents, and the like.
  • the emulsion polymerization dispersant of the present invention is suitable for producing an aqueous emulsion.
  • the aqueous emulsion is suitably used for various adhesives, paint bases, various binders for impregnated paper and nonwoven products, and various coating agents.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/JP2023/013207 2022-03-31 2023-03-30 水溶液、コーティング剤、接着剤、紙加工剤、乳化重合用分散剤、水性エマルジョン、積層体及び水性エマルジョンの製造方法 WO2023190884A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202380031467.XA CN118974109A (zh) 2022-03-31 2023-03-30 水溶液、涂布剂、粘接剂、纸加工剂、乳液聚合用分散剂、水性乳液、层叠体和水性乳液的制造方法
DE112023001013.7T DE112023001013T5 (de) 2022-03-31 2023-03-30 Wässrige lösung, beschichtungsmittel, klebstoff, papierverarbeitungsmittel, dispergiermittel für emulsionspolymerisation, wässrige emulsion, schichtanordnung und verfahren zum herstellen einer wässrigen emulsion
JP2024512807A JPWO2023190884A1 (enrdf_load_stackoverflow) 2022-03-31 2023-03-30

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2022058662 2022-03-31
JP2022058661 2022-03-31
JP2022-058661 2022-03-31
JP2022-058662 2022-03-31

Publications (1)

Publication Number Publication Date
WO2023190884A1 true WO2023190884A1 (ja) 2023-10-05

Family

ID=88202819

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/013207 WO2023190884A1 (ja) 2022-03-31 2023-03-30 水溶液、コーティング剤、接着剤、紙加工剤、乳化重合用分散剤、水性エマルジョン、積層体及び水性エマルジョンの製造方法

Country Status (3)

Country Link
JP (1) JPWO2023190884A1 (enrdf_load_stackoverflow)
DE (1) DE112023001013T5 (enrdf_load_stackoverflow)
WO (1) WO2023190884A1 (enrdf_load_stackoverflow)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6189208A (ja) * 1984-10-08 1986-05-07 Kuraray Co Ltd ポリビニルアルコール系マクロモノマーの製造方法
WO2013187455A1 (ja) * 2012-06-13 2013-12-19 株式会社クラレ エチレン－ビニルアルコール樹脂組成物、多層シート、包装材及び容器
WO2015182567A1 (ja) * 2014-05-28 2015-12-03 日本酢ビ・ポバール株式会社 懸濁重合用分散安定剤、ビニル系重合体の製造方法及び塩化ビニル樹脂
WO2018124241A1 (ja) * 2016-12-28 2018-07-05 株式会社クラレ ポリビニルアルコール組成物及びその用途
WO2022071345A1 (ja) * 2020-10-02 2022-04-07 株式会社クラレ ビニルアルコール系重合体、ビニルアルコール系重合体の製造方法、懸濁重合用分散剤、懸濁重合用分散助剤、及びビニル系重合体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6189208A (ja) * 1984-10-08 1986-05-07 Kuraray Co Ltd ポリビニルアルコール系マクロモノマーの製造方法
WO2013187455A1 (ja) * 2012-06-13 2013-12-19 株式会社クラレ エチレン－ビニルアルコール樹脂組成物、多層シート、包装材及び容器
WO2015182567A1 (ja) * 2014-05-28 2015-12-03 日本酢ビ・ポバール株式会社 懸濁重合用分散安定剤、ビニル系重合体の製造方法及び塩化ビニル樹脂
WO2018124241A1 (ja) * 2016-12-28 2018-07-05 株式会社クラレ ポリビニルアルコール組成物及びその用途
WO2022071345A1 (ja) * 2020-10-02 2022-04-07 株式会社クラレ ビニルアルコール系重合体、ビニルアルコール系重合体の製造方法、懸濁重合用分散剤、懸濁重合用分散助剤、及びビニル系重合体の製造方法

Also Published As

Publication number Publication date
DE112023001013T5 (de) 2025-01-02
JPWO2023190884A1 (enrdf_load_stackoverflow) 2023-10-05

Similar Documents

Publication Publication Date Title
JP6694561B1 (ja) ビニルアルコール系重合体及びその用途
JP7058260B2 (ja) 剥離紙原紙及びその製造方法、並びに剥離紙
US11208550B2 (en) Polyvinyl alcohol composition and use thereof
JP2019038935A (ja) ポリビニルアルコール組成物及びその用途
JP2021098802A (ja) コーティング剤及びそれを用いた剥離紙原紙並びに剥離紙
CN117279961A (zh) 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
WO2023190884A1 (ja) 水溶液、コーティング剤、接着剤、紙加工剤、乳化重合用分散剤、水性エマルジョン、積層体及び水性エマルジョンの製造方法
CN116635503B (zh) 改性乙烯醇系聚合物、改性乙烯醇系聚合物的制造方法、颗粒、水溶液、涂覆液、涂覆物、成形体、剥离纸、分散剂、乙烯基系聚合物的制造方法和混合物
CN118974109A (zh) 水溶液、涂布剂、粘接剂、纸加工剂、乳液聚合用分散剂、水性乳液、层叠体和水性乳液的制造方法
JP7731785B2 (ja) 塗工液、塗工物、成形体及び剥離紙
JP2013237963A (ja) 剥離紙原紙、その製造方法並びにこの剥離紙原紙を用いた剥離紙及び積層体
JP2013237829A (ja) コーティング剤、並びにこのコーティング剤を塗工してなる塗工物及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23780892

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024512807

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202380031467.X

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 112023001013

Country of ref document: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23780892

Country of ref document: EP

Kind code of ref document: A1