WO2023054707A1 - クレーピング用接着剤、クレーピング用接着剤用の粉末、クレーピング用接着剤の製造方法、及びトイレットペーパー、ティシュペーパー、タオルペーパー、キッチンペーパー又はナプキン原紙 - Google Patents

クレーピング用接着剤、クレーピング用接着剤用の粉末、クレーピング用接着剤の製造方法、及びトイレットペーパー、ティシュペーパー、タオルペーパー、キッチンペーパー又はナプキン原紙 Download PDF

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WO2023054707A1
WO2023054707A1 PCT/JP2022/036838 JP2022036838W WO2023054707A1 WO 2023054707 A1 WO2023054707 A1 WO 2023054707A1 JP 2022036838 W JP2022036838 W JP 2022036838W WO 2023054707 A1 WO2023054707 A1 WO 2023054707A1
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Prior art keywords
pva
molecular weight
vinyl alcohol
creping adhesive
powder
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PCT/JP2022/036838
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English (en)
French (fr)
Japanese (ja)
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悠太 田岡
美鈴 藤森
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2023551924A priority Critical patent/JPWO2023054707A1/ja
Priority to EP22876569.9A priority patent/EP4411067A4/en
Priority to US18/696,977 priority patent/US20240409794A1/en
Priority to CN202280065496.3A priority patent/CN118043520A/zh
Publication of WO2023054707A1 publication Critical patent/WO2023054707A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C08G73/0286—Preparatory process from polyamidoamines and epihalohydrins
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/02—Polyamines
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F5/00—Dryer section of machines for making continuous webs of paper
    • D21F5/18—Drying webs by hot air
    • D21F5/181—Drying webs by hot air on Yankee cylinder
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
    • 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
    • D21H21/14—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 characterised by function or properties in or on the paper
    • D21H21/146—Crêping adhesives
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/002—Tissue paper; Absorbent paper
    • 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to a creping adhesive, a creping adhesive powder, a method for producing a creping adhesive, and toilet paper, tissue paper, towel paper, kitchen paper, or napkin base paper.
  • Creping is usually performed in the production of paper with flexibility and bulkiness such as toilet paper and tissue paper. Creping creates fine wrinkles (crepes) in the paper and imparts softness and bulk. Creping is, for example, a process in which wet paper (pre-dried wet paper obtained by papermaking) is attached to the surface of a cylindrical dryer such as a Yankee dryer and dried, and the dried paper is removed from the dryer surface. This is done by scraping with a doctor blade. Scraping with a doctor blade in this manner forms fine wrinkles in the paper.
  • a creping adhesive When creping, a creping adhesive is usually applied to the surface of the cylindrical dryer to form a film of the adhesive on the surface of the dryer. This adhesive film is effective, for example, to increase the adhesion of the paper to the dryer.
  • a creping adhesive it is known to use an aqueous solution containing a vinyl alcohol polymer (hereinafter the vinyl alcohol polymer is also referred to as "PVA”) (see Patent Document 1).
  • Creping adhesives are required to have good adhesion (wet adhesion) to the object (wet paper) in a wet state.
  • the inventors have found that when a creping adhesive with high stringiness is used, it becomes possible to form a good crepe. The reason for this is not clear, but when a creping adhesive with high spinnability is used, the adhesive component (PVA) penetrates into the pulp fibers relatively inside the paper, so the paper and the dryer surface It is speculated that the adhesion is improved and as a result crepe formation is facilitated during scraping with a doctor blade.
  • conventional creping adhesives using PVA are not necessarily sufficient in stringiness, wet adhesion, etc., and improvements are desired.
  • An object of the present invention is to provide a creping adhesive with good stringiness and wet adhesion, a powder and production method for obtaining such a creping adhesive, and toilet paper using such a creping adhesive. , tissue paper, towel paper, kitchen paper or napkin base paper.
  • the PVA (A) contains PVA having a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less, and the number average molecular weight of the PVA (A);
  • the ratio Mw/Mn of the weight average molecular weight Mw to Mn is 2.5 or more.
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA (A) is 3.8 or more.
  • the PVA (A) contains a PVA (A1) containing a structural unit derived from at least one selected from the group consisting of monomers having a carboxy group and derivatives thereof. glue; [3] At least one selected from the group consisting of the above monomers having a carboxy group and derivatives thereof is at least one selected from the group consisting of ethylenically unsaturated dicarboxylic acids, monoesters, diesters and anhydrides thereof.
  • P is the viscosity average degree of polymerization.
  • the creping adhesive according to any one of [2] to [5], wherein the PVA (A1) satisfies the following formula (II); 1.0 ⁇ g A /g B ⁇ 3.0 (II)
  • g A is the degree of branching at an absolute molecular weight of 200,000.
  • g B is the degree of branching at an absolute molecular weight of 800,000.
  • the creping adhesive according to any one of [2] to [6], wherein the degree of saponification of the PVA (A1) is 65 mol% or more and 99 mol% or less; [8]
  • the PVA (A1) is the PVA that satisfies at least the above (i) and has a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less.
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA (A) is 3.8 or more.
  • the powder for creping adhesive according to any one of ⁇ [16]; [18] The powder for creping adhesive according to any one of [14] to [17], further comprising an antifoaming agent (C); [19] The powder for creping adhesive of [18], wherein the antifoaming agent (C) is at least one selected from the group consisting of nonionic surfactants and anionic surfactants; [20]
  • a method for producing a creping adhesive comprising the step of dissolving PVA (A) in water and satisfying at least one of the following (i) and (ii); (i) the PVA (A) contains PVA having a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less, and the number average molecular weight of the PVA (A);
  • the ratio Mw/Mn of the weight average molecular weight Mw to Mn is 2.5
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA (A) is 3.8 or more.
  • the PVA (A) contains PVA having a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less, and the number average molecular weight of the PVA (A);
  • the ratio Mw/Mn of the weight average molecular weight Mw to Mn is 2.5 or more.
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA (A) is 3.8 or more. This is achieved by providing either
  • a creping adhesive having good stringiness and wet adhesion a powder and production method for obtaining such a creping adhesive, and toilet paper using such a creping adhesive , tissue paper, towel paper, kitchen paper or napkin base paper.
  • FIG. 1 is a graph showing the relationship between the absolute molecular weights and the intrinsic viscosities ([ ⁇ ] branch and [ ⁇ ] linear ) of PVA-1 and PVA-17 in Examples.
  • FIG. 2 is a graph showing the relationship between the absolute molecular weight of PVA-1 and the degree of branching (g m ) in Examples.
  • FIG. 3 is a diagram illustrating a fluidity evaluation method in Examples.
  • the creping adhesive of the present invention contains a vinyl alcohol polymer (PVA) (A) and satisfies at least one of the following (i) and (ii).
  • PVA vinyl alcohol polymer
  • the PVA (A) contains PVA having a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less, and the number average molecular weight of the PVA (A);
  • the ratio Mw/Mn of the weight average molecular weight Mw to Mn is 2.5 or more.
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA (A) is 3.8 or more.
  • the creping adhesive has good stringiness and wet adhesion. Furthermore, in one form of the creping adhesive, the fluidity is also good. Therefore, by using the creping adhesive, good crepe can be effectively imparted to paper in the manufacturing process of paper such as toilet paper.
  • the reason why the creping adhesive has good stringiness, wet adhesion, etc. is not clear, but when the molecular weight distribution of PVA (A) is wide or the PVA (A) has many branched structures, the aqueous solution and It is considered that the physical properties (viscosity, etc.) when heated are different from those of ordinary PVA, and that the adhesion to the adherend is improved.
  • the degree of branching of a polymer is an index representing the degree of branching structure of a polymer in the range of 0 to 1, as will be described later in detail, and the smaller the value, the more the branching structure.
  • Each component of the creping adhesive will be described in detail below.
  • PVA having a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less is also referred to as "branched PVA".
  • PVA (A) is a polymer having vinyl alcohol units. PVA (A) satisfies at least one of (i) and (ii) above.
  • the PVA (A) contains branched PVA, and the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA (A) is 2.5 or more.
  • the minimum degree of branching is 0.25 or more and 0.93 or less when the absolute molecular weight is in the range of 200,000 or more and 800,000 or less.
  • the degree of branching is an index representing the degree of branched structure of a polymer, and the degree of branching of a linear polymer, ie, a polymer having no branched structure, is set to 1, and the closer to 0, the more the branched structure.
  • the minimum degree of branching in the absolute molecular weight range of 200,000 or more and 800,000 or less is a value obtained by the following procedure. For PVA to be measured, the degree of branching is obtained for each absolute molecular weight in the range of 200,000 to 800,000. Then, the smallest degree of branching in the above range is set as the minimum degree of branching.
  • the absolute molecular weight of PVA when the absolute molecular weight of PVA is not distributed over the entire range of 200,000 or more and 800,000 or less, for example, when only PVA with an absolute molecular weight of 600,000 or less is included, the absolute molecular weight is 200,000 or more and 60,000.
  • the smallest degree of branching in the range of 10,000 or less is the minimum degree of branching. That is, the branched PVA composed of a plurality of molecules includes molecules with an absolute molecular weight within the range of 200,000 or more and 800,000 or less, but the absolute molecular weight is not distributed over the entire range of 200,000 or more and 800,000 or less. good too.
  • the branched PVA preferably contains PVA with an absolute molecular weight of 200,000 and PVA with an absolute molecular weight of 800,000, and the absolute molecular weights are distributed over the entire range of at least 200,000 to 800,000. more preferred.
  • the degree of branching gm at each absolute molecular weight of PVA is obtained from the following formulas (1) and (2).
  • g m ′ [ ⁇ ] branch /[ ⁇ ] linear (1)
  • gm gm ' (1/ ⁇ ) (2)
  • [ ⁇ ] branch is the intrinsic viscosity at the absolute molecular weight x (x is 200,000 or more and 800,000 or less) of the PVA (branched PVA) to be measured. It is a value calculated from the instrument and the viscosity detector.
  • [ ⁇ ] linear is the intrinsic viscosity of linear PVA at the above absolute molecular weight x, and is similarly a value calculated from a differential refractive index detector, a light scattering detector and a viscosity detector.
  • unmodified PVA synthetic vinyl acetate homopolymer having a 4% by mass aqueous solution viscosity within ⁇ 20% of the PVA to be measured and a degree of saponification within ⁇ 3 mol% is used.
  • the intrinsic viscosity at each absolute molecular weight of PVA and linear PVA to be measured can be measured by the method described in Examples.
  • the relationship between the intrinsic viscosity ratio g m ′ and the degree of branching g m represented by the above formula (1) is given by the above formula (2).
  • the minimum degree of branching is 0.25 or more and 0.93 or less, and an appropriate branched structure (crosslinking) is formed.
  • a creping adhesive containing such a branched PVA has good stringiness and wet adhesion, and tends to be particularly excellent in stringiness.
  • the upper limit of the minimum degree of branching is preferably 0.90, more preferably 0.88, and even more preferably 0.8 or 0.7 in some cases.
  • the lower limit of the minimum degree of branching is preferably 0.30, and more preferably 0.35 in some cases.
  • branched PVA PVA having a branched structure obtained by various conventional methods can be used.
  • Branched PVA can be obtained, for example, by heat-treating PVA having a crosslinkable group (carboxy group, silanol group, etc.). The minimum degree of branching can be adjusted by the content of crosslinkable groups, heat treatment conditions, and the like.
  • Specific structures of the branched PVA include PVA (A1) described later.
  • PVA (A) may contain PVA other than branched PVA.
  • examples of other PVA include unmodified PVA having no branched structure and various modified PVA having no branched structure.
  • the content of branched PVA in PVA (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, 99% by mass or more, or 100% by mass.
  • the minimum branching degree is 0.25 or more and 0.93 or less when the absolute molecular weight of all PVA (A) contained in the creping adhesive is in the range of 200,000 or more and 800,000 or less.
  • a further preferred range of the minimum degree of branching in PVA (A) is the same as the preferred range of the minimum degree of branching in the above-described branched PVA.
  • PVA (A1) PVA (A) preferably includes PVA (A1) containing structural units derived from at least one selected from the group consisting of vinyl alcohol units and monomers having a carboxy group and derivatives thereof.
  • PVA (A1) can form a crosslinked structure by heat treatment, and is suitable as an example of branched PVA. Therefore, by using PVA (A1), the stringiness, wet adhesion, etc. of the adhesive for creping are improved.
  • PVA (A1) is usually obtained by saponifying a vinyl ester polymer (copolymer of monomer (a) and vinyl ester) containing structural units derived from monomer (a).
  • Derivatives of a monomer having a carboxy group include esters, anhydrides and salts of a monomer having a carboxy group.
  • a salt of a monomer having a carboxy group means a monomer in which at least part of the carboxy group (--COOH) is present in the form of a salt (--COONa, etc.).
  • a structural unit derived from the monomer (a) may form a crosslinked structure and bond with other structural units.
  • Monomer (a) includes ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids and derivatives thereof.
  • ethylenically unsaturated monocarboxylic acids and derivatives thereof include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
  • ethylenically unsaturated dicarboxylic acids and their derivatives include ethylenically unsaturated dicarboxylic acids, their monoesters, their diesters, their anhydrides, and the like.
  • Ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.
  • Monoesters of ethylenically unsaturated dicarboxylic acids include monomethyl maleate, monoethyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl citraconate, monoethyl citraconate, monomethyl mesaconate, monoethyl mesaconate, monomethyl itaconate, itaconic acid.
  • Examples include unsaturated dicarboxylic acid monoalkyl esters such as monoethyl.
  • Diesters of ethylenically unsaturated dicarboxylic acids include dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl citraconate, diethyl citraconate, dimethyl mesaconate, diethyl mesaconate, dimethyl itaconate, diethyl itaconate. and unsaturated dicarboxylic acid dialkyl esters such as Examples of anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride and citraconic anhydride.
  • the monomer (a) is preferably an ethylenically unsaturated dicarboxylic acid, and its monoester, diester and anhydride, and maleic acid and monoalkyl maleate.
  • Esters, dialkyl maleates, maleic anhydride, fumaric acid, monoalkyl fumarate and dialkyl fumarate are more preferred, with monomethyl maleate, dimethyl maleate, maleic anhydride, monomethyl fumarate and dimethyl fumarate being particularly preferred.
  • 1 type(s) or 2 or more types can be used for a monomer (a).
  • the lower limit of the content (S) of structural units derived from the monomer (a) with respect to all structural units of PVA (A1) is preferably 0.05 mol%, more preferably 0.1 mol%, and 0 0.2 mol % or 0.3 mol % may be even more preferred.
  • the upper limit of the content (S) is preferably 15 mol%, more preferably 10 mol%, still more preferably 5 mol%, 3 mol%, 2 mol%, 1 mol% or 0.5 mol% is more preferable in some cases.
  • the upper limit of the viscosity average polymerization degree (P) of PVA (A1) may be, for example, 8,000, preferably 7,000, more preferably 6,000, 5,000, 4,500 or 4,000. is more preferred in some cases.
  • the lower limit of the viscosity average degree of polymerization (P) may be, for example, 100 or 200, preferably 300, more preferably 400, further preferably 500 or 1,000, 2,000, 2,500 or 3,000 is particularly preferred in some cases.
  • the viscosity-average degree of polymerization (P) is within the above range, the creping adhesive tends to have better stringiness, wet adhesion, fluidity, and the like.
  • the viscosity average degree of polymerization (P) is a value measured according to JIS K6726:1994. Specifically, it can be determined by the method described in the Examples.
  • the lower limit of the vinyl alcohol unit content relative to all structural units in PVA (A1) is preferably 35 mol%, more preferably 50 mol%, still more preferably 70 mol%, and even more preferably 80 mol% or 85 mol%. In some cases it is preferable.
  • the upper limit of the vinyl alcohol unit content is preferably 99.9 mol %, more preferably 99 mol %.
  • the lower limit of the degree of saponification of PVA (A1) is preferably 65 mol%, more preferably 80 mol%, and even more preferably 85 mol%.
  • the upper limit of the degree of saponification may be 100 mol%, preferably 99 mol%, more preferably 95 mol%, and even more preferably 92 mol% in some cases.
  • the degree of saponification is a value measured by the method described in JIS K6726:1994.
  • PVA (A1) preferably satisfies the following formula (I). S ⁇ P>250 (I)
  • S is the content (mol%) of structural units derived from the monomer (a) with respect to all structural units.
  • P is the viscosity average degree of polymerization.
  • the lower limit of S ⁇ P is more preferably 300, and may be even more preferably 400, 500, 600 or 700.
  • the upper limit of S ⁇ P is preferably 4,000, more preferably 3,000, still more preferably 2,000, and even more preferably 1,500.
  • the minimum degree of branching is preferably 0.25 or more and 0.93 or less. That is, PVA (A1) is preferably branched PVA.
  • the upper limit of the minimum degree of branching of PVA (A1) is preferably 0.90, more preferably 0.88, and even more preferably 0.8 or 0.7 in some cases.
  • the lower limit of the minimum degree of branching of PVA (A1) is preferably 0.30, and more preferably 0.35 in some cases.
  • PVA (A1) preferably satisfies formula (II). 1.0 ⁇ g A /g B ⁇ 3.0 (II)
  • g A is the degree of branching at an absolute molecular weight of 200,000 (the degree of branching of PVA with an absolute molecular weight of 200,000 among PVA (A1)).
  • g B is the branching degree at an absolute molecular weight of 800,000 (the branching degree of PVA with an absolute molecular weight of 800,000 among PVA (A1)).
  • the value of the ratio g A /g B tends to increase as the proportion of PVA that is excessively heated and excessively crosslinked increases. Therefore, as will be described later, when heat-treating a saponified product of a vinyl ester polymer (copolymer), fine powder that is likely to be heated excessively is removed in advance, the heat treatment is performed while removing the fine powder, or the fine powder is removed after the heat treatment. can be removed to reduce the content of the ratio g A /g B.
  • PVA (A1) may contain structural units other than vinyl alcohol units, vinyl ester units, and structural units derived from the monomer (a).
  • monomers that give the other structural units include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene; N-methylacrylamide, N-ethylacrylamide, 2-acrylamido-2-methylpropane acrylamide derivatives such as sulfonic acid; methacrylamide derivatives such as N-methyl methacrylamide and N-ethyl methacrylamide; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether and n-butyl vinyl ether; ethylene glycol vinyl ether, hydroxy group-containing vinyl ethers such as 1,3-propanediol vinyl ether and 1,4-butanediol vinyl ether; allyl acetate; 3,4-di
  • the content of the other structural units with respect to all structural units of PVA (A1) may be preferably 20 mol% or less, more preferably 10 mol% or less, 3 mol% or less, 1 mol% or less, or 0.1 mol % or less may be even more preferable.
  • the content of the other structural unit may be, for example, 0.1 mol % or more, or 1 mol % or more.
  • PVA (A) may contain PVA other than PVA (A1).
  • PVA examples of other PVA include conventionally known PVA such as undenatured PVA and various other modified PVA.
  • the content of PVA (A1) in PVA (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, 99% by mass or more, or 100% by mass. That is, PVA (A) is preferably PVA (A1) having a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less.
  • PVA (A1) is step (1) of obtaining a copolymer of the monomer (a) and a vinyl ester; Step (2) of obtaining a saponified product of the copolymer, and Step (3) of heat-treating the saponified product It can be suitably obtained by a manufacturing method comprising
  • step (1) a copolymer of monomer (a) and vinyl ester is obtained.
  • monomer (a) examples and suitable examples of the monomer (a) are as described above.
  • vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and vinyl versatate. Among them, vinyl acetate is preferred.
  • Examples of polymerization methods include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these methods, a bulk polymerization method performed without a solvent and a solution polymerization method performed using a solvent such as alcohol are preferable, and a solution polymerization method performed in the presence of a lower alcohol is more preferable. As the lower alcohol, alcohols having 3 or less carbon atoms are preferable, methanol, ethanol, n-propanol and isopropanol are more preferable, and methanol is even more preferable. In performing a polymerization reaction by a bulk polymerization method or a solution polymerization method, either a batch system or a continuous system can be employed as the reaction system.
  • initiators used in the polymerization reaction examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy -2,4-dimethylvaleronitrile); and known initiators such as organic peroxide initiators such as benzoyl peroxide and n-propylperoxycarbonate.
  • organic peroxide initiators such as benzoyl peroxide and n-propylperoxycarbonate.
  • a copolymerizable monomer can be further copolymerized within a range that does not impair the gist of the present invention.
  • Specific examples of such other monomers are as described above as monomers that provide other structural units.
  • a chain transfer agent may coexist during copolymerization for the purpose of adjusting the degree of polymerization of the obtained PVA.
  • chain transfer agents include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone and cyclohexanone; mercaptans such as 2-hydroxyethanethiol and 3-mercaptopropionic acid; thiocarboxylic acids such as thioacetic acid.
  • the amount of the chain transfer agent to be added is determined according to the chain transfer constant of the chain transfer agent to be added and the desired degree of polymerization of PVA, but is generally 0.1 to 10% by mass based on the vinyl ester used. is preferred.
  • step (2) the copolymer (vinyl ester polymer) obtained in step (1) above is saponified in a solution using an alkali catalyst or an acid catalyst to obtain a saponified product.
  • an alcoholysis or hydrolysis reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as p-toluenesulfonic acid can be applied.
  • Solvents used in the saponification reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; and aromatic hydrocarbons such as benzene and toluene. These can be used alone or in combination of two or more. Among these, it is convenient and preferable to use methanol or a mixed solution of methanol and methyl acetate as a solvent and perform the saponification reaction in the presence of sodium hydroxide as a basic catalyst.
  • the saponification reaction can be carried out using a belt-type reactor, a kneader-type reactor, a tower-type reactor, or the like.
  • the temperature for saponification is not particularly limited, it is preferably 20° C. or higher and 60° C. or lower.
  • a gel-like product precipitates as the saponification progresses, it is preferable to pulverize the product and further proceed with the saponification. Thereafter, the resulting solution is neutralized to complete saponification and washed to obtain a saponified product.
  • the saponification method is not limited to the methods described above, and known methods can be employed.
  • step (3) the saponified product obtained through step (2) is heat-treated.
  • the heat treatment is preferably performed under an air atmosphere or a nitrogen atmosphere.
  • the heat treatment is preferably performed on a solid saponified product, more preferably on a powdery (particulate) saponified product.
  • the saponified product may be pre-dried, and the saponified product from which volatile matter has been removed to some extent may be subjected to heat treatment.
  • the heat treatment may be performed while stirring the saponified product.
  • the heat treatment can be performed using, for example, a cylindrical agitation dryer or the like.
  • heat treatment is preferably performed at a heat treatment temperature of 100°C or higher and for a heat treatment time of 1 hour or longer.
  • the lower limit of the heat treatment temperature may be 105°C, 110°C, 115°C or 120°C.
  • the upper limit of the heat treatment temperature may be 150°C, 140°C, 130°C, or 125°C.
  • the lower limit of the heat treatment time is preferably 2 hours, more preferably 3 hours, and even more preferably 4 hours.
  • the upper limit of the heat treatment time may be 12 hours, 8 hours, or 5.5 hours. Excessive formation of crosslinks can be suppressed by setting the heat treatment temperature and the heat treatment time to the above upper limits or less.
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of PVA (A) is 2.5 or more.
  • the lower limit of the ratio Mw/Mn is preferably 3.0, more preferably 3.8, still more preferably 4.5, and even more preferably 5.0, 5.5 or 6.0.
  • the ratio Mw/Mn is equal to or higher than the above lower limit, the stringiness, wet adhesion, fluidity, etc. of the adhesive for creping tend to be further improved.
  • the upper limit of the ratio Mw/Mn may be 20 or 15, for example.
  • This PVA (A) ratio Mw/Mn is a value based on all PVA (A) contained in the creping adhesive.
  • the number average molecular weight Mn and weight average molecular weight Mw of PVA (A) can be determined by gel permeation chromatography (GPC) measurement using polymethacrylic acid as a standard substance. Specifically, it can be determined by the method described in Examples.
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of PVA (A) is 3.8 or more.
  • the lower limit of the ratio Mw/Mn is preferably 4.5, more preferably 5.0, 5.5 or 6.0.
  • the upper limit of the ratio Mw/Mn may be 20, 15, 10, 8 or 6, for example.
  • This PVA (A) ratio Mw/Mn is a value based on all PVA (A) contained in the creping adhesive.
  • PVA (A) In a form that satisfies the above (ii), conventionally known undenatured PVA and various denatured PVA can be used as PVA (A).
  • Modified PVA usually has structural units derived from monomers other than vinyl ester. Examples of other monomers include monomers exemplified as monomers that give other structural units that PVA (A1) may contain.
  • PVA (A) can be produced by a conventionally known method.
  • PVA (A) that satisfies the above (i) and has a ratio Mw/Mn of 3.8 or more is also included in the present embodiment.
  • the PVA (A) is preferably a mixture of two or more PVA different in at least one of the number average molecular weight and the viscosity average degree of polymerization.
  • the distribution of molecular weights is widened, so that PVA (A) having a ratio Mw/Mn of 3.8 or more can be easily obtained.
  • PVA (A) may have two or more peaks in, for example, a molecular weight distribution curve. It can be considered that the PVA corresponding to each peak is PVA different in at least one of the number average molecular weight and the viscosity average degree of polymerization.
  • the mixing ratio can be appropriately set so that the molecular weight distribution is broadened. Although it is possible, for example, 10:90 to 90:10 is preferable, and 30:70 to 70:30 is more preferable. Three or more types of PVA having different number average molecular weights and/or viscosity average degrees of polymerization may be mixed and used.
  • the degree of saponification of at least one of the two or more PVA having different at least one of the number average molecular weight and the viscosity average degree of polymerization is preferably 65 mol% or more and 99 mol% or less.
  • the lower limit of the degree of saponification is more preferably 70 mol%, still more preferably 80 mol%.
  • the upper limit of the degree of saponification is more preferably 95 mol%, still more preferably 92 mol%.
  • the upper limit of the viscosity-average degree of polymerization (P) of PVA (A) may be, for example, 8,000, preferably 7,000. 000 is more preferred, and 5,000, 4,500 or 4,000 may be even more preferred.
  • the lower limit of the viscosity average degree of polymerization (P) may be, for example, 100 or 200, preferably 300, more preferably 400, further preferably 500 or 1,000, 2,000, 2,500 or 3,000 is particularly preferred in some cases.
  • the creping adhesive tends to have better stringiness, wet adhesion, fluidity, and the like.
  • the lower limit of the vinyl alcohol unit content relative to all structural units in PVA (A) is preferably 35 mol%, more preferably 50 mol%, and 70 mol % is more preferred, and 80 mol % or 85 mol % are even more preferred in some cases.
  • the upper limit of the vinyl alcohol unit content is preferably 99.9 mol %, more preferably 99 mol %.
  • the lower limit of the degree of saponification of PVA (A) is preferably 65 mol%, more preferably 80 mol%, and even more preferably 85 mol%, regardless of whether the above (i) or (ii) is satisfied.
  • the upper limit of the degree of saponification may be 100 mol%, preferably 99 mol%, more preferably 95 mol%, and even more preferably 92 mol% in some cases.
  • the lower limit of the content of PVA (A) in the solid content in the adhesive for creping of the present invention is preferably 20% by mass, and 40% by mass. More preferably, 60% by mass or 80% by mass is more preferable in some cases.
  • the upper limit of this content may be 100% by mass, and 80% by mass or 60% by mass is preferable in some cases.
  • solid content means components other than a solvent and the component whose normal boiling point is 100 degrees C or less.
  • the creping adhesive of the present invention preferably further contains a polyamide resin (B).
  • a polyamide resin (B) By further including the polyamide-based resin (B) in the creping adhesive, the wet adhesion of the creping adhesive can be enhanced.
  • Polyamide resin (B) preferably has a functional group (e.g., epoxy group, amino group, groups derived from these, etc.) having reactivity such as adhesiveness and crosslinkability, and is derived from an epoxy group or an epoxy group. It is more preferable to have a group that
  • the polyamide-based resin (B) includes polyamide epihalohydrin resin (polyamide epichlorohydrin resin, etc.), polyamide polyamine epihalohydrin resin (polyamide polyamine epichlorohydrin resin, etc.), polyamide polyamine polyurea epihalohydrin resin (polyamide polyamine polyurea epichlorohydrin resin, etc.). phosphorus resin, etc.), polyamide polyamine resin, and the like. Among them, polyamidepolyamine epihalohydrin resin is preferable, and polyamidepolyamine epichlorohydrin resin is more preferable. Polyamide resin (B) can be used alone or in combination of two or more.
  • the lower limit of the content of the polyamide resin (B) in the solid content of the creping adhesive of the present invention is preferably 5% by mass, more preferably 10% by mass, and even more preferably 20% by mass.
  • the upper limit of this content is preferably 80% by mass, more preferably 60% by mass, and even more preferably 40% by mass in some cases.
  • the creping adhesive of the present invention preferably further contains an antifoaming agent (C).
  • an antifoaming agent (C) As a result, foaming of the creping adhesive can be suppressed, and stringiness, wet adhesion, fluidity, etc. can be improved.
  • the creping adhesive powder contains an antifoaming agent (C)
  • the solubility of the powder increases and the insoluble content decreases, resulting in the wetting of the creping adhesive. Adhesion tends to increase.
  • Alcohols such as methanol, ethanol, isopropanol, butanol, 2-ethylhexanol, diisobutylcarbinol, amyl alcohol, Guerbet alcohol (preferably Guerbet alcohol having 8 to 12 carbon atoms, more preferably Guerbet alcohol having 10 carbon atoms) Compound; Silicone compounds such as silicone oil; Alkyl sulfonates, alkyl sulfates, alkyl phosphates, polyoxyalkylene alkyl phosphates, polyoxyalkylene alkyl sulfates, polyoxyalkylene alkylaryl sulfates, polyoxyalkylene aralkylaryl sulfates, anionic surfactants such as alkyl-aryl sulfonates; Sorbitan fatty acid ester, its polyalkylene oxide adduct, glycerin fatty acid ester, various polyalkylene oxide type noni
  • R 1 , R 2 , R 3 and R 4 may be the same or different and are straight-chain or branched-chain alkyl groups having 1 to 5 carbon atoms.
  • the antifoaming agent (C) is preferably at least one selected from the group consisting of nonionic surfactants and anionic surfactants, more preferably nonionic surfactants.
  • the lower limit of the content of the antifoaming agent (C) to the PVA (A) in the creping adhesive of the present invention is preferably 10 ppm, more preferably 100 ppm, and even more preferably 300 ppm.
  • the upper limit of this content is preferably 30,000 ppm, more preferably 10,000 ppm, and even more preferably 3,000 ppm.
  • the creping adhesive of the present invention also preferably contains at least one surfactant (C') selected from the group consisting of nonionic surfactants and anionic surfactants.
  • a nonionic surfactant is more preferable as the surfactant (C').
  • Specific examples of the nonionic surfactant and the anionic surfactant as the surfactant (C') are the same as those exemplified as the antifoaming agent (C).
  • a suitable content of the surfactant (C') is the same as the content of the antifoaming agent (C).
  • the creping adhesive of the present invention is usually an aqueous solution in which PVA (A) and optional components such as polyamide resin (B) and antifoaming agent (C) are dissolved in water as a solvent.
  • the creping adhesive may further contain components other than the PVA (A), the polyamide resin (B) and the antifoaming agent (C) as solid contents.
  • Other components include mineral oil, silica, plasticizers, pH adjusters, release agents, and the like.
  • the content of other components other than PVA (A), polyamide resin (B) and antifoaming agent (C) in the solid content of the creping adhesive is preferably 10% by mass or less, and 1% by mass. or less or 0.1% by mass or less may be more preferable.
  • the creping adhesive is an aqueous solution, it may further contain a solvent other than water.
  • the lower limit of the solid content concentration is preferably 1% by mass, more preferably 2% by mass, and even more preferably 3% by mass.
  • the upper limit of the solid content concentration is preferably 20% by mass, more preferably 15% by mass, and even more preferably 10% by mass.
  • the creping adhesive powder of the present invention contains PVA (A) and satisfies at least one of the following (i) and (ii).
  • the "powder for creping adhesive” is also simply referred to as "powder”.
  • the PVA (A) contains PVA having a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less, and the number average molecular weight of the PVA (A);
  • the ratio Mw/Mn of the weight average molecular weight Mw to Mn is 2.5 or more.
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA (A) is 3.8 or more.
  • the creping adhesive of the present invention By dissolving the powder of the present invention in water, the creping adhesive of the present invention can be obtained. That is, a creping adhesive having good stringiness, wet adhesion, etc. can be obtained from the powder. In addition, the powder has good solubility in water.
  • PVA (A) contained in the powder are the same as the specific form and preferred form of PVA (A) contained in the creping adhesive of the present invention.
  • the powder may be a powder consisting essentially of PVA (A).
  • the lower limit of the content of PVA (A) in the powder is preferably 90% by mass, more preferably 99% by mass, and even more preferably 99.9% by mass.
  • the upper limit of this content may be 100% by mass.
  • the powder preferably further contains an antifoaming agent (C).
  • an antifoaming agent (C) When the powder contains the antifoaming agent (C), the solubility of the powder in water is increased and the insoluble content is reduced, resulting in a tendency to increase the wet adhesiveness of the resulting creping adhesive.
  • the antifoaming agent (C) at least one selected from the group consisting of nonionic surfactants and anionic surfactants is preferred, and nonionic surfactants are more preferred.
  • the powder may also contain at least one surfactant (C') selected from the group consisting of nonionic surfactants and anionic surfactants. preferable. A nonionic surfactant is more preferable as the surfactant (C').
  • the PVA (A) and the antifoaming agent (C) or the surfactant (C') may be in a compatible state, but the antifoaming agent (C) or the surfactant (C ') is preferably present so as to adhere to the surface of the particles of PVA (A).
  • the insoluble matter in the powder tends to be further reduced, and the resulting creping adhesive tends to have higher wet adhesion.
  • the presence of the antifoaming agent (C) or the surfactant (C') on the surface of each particle increases the dispersibility of each particle in water and promotes dissolution. etc. is assumed.
  • particles of PVA (A) to which the antifoaming agent (C) or the surfactant (C') is not attached may be present, and the antifoaming agent (C) or the surfactant Only particles of (C') may be present.
  • the preferred range of the content of the antifoaming agent (C) or the surfactant (C') in the powder is the content of the antifoaming agent (C) or the surfactant (C') in the creping adhesive described above. It is the same as the preferred range.
  • the powder may further contain components other than PVA (A) and antifoaming agent (C).
  • Other components in the powder include those exemplified as other components in the creping adhesive.
  • the polyamide resin (B) and the like are usually added to water together with the powder when preparing the creping adhesive as an aqueous solution. Therefore, the powder may consist essentially of PVA (A) and antifoaming agent (C).
  • the lower limit of the total content of PVA (A) and antifoaming agent (C) in the powder is preferably 90% by mass, more preferably 99% by mass, and even more preferably 99.9% by mass.
  • the upper limit of this total content may be 100% by mass.
  • the upper limit of the content of powder (fine powder) that passes through a 180 ⁇ m sieve is preferably 12% by mass, and may be more preferably 10% by mass, 8% by mass, or 5% by mass.
  • the powder may be obtained through heat treatment as in the method for producing PVA (A1) described above.
  • the fine powder tends to be excessively heated by the heat treatment, and the cross-linking proceeds too much to become an insoluble matter.
  • the insoluble content is large, the wet adhesion and fluidity of the creping adhesive are lowered.
  • the lower limit of the content of powder that passes through a sieve with an opening of 180 ⁇ m may be 0.1% by mass or 1% by mass.
  • the mesh size of the sieve conforms to the nominal mesh size W of JIS Z8801-1:2006 (the same shall apply hereinafter).
  • the content of powder passing through a sieve with an opening of 1.00 mm is 97% by mass or more, and the content of powder passing through a sieve with an opening of 500 ⁇ m is 40% by mass or more.
  • the lower limit of the content of powder that passes through a sieve with an opening of 1.00 mm is more preferably 98% by mass, and even more preferably 99% by mass.
  • the upper limit of the content of powder that passes through a sieve with an opening of 1.00 mm may be 100% by mass or 99.9% by mass.
  • the upper limit of the content of powder that passes through a sieve with an opening of 500 ⁇ m may be 70% by mass or 60% by mass.
  • the particle size distribution of the powder can be adjusted by sieving during the manufacturing process or after manufacturing.
  • the insoluble content may be, for example, 0.1 ppm or more and 5000 ppm or less, but 0.1 ppm or more and less than 2000 ppm. is preferably The insoluble content is more preferably less than 1,800 ppm, even more preferably less than 1,600 ppm.
  • the insoluble content may be 1 ppm or more, 10 ppm or more, or 100 ppm or more. Specifically, the insoluble matter can be obtained by the method described in the Examples.
  • the insoluble content can be reduced by avoiding excessive heat treatment, removing fine powder, and incorporating an antifoaming agent (C).
  • the powder can be produced according to a conventionally known method for producing powdery PVA.
  • a step of heat-treating the powder, a step of sieving the powder, a step of removing fine powder, and the like may be performed.
  • a step of adhering the antifoaming agent (C) to the surface of the PVA (A) powder by mixing the PVA (A) powder and the antifoaming agent (C), etc. may be performed.
  • the method for producing a creping adhesive of the present invention comprises a step of dissolving PVA (A) in water, and satisfies at least one of the following (i) and (ii).
  • the PVA (A) contains PVA having a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less, and the number average molecular weight of the PVA (A);
  • the ratio Mw/Mn of the weight average molecular weight Mw to Mn is 2.5 or more.
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA (A) is 3.8 or more.
  • the production method it is possible to obtain a creping adhesive with good stringiness, wet adhesion, and the like.
  • the specific form and preferred form of the PVA (A) used in the production method are the same as the specific form and preferred form of the PVA (A) contained in the creping adhesive of the present invention.
  • the PVA (A) before dissolution used in the production method is usually powder. That is, in the production method, the powder for creping adhesive of the present invention can be suitably used as the PVA (A) to be dissolved in water.
  • the adhesive for creping may be prepared by dissolving in water two or more PVA having different at least one of the number average molecular weight and the viscosity average degree of polymerization. By doing so, it becomes easier to prepare a creping adhesive containing PVA (A) that satisfies the above (ii).
  • the temperature of water in this step can be, for example, 50° C. or higher and 95° C. or lower.
  • components other than PVA (A) such as polyamide resin (B)
  • the powder containing the antifoaming agent (C) is not used together with the PVA (A)
  • the powder of the antifoaming agent (C) is added to the water separately from the PVA (A) powder. , they may be dissolved.
  • Toilet paper, tissue paper, towel paper, kitchen paper or napkin base paper The toilet paper, tissue paper, towel paper, kitchen paper or napkin base paper of the present invention are produced using the creping adhesive of the present invention.
  • toilet paper, tissue paper, towel paper, kitchen paper or napkin base paper is also referred to as "paper product”.
  • the paper product of the present invention is manufactured using the creping adhesive of the present invention, it forms a good crepe, is bulky, and has good flexibility.
  • the paper product can be produced in the same manner as conventionally known paper products, except that the creping adhesive of the present invention is used.
  • the paper product is produced by creping using the creping adhesive of the present invention.
  • the manufacturing method of the paper product is, for example, It comprises a step of drying wet paper by attaching it to the surface of a cylindrical dryer, and a step of scraping off the dried paper from the surface of the dryer through the above steps with a doctor blade.
  • creping adhesive is applied to the surface of the dryer in advance. This forms a film of the creping adhesive on the surface of the dryer. Creping adhesive may also be pre-applied to the wet paper during the drying step. However, in order to fully exhibit the effect of the creping adhesive, it is preferable to apply the creping adhesive to the surface of the dryer.
  • the creping adhesive can be applied by spraying or the like.
  • the wet paper in the drying process may be wet paper before drying obtained by papermaking.
  • a Yankee dryer is widely used as a cylindrical dryer.
  • a crepe is formed on the paper by scraping the dried paper from the dryer surface with a doctor blade after the drying process.
  • the manufacturing method may further include a step of making paper, a step of winding up the crepe-formed paper, and the like.
  • the paper products thus produced have attached PVA, which was normally included in the creping adhesive. That is, paper products containing PVA (A) and satisfying at least one of the following (i) and (ii) are also included in the present invention.
  • the PVA (A) contains PVA having a minimum branching degree of 0.25 or more and 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less, and the number average molecular weight of the PVA (A);
  • the ratio Mw/Mn of the weight average molecular weight Mw to Mn is 2.5 or more.
  • the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA (A) is 3.8 or more.
  • the specific form and preferred form of the PVA (A) contained in the paper product are the same as the specific form and preferred form of the PVA (A) contained in the creping adhesive of the present invention.
  • the paper product also has good crepe formation, high bulk and good flexibility.
  • Components other than PVA (A) in the paper product may be the same as in conventionally known paper products.
  • the content (modification rate) of structural units derived from the monomer (a) in PVA was determined by a method using 1 H-NMR using a vinyl ester polymer that is a precursor of PVA.
  • the modification rate is obtained by the following procedure. That is, the vinyl ester polymer, which is the precursor of PVA, was sufficiently purified by reprecipitation three times or more using n-hexane/acetone as a solvent, and then the resulting purified product was dried at 70°C for one day. to prepare a sample for analysis.
  • GPC column Two "GMHHR (S)" manufactured by Tosoh Corporation
  • Mobile phase Hexafluoroisopropanol (containing sodium trifluoroacetate at a concentration of 20 mmol/L)
  • Flow rate 0.2 mL/min
  • Sample concentration 0.100 wt/vol%
  • Sample injection volume 10 ⁇ L
  • Detector Differential refractive index detector Standard substance: Polymethacrylic acid ("EasiVial PMMA 4 mL tri-pack" manufactured by Agilent Technologies)
  • hexafluoroisopropanol is used as a mobile phase, and gel permeation chromatography (GPC) is measured using a differential refractive index detector, a light scattering detector, and a viscosity detector.
  • the intrinsic viscosity for each absolute molecular weight of 200,000 or more and 800,000 or less of the linear PVA was obtained.
  • the straight-chain PVA used was unmodified PVA having a 4% by mass aqueous solution viscosity within ⁇ 20% of the PVA to be measured and a degree of saponification within ⁇ 3 mol%. Specific measurement conditions for GPC are shown below.
  • Solvent Hexafluoroisopropanol (containing sodium trifluoroacetate at a concentration of 20 mmol/L)
  • Intrinsic viscosity [ ⁇ ] of PVA to be measured for each measured absolute molecular weight The degree of branching gm for each absolute molecular weight was determined by the formulas (1) and (2).
  • FIG. 1 is a graph (Mark-Houwink plot) plotting the absolute molecular weights and intrinsic viscosities ([ ⁇ ] branch or [ ⁇ ] linear ) of PVA-1 to be measured and PVA-17, which is the corresponding linear PVA. be.
  • FIG. 2 is a graph plotting the degree of branching (g m ) for each absolute molecular weight of PVA-1 determined by the above formulas (1) and (2) based on the results shown in FIG. 1 above.
  • the particle size distribution of the powder for creping adhesive was measured by the dry sieving method described in JIS Z8815:1994. Using 1.00 mm, 500 ⁇ m and 180 ⁇ m sieves, the ratio of the mass of the powder passing through the 1.00 mm sieve to the mass of the creping adhesive powder before sieving (content: mass%), the mass ratio of powder that passes through a sieve with an opening of 500 ⁇ m (content: mass%), and the mass ratio of powder that passes through a sieve with an opening of 180 ⁇ m (content: mass%). .
  • the above-mentioned opening complies with the nominal opening W of JIS Z8801-1:2006.
  • the filter was thoroughly washed with hot water at 30°C to remove the solution adhering to the filter, leaving only undissolved particles on the filter, and then the filter was dried in a heat dryer at 120°C for 1 hour.
  • the mass of the undissolved particles was calculated by comparing the mass of the filter after drying with the mass of the filter before being used for filtration.
  • the mass of the insoluble particles with respect to the creping adhesive powder (12 g) used was defined as the insoluble content (ppm).
  • Crepetrol registered trademark 9750 manufactured by SOLENIS, which is a polyamide polyamine epihalohydrin resin
  • SOLENIS which is a polyamide polyamine epihalohydrin resin
  • a piece of kitchen paper was attached to a parallel plate having a diameter of 2 cm and a weight of 26 g, and the kitchen paper was evenly moistened with 0.05 g of distilled water.
  • a weight of 20 g was attached to the aluminum cup, the wet kitchen paper part was pressed with its own weight, the parallel plate was lifted after 20 seconds, and the time required for the aluminum cup to fall from the kitchen paper was evaluated according to the following criteria.
  • C 5 seconds or more and less than 20 seconds
  • D Less than 5 seconds
  • the methanol solution of monomethyl maleate was added dropwise to polymerize at 60° C. for 2 hours while maintaining a constant monomer composition ratio in the polymerization solution, and then the polymerization was terminated by cooling.
  • the total amount of the monomer (a) added until the termination of the polymerization was 0.6 parts by mass, the solid content concentration at the termination of the polymerization was 22.9%, and the polymerization rate was 25%.
  • unreacted monomers were removed at 30° C. under reduced pressure while occasionally adding methanol to obtain a methanol solution of a vinyl ester polymer (concentration: 25.3%).
  • a 10% methanol solution of sodium hydroxide was added to 736.7 parts by mass of a methanol solution of a vinyl ester polymer prepared by further adding methanol to this methanol solution (150.0 parts by mass of the polymer in the solution). 6.98 parts by mass and water were added so that the water content in the system was 1%, and saponification was performed at 40° C. (the concentration of the polymer in the saponification solution was 20%, the vinyl acetate in the polymer was 0.01 molar ratio of sodium hydroxide to the unit, 1% moisture content). About 10 minutes after the addition of the methanol solution of sodium hydroxide, a gel-like substance was formed. was added to neutralize the remaining alkali.
  • the mixture was separated by filtration to obtain a white solid. 600 parts by mass of methanol was added to this white solid, and the white solid was left to stand and washed at 40° C. for 30 minutes. After repeating this washing operation twice, the white solid obtained by centrifugal deliquoring was pre-dried overnight. After that, while removing the fine powder, it was heat-treated in a dryer at 120° C. for 4.5 hours to obtain a powder of PVA-1.
  • a nonionic surfactant (FOAMASTER (registered trademark) WO2323 manufactured by BASF), which is an antifoaming agent, is added to the PVA-1 powder at room temperature so that it becomes 1000 ppm with respect to the mass of PVA-1, and the whole is Powder-1 was obtained by sprinkling uniformly.
  • Tables 2 and 3 show the physical properties of PVA-1 and powder-1 measured by the above methods.
  • the solid content concentration at the time of stopping the polymerization was 9.0%, and the polymerization rate was 25%. Subsequently, unreacted monomers were removed at 30° C. under reduced pressure while occasionally adding methanol to obtain a methanol solution of a vinyl ester polymer (concentration: 25.3%). Next, 724.07 parts by mass of a methanol solution of a vinyl ester polymer prepared by further adding methanol to this methanol solution (150 parts by mass of the polymer in the solution) was added with a 10% methanol solution of sodium hydroxide. 97 parts by mass and water were added so that the water content in the system was 1%, and saponification was performed at 40 ° C.
  • the concentration of the polymer in the saponification solution was 20%, the vinyl acetate unit in the polymer was molar ratio of sodium hydroxide 0.01, moisture content 1%).
  • a gel-like substance was formed. was added to neutralize the remaining alkali.
  • the mixture was separated by filtration to obtain a white solid. 750 parts by mass of methanol was added to this white solid, and the white solid was left to stand and washed at 40° C. for 3 hours. After repeating this washing operation three times, the white solid obtained by centrifugal deliquoring was vacuum-dried overnight at 40°C.
  • PVA-15 corresponds to PVA-13
  • PVA-16 corresponds to PVA-2 and 6
  • PVA-17 corresponds to PVA-1
  • PVA-18 corresponds to PVA-14
  • PVA-19 corresponds to PVA-3
  • PVA-20 corresponds to PVA-4
  • PVA-21 corresponds to PVA-10,12.
  • Example 1 5 parts by mass of Powder-1 was added to 95 parts by mass of water, and the mixture was heated to 90° C. with stirring and cooled after 1 hour to produce a creping adhesive. Using the resulting creping adhesive, the fluidity was evaluated by the method described above. Table 4 shows the evaluation results. Also, 7 parts by mass of Powder-1 was added to 93 parts by mass of water, and the mixture was heated to 90° C. with stirring and cooled after 1 hour to produce an adhesive for creping. Using the resulting creping adhesive, the stringiness and wet adhesion were evaluated by the methods described above.
  • Example 10 Powder-15 and Powder-16 were blended at a mass ratio of 40/60.
  • a creping adhesive was produced and evaluated in the same manner as in Example 1 except that the obtained blend was used instead of Powder-1.
  • Table 3 shows the measured physical properties of the blend, and Table 4 shows the evaluation results.
  • each of the creping adhesives of Examples 1 to 10 using the powder containing PVA that satisfies at least one of the above (i) and (ii) has good spinnability (A or B), and the wet adhesion was also good (A or B).
  • the creping adhesives of Examples 1 to 7, 9, and 10 using powders with a low content of powder that passes through a sieve with a mesh size of 180 ⁇ m and a small amount of insoluble matter have good fluidity (A or B). Met.
  • Example 1 when comparing Example 1 and Example 9, which differed only in whether or not the powder contained an antifoaming agent, as in Example 1, the powder contained an antifoaming agent, so that the insoluble matter was reduced and the wettability was reduced. It can be seen that the adhesiveness increases.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2022/036838 2021-09-30 2022-09-30 クレーピング用接着剤、クレーピング用接着剤用の粉末、クレーピング用接着剤の製造方法、及びトイレットペーパー、ティシュペーパー、タオルペーパー、キッチンペーパー又はナプキン原紙 Ceased WO2023054707A1 (ja)

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JP2023551924A JPWO2023054707A1 (https=) 2021-09-30 2022-09-30
EP22876569.9A EP4411067A4 (en) 2021-09-30 2022-09-30 CREATING ADHESIVE, POWDER FOR CREATING ADHESIVE, PROCESS FOR PRODUCING CREATING ADHESIVE, AND TOILET PAPER, TISSUE PAPER, PAPER TOWEL, KITCHEN PAPER OR NAPKIN BASE PAPER
US18/696,977 US20240409794A1 (en) 2021-09-30 2022-09-30 Creping adhesive, powder for use as creping adhesive, method for producing creping adhesive, and toilet paper, tissue paper, paper towel, kitchen paper, or napkin base paper
CN202280065496.3A CN118043520A (zh) 2021-09-30 2022-09-30 起绉用粘接剂、起绉用粘接剂用粉末、起绉用粘接剂的制造方法、以及卫生纸、面巾纸、手巾纸、厨房用纸或餐巾纸原纸

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WO2025005282A1 (ja) 2023-06-30 2025-01-02 ダイキン工業株式会社 容器

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JP7846680B2 (ja) * 2021-04-27 2026-04-15 株式会社クラレ ビニルアルコール系重合体、これを含む粉末、これらの製造方法、紙加工剤及び乳化重合用分散剤
EP4332126A4 (en) * 2021-04-27 2025-10-01 Kuraray Co VINYL ALCOHOL-BASED POLYMER, POWDER CONTAINING SAME, PROCESS FOR PRODUCING THE POWDER, COATING AGENT, COATED PRODUCT, PROCESS FOR PRODUCING A COATED PRODUCT, STABILIZER FOR EMULSION POLYMERIZATION, AQUEOUS EMULSION, AND ADHESIVE AGENT

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US20120247697A1 (en) * 2011-03-29 2012-10-04 Kemira Oyj Polyamine Polyamidoamine Epihaloohydrin Compositions and Processes for Preparing and Using the Same
WO2020080988A1 (en) * 2018-10-19 2020-04-23 Valmet Aktiebolag Yankee adhesive compositions and methods of using these compositions
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