EP3978683A1 - Agent résistant à l'huile pour papier - Google Patents

Agent résistant à l'huile pour papier Download PDF

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Publication number
EP3978683A1
EP3978683A1 EP20814375.0A EP20814375A EP3978683A1 EP 3978683 A1 EP3978683 A1 EP 3978683A1 EP 20814375 A EP20814375 A EP 20814375A EP 3978683 A1 EP3978683 A1 EP 3978683A1
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EP
European Patent Office
Prior art keywords
group
oil
paper
resistant agent
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP20814375.0A
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German (de)
English (en)
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EP3978683B1 (fr
EP3978683A4 (fr
Inventor
Tetsuya Uehara
Michio Matsuda
Hirotoshi Sakashita
Yuuki Yamamoto
Daisuke Noguchi
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Daikin Industries Ltd
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Daikin Industries Ltd
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Classifications

    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • 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
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic 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
    • 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
    • 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
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/24—Addition to the formed paper during paper manufacture
    • 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
    • D21H27/10—Packing paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J3/00—Manufacture of articles by pressing wet fibre pulp, or papier-mâché, between moulds
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp

Definitions

  • the present disclosure relates to an oil-resistant agent for paper, and paper treated with the oil-resistant agent for paper.
  • Paper may be required to have oil resistance.
  • an oil-resistant agent is internally or externally applied to the paper.
  • Patent Literature 1 JP 2015-129365 A discloses a method of forming a cellulose article, comprising: attaching cellulose fibers to a compound comprising an aqueous dispersion comprising at least one polymer selected from the group consisting of an ethylene thermoplastic polymer, a propylene thermoplastic polymer, and a mixture thereof; at least one polymer stabilizer; and water.
  • Patent Literature 2 ( WO 2015/008868 A1 ) discloses a fine cellulose fiber sheet comprising fine cellulose fibers having an average fiber diameter of 2 nm or more and 1,000 nm or less, wherein a weight ratio of the fine cellulose fibers is 50% to 99% by weight, and the block polyisocyanate aggregate is contained in a weight ratio of 1 to 100% by weight, based on the fine cellulose fiber weight.
  • Patent Document 3 JP 2004-148307 A discloses a method for producing a coated support comprising: a) forming a composite multilayer free-flowing curtain comprising at least two layers imparting barrier functionalities, and b) bringing the curtain into contact with a continuous web support to give a coated support.
  • An object of the present disclosure is to provide an oil-resistant agent capable of imparting excellent oil resistance to paper.
  • the present disclosure relates to an oil-resistant agent comprising (1) a fluorine-free polymer and (2) particles selected from inorganic particles and/or organic particles.
  • the oil-resistant agent may be externally or internally added, and preferably the oil-resistant agent is internally added.
  • the fluorine-free polymer is favorably dispersed in an aqueous medium, particularly water.
  • the oil-resistant agent imparts high oil resistance to paper.
  • the oil-resistant agent can impart high water resistance and high gas barrier properties.
  • the oil-resistant agent comprises (1) a fluorine-free polymer, and (2) particles.
  • the oil-resistant agent may be a one-, two-, or three-part liquid.
  • the one-part liquid is a liquid comprising the fluorine-free polymer (1) and the particles (2).
  • the two-part liquid (two components) is a combination of a liquid comprising fluorine-free polymer (1) and a liquid comprising the particles (2) (or only particles (2)).
  • a liquid comprising an additive for paper is added for use.
  • the liquid comprising the particles (2) may be a solid (for example, particles only).
  • the fluorine-free polymer may be, for example, an acrylic polymer, polyester polymer, polyether polymer, silicone polymer, or urethane polymer.
  • a polymer having an ester bond, an amide bond, and/or a urethane bond is preferable.
  • an acrylic polymer i.e., a fluorine-free acrylic polymer
  • the acrylic polymer preferably has an ester bond and/or an amide bond.
  • the fluorine-free polymer may be a homopolymer or a copolymer.
  • the fluorine-free polymer is preferably a copolymer.
  • a homopolymer has only a repeating unit formed from one monomer.
  • the homopolymer is preferably formed only from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms.
  • a copolymer has repeating units formed from two or more monomers.
  • the fluorine-free polymer preferably has:
  • the fluorine-free polymer preferably has a repeating unit formed of (c) a monomer having an ion donating group in addition to the monomers (a) and (b).
  • the fluorine-free polymer may have a repeating unit formed from (d) another monomer, in addition to the monomers (a), (b), and (c).
  • the acrylic monomer having a long-chain hydrocarbon group (a) has a long-chain hydrocarbon group having 7 to 40 carbon atoms.
  • the long-chain hydrocarbon group having 7 to 40 carbon atoms is preferably a linear or branched hydrocarbon group having 7 to 40 carbon atoms.
  • the number of carbon atoms of the long-chain hydrocarbon group is preferably 10 to 40, such as 12 to 30, particularly 15 to 30. Alternatively, the number of carbon atoms of the long-chain hydrocarbon group may be 18 to 40 carbon atoms.
  • X 1 may be a hydrogen atom, a methyl group, halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
  • Examples of X 1 include a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group.
  • X 1 is preferably a hydrogen atom, a methyl group, or a chlorine atom.
  • X 1 is particularly preferably a hydrogen atom.
  • Y 1 is a divalent to tetravalent group. Y 1 is preferably a divalent group.
  • R 1 is preferably a linear or branched hydrocarbon group.
  • the hydrocarbon group may be particularly a linear hydrocarbon group.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group.
  • the number of carbon atoms of the hydrocarbon group is preferably 12 to 30, such as 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22.
  • acrylic monomer having a long-chain hydrocarbon group (a) examples include:
  • the acrylic monomer (a1) is a long-chain acrylate ester monomer wherein Y 2 is -O- or a long-chain acrylamide monomer wherein Y 2 is -NH-.
  • R 2 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group.
  • the number of carbon atoms of the hydrocarbon group is preferably 12 to 30, such as 16 to 26, particularly 18 to 22.
  • X 4 may be a hydrogen atom, a methyl group, halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.
  • long-chain acrylate ester monomer examples include lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl ⁇ -chloroacrylate, icosyl ⁇ -chloroacrylate, and behenyl ⁇ -chloroacrylate.
  • the long-chain acrylamide monomer examples include stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.
  • the acrylic monomer (a2) is a monomer different from the acrylic monomer (a1).
  • R 3 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group.
  • the number of carbon atoms of the hydrocarbon group is preferably 12 to 30, such as 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22.
  • X 5 may be a hydrogen atom, a methyl group, halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.
  • Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear structure or a branched structure.
  • the number of carbon atoms of Z is preferably 2 to 4, particularly 2.
  • Z is preferably not a direct bond, and Y 4 and Z are simultaneously not direct bonds.
  • the acrylic monomer (a2) can be produced by reacting hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with long-chain alkyl isocyanate.
  • long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate.
  • the acrylic monomer (a2) can also be produced by reacting (meth)acrylate having an isocyanate group in a side chain, such as 2-methacryloyloxyethyl methacrylate, with long-chain alkylamine or long-chain alkyl alcohol.
  • long-chain alkylamine include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine.
  • Examples of the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.
  • long-chain hydrocarbon group-containing acrylic monomer Preferable examples of the long-chain hydrocarbon group-containing acrylic monomer are as follows:
  • the compounds of the above chemical formulae are acrylic compounds in which the ⁇ -position is a hydrogen atom, and specific examples may be methacrylic compounds in which the ⁇ -position is a methyl group and ⁇ -chloroacrylic compounds in which the ⁇ -position is a chlorine atom.
  • the melting point of the acrylic monomer having a long-chain hydrocarbon group (a) is preferably 10°C or higher, and more preferably 25°C or higher.
  • the acrylic monomer having a long-chain hydrocarbon group (a) is preferably an acrylate in which X 1 , X 4 , and X 5 are hydrogen atoms.
  • R 11 may have various organic groups other than the ethylenically unsaturated polymerizable group, e.g., organic groups such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents.
  • R 12 is a hydrocarbon group having 7 to 40 carbon atoms and preferably an alkyl group, such as a chain hydrocarbon group or a cyclic hydrocarbon group. Among them, a chain hydrocarbon group is preferable, and a linear saturated hydrocarbon group is particularly preferable.
  • the number of carbon atoms of R 12 is 7 to 40, preferably 11 to 27, and particularly preferably 15 to 23.
  • R 13 is a hydrocarbon group having 1 to 5 carbon atoms, and preferably an alkyl group.
  • the hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, may have an unsaturated bond, and is preferably linear.
  • the number of carbon atoms of R 13 is preferably 2 to 4, and particularly preferably 2.
  • R 13 is preferably an alkylene group.
  • the amide group-containing monomer may be a monomer having one type of R 12 (for example, a compound in which R 12 has 17 carbon atoms) or a monomer having a combination of multiple types of R 12 (for example, a mixture of a compound in which R 12 has 17 carbon atoms and a compound in which R 12 has 15 carbon atoms).
  • amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate.
  • amide group-containing monomer examples include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristic acid amide ethyl (meth)acrylate, lauric acid amide ethyl (meth)acrylate, isostearic acid ethylamide (meth)acrylate, oleic acid ethylamide (meth)acrylate, tert-butylcyclohexylcaproic acid amide ethyl (meth)acrylate, adamantanecarboxylic acid ethylamide (meth)acrylate, naphthalenecarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)
  • the amide group-containing monomer is preferably stearic acid amide ethyl (meth)acrylate.
  • the amide group-containing monomer may be a mixture comprising stearic acid amide ethyl (meth)acrylate.
  • the amount of stearic acid amide ethyl (meth)acrylate is, for example, 55 to 99% by weight, preferably 60 to 85% by weight, and more preferably 65 to 80% by weight, based on the weight of the entirety of the amide group-containing monomer, and the remainder of the monomer may be, for example, palmitic acid amide ethyl (meth)acrylate.
  • the acrylic monomer having a hydrophilic group (b) is a monomer different from the monomer (a), and is a hydrophilic monomer.
  • the hydrophilic group is preferably an oxyalkylene group (the number of carbon atoms of the alkylene group is 2 to 6).
  • the acrylic monomer having a hydrophilic group (b) is preferably polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, and/or polyalkylene glycol mono(meth)acrylamide.
  • R may be a linear or branched alkylene group such as a group represented by formula -(CH 2 ) x - or -(CH 2 ) x1 -(CH(CH 3 )) x2 - wherein x1 and x2 are 0 to 6 such as 2 to 5, and the sum of x1 and x2 is 1 to 6; and the order of - (CH 2 ) x1 - and-(CH(CH 3 )) x2 - is not limited to the formula shown, and may be random.
  • -(RO) n - there may be two or more types (such as 2 to 4 types, particularly 2 types) of R, and thus - (RO) n - may be a combination of, for example, -(R 1 O) n1 - and -(R 2 O) n2 - wherein R 1 and R 2 are mutually different and an alkylene group having 2 to 6 carbon atoms, n1 and n2 are a number of 1 or more, and the sum of n1 and n2 is 2 to 90.
  • R in general formulae (b1), (b2), and (b3) is particularly preferably an ethylene group, a propylene group, or a butylene group.
  • R in general formulae (b1), (b2), and (b3) may be a combination of two or more types of alkylene groups.
  • at least one R is preferably an ethylene group, a propylene group, or a butylene group.
  • Examples of the combination of R include a combination of an ethylene group/a propylene group, a combination of an ethylene group/a butylene group, and a combination of a propylene group/a butylene group.
  • the monomer (b) may be a mixture of two or more types.
  • R in general formula (b1), (b2), or (b3) is preferably an ethylene group, a propylene group, or a butylene group.
  • Polyalkylene glycol di(meth)acrylate represented by general formula (b2) is not preferably used solely as the monomer (b), and is preferably used in combination with the monomer (b1). In this case as well, the compound represented by general formula (b2) is preferably less than 30% by weight in the monomer (b) used.
  • acrylic monomer having a hydrophilic group (b) include, but are not limited to, the following.
  • CH 2 CHCOO-CH 2 CH 2 O-H
  • CH 2 CHCOO-CH 2 CH 2 CH 2 O-H
  • CH 2 CHCOO-CH 2 CH(CH 3 )O-H
  • CH 2 CHCOO-CH(CH 3 )CH 2 O-H
  • CH 2 CHCOO-CH 2 CH 2 CH 2 CH 2 O-H
  • CH 2 CHCOO-CH 2 CH 2 CH(CH 3 )O-H
  • CH 2 CHCOO-CH 2 CH(CH 3 )CH 2 O-H
  • CH 2 CHCOO-CH(CH 3 )CH 2 CH 2 O-H
  • CH 2 CHCOO-CH(CH 3 )CH 2 CH 2 O-H
  • CH 2 CHCOO-CH 2 CH(CH 2 CH 3 )O-H
  • the monomer (b) is preferably acrylate or acrylamide in which X 2 is a hydrogen atom. Particularly, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide is preferable.
  • the monomer having an ion donating group (c) is a monomer different from the monomer (a) and the monomer (b).
  • the monomer (c) is preferably a monomer having an olefinic carbon-carbon double bond and an ion donating group.
  • the ion donating group is an anion donating group and/or a cation donating group.
  • Examples of the monomer having an anion donating group include monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
  • Specific examples of the monomer having an anion donating group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinyl sulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, phosphoric acid (meth)acrylate, vinylbenzenesulfonic acid, acrylamide tert-butyl sulfonic acid, and salts thereof.
  • salts of the anion donating group include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as a methyl ammonium salt, an ethanol ammonium salt, and a triethanol ammonium salt.
  • examples of the cation donating group include an amino group and preferably a tertiary amino group and a quaternary amino group.
  • the tertiary amino group two groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group such as a benzyl group (C 6 H 5 -CH 2 -)).
  • three groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group such as a benzyl group (C 6 H 5 -CH 2 -)).
  • the remaining one group bonded to the nitrogen atom may have a carbon-carbon double bond.
  • the cation donating group may be in the form of a salt.
  • a cation donating group which is a salt is a salt formed with an acid (an organic acid or an inorganic acid).
  • Organic acids such as carboxylic acids having 1 to 20 carbon atoms (particularly, monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferable.
  • Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and salts thereof are preferable.
  • the monomer having an ion donating group (c) is preferably methacrylic acid, acrylic acid, and dimethylaminoethyl methacrylate, and more preferably methacrylic acid and dimethylaminoethyl methacrylate.
  • Another monomer (d) is a monomer different from the monomers (a), (b), and (c).
  • the other monomer include ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, halogenated vinyl styrene, ⁇ -methylstyrene, p-methylstyrene, polyoxyalkylene mono(meth)acrylate, (meth)acrylamide, diacetone (meth)acrylamide, methylollated (meth)acrylamide, N-methylol (meth)acrylamide, alkyl vinyl ether, halogenated alkyl vinyl ether, alkyl vinyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, aziridinyl (meth)acrylate, benzyl (meth)acrylate, isocyanate ethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)
  • the amount of the repeating unit formed from the monomer (a) may be 30 to 95% by weight, preferably 40 to 88% by weight, and more preferably 50 to 85% by weight, based on the fluorine-free polymer (particularly, an acrylic polymer).
  • the amount of the repeating unit formed from the monomer (b) may be 5 to 70% by weight, preferably 8 to 50% by weight, and more preferably 10 to 40% by weight, based on the fluorine-free polymer.
  • the amount of the repeating unit formed from the monomer (c) may be 0.1 to 30% by weight, preferably 0.5 to 20% by weight, and more preferably 1 to 15% by weight, based on the fluorine-free polymer.
  • the amount of the repeating unit formed from the monomer (d) may be 0 to 20% by weight, such as 1 to 15% by weight, particularly 2 to 10% by weight, based on the fluorine-free copolymer.
  • the weight-average molecular weight of the fluorine-free polymer may be 1,000 to 10,000,000, preferably 5,000 to 8,000,000, and more preferably 10,000 to 4,000,000.
  • the weight-average molecular weight is a value obtained in terms of polystyrene by gel permeation chromatography.
  • (meth)acryl means acryl or methacryl.
  • (meth)acrylate means acrylate or methacrylate.
  • the fluorine-free polymer (particularly, an acrylic polymer) is preferably a random copolymer rather than a block copolymer.
  • Polymerization for the fluorine-free polymer is not limited, and various polymerization methods can be selected, such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization.
  • solution polymerization involving an organic solvent and emulsion polymerization involving water or involving an organic solvent and water in combination, are selected.
  • the fluorine-free copolymer after polymerization is diluted with water to be emulsified in water and thus formed into a treatment liquid.
  • polymerization for example, solution polymerization or emulsion polymerization, preferably solution polymerization
  • water is added, and then the solvent is removed to disperse the polymer in water.
  • An emulsifier does not need to be added, and a self-dispersive product can be produced.
  • organic solvents examples include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl acetate, glycols such as propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, and low molecular weight polyethylene glycol, and alcohols such as ethyl alcohol and isopropanol.
  • ketones such as acetone and methyl ethyl ketone
  • esters such as ethyl acetate and methyl acetate
  • glycols such as propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, and low molecular weight polyethylene glycol
  • NMP N-methyl-2-pyrrolidone
  • alcohols such as ethyl alcohol and iso
  • peroxide an azo compound, or a persulfate compound
  • peroxide an azo compound, or a persulfate compound
  • the polymerization initiator is, in general, water-soluble and/or oil-soluble.
  • oil-soluble polymerization initiator preferably include 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis(cyclohexan-1-carbonitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile), benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and t-butyl perpivalate.
  • water-soluble polymerization initiator preferably include 2,2'-azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropionamidine) hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, and hydrogen peroxide.
  • the polymerization initiator is used in the range of 0.01 to 5 parts by weight, based on 100 parts by weight of the monomers.
  • a chain transfer agent such as a mercapto group-containing compound may be used, and specific examples thereof include 2-mercaptoethanol, thiopropionic acid, and alkyl mercaptan.
  • the mercapto group-containing compound is used in the range of 10 parts by weight or less, or 0.01 to 5 parts by weight, based on 100 parts by weight of the monomers.
  • the fluorine-free polymer can be produced as follows.
  • solution polymerization a method is employed that involves dissolving the monomers in an organic solvent, performing nitrogen purge, then adding a polymerization initiator, and heating and stirring the mixture, for example, in the range of 40 to 120°C for 1 to 10 hours.
  • the polymerization initiator may be, in general, an oil-soluble polymerization initiator.
  • the organic solvent is inert to and dissolves the monomers, and examples include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl acetate, glycols such as propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, and low molecular weight polyethylene glycol, alcohols such as ethyl alcohol and isopropanol, and hydrocarbon solvents such as n-heptane, n-hexane, n-octane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffin hydrocarbon, liquid paraffin, decane, undecane, dodecane, mineral spirit, mineral turpen, and naphtha.
  • the solvent include acetone, chloroform, HCHC 225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, N-methyl-2-pyrrolidone (NMP), and dipropylene glycol monomethyl ether (DPM).
  • the organic solvent is used in the range of 50 to 2,000 parts by weight, such as 50,
  • emulsion polymerization a method is employed that involves emulsifying the monomers in water in the presence of an emulsifier, performing nitrogen purge, then adding a polymerization initiator, and stirring the mixture in the range of 40 to 80°C for 1 to 10 hours for polymerization.
  • a water-soluble polymerization initiator such as 2,2'-azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropionamidine) hydrochloride.
  • the monomers are formed into particles in water by using an emulsifying apparatus capable of applying strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer, and polymerized by using an oil-soluble polymerization initiator.
  • an emulsifying apparatus capable of applying strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer, and polymerized by using an oil-soluble polymerization initiator.
  • Various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in the range of 0.5 to 20 parts by weight, based on 100 parts by weight of the monomers.
  • An anionic and/or nonionic and/or cationic emulsifier is preferably used.
  • a compatibilizer such as a water-soluble organic solvent or a low molecular weight monomer that causes the monomers to be sufficiently compatible is preferably added.
  • a compatibilizer By adding a compatibilizer, emulsifiability and copolymerizability can be increased.
  • water-soluble organic solvent examples include acetone, propylene glycol, dipropylene glycol monomethyl ether (DPM), dipropylene glycol, tripropylene glycol, ethanol, N-methyl-2-pyrrolidone (NMP), 3-methoxy-3-methyl-1-butanol, or isoprene glycol, and the water-soluble organic solvent may be used in the range of 1 to 50 parts by weight, such as 10 to 40 parts by weight, based on 100 parts by weight of water.
  • DPM dipropylene glycol monomethyl ether
  • NMP N-methyl-2-pyrrolidone
  • 3-methoxy-3-methyl-1-butanol or isoprene glycol
  • the stability of the composition is increased.
  • the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, and the low molecular weight monomer may be used in the range of 1 to 50 parts by weight, such as 10 to 40 parts by weight, based on total 100 parts by weight of the monomers.
  • the amount of the fluorine-free polymer (1) is 0.1 to 99% by weight, based on the total weight of the fluorine-free polymer (1) and the particles (2).
  • the lower limit of the amount of the fluorine-free polymer (1) may be 1% by weight, such as 5% by weight, particularly 10% by weight, and especially 20% by weight or 30% by weight.
  • the upper limit of the amount of the fluorine-free polymer (1) may be 90% by weight, such as 70% by weight, particularly 60% by weight, and especially 50% by weight or 40% by weight.
  • the particles (2) comprise at least one type of inorganic particles or organic particles.
  • the particles (2) preferably comprise organic particles.
  • the particles (2) more preferably comprise both inorganic particles and organic particles.
  • the inorganic particles are particles made of inorganic materials.
  • the inorganic materials constituting the inorganic particles include calcium carbonate, talc, kaolin (and calcined kaolin), clay(and calcined clay), mica, aluminum hydroxide, barium sulfate, calcium silicate, calcium sulfate, silica, zinc carbonate, zinc oxide, titanium oxide, bentonite, and white carbon.
  • Calcium carbonate, silica, and calcined clay are preferable. Calcium carbonate is particularly preferable.
  • the organic particles are particles made of organic materials.
  • the organic materials constituting the organic particles include polysaccharides and thermoplastic resins (such as polyvinyl alcohol, polyolefin, polystyrene).
  • the organic particles (such as particles of polysaccharides and particles of thermoplastic resins) may be modified (for example, cation-modified or anion-modified). Polysaccharides are preferable.
  • the polysaccharides are biopolymers synthesized in biological systems by the condensation and polymerization of various monosaccharides, including those that have been chemically modified (denatured).
  • polysaccharides include starch, cellulose, modified cellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, and chitosan.
  • modified cellulose include hydroxymethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose.
  • the polysaccharides are preferably starch.
  • Starch particles have excellent dispersibility in the pulp slurry.
  • the starch may be an undenatured starch.
  • examples of the starches include rice flour starch, wheat starch, corn starch, potato starch, tapioca starch, sweet potato starch, adzuki bean starch, mung bean starch, kudzu starch, and dogtooth violet starch.
  • the starch may be those that have been denatured, such as enzymatic denaturation, thermochemical denaturation, acetate esterification, phosphate esterification, carboxy etherification, hydroxy etherification, and cationic denaturation.
  • the starch is preferably amphoterized starch (starch having a cation group and an anion group) or cationized starch (starch having a cation group).
  • amphoterized starch and cationized starch at a preferred weight ratio of 0.1:9.9 to 4:6 or 0.5:9.5 to 2:8) is preferable since it also increases water resistance.
  • the cation group (particularly, the cation group in the amphoterized starch or the cationized starch) may be a cation group similar to the cation group in the monomer having the ion donating group (c), such as an amino group
  • the anion group (particularly, the anion group in the amphoterized starch) may be an anion group similar to the anion group in the monomer having the ion donating group (c), such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
  • the particles (2) may have a powdery, granular, fibrous, flaky, or a like form.
  • the particles are preferably insoluble in water at 40°C.
  • Insoluble in water means that the solubility in 100 g of water at 40°C is 1 g or less, such as 0.5 g or less.
  • the average particle size of the particles may be 0.01 to 100 ⁇ m, such as 0.1 to 50 ⁇ m, particularly 1.0 to 20 ⁇ m.
  • the average particle size can be measured by a laser diffraction particle size distribution measurement apparatus (applying light scattering theory) using a water dispersion of the particles.
  • the dissolution temperature of organic particles in water is preferably about 55°C or more (for example, 60°C to 100°C).
  • the "dissolution temperature” means the highest temperature at which the appearance of the liquid changes from cloudy to transparent after adding 5 parts by weight of organic particles based on 100 parts by weight of water maintained at the target temperature with stirring by visual observation under atmospheric pressure (the liquid might be cloudy at the time of addition), and maintaining the liquid at the temperature for 30 minutes with continuous stirring.
  • organic particles examples include undenatured starch, denatured starch (such as cationized starch), locust bean gum, carboxymethyl cellulose, and polyvinyl alcohol.
  • the organic particles may be ionic or nonionic. If the pulp is ionic, the organic particles are preferably ionic, more specifically anionic, cationic, or amphoteric organic particles, so that they can be easily anchored to the pulp in the pulp slurry and the product. Particularly, if the pulp is ionic, it is preferable to use organic particles having the opposite ionic part to the pulp, so that the organic particles can be effectively anchored to the pulp (preferably together with an oil-resistant agent) and the gas barrier properties of the finally obtained molded pulp container can be enhanced. Pulps are usually anionic, and for such pulps, it is preferable that the organic particles have a cationic moiety, or more particularly are cationized or amphoterized.
  • Organic particles having cation moieties include cationized starch, amphoteric starch, and cation-modified polyvinyl alcohol.
  • the amount of the particles (2) is 1 to 99.9% by weight, based on the total weight of the fluorine-free polymer (1) and the particles (2).
  • the lower limit of the amount of the particles (2) may be 10% by weight, such as 30% by weight or 40% by weight, particularly 50% by weight or 60% by weight, and especially 65% by weight or 70% by weight.
  • the upper limit of the amount of the particles (2) may be 99% by weight or 98% by weight, such as 97% by weight or 95% by weight, particularly 90% by weight, and especially 80% by weight or 70% by weight.
  • the amount of the particles (2) may be 60 to 99% by weight, such as 65 to 98% by weight, particularly 70 to 97% by weight, based on the total weight of the fluorine-free polymer (1) and the particles (2) .
  • the oil-resistant agent may comprise another component (3) other than the fluorine-free polymer (1) and the particles (2).
  • the other component (3) include an aqueous medium and an emulsifier.
  • the aqueous medium is water or a mixture of water and an organic solvent (an organic solvent miscible with water).
  • the amount of the aqueous medium may be 50% by weight to 99.99% by weight, based on the total amount of the fluorine-free polymer (1) (and the particles (2), if necessary) and the aqueous medium.
  • the amount of the emulsifier may be 0 to 30 parts by weight, such as 0.1 to 10 parts by weight, based on 100 parts by weight of the fluorine-free polymer (1).
  • the oil-resistant agent may be in the form of a solution, an emulsion, or an aerosol.
  • the oil-resistant agent may comprise the fluorine-free polymer (1) and a liquid medium.
  • the liquid medium is, for example, an organic solvent and/or water, and preferably an aqueous medium.
  • the aqueous medium is water or a mixture of water and an organic solvent (such as polypropylene glycol and/or a derivative thereof).
  • the fluorine-free polymer is a water dispersion type which is dispersed in an aqueous medium, and the fluorine-free polymer(1) may be self-emulsified, dispersed in the aqueous medium in the form of a neutralized salt, or emulsified using an emulsifier.
  • the particles (2) may be used in the form of solid or dispersed in a liquid medium.
  • the fluorine-free polymer(1) and the particles (2) may be dispersed in the same liquid medium or may be dispersed in different liquid media.
  • the concentration of the fluorine-free polymer may be, for example, 0.01 to 50% by weight.
  • the oil-resistant agent may either comprise or not comprise an emulsifier, but it is preferable not to comprise an emulsifier.
  • the oil-resistant agent can be used to treat a paper substrate.
  • the "treatment” means that the oil-resistant agent is applied to interior and/or exterior of paper.
  • the oil-resistant agent can be applied to the substrate by a conventionally known method.
  • the oil-resistant agent is mainly present inside the paper through internal treatment.
  • Examples of the paper substrate to be treated include paper, a container made of paper, and a molded article made of paper (for example, molded pulp).
  • the fluorine-free polymer favorably adheres to the paper substrate.
  • the oil-resistant agent should be used such that the amount of fluorine-free polymer (1) and the particles (2) is 0.01 to 75 parts by weight, such as 0.1 to 60 parts by weight, based on 100 parts by weight of pulp solids.
  • Paper can be produced by a conventionally known papermaking method.
  • An internal treatment method in which the oil-resistant agent is added to a pulp slurry before papermaking, or an external treatment method in which the oil-resistant agent is applied to paper after papermaking, can be used.
  • the method of treatment with the oil-resistant agent in the present disclosure is preferably an internal treatment method. Even if the oil-resistant agent of the present disclosure is used in the internal treatment, no new equipment is required.
  • paper treated by the oil-resistant agent may be produced by mixing the oil-resistant agent with pulp slurry and paper making.
  • the paper treated by the oil-resistant agent is oil-resistant paper having oil resistance.
  • the oil-resistant paper can be thin or thick, or molded pulp.
  • Paper thus treated after rough drying at room temperature or high temperature, is optionally subjected to a heat treatment that can have a temperature range of up to 300°C, such as up to 200°C, particularly 80°C to 180°C, depending on the properties of the paper, and thus shows excellent oil resistance and water resistance.
  • a heat treatment that can have a temperature range of up to 300°C, such as up to 200°C, particularly 80°C to 180°C, depending on the properties of the paper, and thus shows excellent oil resistance and water resistance.
  • the present disclosure can be used in gypsum board base paper, coated base paper, wood containing paper, commonly used liner and corrugating medium, neutral machine glazed paper, neutral liner, rustproof liner and metal laminated paper, kraft paper, and the like.
  • the present disclosure can also be used in neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral heat sensitive paper, neutral pressure sensitive base paper, neutral inkjet paper, and neutral communication paper.
  • a pulp may be any of bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high yield pulp such as ground pulp, mechanical pulp, or thermomechanical pulp, waste paper pulp such as waste newspaper, waste magazine, waste corrugated cardboard, or waste deinked paper, and non-wood pulp such as bagasse pulp, kenaf pulp, or bamboo pulp.
  • the pulp raw material may be a combination of one or more of these.
  • a mixture of the above pulp raw material and one or more of synthetic fiber of asbestos, polyamide, polyimide, polyester, polyolefin, or the like can be used as well.
  • a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight is preferably formed into paper.
  • An additive such as a sizing agent, a paper strengthening agent, a flocculant, a retention aid, or a coagulant
  • the fluorine-free polymer can be added to the pulp slurry. Since the pulp is generally anionic, at least one of the additive and the fluorine-free polymer is preferably cationic or amphoteric such that the additive and the fluorine-free polymer are favorably anchored to paper.
  • a combination of a cationic or amphoteric additive and an anionic fluorine-free polymer, a combination of an anionic additive and a cationic or amphoteric fluorine-free polymer, and a combination of a cationic or amphoteric additive and fluorine-free polymer are preferably used.
  • additives may be used in addition to the oil-resistant agent.
  • examples of the other components are cationic coagulants, water-resistant agents, paper strength additives, flocculants, fixing agents, and yield improvers.
  • Cationic coagulants, paper strength additives, flocculants, fixing agents, and yield improvers can be polymers or inorganic materials which are cationic or amphoteric.
  • the cationic coagulants, paper strength additives, flocculants, fixing agents, and yield improvers can effectively anchor the oil-resistant agent consisting of the fluorine-free polymer (1) and the particles (2) to the pulp, which is generally anionic, and the gas barrier properties and/or water resistance and oil resistance of the finally obtained molded pulp container can be enhanced.
  • Examples of cationic coagulants, paper strength additives, flocculants, fixing agents, and yield improvers include a polyamine epichlorohydrin resin, a polyamide epichlorohydrin resin, cationic polyacrylamide (an acrylamide-allylamine copolymer, an acrylamide-dimethylaminoethyl (meth)acrylate copolymer, an acrylamide-diethylaminoethyl (meth)acrylate copolymer, an acrylamide-quaternized dimethylaminoethyl (meth)acrylate copolymer, an acrylamide-quaternized diethylaminoethyl (meth)acrylate copolymer, or the like), polydiallyldimethylammonium chloride, polyallylamine, polyvinylamine, polyethyleneimine, an N-vinylformamide-vinylamine copolymer, a melamine resin, a polyamide epoxy resin, sulfate band,
  • a water-resistant agent may be used in addition to the oil-resistant agent.
  • the "water-resistant agent” refers to a component that, when added to the pulp slurry, is capable of increasing the water resistance of a molded pulp product as compared to the case where it is not added (provided that the above-described oil-resistant agent is excluded). Due to the water-resistant agent, the water resistance of the finally obtained molded pulp container can be increased.
  • the above-described cationic coagulant is generally incapable of increasing water resistance by itself and can be understood as being different from the water-resistant agent.
  • a sizing agent or the like used in ordinary papermaking is usable as a water-resistant agent.
  • the water-resistant agent include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (such as acidic rosin-based sizing agents or neutral rosin-based sizing agents), and cationic sizing agents are preferable.
  • a styrenecontaining polymer such as a styrene-(meth)acrylate copolymer, an alkenyl succinic anhydride, and an alkyl ketene dimer are preferable.
  • a dye, a fluorescent dye, a slime control agent, an antislip agent, an antifoaming agent, and a pitch control agent which are usually used as paper making chemicals in paper treatment agents may also be used.
  • Paper is preferably a molded pulp product.
  • the molded pulp product can be produced by a producing method comprising: preparing a formulated pulp slurry by adding an oil-resistant agent to a slurry in which pulp is dispersed in an aqueous medium, making a molded pulp intermediate, followed by dehydrating and then at least drying to obtain a molded pulp product.
  • the preparation of the formulated pulp slurry is preferably performed such that the organic particles remain in a solid state.
  • the formulated pulp slurry is prepared at a temperature lower than, for example, a temperature at least 5°C lower than the dissolution temperature of the organic particles.
  • the organic particles remain in a solid state (powdery, granular, fibrous, flaky, or the like depending on the organic particles used as a raw material), and for example, when starch powder is used as a raw material, the starch powder may remain dispersed in an aqueous medium.
  • the oil-resistant agent and the organic particles, and optionally the cationic coagulant and/or the water-resistant agent or the like may be added to the pulp slurry in any order as long as the organic particles remain in a solid state.
  • each component in the formulated pulp slurry can be suitably selected so as to attain a high freeness suitable for papermaking and dehydrating and the physical properties desired of a molded pulp product, and, for example, can be as follows.
  • each component is in the form of, for example, a dispersion
  • the above content indicates the solid content (based on all components) of each component in the formulated pulp slurry.
  • the content of each of the pulp and the oil-resistant agent based on the aqueous medium in the formulated pulp slurry can be suitably selected so as to attain a high freeness suitable for papermaking and dehydrating, and for example, can be as follows.
  • the resulting aqueous composition has a reduced freeness.
  • the organic particles remain in a solid state without being dissolved in the aqueous medium, and therefore, as compared to the case where the organic particles are dissolved in the aqueous medium, a larger amount of the organic particles can be added while maintaining the high freeness of the formulated pulp slurry.
  • the formulated pulp slurry prepared above is made to form a molded pulp intermediate, the molded pulp intermediate is dehydrated and then at least dried to obtain a molded pulp product.
  • Papermaking, dehydrating, and drying can be performed according to conventionally known methods concerning molded pulp.
  • the aqueous medium can be at least partially removed from the formulated pulp slurry, and a molded pulp intermediate having a shape that corresponds to the mold can be obtained.
  • the process from the preparation to the dehydration of the formulated pulp slurry is performed, with the organic particles remaining in a solid state.
  • dehydrating is performed at a temperature lower than, such as a temperature at least 5°C lower than the dissolution temperature of the organic particles.
  • the aqueous medium is removed from the formulated pulp slurry through a mold (and optionally a filter), and therefore, an excessively lowered freeness of the formulated pulp slurry due to dissolution of the organic particles makes it substantially impossible to perform papermaking and dehydrating and is thus not preferable.
  • the freeness of the formulated pulp slurry is not lowered, and papermaking and dehydrating can be appropriately performed.
  • the organic particles After dehydrating, in the resulting molded pulp intermediate, the organic particles remain in a solid state (powdery, granular, fibrous, flaky, or the like depending on the organic particles used as raw materials) and, for example, when starch powder is used as a raw material, the starch powder may be dispersed in the pulp.
  • Drying does not need to be performed such that the organic particles remain in a solid state, and can be performed at a temperature at which the remaining aqueous medium can be effectively removed (if applicable, it can be a temperature equal to or higher than the dissolution temperature of the organic particles), for example, 90 to 250°C, particularly 100 to 200°C.
  • the drying time is not limited, and can be selected such that the aqueous medium remaining in the molded pulp intermediate is substantially removed.
  • the drying atmosphere is not limited, and may be conveniently an ambient atmosphere (air under normal pressure).
  • molded pulp During and/or after drying, other steps which are conventionally known concerning molded pulp, for example, press molding (including heat pressing), may be performed if necessary.
  • press molding including heat pressing
  • causing the organic particles to at least partially dissolve makes it possible to obtain even higher gas barrier properties.
  • the organic particles do not need to dissolve entirely, and the organic particles may partially remain in a solid state.
  • This molded pulp product comprises a pulp, an oil-resistant agent, and can achieve high gas barrier properties and excellent water resistance and oil resistance.
  • the content of the organic particles based on the pulp is 0.0001 to 75% by weight, such as 0.1 to 60% by weight, particularly 2 to 50% by weight.
  • a molded pulp product is obtained by adding an aqueous solution in which organic particles such as starch are dissolved in advance in an aqueous medium to a pulp slurry to increase strength, a sufficient strength improving effect can be obtained even when the content of organic particles based on the pulp is low, and it was thus not required to increase the content of the organic particles based on the pulp.
  • the content of the organic particles based on the pulp is preferably high, and the lower limit of the content of the organic particles based on the pulp may be 3% by weight or 5% by weight, such as 8% by weight or 10% by weight, particularly 15% by weight.
  • the upper limit of the content of the organic particles based on the pulp may be 60% by weight, such as 50% by weight or 40% by weight, particularly 30% by weight or 20% by weight.
  • the content of the organic particles based on the pulp may be 3 to 70% by weight or 5 to 60% by weight, such as 8 to 50% by weight or 8 to 40% by weight.
  • the content of the organic particles may be 3 to 70 parts by weight or 5 to 60 parts by weight, such as 8 to 50 parts by weight or 8 to 40 parts by weight, based on the 100 parts by weight of the pulp.
  • the content of the organic particles may be 3 to 70 parts by weight or 5 to 60 parts by weight, such as 8 to 50 parts by weight or 8 to 40 parts by weight, based on the 100 parts by weight of the pulp.
  • the organic particles may be derived from starch powder dispersed in the aqueous medium (in the formulated pulp slurry).
  • the proportions of the pulp, the organic particles, the oil-resistant agent, and optionally the cationic coagulant and/or the water-resistant agent contained in the molded pulp product can be considered substantially the same as the solid contents of these components used as raw materials (usually, the aqueous medium and, if present, other liquid media can be removed by drying and press molding, but the solids can remain without being removed or decomposed).
  • the content of each component (a component that can remain in the molded pulp product) based on the pulp (solids) can be suitably selected according to the physical properties desired of the molded pulp product, and, for example, can be as follows.
  • the oil-resistant agent are internally added to the molded pulp product (they are added to a pulp slurry, and the molded pulp product is produced by a pulp molding method). Accordingly, after the molded pulp product is used, the entirety of the product can be crushed to bring it back to the original raw materials, and is thus suitable for recycle use. Furthermore, it is possible to utilize the intrinsic biodegradability of the pulp, the molded pulp product can extremely reduce and preferably can substantially eliminate the environmental burden. Also, with the molded pulp product, the texture of the pulp can be maintained on the front side of the product, and the appearance is not impaired unlike when the front side is laminated with a plastic film and becomes glossy.
  • the molded pulp product can be suitably used as food containers (including trays and the like), for example, storage containers for frozen food and chilled food.
  • the molded pulp product of the present disclosure has excellent water resistance and oil resistance, moisture and oil derived from food do not impregnate the molded pulp product (a container), and it is thus possible to prevent deterioration of container strength resulting from impregnation with water and oil and prevent staining of the table surface or the like facing the bottom surface of the container with moisture and oil permeated through the container.
  • the molded pulp product of the present disclosure has high gas barrier properties and unlikely allows gas and water vapor to permeate, and thus, when accommodating hot and wet food or when heated in a microwave with food being accommodated therein, it is possible to prevent the problem that gas and water vapor derived from food permeate through the container and leak to the outside and, particularly, condense on the table surface or the like facing the bottom surface of the container.
  • the molded pulp product of the present disclosure has high gas barrier properties and unlikely allow gas and water vapor (or moisture) to permeate, and thus, when refrigerating accommodated food, evaporation of water from food and exposure of food to oxygen can be effectively reduced, freezer burn resulting therefrom can be effectively prevented, and the flavor of food can be maintained for a long period of time.
  • a part, %, and a ratio indicate a part by weight, % by weight, and a weight ratio, respectively, unless otherwise specified.
  • an evaluation liquid (tap water) at 90°C was poured into a molded pulp product molded into a container shape, the molded pulp product was left to stand still for 30 minutes, then the evaluation liquid was discarded, and the extent of impregnation of the molded pulp product (the container) with the evaluation liquid was visually evaluated according to the following criteria.
  • the air permeance (air resistance) at the bottom part of a molded pulp product molded into a container shape was measured in accordance with JIS P 8117 (2009) using an automatic Gurley densometer manufactured by YASUDA SEIKI SEISAKUSHO, LTD. (Product No. 323-AUTO, vent hole diameter 28.6 ⁇ 0.1 mm). The measured value of air permeance was evaluated according to the following criteria.
  • a reactor having a volume of 500 ml and equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was provided, and 100 parts of a methyl ethyl ketone (MEK) solvent was added.
  • MEK methyl ethyl ketone
  • a monomer composed of 78 parts of stearyl acrylate (StA, melting point: 30°C), 16 parts of hydroxyethyl acrylate (HEA), and 6 parts of methacrylic acid (MAA) (the monomer being 100 parts in total) as well as 1.2 parts of a perbutyl PV (PV) initiator were added in this order, and the mixture was mixed by being stirred for 12 hours in a nitrogen atmosphere at 65 to 75°C to carry out copolymerization.
  • the solid content concentration of the resulting copolymer-containing solution was 50% by weight.
  • the weight-average molecular weight in terms of polystyrene was 230,000.
  • the melting point of the copolymer was 48°C.
  • a reactor having a volume of 500 ml and equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater was provided, and 100 parts of a methyl ethyl ketone (MEK) solvent was added.
  • MEK methyl ethyl ketone
  • a monomer composed of 78 parts of stearic acid amide ethyl acrylate (C18AmEA, melting point: 70°C), 16 parts of hydroxybutyl acrylate (HBA, Tg: -40°C), and 6 parts of dimethylaminoethyl methacrylate (DM) (the monomer being 100 parts in total) as well as 1.2 parts of a perbutyl PV (PV) initiator were added in this order, and mixed by being stirred for 12 hours in a nitrogen atmosphere at 65 to 75°C to carry out copolymerization.
  • the solid content concentration of the resulting copolymer-containing solution was 50% by weight.
  • the above pulp slurry was placed in a metal tank.
  • a metal pulp mold with many suction holes was present with a reticular body placed on top of the mold.
  • the pulp-containing aqueous composition was suctioned and dehydrated through the pulp mold and the reticular body using a vacuum pump, and the solids (such as a pulp) contained in the pulp-containing aqueous composition were deposited on the reticular body to obtain a molded pulp intermediate.
  • the resulting molded pulp intermediate was dried by applying pressure from top and bottom with metal male and female molds heated to 60 to 200°C.
  • Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1, except that 1.2 g of calcium carbonate in Example 2 was added, and 2.4 g of cationized starch powder was added. Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1, except that 2.4 g of the water dispersion of the fluorine-free copolymer of Synthesis Example 2 in Example 3 diluted with water to a solid content of 10% was added. Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1, except that 4.8 g of cationized starch powder in Example 4 was added. Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1, except that calcium carbonate in Example 5 was not added, and 3.6 g of the water dispersion of the fluorine-free copolymer of Synthesis Example 2 diluted with water to a solid content of 10% was added. Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1, except that a 5% solid aqueous solution of amphoterized starch in Example 5 was not added, and a 5% solid aqueous solution of alkyl ketene dimer (AKD) was not added.
  • Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1, except that 0.6 g of calcium carbonate in Example 1 was added. Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1, except that 3.6 g of the water dispersion of the fluorine-free copolymer of Synthesis Example 2 in Example 8 diluted with water to a solid content of 10% was added and kept stirring for 1 minute, and then 6.0 g of the water dispersion of the fluorine-free copolymer of Synthesis Example 1 diluted with water to a solid content of 10% was added and kept stirring for 1 minute.
  • Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1, except that a 5% solid aqueous solution of the alkyl ketene dimer (AKD) in Example 3 was not added.
  • Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1, except that calcium carbonate in Example 1 was not added, and 3.6 g of styrene-butadiene latex diluted with water to a solid content of 10% was added in place of the water dispersion of the fluorine-free copolymer of Synthesis Example 2 diluted with water to a solid content of 10%.
  • Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance.
  • Example 1 The experiment was performed in the same manner as in Example 1 except that 3.6 g of styrene-butadiene latex diluted with water to a solid content of 10% was added in place of the water dispersion of the fluorine-free copolymer of Synthesis Example 2 in Example 2 diluted with water to a solid content of 10%.
  • Table 1 shows the results of evaluating the content of each component based on the pulp in the resulting molded pulp product, as well as high-temperature oil-resistant characteristics, high-temperature water-resistant characteristics, and air permeance. [Table 1] Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Com. Ex. 1 Com. Ex.
  • the oil-resistant agent of the present disclosure is applicable to a variety of paper, particularly paper for use in a food container and a food packaging material.
  • the oil-resistant agent is externally or internally, particularly internally incorporated into the paper.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paper (AREA)
EP20814375.0A 2019-05-28 2020-05-27 Agent résistant à l'huile pour papier Active EP3978683B1 (fr)

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PCT/JP2020/020972 WO2020241709A1 (fr) 2019-05-28 2020-05-27 Agent résistant à l'huile pour papier

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EP4349922A4 (fr) 2021-07-08 2024-08-07 Daikin Ind Ltd Composition d'agent résistant à l'huile
JP7381953B2 (ja) 2021-07-08 2023-11-16 ダイキン工業株式会社 耐油剤組成物
CN114573767B (zh) * 2022-03-10 2023-02-28 北京马普新材料有限公司 共聚物、纸张用处理剂和纸制品
CN115926073B (zh) * 2022-12-02 2024-07-02 西南石油大学 一种纳米碳酸钙改性丙烯酰胺两性共聚物及其制备方法

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EP3978683B1 (fr) 2024-10-02
US20220081842A1 (en) 2022-03-17
TW202106949A (zh) 2021-02-16
JP7299526B2 (ja) 2023-06-28
JPWO2020241709A1 (fr) 2020-12-03
CN113891972A (zh) 2022-01-04
EP3978683A4 (fr) 2023-05-10
WO2020241709A1 (fr) 2020-12-03

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