WO2021200739A1 - Adhésif à base d'eau pour pailles de papier et paille de papier - Google Patents

Adhésif à base d'eau pour pailles de papier et paille de papier Download PDF

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Publication number
WO2021200739A1
WO2021200739A1 PCT/JP2021/013081 JP2021013081W WO2021200739A1 WO 2021200739 A1 WO2021200739 A1 WO 2021200739A1 JP 2021013081 W JP2021013081 W JP 2021013081W WO 2021200739 A1 WO2021200739 A1 WO 2021200739A1
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WIPO (PCT)
Prior art keywords
water
mass
vinyl alcohol
polymer
paper
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PCT/JP2021/013081
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English (en)
Japanese (ja)
Inventor
悠太 田岡
多江子 香春
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株式会社クラレ
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Priority to JP2022512157A priority Critical patent/JPWO2021200739A1/ja
Publication of WO2021200739A1 publication Critical patent/WO2021200739A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G21/00—Table-ware
    • A47G21/18—Drinking straws or the like
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • 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
    • 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
    • D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate

Definitions

  • This disclosure relates to water-based adhesives for paper straws and paper straws.
  • paper straws are manufactured by, for example, applying an adhesive to the base paper, laminating it on a metal core rod, and spirally winding it.
  • an adhesive starch, polyvinyl alcohol (hereinafter, may be referred to as PVA), vinyl acetate resin emulsion and the like are used.
  • Patent Document 1 an emulsion obtained by copolymerizing a vinyl acetate monomer and N-methylolacrylamide using PVA as a protective colloid has been proposed (Patent Document 1). Further, various modified PVAs have been developed in order to improve the specific performance of PVA. For example, in Patent Document 2, the number of carbon atoms is as an aqueous emulsion that exhibits higher water resistance than conventional PVA. A (co) polymer using one or more monomers selected from ethylenically unsaturated monomers is dispersed using PVA containing 4 or less ⁇ -olefin units in a specific ratio as a dispersant. Aqueous emulsions of quality have been proposed. Further, Patent Documents 3 and 4 propose a method of emulsifying (co) polymerizing vinyl acetate or vinyl acetate and (meth) acrylic acid ester using an ethylene-vinyl alcohol copolymer as a protective colloid.
  • This disclosure is [1] Contains vinyl alcohol-based polymer (X), cellulose nanofibers and water, and the content of cellulose nanofibers is 0.1 to 100 parts by mass with respect to 100 parts by mass of vinyl alcohol-based polymer (X).
  • Water-based adhesive for paper straws [2] The water-based adhesive for paper straws according to [1], wherein the vinyl alcohol-based polymer (X) has an average degree of polymerization of 200 to 5000 and a degree of saponification of 80 to 99.9 mol%; [3] The vinyl alcohol-based polymer (X) is one or more polymers selected from the group consisting of the ethylene-vinyl alcohol copolymer (A) and the polyvinyl alcohol (B), [1] or [ 2] A water-based adhesive for paper straws; [4] The water-based adhesive for paper straws according to [3], wherein the ethylene-vinyl alcohol copolymer (A) has a content of ethylene units of 1 mol% or more and less than 20 mol%; [5] The water-based adhesive for paper straws according to any one of [1] to [4], wherein the vinyl alcohol polymer (X) is dissolved in water; [6] Further, it is composed of an aqueous emulsion containing
  • the water-based adhesive for paper straws according to any one of [1] to [5]; [7] A single amount of the polymer (C) derived from at least one selected from the group consisting of a vinyl ester monomer, a (meth) acrylic acid ester monomer, a styrene monomer and a diene monomer.
  • Water-based adhesive for paper straw described in Crab [10] The contents of the vinyl alcohol-based polymer (X), the polymer (C) and the cellulose nanofibers in the solid content contained in the water-based adhesive for paper straw are 55% by mass or more, [6] to [ 9] A water-based adhesive for paper straws according to any one of; [11] A paper straw formed by adhering paper substrates to each other using the adhesive according to any one of [1] to [10]. [12] The present invention relates to a paper straw having a vinyl alcohol-based polymer (X) and cellulose nanofibers on an adhesive surface between paper substrates.
  • the water-based adhesive for paper straws of the present disclosure contains a vinyl alcohol-based polymer (X), cellulose nanofibers (hereinafter, may be referred to as "CNF”) and water, and the CNF content is vinyl alcohol-based. It is 0.1 to 100 parts by mass with respect to 100 parts by mass of the polymer (X).
  • the viscosity average degree of polymerization of the vinyl alcohol polymer (X) is preferably 200 or more, more preferably 250 or more, still more preferably 300 or more, 400 or more, 500 or more, 600 or more, 700 or more, 900. As mentioned above, 1100 or more or 1300 or more may be preferable. When the viscosity average degree of polymerization is at least the above lower limit value, the film strength is more excellent.
  • the viscosity average degree of polymerization is preferably 5000 or less, more preferably 4500 or less, still more preferably 4000 or less, and 3800 or less, 3500 or less, 3000 or less, 2700 or less, 2500 or less, 2300 or less, or 2000 or less. In some cases it is preferable. When the viscosity average degree of polymerization is not more than the above upper limit value, the viscosity of the water-based adhesive for paper straws does not become too high, and the coatability tends to be excellent.
  • the viscosity average degree of polymerization of the vinyl alcohol polymer (X) is measured according to JIS K 6726: 1994. Specifically, the ultimate viscosity [ ⁇ ] (liter / g) of the vinyl alcohol polymer (X) is measured in water at 30 ° C., and the value of the ultimate viscosity [ ⁇ ] is used to average the viscosity by the following formula.
  • the degree of polymerization P is calculated. When the saponification degree of the vinyl alcohol polymer (X) is less than 99.5 mol%, the saponification is performed until the saponification degree is 99.5 mol% or more, and then the ultimate viscosity [ ⁇ ] is measured.
  • P ([ ⁇ ] ⁇ 10 4 / 8.29) (1 / 0.62)
  • the saponification degree of the vinyl alcohol polymer (X) is preferably 80 mol% or more, more preferably 83 mol% or more, still more preferably 85 mol% or more, and 87 mol% or more or 90 mol% or more. May be preferable.
  • the vinyl alcohol-based polymer (X) has excellent water solubility, and the water-based adhesive for paper straws of the present disclosure can be easily produced.
  • the saponification degree of the vinyl alcohol polymer (X) is preferably 99.9 mol% or less, more preferably 99.5 mol% or less, still more preferably 99 mol% or less, and particularly preferably 98.5 mol% or less. It is less than mol%.
  • the saponification degree is not more than the upper limit value, the vinyl alcohol polymer (X) can be easily produced stably.
  • the saponification degree of the vinyl alcohol polymer (X) is measured according to JIS K 6726: 1994.
  • the vinyl alcohol-based polymer (X) is a polymer containing a vinyl alcohol unit.
  • the vinyl alcohol-based polymer (X) include an ethylene-vinyl alcohol copolymer (hereinafter, may be referred to as “ethylene-vinyl alcohol copolymer (A)") and polyvinyl alcohol (hereinafter, "PVA (hereinafter,” PVA (hereinafter, "PVA”). B) ”) and the like. Among them, it is preferably one selected from the group consisting of ethylene-vinyl alcohol copolymer (A) and PVA (B), and from the viewpoint of water resistance of the film, ethylene-vinyl alcohol copolymer (A). ) Is more preferable.
  • the vinyl alcohol-based polymer (X) may contain one kind alone or two or more kinds.
  • the content of ethylene units contained in the ethylene-vinyl alcohol copolymer (A) is preferably 1 mol% or more, more preferably 1.5 mol% or more, still more preferably 2 mol% or more. In some cases, 2.5 mol% or more, 3 mol% or more, or 3.5 mol% or more is preferable. When the content of the ethylene unit is at least the above lower limit value, the water resistance of the film tends to be excellent.
  • the content of the ethylene unit is preferably less than 20 mol%, more preferably less than 15 mol%, further preferably less than 13 mol%, particularly preferably less than 10 mol%, less than 8 mol% or In some cases, less than 5 mol% is preferred. When the content of the ethylene unit is less than the above upper limit value, the water solubility of the ethylene-vinyl alcohol copolymer (A) is excellent, and the water-based adhesive for paper straws of the present disclosure can be easily produced.
  • the content of ethylene units in the ethylene-vinyl alcohol copolymer (A) can be determined by 1 1 H-NMR measurement. For example, it is obtained from 1 H-NMR measurement of a vinyl ester-based copolymer containing an ethylene unit which is a precursor of an ethylene-vinyl alcohol copolymer (A) or a revinegared product. More specifically, the vinyl ester-based copolymer is subjected to reprecipitation purification with a mixed solution of n-hexane and acetone three times or more, and then dried under reduced pressure at 80 ° C. for 3 days to carry out vinyl ester for analysis. Obtain a system copolymer.
  • the content of the 1,2-glycol bond unit of the ethylene-vinyl alcohol copolymer (A) is preferably 1.2 mol% or more, more preferably 1.3 mol% or more, and further preferably 1. It is 4 mol% or more.
  • the content of the 1,2-glycol bond unit is at least the above lower limit, the productivity of the ethylene-vinyl alcohol copolymer (A) tends to be excellent, and the viscosity stability of the water-based adhesive for paper straws tends to be excellent. It is in.
  • the content of the 1,2-glycol bond unit of the ethylene-vinyl alcohol copolymer (A) is preferably 2.0 mol% or less, more preferably 1.9 mol% or less, and further preferably 1.
  • the content of the 1,2-glycol bond unit of the ethylene-vinyl alcohol copolymer (A) can be determined from 1 1 H-NMR measurement. Specifically, the ethylene-vinyl alcohol copolymer (A) is saponified to a saponification degree of 99.9 mol% or more, thoroughly washed with methanol, and dried under reduced pressure at 90 ° C. for 2 days. The resulting fully saponified ethylene - vinyl alcohol copolymer is dissolved in DMSO-d 6, for a few drops added sample of trifluoroacetic acid is measured at 80 ° C. using 1 H-NMR of 500 MHz.
  • the peak derived from the methine proton of vinyl alcohol unit is 3.2 to 4.0 ppm (integral value S), and the peak derived from one methine proton of 1,2-glycol bond is around 3.15 to 3.35 ppm (integral value). It belongs to T).
  • the block character of the ethylene unit of the ethylene-vinyl alcohol copolymer (A) is preferably 0.8 or more, more preferably 0.9 or more, and sometimes 0.93 or more or 0.95 or more is preferable. be.
  • the block character of the ethylene unit of the ethylene-vinyl alcohol copolymer (A) is preferably 1.1 or less, and may be 1.05 or less, 1.0 or less, or 0.99 or less in some cases.
  • the block character is not more than the above upper limit value, the water-based adhesive for paper straws of the present disclosure tends to have better water resistance.
  • the block character is a numerical value representing the distribution of the ethylene unit and the vinyl alcohol unit generated by the saponification of the vinyl ester unit, and takes a value between 0 and 2. 0 indicates that ethylene units or vinyl alcohol units are distributed completely in blocks, and as the value increases, the alternation increases, and 1 indicates that ethylene units and vinyl alcohol units are completely randomly present. 2 indicates that ethylene units and vinyl alcohol units are completely alternated.
  • the block character is obtained by 13 C-NMR as follows. First, the ethylene-vinyl alcohol copolymer (A) is saponified to a saponification degree of 99.9 mol% or more, thoroughly washed with methanol, and dried under reduced pressure at 90 ° C. for 2 days.
  • the vinyl alcohol-based polymer (X) may contain a monomer unit other than the vinyl alcohol unit, the ethylene unit and the vinyl ester unit as long as the effects of the present disclosure are not impaired.
  • monomers include ⁇ -olefins such as propylene, n-butene, and isobutylene; acrylic acid and salts thereof; acrylate esters; methacrylic acid and salts thereof; methacrylic acid esters; acrylamide; N-methylacrylamide, N.
  • -Acrylamide derivatives such as ethyl acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide, acrylamide propanesulfonic acid and its salts, acrylamide propyl dimethylamine and its salts or quaternary salts thereof, N-methylol acrylamide and its derivatives; methacrylic amides.
  • Methalamide derivatives such as N-methylmethacrylate, N-ethylmethacrylate, methacrylicamide propanesulfonic acid and its salts, methacrylicamidepropyldimethylamine and its salts or quaternary salts thereof, N-methylolmethacrylate and its derivatives; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; chloride.
  • Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether
  • Vinyl halides such as vinyl and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and salts thereof. Alternatively, an ester thereof; a vinylsilyl compound such as vinyltrimethoxysilane; isopropenyl acetate and the like can be mentioned.
  • the content of these monomers varies depending on the purpose of use, application, etc., but is preferably 10 mol% or less, more preferably less than 5 mol%, still more preferably less than 1 mol%, particularly preferably. Is less than 0.5 mol% and may be 0 mol%.
  • PVA (B) can be produced by a known method. Alternatively, commercially available PVA may be used.
  • the ethylene-vinyl alcohol copolymer (A) is obtained by, for example, copolymerizing ethylene and a vinyl ester-based monomer to obtain an ethylene-vinyl ester copolymer, and then hydroxylating the ethylene-vinyl ester copolymer. It can be obtained by saponification using a saponification polymer such as sodium, and pulverizing or drying as necessary.
  • Examples of the method for copolymerizing ethylene with a vinyl ester-based monomer include known methods such as a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among them, a massive polymerization method or a solution polymerization method in which polymerization is carried out without a solvent or in a solvent such as alcohol is usually adopted.
  • the alcohol include lower alcohols such as methanol, ethanol and propanol.
  • the initiators used in the copolymerization include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis. Examples thereof include azo-based initiators such as (2,4-dimethyl-valeronitrile), benzoyl peroxide, n-propylperoxydicarbonate, and known initiators such as peroxide-based initiators.
  • the polymerization temperature is not particularly limited, and is preferably 0 ° C. to 150 ° C., more preferably room temperature or higher and 150 ° C. or lower, further preferably room temperature or higher and lower than the boiling point of the solvent used, and particularly preferably 30 to 60 ° C.
  • vinyl ester-based monomer examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatic acid and the like. Be done. Of these, vinyl acetate is preferable.
  • a chain transfer agent may be used when copolymerizing ethylene with a vinyl ester-based monomer.
  • the chain transfer agent include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone and cyclohexanone; mercaptans such as 2-hydroxyethanethiol; thiocarboxylic acids such as thioacetic acid; trichloroethylene and perchloro. Examples thereof include halogenated hydrocarbons such as ethylene. Of these, aldehydes and ketones are preferable.
  • the amount used can be determined according to the chain transfer coefficient of the chain transfer agent used and the degree of polymerization of the target ethylene-vinyl alcohol copolymer (A), and is particularly limited. However, 0.1 to 10 parts by mass is preferable with respect to 100 parts by mass of the vinyl ester-based monomer.
  • the ethylene-vinyl alcohol copolymer (A) is obtained by saponifying the ethylene-vinyl ester copolymer obtained in the polymerization step. At this time, it is preferable to saponify the ethylene-vinyl ester copolymer in an organic solvent by alcoholic decomposition or hydrolysis reaction in the presence of a catalyst.
  • the catalyst used in the saponification step include basic catalysts such as sodium hydroxide, potassium hydroxide and sodium methoxyde; and acidic catalysts such as sulfuric acid, hydrochloric acid and p-toluenesulfonic acid.
  • the organic solvent used in the saponification step is not particularly limited, and examples thereof include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene. These can be used alone or in combination of two or more. Above all, it is convenient and preferable to carry out 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.
  • alcohols such as methanol and ethanol
  • esters such as methyl acetate and ethyl acetate
  • ketones such as acetone and methyl ethyl ketone
  • aromatic hydrocarbons such as benzene and toluene.
  • the amount of the saponification catalyst used is preferably 0.001 to 0.5 in terms of molar ratio to the vinyl ester unit in the ethylene-vinyl ester copolymer.
  • the molar ratio is more preferably 0.002 or more.
  • the molar ratio is more preferably 0.4 or less, and further preferably 0.3 or less.
  • a crushing step and a drying step may be performed. Further, the crushing step may be divided into a preliminary crushing step and a main crushing step. After performing the saponification step, a washing step for removing impurities such as sodium acetate may be further performed if necessary.
  • the water-based adhesive for paper straws of the present disclosure contains CNF.
  • the average fiber diameter of CNF contained in the water-based adhesive for paper straws of the present disclosure is preferably 1 nm or more, more preferably 3 nm or more, and further preferably 4 nm or more. When the average fiber diameter is at least the above lower limit value, production tends to be easy.
  • the average fiber diameter is preferably 1000 nm or less, more preferably 500 nm or less, still more preferably 400 nm or less, and may be preferably 300 nm or less, 200 nm or less, or 100 nm or less.
  • the average fiber diameter of CNF is a number average fiber diameter calculated by microscopic observation.
  • the number average fiber diameter is determined by observing any 10 CNFs with a scanning electron microscope (SEM), obtaining the CNF fiber diameter using analysis software for the observed image (SEM image), and then obtaining the CNF fiber diameter.
  • SEM scanning electron microscope
  • the average value of 10 diameters can be calculated as a number average fiber diameter.
  • the average fiber length of CNF is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and further preferably 0.2 ⁇ m or more.
  • the average fiber length of CNF is preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, still more preferably 100 ⁇ m or less, particularly preferably 50 ⁇ m or less, and may be 5 ⁇ m or less or 2 ⁇ m or less.
  • the average fiber length of CNF is not more than the above upper limit value, the water-based adhesive for paper straws of the present disclosure tends to have excellent initial adhesiveness and film strength.
  • the average fiber length of CNF is the number average fiber length calculated by microscopic observation.
  • the number average fiber length is determined by, for example, observing any 10 CNFs with a scanning electron microscope (SEM), obtaining the CNF fiber length using analysis software for the observed image (SEM image), and then obtaining the CNF fiber length.
  • SEM scanning electron microscope
  • the average value of 10 lengths can be calculated as the number average fiber length.
  • the aspect ratio of CNF that is, the ratio of the average fiber length to the average fiber diameter (average fiber length / average fiber diameter) is preferably 3 or more, more preferably 10 or more, and further preferably 50 or more.
  • the aspect ratio of CNF is at least the above lower limit value, the water-based adhesive for paper straws of the present disclosure tends to have excellent initial adhesiveness and film strength.
  • fibrillated cellulose fiber can be preferably used.
  • the raw material of the fibrillated cellulose fiber include wood, straw, bamboo, bagasse, bamboo grass, reeds and rice husks. Fibrilization can be performed by applying a mechanical shearing force to the cellulose fibers using a beating machine, a homogenizer, or the like.
  • the cellulose fibers can be fibrillated by chemical treatment.
  • CNF may contain lignin. Lignin is a component contained in the raw material of fibrillated cellulose fiber. The content of lignin can be adjusted by adjusting the removal rate of lignin during fibrillation.
  • the CNF may be modified with a carboxyl group or the like, or may be non-modified.
  • the water-based adhesive for paper straws of the present disclosure contains a vinyl alcohol-based polymer (X), CNF and water, and the CNF content is 0.1 with respect to 100 parts by mass of the vinyl alcohol-based polymer (X). ⁇ 100 parts by mass. If the CNF content is less than 0.1 parts by mass with respect to 100 parts by mass of the vinyl alcohol polymer (X), the initial adhesiveness and the water resistance of the film are inferior. On the other hand, when the CNF content is more than 100 parts by mass with respect to 100 parts by mass of the vinyl alcohol polymer (X), the initial adhesiveness, the film strength and the water resistance of the film are inferior.
  • the content of CNF is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, and further preferably 0.3 part by mass with respect to 100 parts by mass of the vinyl alcohol-based polymer (X).
  • Parts or more, particularly preferably 0.5 parts by mass or more, and 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more, or 10 parts by mass or more may be preferable.
  • the aqueous adhesive for paper straw of the present disclosure is composed of an aqueous emulsion as described later, the content of CNF is 15 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the vinyl alcohol polymer (X).
  • the content of CNF is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less with respect to 100 parts by mass of the vinyl alcohol polymer (X).
  • the aqueous adhesive for paper straw of the present disclosure is composed of an aqueous dispersion in which CNF is dispersed in an aqueous solution of a vinyl alcohol polymer (X) as described later, the content of CNF is the vinyl alcohol polymer (X). ) 60 parts by mass or less, preferably 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less with respect to 100 parts by mass.
  • the content of the vinyl alcohol-based polymer (X) in the aqueous adhesive for paper straws of the present disclosure is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass. % Or more.
  • the content of the vinyl alcohol-based polymer (X) is preferably 30% by mass or less, more preferably 27% by mass or less, still more preferably 23% by mass or less, and particularly preferably 20% by mass or less. In some cases, 17% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, or 8% by mass or less is preferable.
  • the content of the vinyl alcohol-based polymer (X) is not more than the above upper limit value, an appropriate viscosity can be maintained, so that the water-based adhesive for paper straws can be easily handled.
  • the total content of the vinyl alcohol polymer (X) and CNF in the aqueous adhesive for paper straws of the present disclosure is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably. 1% by mass or more, particularly preferably 1.5% by mass or more.
  • the total content of the vinyl alcohol polymer (X) and CNF in the aqueous adhesive for paper straw of the present disclosure is preferably 30% by mass or less, more preferably 27% by mass or less, and further preferably 23% by mass.
  • % Or less particularly preferably 20% by mass or less, and 17% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, or 8% by mass or less may be preferable.
  • the total content of the vinyl alcohol polymer (X) and CNF is not more than the above upper limit value, an appropriate viscosity can be maintained, so that the water-based adhesive for paper straws can be easily handled.
  • the water-based adhesive for paper straws disclosed in the present disclosure contains water.
  • the content of water contained in the medium in the water-based adhesive for paper straws of the present disclosure is preferably 40% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 90% by mass or more. It is 95% by mass or more, and may be 100% by mass.
  • the medium may contain an organic solvent, but the content thereof is preferably 60% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass. It is as follows.
  • the organic solvent include water-soluble organic solvents (alcohols, ketones, etc.) that are soluble in water at an arbitrary ratio.
  • vinyl alcohol-based polymer (X) is dissolved in water.
  • "Vinyl alcohol-based polymer (X) is dissolved in water” means that some or all of the vinyl alcohol-based polymer (X) is dissolved in water, and substantially all. It is preferable that the vinyl alcohol polymer (X) is dissolved in water.
  • the aqueous adhesive for paper straws of the present disclosure may be composed of an aqueous dispersion in which CNF is dispersed in an aqueous solution of a vinyl alcohol-based polymer (X), and the polymer (C) containing an ethylenically unsaturated monomer unit. ) (Hereinafter, may be referred to as "polymer (C)”) may be composed of an aqueous emulsion containing as a dispersoid.
  • the aqueous adhesive for paper straws of the present disclosure is preferably composed of an aqueous emulsion containing the polymer (C) as a dispersoid.
  • Such a water-based adhesive for paper straws has further excellent initial adhesiveness and water resistance of the film.
  • the polymer (C) is a polymer containing an ethylenically unsaturated monomer unit.
  • the ethylenically unsaturated monomer include a vinyl ester monomer, an olefin monomer, (meth) acrylic acid and a salt thereof, and a (meth) acrylic acid ester monomer (monofunctional (meth) acrylic acid).
  • Ester monomer polyfunctional (meth) acrylic acid ester monomer), (meth) acrylamide monomer, vinyl ether monomer, nitrile monomer, allyl monomer, ⁇ , ⁇ -unsaturated mono or Examples thereof include a dicarboxylic acid monomer, a diene monomer, an aromatic vinyl monomer (for example, a styrene monomer, a condensed polycyclic aromatic monomer), and a heterocyclic vinyl monomer.
  • At least one selected from the group consisting of a vinyl ester monomer, a (meth) acrylic acid ester monomer, a styrene monomer and a diene monomer is preferable, and a vinyl ester monomer is more preferable.
  • a vinyl ester monomer is preferable, and a vinyl ester monomer is more preferable.
  • One of these may be used alone, or two or more thereof may be used in combination.
  • "(meth) acrylic” means one or more selected from the group consisting of acrylic and methacryl.
  • vinyl ester monomer examples include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatic acid, vinyl laurate, vinyl crotonate, vinyl decanoate, vinyl hexanoate, and the like.
  • vinyl and vinyl benzoate examples include vinyl acetate is particularly preferable from an industrial point of view.
  • Examples of the olefin monomer include ethylene and propylene.
  • Examples of (meth) acrylic acid and salts thereof include acrylic acid, methacrylic acid, sodium salts and potassium salts thereof.
  • Examples of the monofunctional (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth).
  • N-butyl acrylate N-butyl acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, etc. Be done.
  • the polyfunctional (meth) acrylic acid ester monomer include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Can be mentioned.
  • Examples of the (meth) acrylamide monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, and (meth) acrylamide. ) Acrylamide propanesulfonic acid and its salts, (meth) acrylamidepropyldimethylamine and its salts or quaternary salts thereof, N-methylol (meth) acrylamide and its derivatives and the like.
  • Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether and the like.
  • Examples of the nitrile monomer include acrylonitrile and methacrylonitrile.
  • Examples of the allyl monomer include allyl acetate and allyl chloride.
  • Examples of the ⁇ , ⁇ -unsaturated mono or dicarboxylic acid monomer include aliphatic unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid, salts thereof, and esters thereof.
  • Examples of the diene monomer include butadiene, isoprene, chloroprene and the like.
  • Examples of the aromatic vinyl monomer include styrene monomers such as styrene, ⁇ -methylstyrene, p-methylstyrene, chlorostyrene, ⁇ -butoxystyrene, 1-ethyl-2-vinylbenzene, and vinylbiphenyl; vinylnaphthalene.
  • Examples of the heterocyclic vinyl monomer include N-vinyl-2-pyrrolidone and the like.
  • the content of the ethylenically unsaturated monomer unit with respect to all the monomer units of the polymer (C) is preferably 70% by mass or more, preferably 80% by mass or more, 90% by mass or more, or 95% by mass or more. In some cases, it may be 100% by mass.
  • the content of the ethylenically unsaturated monomer unit is at least the above lower limit value, the emulsion polymerization stability of the vinyl alcohol polymer (X) is more excellent.
  • the dispersant contained in the aqueous emulsion is not particularly limited, and a known dispersant used for emulsion polymerization of an ethylenically unsaturated monomer is used.
  • the dispersant is preferably a vinyl alcohol polymer (X), and the ethylene-vinyl alcohol copolymer (A). , Or PVA (B), and even more preferably an ethylene-vinyl alcohol copolymer (A).
  • Ethylene-vinyl alcohol copolymer (A) and PVA (B) may be used in combination as the dispersant.
  • the PVA (B) may be unmodified PVA or modified PVA.
  • modified PVA examples include anion-modified PVA such as sulfonic acid group-modified PVA and carboxylic acid group-modified PVA; cation-modified PVA such as quaternary amine group-modified PVA; amide-modified PVA; polyoxyalkylene group-modified PVA; acetoacetyl group.
  • Modified PVA examples thereof include diacetone acrylamide modified PVA.
  • Ethylene-modified PVA is not contained in PVA (B), but is contained in ethylene-vinyl alcohol copolymer (A).
  • the total content of the vinyl alcohol-based polymer (X) and CNF in the aqueous adhesive for paper straws of the present disclosure is preferably 2 parts by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the polymer (C). It is 2.5 parts by mass or more, more preferably 3 parts by mass or more, and 4 parts by mass or more or 5 parts by mass or more may be preferable.
  • the total content of the vinyl alcohol polymer (X) and CNF is at least the above lower limit value, the water-based adhesive for paper straws of the present disclosure tends to have excellent initial adhesiveness.
  • the total content of the vinyl alcohol-based polymer (X) and CNF in the aqueous adhesive for paper straw of the present disclosure is preferably 60 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the polymer (C). It may be 50 parts by mass or less, preferably 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, and 25 parts by mass or less.
  • the total content of the vinyl alcohol polymer (X) and CNF is not more than the above upper limit value, the initial adhesiveness and the water resistance of the film tend to be more excellent.
  • the solid content concentration in the water-based adhesive for paper straws of the present disclosure is preferably 10 to 80% by mass.
  • the solid content concentration is 10% by mass or more, the viscosity of the water-based adhesive for paper straws does not become too low and the particles are less likely to settle.
  • the solid content concentration is more preferably 15% by mass or more, and may be 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more.
  • the solid content concentration is 80% by mass or less, aggregates are less likely to be formed during emulsion polymerization, and an aqueous emulsion can be easily produced.
  • the solid content concentration is more preferably 75% by mass or less, and in some cases, 70% by mass or less, 65% by mass or less, or 60% by mass or less.
  • the solid content means the total amount of dry solids contained in the water-based adhesive for paper straws, that is, the total amount of solids remaining when a medium such as water is removed.
  • the aqueous adhesive for paper straw of the present disclosure is composed of the above aqueous emulsion
  • the dispersant contains a vinyl alcohol-based polymer (X)
  • the aqueous adhesive is aqueous in addition to those contained in the aqueous emulsion.
  • a vinyl alcohol-based polymer (X) may be contained as a component other than the emulsion.
  • the content ratio of the vinyl alcohol-based polymer (X), the polymer (C) and the cellulose nanofibers in the solid content contained in the aqueous adhesive for paper straw of the present disclosure is preferably 55% by mass or more, more preferably 55% by mass or more. It is 60% by mass or more, more preferably 80% by mass or more, and 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass may be preferable.
  • the total content of the vinyl alcohol-based polymer (X), the polymer (C) and the CNF is at least the above lower limit, the film strength tends to be further excellent.
  • the aqueous adhesive for paper straw of the present disclosure is composed of an aqueous dispersion in which CNF is dispersed in an aqueous solution of a vinyl alcohol polymer (X)
  • the production method thereof is not particularly limited.
  • Examples thereof include a method of adding a vinyl alcohol-based polymer (X) to an aqueous dispersion in which (iii) CNF is dispersed in water.
  • (i) or (ii) is preferable from the viewpoint of reducing the insoluble content of the vinyl alcohol-based polymer (X) and from the viewpoint of more uniformly dispersing CNF.
  • the method for producing the aqueous emulsion is not particularly limited, but for example, using a dispersion medium, in the presence of the vinyl alcohol polymer (X).
  • a production method comprising a step (1) of emulsion polymerization of an ethylenically unsaturated monomer to obtain an aqueous emulsion and a step (2) of blending CNF into the aqueous emulsion, or a vinyl alcohol-based polymer (X).
  • a production method including a step (3) of obtaining an aqueous dispersion containing CNF and a step (4) of mixing the aqueous dispersion and an ethylenically unsaturated monomer and performing emulsion polymerization.
  • An aqueous solution of the vinyl alcohol-based polymer (X) may be further added to the aqueous emulsions obtained by these production methods.
  • the step (2) is preferably carried out by a method of adding and mixing an aqueous dispersion of CNF to the aqueous emulsion obtained in the step (1).
  • Step (3) includes a method of adding CNF to an aqueous solution of a vinyl alcohol polymer (X) and dispersing it, a method of mixing an aqueous solution of a vinyl alcohol polymer (X) and an aqueous dispersion of CNF, and an aqueous dispersion of CNF.
  • a method of obtaining an aqueous dispersion liquid containing CNF for example, a method of mixing water and CNF and dispersing them using a medium stirring type disperser, a high pressure type disperser, a rotary disperser or the like can be mentioned. ..
  • Examples of the ethylenically unsaturated monomer used in the steps (1) and (4) include those described above as examples of the ethylenically unsaturated monomer contained in the polymer (C).
  • Examples of the method for obtaining an aqueous emulsion in the step (1) include a method in which a dispersant and an ethylenically unsaturated monomer are charged, and then an appropriately selected polymerization initiator is added to emulsion-polymerize the monomer. Be done.
  • the method of charging the dispersant and the method of adding the dispersant are not particularly limited, and examples thereof include a method of charging the dispersant in a batch at an initial stage and a method of continuously adding the dispersant during the polymerization.
  • the dispersant is initially charged in the polymerization system in a batch.
  • the polymerization reaction can be adjusted by appropriately adjusting the amount of the dispersant, the amount of the ethylenically unsaturated monomer, and the amount of the solvent.
  • an ethylenically unsaturated monomer and an appropriately selected polymerization initiator are added to the aqueous dispersion obtained in the step (3) to emulsify the monomer.
  • a method of polymerization can be mentioned. In such a method, the polymerization reaction can be adjusted by appropriately adjusting the amount of the dispersant, the amount of the ethylenically unsaturated monomer, and the amount of the solvent.
  • the amount of the dispersant used with respect to 100 parts by mass of the polymer (C) is not particularly limited, but is preferably 2 parts by mass or more and 60 parts by mass or less.
  • the amount used is more preferably 2.5 parts by mass or more, and may be 3 parts by mass or more, 4 parts by mass or more, or 5 parts by mass or more.
  • the amount of the dispersant used is more preferably 60 parts by mass or less, further preferably 50 parts by mass or less, and may be 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, and 25 parts by mass or less. ..
  • the amount of the dispersant used is not more than the above upper limit value, the water-resistant adhesiveness of the water-based adhesive for paper straws tends to be excellent.
  • the amount of the dispersant used is not more than the above upper limit value, the water-resistant adhesiveness of the water-based adhesive for paper straws tends to be excellent.
  • the monomer is emulsion-polymerized in the presence of a dispersant to produce an aqueous emulsion, almost all of the monomer is polymerized to become a polymer (C). Therefore, the amount of monomer remaining in the aqueous emulsion is very small and can be ignored.
  • a water-soluble single initiator or a water-soluble redox-based initiator usually used for emulsion polymerization can be used.
  • These polymerization initiators may be used alone or in combination of two or more. Of these, redox-based initiators are preferred.
  • water-soluble single initiator examples include azo-based initiators, hydrogen peroxide, and peroxides such as persulfate (potassium, sodium, or ammonium salt).
  • azo-based initiator examples include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (4-methoxy-2). , 4-Dimethylvaleronitrile) and the like.
  • a combination of an oxidizing agent and a reducing agent can be used.
  • Peroxide is preferable as the oxidizing agent.
  • the reducing agent include metal ions and reducing compounds.
  • the combination of the oxidizing agent and the reducing agent include a combination of a peroxide and a metal ion, a combination of a peroxide and a reducing compound, and a combination of a peroxide and a metal ion and a reducing compound. ..
  • peroxide examples include hydrogen peroxide, cumene hydroperoxide, hydroperoxide such as t-butyl hydroperoxide, persulfate (potassium, sodium or ammonium salt), t-butyl peracetic acid, and peracid ester (perbenzoic acid t). -Butyl) and the like.
  • the metal ion examples include metal ions capable of receiving one electron transfer such as Fe 2+ , Cr 2+ , V 2+ , Co 2+ , Ti 3+ , and Cu +.
  • Examples of the reducing compound include sodium hydrogen sulfite, sodium hydrogen carbonate, tartrate acid, fructose, dextrose, sorbose, inositol, longalite and ascorbic acid.
  • one or more oxidizing agents selected from the group consisting of hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate, and the group consisting of sodium hydrogen sulfite, sodium hydrogen carbonate, tartrate acid, longalite and ascorbic acid.
  • a combination of one or more selected reducing agents is preferable, and a combination of hydrogen peroxide and one or more reducing agents selected from the group consisting of sodium bisulfite, sodium hydrogen carbonate, tartrate acid, longalite and ascorbic acid is more preferable. preferable.
  • an alkali metal compound, a surfactant, a buffer, a degree of polymerization adjusting agent and the like may be appropriately used as long as the effects of the present disclosure are not impaired.
  • the alkali metal compound is not particularly limited as long as it contains an alkali metal (sodium, potassium, rubidium, cesium), and may be an alkali metal ion itself or a compound containing an alkali metal.
  • alkali metals include weak bases such as alkali metal carbonates, alkali metal acetates, alkali metal bicarbonates, alkali metal phosphates, alkali metal sulfates, alkali metal halide salts, and alkali metal nitrates.
  • Acidic alkali metal salts Examples thereof include strongly basic alkali metal compounds such as alkali metal hydroxides and alkali metal alkoxides. These alkali metal compounds may be used alone or in combination of two or more.
  • weakly basic alkali metal salts include alkali metal carbonates such as sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; sodium phosphate and phosphoric acid.
  • Alkali metal phosphates such as potassium; alkali metal carboxylates such as sodium acetate, potassium acetate, cesium acetate; alkali metal sulfates such as sodium sulfate, potassium sulfate, cesium sulfate; cesium chloride, cesium iodide, potassium chloride, Alkali metal halide salts such as sodium chloride; alkali metal nitrates such as sodium nitrate, potassium nitrate and cesium nitrate can be mentioned.
  • alkali metal carboxylates alkali metal carbonates, and alkali metal bicarbonates, which behave as salts of weak acids and strong bases at the time of dissociation, are preferable, and alkali metal carboxylates are more preferable, from the viewpoint of basicity in the emulsion. ..
  • the weakly basic alkali metal salts act as a pH buffer in the emulsion polymerization, so that the emulsion polymerization can be stably promoted.
  • the content of the alkali metal compound (alkali metal conversion) can be appropriately selected according to the type of alkali metal compound used, but the content of the alkali metal compound (alkali metal conversion) is an aqueous emulsion (solid conversion). With respect to the total mass of the above, 100 to 15,000 ppm is preferable, 120 to 12000 ppm is more preferable, and 150 to 8000 ppm is further preferable. When the content of the alkali metal compound is 100 ppm or more, the stability of emulsion polymerization of the aqueous emulsion tends to be excellent, and when it is 15,000 ppm or less, the coloring of the film composed of the aqueous emulsion is easily suppressed.
  • the content of the alkali metal compound can be measured by an ICP emission spectrometer or the like.
  • ppm means "mass ppm".
  • any of nonionic surfactant, anionic surfactant and cationic surfactant may be used.
  • the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyethylene derivative, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid. Examples thereof include esters, polyoxyethylene sorbitol fatty acid esters, and glycerin fatty acid esters.
  • anionic surfactant examples include alkyl sulfates, alkylaryl sulfates, alkyl sulphonates, sulfates of hydroxyalkanols, dialkyl sulfosuccinate salts, sulfates and phosphates of alkyl or alkylaryl polyethoxyalkanols, and the like. ..
  • examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamines and the like.
  • the amount of the surfactant used is preferably 2% by mass or less based on the total amount of the ethylenically unsaturated monomer. When the amount of the surfactant used is 2% by mass or less, the water resistance of the water-based adhesive for paper straws of the present disclosure is more excellent.
  • buffer examples include acids such as acetic acid, hydrochloric acid and sulfuric acid; bases such as ammonia, amines, cargo-bearing soda, cargo-bearing potash and calcium hydroxide; or alkaline carbonates, phosphates and acetates.
  • bases such as ammonia, amines, cargo-bearing soda, cargo-bearing potash and calcium hydroxide; or alkaline carbonates, phosphates and acetates.
  • degree of polymerization adjusting agent examples include mercaptans and alcohols.
  • the dispersion medium in the 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 any proportion with water.
  • the "water-based aqueous medium containing water as a main component” is a dispersion medium containing 50% by mass or more of water. From the viewpoint of cost and environmental load, the dispersion medium is preferably an aqueous medium containing 90% by mass or more of water, and more preferably water.
  • the dispersant is dissolved in a dispersion medium, heated, cooled, and replaced with nitrogen before the start of emulsion polymerization.
  • the heating temperature is preferably 80 to 100 ° C.
  • the temperature of emulsion polymerization is preferably about 20 to 95 ° C, more preferably about 40 to 90 ° C.
  • the water-based adhesive for paper straws of the present disclosure contains vinyl alcohol-based polymer (X), polymer (C), CNF and other components other than water.
  • the other components include resins other than the vinyl alcohol polymer (X) and the polymer (C), organic solvents, plasticizers, cross-linking agents, precipitation inhibitors, thickeners, fluidity improvers, preservatives, etc.
  • the other components include metal salts of phosphoric acid compounds such as sodium polyphosphate and sodium hexametaphosphate and dispersants of inorganic substances such as water glass; polyacrylic acid and its salts; sodium alginate; ⁇ -olefin-maleine anhydride.
  • Anionic polymer compounds such as acid copolymers and metal salts thereof; surfactants such as ethylene oxide adducts of higher alcohols and nonionic surfactants such as copolymers of ethylene oxide and propylene oxide can also be mentioned. By adding these, the fluidity of the adhesive is improved.
  • one or more cross-linking agents selected from the group consisting of water-soluble metal compounds, colloidal inorganic substances, polyamide amine epichlorohydrin adducts and glioxal resins can also be contained.
  • the water-soluble metal compound include aluminum chloride, aluminum nitrate, zirconium ammonium carbonate, titanium lactate and the like.
  • the colloidal inorganic substance include colloidal silica and alumina sol.
  • the polyamide amine epichlorohydrin adduct include those obtained by adding epichlorohydrin to various polyamide amines.
  • the glyoxal-based resin include urea-glyoxal-based resins.
  • the water resistance can be further improved by using a water-soluble metal salt or a colloidal inorganic substance and a polyamide amine epichlorohydrin adduct or a glioxal resin in combination.
  • a water-soluble metal salt or a colloidal inorganic substance and a polyamide amine epichlorohydrin adduct or a glioxal resin in combination.
  • a water-soluble boric acid compound such as boric acid; borax; a boric acid ester of a polyhydric alcohol such as glycerin or ethylene glycol, a sodium sodium formaline condensate of naphthalene sulfonate, or the like can be added.
  • Natural pastes such as starch, casein, gelatin, guar gum, gum arabic, sodium alginate; processed natural pastes such as carboxymethyl cellulose, oxidized starch, methyl cellulose and the like can also be added. These may be used alone or in combination of two or more.
  • the content of the above other components in the water-based adhesive for paper straws of the present disclosure is preferably 100% by mass or less, 50% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 2 In some cases, it is preferably mass% or less, 1 mass% or less, or 0.5 mass% or less.
  • Another preferred embodiment according to the present disclosure is a paper straw having a paper base material and having the paper base materials bonded to each other using the water-based adhesive for paper straws of the present disclosure.
  • the paper straw is excellent in strength and water resistance.
  • the water-based adhesive for paper straws of the present disclosure which is excellent in initial adhesiveness and film strength, such a paper straw can be efficiently produced.
  • the present disclosure also provides a paper straw having a vinyl alcohol polymer (X) and CNF on the adhesive surface between paper substrates.
  • the paper straw is excellent in strength and water resistance.
  • the preferred embodiments of the vinyl alcohol-based polymer (X) and CNF, and the preferred content of CNF with respect to the vinyl alcohol-based polymer (X) are the same as those described above.
  • paper straws can be obtained by a general manufacturing method.
  • the water-based adhesive for paper straws of the present disclosure is applied to a tape-shaped paper base material, and the paper base material is laminated on a metal core rod. It can be manufactured by a method of winding it in a spiral shape and then drying it.
  • Viscosity average degree of polymerization and saponification The viscosity average degree of polymerization and the degree of saponification of the vinyl alcohol polymer were determined by the method described in JIS K 6726: 1994.
  • Young's modulus 50 kgf / mm 2 or more
  • B Young's modulus 40 kgf / mm 2 or more 50 kgf / mm 2 less
  • C less than Young's modulus 30 kgf / mm 2 or more 40kgf / mm 2
  • D Young's modulus of less than 30 kgf / mm 2
  • a 2.8 g / L solution prepared by dissolving 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (AMV) as a polymerization initiator in methanol was prepared, and bubbling with nitrogen gas was performed to nitrogen. Replaced.
  • AMV 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile)
  • ethylene was introduced to maintain the reaction vessel pressure at 1.4 kg / cm 2 and the polymerization temperature at 60 ° C., and AMV was continuously added at 168 ml / hr using the above-mentioned polymerization initiator solution for polymerization.
  • the molar ratio [MR] 0.10) of the amount of NaOH was added, and saponification was carried out at 40 ° C.
  • the gelled product was pulverized with a pulverizer, and a saponification reaction was carried out for a total of 1 hour, and then 1000 g of methyl acetate was added to neutralize the remaining alkali.
  • 1000 g of methanol was added to the white solid obtained by filtration, and the mixture was washed at room temperature for 3 hours. After repeating the above washing operation three times, the solid obtained by centrifugal deflation was left in a dryer at 70 ° C. for 2 days to obtain an ethylene-vinyl alcohol copolymer (PVA-1).
  • Example 1 (Preparation of water-based adhesive)
  • the obtained ethylene-vinyl alcohol copolymer (PVA-1) powder (15 parts) is put into stirring water (85 parts, 20 ° C.) and heated to 95 ° C. for both ethylene-vinyl alcohol.
  • the polymer was dissolved to obtain an aqueous solution.
  • 100 parts by mass of a 2% by mass aqueous dispersion of unmodified CNF (aspect ratio of about 200, average fiber diameter of 50 nm, average fiber length of 10 ⁇ m) is added, and the mixture is stirred with a magnetic stirrer for 1 hour to form an aqueous adhesive.
  • Example 2 As shown in Table 2, an aqueous adhesive was prepared in the same manner as in Example 1 except that a predetermined amount of PVA-2 or PVA-3 was used instead of PVA-1 and the amount of CNF added was changed. The water-based adhesive was evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • Example 5 (Preparation of water-based adhesive) To 100 parts by mass of the aqueous emulsion (Em-1), 100 parts by mass of a 2% by mass aqueous dispersion of unmodified CNF (aspect ratio of about 200, average fiber diameter of 50 nm, average fiber length of 10 ⁇ m) was added, and 1 with a magnetic stirrer. Aqueous adhesive was obtained by stirring for a time. The amount of CNF added was 2 parts by mass with respect to 100 parts by mass of the aqueous emulsion (Em-1). The initial adhesiveness, film strength and water resistance of the film of the obtained water-based adhesive were evaluated according to the above method. The results are shown in Table 2.
  • Example 6 As shown in Table 2, an aqueous adhesive was prepared in the same manner as in Example 5 except that Em-2 was used instead of Em-1. The initial adhesiveness, film strength and water resistance of the film of the obtained water-based adhesive were evaluated according to the above method. The results are shown in Table 2.
  • Example 7 (Preparation of water-based adhesive) A powder (15 parts) of an ethylene-vinyl alcohol copolymer (PVA-1) is put into stirring water (85 parts, 20 ° C.) and heated to 95 ° C. to prepare an ethylene-vinyl alcohol copolymer. It was dissolved to obtain an aqueous solution having a concentration of 15%.
  • PVA-1 ethylene-vinyl alcohol copolymer
  • aqueous adhesive 100 parts by mass of the obtained aqueous solution of PVA-1 and 100 parts by mass of an aqueous emulsion (Em-1) are blended at room temperature, and further unmodified CNF (aspect ratio of about 200, average fiber diameter of 50 nm, average fiber length of 10 ⁇ m) 2
  • An aqueous adhesive was obtained by adding 200 parts by mass of a mass% aqueous dispersion and stirring with a magnetic stirrer for 1 hour.
  • the amount of CNF added was 2 parts by mass with respect to 100 parts by mass of the mixed aqueous dispersion of PVA-1 aqueous solution and Em-1.
  • the initial adhesiveness, film strength and water resistance of the film of the obtained water-based adhesive were evaluated according to the above method. The results are shown in Table 2.
  • Example 8 and 9 As shown in Table 2, except that Em-2 was used instead of Em-1 (Examples 8 and 9) and PVA-3 aqueous solution was used instead of PVA-1 aqueous solution (Example 9 only).
  • An aqueous adhesive was obtained in the same manner as in Example 7. The initial adhesiveness, film strength and water resistance of the film of the obtained water-based adhesive were evaluated according to the above method. The results are summarized in Table 2.
  • Example 2 As shown in Table 2, an aqueous adhesive was obtained in the same manner as in Example 1 except that the amount of CNF added was changed. The initial adhesiveness, film strength and water resistance of the film of the obtained water-based adhesive were evaluated according to the above method. The results are shown in Table 2.
  • aqueous adhesive was obtained by adding 100 parts by mass of water to 100 parts by mass of an aqueous emulsion (Em-1) and stirring with a magnetic stirrer for 1 hour.
  • the initial adhesiveness, film strength and water resistance of the film of the obtained water-based adhesive were evaluated according to the above method. The results are shown in Table 2.
  • the aqueous adhesive is composed of an aqueous dispersion in which CNF is dispersed in an aqueous solution of the vinyl alcohol polymer (X), and the content of CNF is 0.1 to 100 parts by mass with respect to 100 parts by mass of the vinyl alcohol polymer (X).
  • the initial adhesiveness and the film strength were excellent (Examples 1 to 4).
  • the vinyl alcohol-based polymer (X) is an ethylene-vinyl alcohol copolymer (A)
  • the water resistance of the film is also better than that of Comparative Examples 1 to 5. There were (Examples 1, 2, and 4).
  • the aqueous adhesive contains vinyl alcohol-based polymer (X), CNF and water, and the content of CNF is 0.1 to 100 parts by mass with respect to 100 parts by mass of the vinyl alcohol-based polymer (X).
  • the initial adhesiveness and the film strength were further excellent, and the water resistance of the film was further excellent (Examples 5 to 9).
  • the water-based adhesive for paper straws of the present disclosure is excellent in initial adhesiveness and film strength, and is suitable for producing paper straws.
  • the aqueous adhesive was an aqueous solution of a vinyl alcohol polymer (X) and did not contain CNF, the initial adhesiveness and the water resistance of the film were significantly inferior (Comparative Examples 1 and 3). Further, when the aqueous adhesive is composed of an aqueous solution of the vinyl alcohol polymer (X) and the CNF content is more than 100 parts by mass with respect to 100 parts by mass of the vinyl alcohol polymer (X), the initial adhesiveness and the film In addition to the significantly inferior water resistance, the film strength was also insufficient (Comparative Example 2).
  • the aqueous adhesive was composed of an aqueous emulsion containing the polymer (C) as a dispersoid and did not contain CNF, the water resistance of the film was significantly inferior, and the initial adhesiveness or film strength was insufficient (comparative). Examples 4 and 5).

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Abstract

La présente invention concerne un adhésif à base d'eau pour pailles de papier qui présente une adhésivité initiale et une résistance de film excellentes. Plus particulièrement, l'invention concerne un adhésif à base d'eau pour pailles de papier qui contient un polymère d'alcool polyvinylique (X), des nanofibres de cellulose et de l'eau, la teneur en nanofibres de cellulose allant de 0,1 à 100 parties en masse pour 100 parties en masse du polymère d'alcool polyvinylique (X).
PCT/JP2021/013081 2020-03-30 2021-03-26 Adhésif à base d'eau pour pailles de papier et paille de papier WO2021200739A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11106727A (ja) * 1997-10-03 1999-04-20 Showa Highpolymer Co Ltd 紙管用接着剤およびこれを用いた紙管
JP2006124616A (ja) * 2004-11-01 2006-05-18 Daicel Chem Ind Ltd 接着剤、その製造法及び紙管
JP2014132072A (ja) * 2012-12-05 2014-07-17 Nippon Paper Industries Co Ltd 水系接着剤組成物
JP2018044097A (ja) * 2016-09-16 2018-03-22 第一工業製薬株式会社 接着剤組成物
JP2020012031A (ja) * 2018-07-13 2020-01-23 リンテック株式会社 粘着剤組成物、及び粘着シート
WO2020059635A1 (fr) * 2018-09-21 2020-03-26 日本製紙株式会社 Tube en papier
WO2021006234A1 (fr) * 2019-07-08 2021-01-14 株式会社クラレ Adhésif à base d'eau pour paille de papier, et paille de papier l'utilisant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11106727A (ja) * 1997-10-03 1999-04-20 Showa Highpolymer Co Ltd 紙管用接着剤およびこれを用いた紙管
JP2006124616A (ja) * 2004-11-01 2006-05-18 Daicel Chem Ind Ltd 接着剤、その製造法及び紙管
JP2014132072A (ja) * 2012-12-05 2014-07-17 Nippon Paper Industries Co Ltd 水系接着剤組成物
JP2018044097A (ja) * 2016-09-16 2018-03-22 第一工業製薬株式会社 接着剤組成物
JP2020012031A (ja) * 2018-07-13 2020-01-23 リンテック株式会社 粘着剤組成物、及び粘着シート
WO2020059635A1 (fr) * 2018-09-21 2020-03-26 日本製紙株式会社 Tube en papier
WO2021006234A1 (fr) * 2019-07-08 2021-01-14 株式会社クラレ Adhésif à base d'eau pour paille de papier, et paille de papier l'utilisant

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JPWO2021200739A1 (fr) 2021-10-07

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