WO2020054856A1 - 紙用耐油剤 - Google Patents
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- WO2020054856A1 WO2020054856A1 PCT/JP2019/036157 JP2019036157W WO2020054856A1 WO 2020054856 A1 WO2020054856 A1 WO 2020054856A1 JP 2019036157 W JP2019036157 W JP 2019036157W WO 2020054856 A1 WO2020054856 A1 WO 2020054856A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09D103/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09D103/04—Starch derivatives
- C09D103/08—Ethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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
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- 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
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- 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
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
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- 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
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- 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
- D21H21/18—Reinforcing agents
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Definitions
- the present disclosure relates to a paper oil repellent and paper treated with the paper oil repellent.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2013-237941 discloses that an oil-resistant agent layer contains starch, a styrene-acrylic resin having an alkyl (meth) acrylate group having 8 to 24 carbon atoms, and a wax, and Discloses an oil-resistant paper having an Oken-type air permeability of 2000 seconds or less and a solid content of an oil-resistant agent layer of 2.0 to 10.0 g / m 2 .
- Patent Document 2 (WO 2013/008938) discloses that one or two or more (meth) acrylate monomers and one or two or more vinyl monomers are formed and have a glass transition point of -10.
- Patent Document 3 Japanese Patent Application Laid-Open No. 2006-028697 discloses an oil-resistant paper for food in which an acrylic synthetic resin emulsion is applied to a paper base to form an oil-resistant synthetic resin layer.
- An object of the present disclosure is to provide an oil-proofing agent capable of giving paper excellent oil resistance and water resistance.
- the present disclosure (A) a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, and (b) a non-fluorine having a repeating unit formed from an acrylic monomer having a hydrophilic group
- the present invention relates to a paper oil-resistant agent comprising a copolymer.
- the oil proofing agent for paper also contains a liquid medium which is water and / or an organic solvent, preferably water or a mixture of water and an organic solvent (aqueous medium).
- the present disclosure provides greaseproof paper that has been treated with a greaseproof paper. The paper treatment is external or internal.
- the oil-resistant paper has an oil-resistant layer containing a paper oil-resistant agent and starch by an external treatment method of a paper oil-resistant agent.
- the oil-resistant paper contains the oil-resistant agent for paper inside the paper by a method of internally adding the oil-resistant agent for paper.
- R 1 is independently a hydrocarbon group having 7 to 40 carbon atoms
- X 1 is a hydrogen atom, a monovalent organic group or a halogen atom
- a group composed of at least one or more selected members (excluding a hydrocarbon group), k is 1-3.
- the oil-resistant agent for paper according to claim 1 which is a monomer represented by the formula: [3] The paper according to [1] or [2], wherein in the acrylic monomer (a) having a long-chain hydrocarbon group, X 1 is a hydrogen atom, and the long-chain hydrocarbon group has 18 to 40 carbon atoms. Oil resistant agent.
- An acrylic monomer (a) having a long-chain hydrocarbon group, Equation (a1): CH 2 CC (—X 4 ) —C ( O) —Y 2 —R 2 [Wherein, R 2 is a hydrocarbon group having 7 to 40 carbon atoms; X 4 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 2 is —O— or —NH—.
- R 3 is each independently a hydrocarbon group having 7 to 40 carbon atoms
- X 5 is a hydrogen atom, a monovalent organic group or a halogen atom
- Y 3 is —O— or —NH—
- Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2.
- X 2 represents a hydrogen atom or a methyl group
- X 3 is a hydrogen atom or an unsaturated or saturated hydrocarbon group R having 1 to 22 carbon atoms, an alkylene group having 2 to 6 carbon atoms
- n is an integer of 1 to 90.
- the non-fluorinated copolymer is formed from a monomer (c) having an olefinic carbon-carbon double bond and an anionic or cationic donor other than the monomers (a) and (b).
- the oil-resistant agent for paper according to any one of [1] to [5], further comprising a repeating unit.
- the amount of the repeating unit formed from the acrylic monomer (a) having a long-chain hydrocarbon group is 30 to 90% by weight based on the copolymer, and the acrylic monomer (b) having a hydrophilic group Is from 5 to 70% by weight based on the copolymer, and the amount of the repeating unit formed from the monomer (c) having an anionic donating group or a cationic donating group is 0.1 to 30% by weight based on the non-fluorine copolymer,
- the oil resistant agent for paper according to any one of [1] to [8], wherein the non-fluorinated copolymer is a random copolymer.
- the melting point or glass transition point of the non-fluorinated copolymer is 20 ° C. or higher, and / or the dynamic viscoelasticity (complex viscosity) of the non-fluorinated copolymer is 10 to 5000 Pa ⁇ s at 90 ° C.
- the oil-resistant agent for paper according to any one of [1] to [9].
- the oil resistant agent for paper according to any one of [1] to [10] further comprising water or a liquid medium that is a mixture of water and an organic solvent.
- An oil-resistant paper having an oil-resistant layer containing the oil-resistant agent for paper according to any one of [1] to [11] and starch or modified starch on the surface of the paper.
- the non-fluorinated copolymer is well dispersed in an aqueous medium, particularly water. Oil resistant agents impart high oil and water resistance to paper.
- Non-fluorine copolymer It has (a) a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, and (b) a repeating unit formed from an acrylic monomer having a hydrophilic group. Further, the non-fluorinated copolymer, in addition to the monomers (a) and (b), (C) It is preferable to have a repeating unit formed by a monomer having an ion donating group. The non-fluorinated copolymer, in addition to the monomers (a), (b) and (c), (D) It may have a repeating unit formed from another monomer.
- (A) acrylic monomer having an acrylic monomer long chain hydrocarbon group 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 carbon number of the long-chain hydrocarbon group is preferably 10 to 40, for example, 12 to 30, particularly preferably 15 to 30.
- the long chain hydrocarbon group may have 18 to 40 carbon atoms.
- R 1 is independently a hydrocarbon group having 7 to 40 carbon atoms
- X 1 is a hydrogen atom, a monovalent organic group or a halogen atom
- a group composed of at least one or more selected from S ( ⁇ O) 2 — or —NH— (excluding a hydrocarbon group); k is 1-3. ] It is preferable that the monomer is represented by
- X 1 may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
- Examples of X 1 are 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 groups may in particular be straight-chain hydrocarbon groups.
- the hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, especially an alkyl group.
- the hydrocarbon group preferably has 12 to 30, for example 16 to 26 or 15 to 26, especially 18 to 22, or 17 to 22 carbon atoms.
- an acrylic monomer represented by the following formula (a2): CH 2 CC (-X 5 ) -C ( O) -Y 3 -Z (-Y 4 -R 3 ) n
- R 3 is each independently a hydrocarbon group having 7 to 40 carbon atoms
- X 5 is a hydrogen atom, a monovalent organic group or a halogen atom
- Y 3 is —O— or —NH—
- Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms
- n is 1 or 2.
- the acrylic monomer (a1) is a long-chain acrylate ester monomer in which Y 2 is —O— or a long-chain acrylamide monomer in which Y 2 is —NH—.
- R 2 is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, especially an alkyl group.
- the hydrocarbon group preferably has 12 to 30, for example, 16 to 26, particularly 18 to 22, carbon atoms.
- X 4 may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. It is preferably a hydrogen atom, a methyl group or a chlorine atom.
- Preferred specific examples of the long-chain acrylate ester monomer include lauryl (meth) acrylate, stearyl (meth) acrylate, icosyl (meth) acrylate, behenyl (meth) acrylate, stearyl ⁇ -chloroacrylate, icosyl ⁇ -chloroacrylate, and behenyl ⁇ -chloroacrylate.
- Acrylate Preferred specific examples of the long-chain acrylamide monomer are 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 each independently a hydrocarbon group having 7 to 40 carbon atoms
- X 5 is a hydrogen atom, a monovalent organic group or a halogen atom
- Y 3 is —O— or —NH—
- Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms
- n is 1 or 2.
- R 3 is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, especially an alkyl group.
- the hydrocarbon group preferably has 12 to 30, for example, 16 to 26 or 15 to 26, particularly 18 to 22, or 17 to 22 carbon atoms.
- X 5 may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. It 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 straight-chain structure or a branched structure.
- the carbon number of Z is preferably 2 to 4, especially 2.
- Z is not a direct bond, Y 4 and Z are not direct bonds at the same time
- the acrylic monomer (a2) can be produced by reacting hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide with a long-chain alkyl isocyanate.
- the 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 a (meth) acrylate having an isocyanate group in the side chain, for example, 2-methacryloyloxyethyl methacrylate with a long-chain alkylamine or a long-chain alkyl alcohol.
- a long-chain alkylamine include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine.
- the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.
- Preferred examples of the long-chain hydrocarbon group-containing acrylic monomer are as follows. Stearyl (meth) acrylate, behenyl (meth) acrylate, stearyl ⁇ -chloroacrylate, behenyl ⁇ -chloroacrylate; Stearyl (meth) acrylamide, behenyl (meth) acrylamide;
- n is a number of 7 to 40
- m is a number of 1 to 5.
- the compound of the above formula is an acrylic compound in which the ⁇ -position is a hydrogen atom, and specific examples may be a methacle compound in which the ⁇ -position is a methyl group and an ⁇ -chloroacryl compound in which the ⁇ -position is a chlorine atom.
- the melting point of the acrylic monomer (a) having a long-chain hydrocarbon group is preferably 10 ° C. or higher, more preferably 25 ° C. or higher.
- the acrylic monomer (a) having a long-chain hydrocarbon group is preferably an acrylate in which X 1 , X 4 and X 5 are hydrogen atoms.
- R 11 is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a double bond between carbon atoms.
- -CHR 14 CH 2
- R 14 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 11 may have various organic groups other than the ethylenically unsaturated polymerizable group, and examples thereof include organic groups such as a chain hydrocarbon, a cyclic hydrocarbon, a polyoxyalkylene group, and a polysiloxane group. These organic groups may be substituted with various substituents.
- R 12 is a hydrocarbon group having 7 to 40 carbon atoms, 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. R 12 has 7 to 40 carbon atoms, preferably 11 to 27, particularly preferably 15 to 23.
- R 13 is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group.
- the hydrocarbon group having 1 to 5 carbon atoms may be linear or branched and may have an unsaturated bond, but is preferably linear.
- R 13 preferably has 2 to 4 carbon atoms, and more preferably 2 carbon atoms.
- R 13 is preferably an alkylene group.
- the amide group-containing monomer is one in which R 12 is one kind (for example, only a compound in which R 12 has 17 carbon atoms) or one in which R 12 is a plurality of combinations (for example, R 12 has a carbon number of 12 ). 17 and a compound in which R 12 has 15 carbon atoms).
- an amide group-containing monomer is a carboxylic acid amide alkyl (meth) acrylate.
- Specific examples of the amide group-containing monomer include amide ethyl palmitate (meth) acrylate, amide ethyl stearate (meth) acrylate, amide ethyl behenate (meth) acrylate, amide ethyl myristate (meth) acrylate, and amide laurate (meth) ethyl 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 amideethyl (meth) acrylate
- the amide group-containing monomer is preferably amide ethyl stearate (meth) acrylate.
- the amide group-containing monomer may be a mixture containing amide ethyl stearate (meth) acrylate.
- the amount of amide ethyl stearate (meth) acrylate is, for example, 55 to 99% by weight, preferably 60 to 85% by weight based on the total weight of the amide group-containing monomer.
- the remaining monomer may be, for example, amidoethyl palmitate (meth) acrylate.
- the acrylic monomer (b) having a hydrophilic group is a monomer other than the monomer (a) and is a hydrophilic monomer.
- the hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms).
- the acrylic monomer (b) having a hydrophilic group is preferably a polyalkylene glycol mono (meth) acrylate and / or a polyalkylene glycol di (meth) acrylate or a polyalkylene glycol mono (meth) acrylamide.
- X 2 is each independently a hydrogen atom or a methyl group
- X 3 is each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group R having 1 to 22 carbon atoms, an alkylene group having 2 to 6 carbon atoms
- n is an integer of 1 to 90.
- n may for example be 1 to 50, in particular 1 to 30, especially 1 to 15 or 2 to 15.
- R can be a linear or branched alkylene group, for example, of the formula — (CH 2 ) x — or — (CH 2 ) x1 — (CH (CH 3 )) x2 — where x1 and x2 are 0 to 6, for example 2 to 5, and the sum of x1 and x2 is 1 to 6.
- the order of — (CH 2 ) x1 — and — (CH (CH 3 )) x2 — is not limited to the described formula, and may be random.
- R may be two or more types (for example, 2 to 4, particularly 2 types), and-(RO) n -is, for example,-(R 1 O) n1-and- (R 2 O) n2 — wherein R 1 and R 2 are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are 1 or more, and n1 and n2 are The total is 2 to 90. ] May be combined.
- R in the general formulas (b1), (b2) and (b3) is particularly preferably an ethylene group, a propylene group or a butylene group.
- R in the general formulas (b1), (b2) and (b3) may be a combination of two or more alkylene groups. In that case, at least one of R is preferably an ethylene group, a propylene group or a butylene group.
- Examples of the combination of R include an ethylene group / propylene group combination, an ethylene group / butylene group combination, and a propylene group / butylene group combination.
- the monomer (b) may be a mixture of two or more types.
- At least one of the monomers (b) is preferably R in the general formula (b1) or (b2) or (b3) is an ethylene group, a propylene group or a butylene group.
- R in the general formula (b1) or (b2) or (b3) is an ethylene group, a propylene group or a butylene group.
- the polyalkylene glycol di (meth) acrylate represented by the general formula (b2) it is not preferable to use the polyalkylene glycol di (meth) acrylate alone as the monomer (b). preferable.
- the compound represented by the general formula (b2) is less than 30% by weight in the monomer (b) used.
- C 4 H 9 CH 2 CHCOO- (CH 2 CH 2 O) 23 -OOC (CH 3 )
- the monomer (b) is preferably acrylate or acrylamide where X 2 is a hydrogen atom. Particularly, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethylacrylamide is preferred.
- the monomer (c) having an ion donating group is a monomer other than 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, vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, phosphorus Acid (meth) acrylate, vinyl benzene sulfonic acid, acrylamide tertiary butyl sulfonic acid and the like, or salts thereof.
- Examples of the salt of the anion donating group include an alkali metal salt, an alkaline earth metal salt, and an ammonium salt such as a methyl ammonium salt, an ethanol ammonium salt, and a triethanol ammonium salt.
- examples of the cation donating group are an amino group, preferably a tertiary amino group and a quaternary amino group.
- the two groups bonded to the nitrogen atom may be the same or different and each may be an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group) or an aromatic group having 6 to 20 carbon atoms (aryl group).
- it is preferably an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C 6 H 5 —CH 2 —)).
- the three groups bonded to the nitrogen atom may be the same or different and each may be an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group) or an aromatic group having 6 to 20 carbon atoms (aryl group). Alternatively, it is preferably an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, 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.
- the cation donating group which is a salt is a salt with an acid (organic acid or inorganic acid).
- Organic acids for example, carboxylic acids having 1 to 20 carbon atoms (particularly, monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.
- Dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate and their salts are preferred.
- CH 2 CHCOO—CH 2 CH 2 —N (CH 3 ) 2 and its salts (eg, acetate)
- CH 2 CHCOO—CH 2 CH 2 —N (CH 2 CH 3 ) 2 and its salts (eg acetate)
- CH 2 C (CH 3 ) COO—CH 2 CH 2 —N (CH 3 ) 2 and its salts (eg acetate)
- CH 2 C (CH 3 ) COO—CH 2 CH 2 —N (CH 2 CH 3 ) 2 and its salts (eg, acetate)
- CH 2 CHC (O) N (H) —CH 2 CH 2 CH 2 —N (CH 3 ) 2 and its salts (eg, acetate)
- CH 2 CHCOO-CH 2 CH 2 -N (-CH 3 ) (-CH 2 -C 6 H 5 ) and its salt (eg, acetate)
- CH 2 C (CH 3 ) COO—
- the monomer (c) having an ion donating group methacrylic acid, acrylic acid and dimethylaminoethyl methacrylate are preferable, and methacrylic acid and dimethylaminoethyl methacrylate are more preferable.
- the other monomer (d) is a monomer other than the monomers (a), (b) and (c).
- examples of such other monomers include ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinylstin halide, ⁇ -methylstyrene, p-methylstyrene, polyoxyalkylene mono (meth) acrylate, (meth) acrylamide , Diacetone (meth) acrylamide, methylolated (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, isocyanatoethyl (meth) acrylate, cyclohexyl (meth)
- the amount of the repeating unit (the repeating unit (a)) formed from the monomer (a) is based on the amount of the non-fluorinated copolymer (or the total of the repeating unit (a) and the repeating unit (b)). , 30-95% by weight or 30-90% by weight, preferably 40-88% by weight (or 45-95% by weight), more preferably 50-85% by weight.
- the amount of the repeating unit (the repeating unit (b)) formed from the monomer (b) is based on the amount of the non-fluorinated copolymer (or the total of the repeating unit (a) and the repeating unit (b)).
- the amount of the repeating unit formed from the monomer (c) is from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight, based on the non-fluorinated copolymer. %.
- the amount of the repeating unit formed from the monomer (d) may be 0 to 20% by weight, for example, 1 to 15% by weight, particularly 2 to 10% by weight, based on the non-fluorinated copolymer.
- the weight average molecular weight of the non-fluorinated copolymer may be from 1,000 to 1,000,000 or 10,000,000, preferably from 5,000 to 800,000 or 8,000,000, more preferably from 10,000 to 400,000 or 4,000,000.
- the weight average molecular weight is a value determined in terms of polystyrene by gel permeation chromatography.
- (meth) acryl means acryl or methacryl.
- (meth) acrylate means acrylate or methacrylate.
- the non-fluorine copolymer is preferably a random copolymer rather than a block copolymer from the viewpoint of oil resistance.
- the melting point or glass transition point of the non-fluorinated copolymer is preferably at least 20 ° C, more preferably at least 30 ° C, particularly preferably at least 35 ° C, for example at least 40 ° C.
- the dynamic viscoelasticity (complex viscosity) of the non-fluorine copolymer at 90 ° C. is preferably 10 to 5000 Pa ⁇ s, for example, 20 to 3000 Pa ⁇ s, and particularly preferably 50 to 1000 Pa ⁇ s.
- the dynamic viscoelasticity (complex viscosity) of the non-fluorine copolymer at 70 ° C. is preferably 500 to 100,000 Pa ⁇ s, particularly preferably 1,000 to 50,000 Pa ⁇ s. Further, the dynamic viscoelasticity (complex viscosity) of the non-fluorine copolymer is preferably from 10 to 5,000 Pa ⁇ s, for example, from 20 to 3,000 Pa ⁇ s, particularly preferably from 50 to 1,000 Pa ⁇ s at 80 to 90 ° C.
- the polymerization of the non-fluorine copolymer is not particularly limited, and various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be selected.
- solution polymerization using an organic solvent or emulsion polymerization using water or an organic solvent and water in combination is generally selected.
- the mixture is diluted with water and emulsified in water to prepare a treatment liquid.
- organic solvent examples include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl acetate, propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, and tripropylene glycol.
- ketones such as acetone and methyl ethyl ketone
- esters such as ethyl acetate and methyl acetate
- propylene glycol dipropylene glycol monomethyl ether
- NMP N-methyl-2-pyrrolidone
- dipropylene glycol dipropylene glycol
- tripropylene glycol examples include dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, and tripropylene glycol.
- low molecular weight glycols such as polyethylene glycol, and alcohols such as ethyl alcohol and iso
- the polymerization initiator for example, a peroxide, an azo compound or a persulfate-based compound can be used.
- the polymerization initiator is generally water-soluble and / or oil-soluble.
- Specific examples of the oil-soluble polymerization initiator 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 (cyclohexane-1-carbonitrile), dimethyl 2,2′-azobis (2 -Methylpropionate), 2,2'-azobis (2-isobutyronitrile), benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxy Pivalate, diisopropyl peroxydicarbonate
- water-soluble polymerization initiator examples include 2,2′-azobisisobutylamidine dihydrochloride, 2,2′-azobis (2-methylpropionamidine) hydrochloride, and 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, hydrogen peroxide and the like are preferred.
- the polymerization initiator is used in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the monomer.
- 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 an amount of 10 parts by weight or less and 0.01 to 5 parts by weight based on 100 parts by weight of the monomer.
- the non-fluorine copolymer can be produced as follows.
- a method is employed in which a monomer is dissolved in an organic solvent, and after purging with nitrogen, a polymerization initiator is added and the mixture is heated and stirred, for example, in a range of 40 to 120 ° C. for 1 to 10 hours.
- the polymerization initiator may generally be an oil-soluble polymerization initiator.
- organic solvent those which are inactive in a monomer and dissolve them, are acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate and methyl acetate, propylene glycol, dipropylene glycol monomethyl ether, N-methyl -Glycols such as 2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol and low molecular weight polyethylene glycol, alcohols such as ethyl alcohol and isopropanol, n-heptane, n-hexane, n-octane, cyclohexane and methyl Charcoal such as cyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffin hydrocarbon, liquid paraffin, decane, undecane, dodecane, mineral spirit, mineral terpen, naphtha Hydro
- Preferred examples of the solvent include, for example, acetone, chloroform, HCHC225, 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 an amount of 50 to 2000 parts by weight,
- emulsion polymerization a method is employed in which a monomer is emulsified in water in the presence of an emulsifier and the like, and after polymerization with nitrogen, a polymerization initiator is added and the mixture is stirred and polymerized at 40 to 80 ° C. for 1 to 10 hours. Is done.
- the polymerization initiator is a water-soluble polymerization initiator, for example, 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, hydrogen peroxide, And an oil-soluble polymerization initiator such as 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl4-methoxyvaler
- a monomer is finely divided into water using an emulsifying device such as a high-pressure homogenizer or an ultrasonic homogenizer that can apply strong crushing energy, and the oil-soluble It is desirable to carry out the polymerization using a polymerization initiator.
- an emulsifying device such as a high-pressure homogenizer or an ultrasonic homogenizer that can apply strong crushing energy
- the oil-soluble It is desirable to carry out the polymerization using a polymerization initiator.
- the emulsifier various anionic, cationic or nonionic emulsifiers can be used, and are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers.
- a compatibilizing agent that sufficiently compatibilizes the monomers, for example, a water-soluble organic solvent or a low-molecular-weight monomer.
- a compatibilizer By adding a compatibilizer, emulsifiability and copolymerizability can be improved.
- water-soluble organic solvents include acetone, propylene glycol, dipropylene glycol monomethyl ether (DPM), dipropylene glycol, tripropylene glycol, ethanol, N-methyl-2-pyrrolidone (NMP), and 3-methoxy-3-methyl- Examples thereof include 1-butanol and isoprene glycol, which may be used in an amount of 1 to 50 parts by weight, for example, 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- Examples thereof include 1-butanol and isoprene glycol, which may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight based on 100 parts by weight of water.
- NMP or DPM or 3-methoxy-3-methyl-1-butanol or isoprene glycol are, for example, from 1 to 20% by weight, especially from 3 to 10% by weight, based on the composition
- the stability of (especially the emulsion) is improved.
- the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate and the like, and 1 to 50 parts by weight, For example, it may be used in the range of 10 to 40 parts by weight.
- the oil resistant agent is preferably in the form of a solution, emulsion or aerosol.
- the oil resistant agent comprises a non-fluorinated copolymer and a medium (eg, a liquid medium such as an organic solvent and water).
- the oil resistant agent is preferably an aqueous dispersion of a non-fluorinated copolymer.
- the concentration of the non-fluorine copolymer may be, for example, 0.01 to 50% by weight.
- the oil resistant agent preferably does not contain an emulsifier.
- the removal of the organic solvent from the polymer solution can be performed by heating the polymer solution (preferably under reduced pressure) (for example, at 30 ° C. or higher, for example, 50 to 120 ° C.).
- Oilproofing agents can be used to treat (eg, surface treat) paper substrates.
- the oil resistant agent can be applied to the object by a conventionally known method. Usually, a method is used in which the oil-resistant agent is dispersed in an organic solvent or water, diluted, adhered to the surface of the object to be treated, and dried by a known method such as dip coating, spray coating, foam coating, or the like ( surface treatment).
- Examples of the paper substrate of the object to be processed include paper, a container made of paper, and a molded article made of paper (for example, pulp mold).
- the non-fluorinated copolymers of the present disclosure adhere well to paper substrates.
- Paper can be manufactured by a conventionally known papermaking method.
- An internal addition method of adding an oil-resistant agent to the pulp slurry before papermaking or an external addition method of applying an oil-resistant agent to paper after papermaking can be used.
- the treatment method of the oil resistant agent in the present disclosure is preferably an external treatment method.
- the size press of the external addition method can be divided as follows according to the coating method.
- One coating method supplies a coating liquid (size liquid) to a nip portion formed by passing paper between two rubber rolls, creates a coating liquid pool called a pound, passes the paper through the coating liquid pool, and puts both sides of the paper.
- This is a so-called pound-to-roll size press in which a size liquid is applied.
- Other coating methods include a gate roll type in which a size liquid is applied by a surface transfer type, and a rod metering size press. In the pound type two-roll size press, the size liquid easily permeates into the paper, and in the surface transfer type, the size liquid component tends to stay on the surface of the paper.
- the coating layer easily stays on the surface of the paper, and the oil-resistant layer formed on the surface is larger than that of the pound-type two-roll size press.
- oil resistance can be imparted to paper.
- the paper thus treated after simple drying at room or elevated temperature, may optionally take a temperature range up to 300 ° C., for example up to 200 ° C., in particular from 80 ° C. to 180 ° C., depending on the nature of the paper. With heat treatment, it shows excellent oil resistance and water resistance.
- the present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal interleaving paper, kraft paper, and the like. It can also be used in neutral printing / writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive raw paper, neutral inkjet paper, and neutral information paper.
- Pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulphite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, waste newspaper, magazine waste paper, corrugated waste paper or waste paper. Any of used paper pulp such as used ink paper can be used. Also, a mixture of the above pulp raw material and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can be used.
- the water resistance of paper can be improved by adding a sizing agent.
- the sizing agent are a cationic sizing agent, an anionic sizing agent, and a rosin-based sizing agent (for example, an acidic rosin-based sizing agent and a neutral rosin-based sizing agent).
- the amount of sizing agent may be from 0.01 to 5% by weight, based on the pulp.
- paper-forming agents that are generally used include paper-strength agents such as starch, modified starch, carboxymethylcellulose, polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, retention improvers, dyes.
- Additives used in the production of paper such as a fluorescent dye, a slime control agent and an antifoaming agent, can be used. It is preferred to use starch and modified starch.
- an oil-proofing agent can be applied to paper by starch, polyvinyl alcohol, dye, coating color, anti-slip agent, etc. by a size press, gate roll coater, bill blade coater, calender or the like.
- the amount of the non-fluorinated copolymer contained in the oil-resistant layer is preferably from 0.01 to 2.0 g / m 2 , particularly preferably from 0.1 to 1.0 g / m 2 .
- the oil-resistant layer is preferably formed of an oil-resistant agent and starch and / or modified starch.
- the solid content of the paper oil-resistant agent in the oil-resistant layer is preferably 2 g / m 2 or less.
- the amount of the oil-proofing agent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example, 0.01 to 10 parts by weight, especially 0.1 to 10 parts by weight, based on 100 parts by weight of the pulp forming the paper.
- the oil-proofing agent with the pulp so as to be 2 to 5.0 parts by weight.
- the weight ratio of starch and modified starch to non-fluorinated copolymer may be from 10:90 to 98: 2.
- the processing liquid is stored between the rolls, so that the base paper is passed through the processing liquid between the rolls at an arbitrary roll speed and nip pressure. Can be provided.
- the non-fluorinated copolymer may be nonionic, cationic, anionic or amphoteric.
- the paper substrate may contain additives such as sizing agents, paper strength agents, flocculants, retention agents or coagulants.
- Additives may be nonionic, cationic, anionic or amphoteric.
- the ionic charge density of the additive may be from -10000 to 10000 ⁇ eq / g, preferably from -4000 to 8000 ⁇ eq / g, more preferably from -1000 to 7000 ⁇ eq / g.
- Additives such as sizing agents, paper strength agents, flocculants, retention agents or coagulants are generally from 0.1 to 10% by weight, based on pulp (eg from 0.2 to 10% by weight). 5.0% by weight).
- the oil resistant agent is preferably anionic.
- a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight).
- Additives eg, sizing agents, paper strength agents, flocculants, retention agents or coagulants, etc.
- non-fluorinated copolymers can be added to the pulp slurry. Since pulp is generally anionic, it is preferred that at least one of the additive and the non-fluorinated copolymer is cationic or amphoteric so that the additive and the non-fluorinated copolymer adhere well to the paper.
- the ionic charge density of the additives constituting the sizing agent, paper strength enhancer, flocculant, retention agent or coagulant is from -1000 to 7000 ⁇ eq / g, and the ionic charge density is from 100 to 1000 ⁇ eq / g. (For example, 330 ⁇ eq / g, 420 ⁇ eq / g or 680 ⁇ eq / g) is more preferable.
- additives examples include alkyl ketene dimers, alkenyl succinic anhydrides, styrenic polymers (styrene / maleic acid polymers, styrene / Acrylic acid polymer), urea-formaldehyde polymer, polyethyleneimine, melamine-formaldehyde polymer, polyamidoamine-epichlorohydrin polymer, polyacrylamide polymer, polyamine polymer, polydiallyldimethylammonium chloride, alkylamine.
- alkyl ketene dimers alkenyl succinic anhydrides
- styrenic polymers styrene / maleic acid polymers, styrene / Acrylic acid polymer
- urea-formaldehyde polymer polyethyleneimine
- melamine-formaldehyde polymer polyamidoamine-epichlorohydrin polymer
- polyacrylamide polymer polyamine polymer, polydial
- Epichlorohydrin condensate condensate of alkylene dichloride and polyalkylene polyamine, dicyandiamide / formalin condensate, dimethyldiallylammonium chloride polymer, and olefin / maleic anhydride polymer.
- the article to be treated is treated with an oil resistant agent.
- “Treatment” means applying an oil-resistant agent to an object to be treated by dipping, spraying, coating, or the like.
- the non-fluorinated copolymer which is an effective component of the oil resistant agent, penetrates into the inside of the object to be treated and / or adheres to the surface of the object to be treated.
- Dynamic viscoelasticity (complex viscosity) The aqueous dispersion of the non-fluorine copolymer was dried in an oven at about 130 ° C. for 30 minutes to obtain a sample copolymer for measurement.
- the complex viscosity ( ⁇ *) of the copolymer was measured by a dynamic viscoelasticity measuring device RHEOSOL-G3000 (manufactured by UBM Co., Ltd.) at a heating rate of 1 ° C./min.
- Measurement of Weight Average Molecular Weight The weight average molecular weight of the fluorinated copolymer was determined by GPC (gel permeation chromatography) (in terms of polystyrene).
- KIT Oil resistance
- KIT method Oil resistance (KIT method) was measured according to TAPPI T-559cm-02.
- the KIT test solution is a test solution in which castor oil, toluene, and heptane are mixed in the ratio shown in Table 1.
- One drop of the test solution shown in Table 1 was placed on paper, and after 15 seconds, the state of penetration of the oil was observed.
- the highest point of the oil resistance provided by the KIT test solution that did not show penetration was defined as oil resistance.
- Water resistance (Cobb value) Water resistance (Cobb value) was measured in accordance with JIS P 8140. The weight (g) of water absorbed in one minute by 100 square centimeters of paper supporting the height of one centimeter of water was measured, and the numerical value was converted to the weight per square meter (g / m 2 ).
- Oil resistance (Practical oil test 1) About 1 g of commercially available olive oil (about 0.1 g of treated paper) is applied to the obtained paper plate or treated paper, and left at room temperature (20 ° C.) for 15 minutes. Was observed. Evaluation values were set as follows depending on the degree of penetration on the back side.
- Synthesis Example 1 A 500 ml reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating device was prepared, and 100 parts of methyl ethyl ketone (MEK) as a solvent was added.
- MEK methyl ethyl ketone
- the weight average molecular weight in terms of polystyrene was 230,000.
- 142 g of a 0.3% NaOH aqueous solution was added to 50 g of the obtained copolymer solution and dispersed, and then MEK was distilled off under reduced pressure while heating using an evaporator to obtain a milky white copolymer.
- a polymerization aqueous dispersion (the content of the volatile organic solvent was 1% by weight or less) was obtained.
- Ion exchange water was further added to this aqueous dispersion to obtain an aqueous dispersion having a solid content concentration of 15% by weight.
- This copolymer was dissolved in chloroform, spin-coated on a PET film, and the contact angle of the air-dried surface was measured. The contact angle with water was 108 ° and the contact angle with n-hexadecane was 57 to 59 °. .
- Synthesis Example 2 A 500 ml reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating device was prepared, and 100 parts of methyl ethyl ketone (MEK) as a solvent was added.
- MEK methyl ethyl ketone
- Synthesis Example 3 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 2 except that 60 parts of StA and 34 parts of HEA were used in Synthesis Example 2 to obtain an aqueous dispersion having a solid concentration of 15% by weight.
- Synthesis Example 4 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1 except that 6 parts of acrylic acid (AA) was used instead of methacrylic acid (MAA) in Synthesis Example 1 to obtain an aqueous dispersion having a solid content concentration of 15% by weight. I got a body.
- AA acrylic acid
- MAA methacrylic acid
- Synthesis Example 5 Copolymerization and post-treatment were performed in the same manner as in Synthesis Example 1 except that 16 parts of hydroxylethyl methacrylate (HEMA) was used instead of hydroxylethyl acrylate (HEA) in Synthesis Example 1, and the solid content concentration was 15% by weight. An aqueous dispersion was obtained. The copolymer was dissolved in chloroform, spin-coated on a PET film, and the contact angle of the air-dried surface was measured. The contact angle with water was 102 ° and the contact angle with n-hexadecane was 48 °.
- HEMA hydroxylethyl methacrylate
- HOA hydroxylethyl acrylate
- Synthesis Example 6 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1 except that 78 parts of lauryl methacrylate (LMA, melting point: -7 ° C.) was used instead of StA in Synthesis Example 1, and the solid content concentration was 15% by weight. An aqueous dispersion was obtained.
- LMA lauryl methacrylate
- Synthesis Example 7 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1 except that 78 parts of stearyl methacrylate (StMA, melting point: 18 ° C.) was used instead of StA in Synthesis Example 1, and water having a solid content concentration of 15% by weight was used. A dispersion was obtained.
- StMA stearyl methacrylate
- Synthesis Example 8 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1 except that 78 parts of stearic acid amide ethyl acrylate (C18AmEA, melting point: 70 ° C.) was used instead of StA in Synthesis Example 1 to obtain a solid content concentration of 15% by weight. An aqueous dispersion was obtained.
- C18AmEA stearic acid amide ethyl acrylate
- Synthesis Example 9 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 8 except that 39 parts of C18AmEA and 39 parts of StA were used instead of 78 parts of StA of Synthesis Example 1 to obtain water having a solid content concentration of 15% by weight. A dispersion was obtained.
- Synthesis Example 10 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 8 except that 6 parts of DM was used instead of MAA in Synthesis Example 8, to obtain an aqueous dispersion having a solid content of 15% by weight.
- the melting point of this copolymer was 64 ° C.
- the complex viscosity of this copolymer was measured. The results are shown in FIG.
- Synthesis Example 11 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 10 except that 16 parts of hydroxybutyl acrylate (HBA, Tg: -40 ° C.) was used instead of HEA in Synthesis Example 10, and the solid content concentration was 15% by weight. An aqueous dispersion was obtained. The melting point of this copolymer was 66 ° C. The complex viscosity of this copolymer was measured. The results are shown in FIG.
- HBA hydroxybutyl acrylate
- Synthesis Example 12 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 11 except that 49 parts of C18AmEA and 27 parts of HBA were used to obtain an aqueous dispersion having a solid content of 15% by weight.
- Comparative Synthesis Example 1 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1 except that 78 parts of methyl methacrylate (MMA, melting point: -48 ° C.) was used instead of StA in Synthesis Example 1, and the solid content concentration was 15% by weight. An aqueous dispersion was obtained. Comparative Synthesis Example 2 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1 except that 16 parts of N-vinylpyrrolidone (NVP) was used instead of HEA in Synthesis Example 2 to obtain an aqueous dispersion having a solid content of 15% by weight. Was.
- NDP N-vinylpyrrolidone
- Example 1 As the wood pulp, pulp slurry in which the weight ratio of LBKP (hardwood bleached kraft pulp) to NBKP (softwood bleached kraft pulp) is 60% by weight and 40% by weight, and the freeness of the pulp is 400 ml (Canadian Standard Freeness) was prepared and wet strength agent to the pulp slurry, the Fourdrinier by adding a sizing agent, external treatment of paper having a basis weight of 45 g / m 2 paper density 0.58 g / cm 3 (size Press processing). This base paper had an oil resistance (KIT value) of 0 and a water resistance (Cobb value) of 52 g / m 2 .
- KIT value oil resistance
- Cobb value water resistance
- an oil-resistant paper (processed paper) was obtained according to the following formulation.
- the treatment liquid was prepared by preparing an aqueous dispersion of the copolymer obtained in Synthesis Example 1 so that the solid content concentration was 2.4% by weight and the starch solid content concentration was 7%. After the treatment, it was dried with a drum dryer to obtain oil-resistant paper (processed paper).
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- the kit test (Kit Test) was performed using the obtained base paper as a test paper. Table 2 shows the evaluation results.
- starch general hydroxyethylated starch (Penford 290: manufactured by Penford) was used.
- a size press treatment using a size press machine manufactured by Mathis), a processing liquid is stored between rolls, and a base paper is passed through the processing liquid between the rolls at an arbitrary roll speed and nip pressure. A two-roll size press was used.
- Example 2 The same treatment as in Example 1 was performed except that the copolymer of Synthesis Example 2 was used.
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 2 shows the results.
- Example 3 A process similar to that of Example 1 was performed except that the copolymer of Synthesis Example 3 was used.
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 2 shows the results.
- Example 4 A process similar to that of Example 1 was performed except that the copolymer of Synthesis Example 4 was used.
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 2 shows the results.
- Example 5 A process similar to that of Example 1 was performed except that the copolymer of Synthesis Example 5 was used.
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 2 shows the results.
- Example 6 A process similar to that of Example 1 was performed except that the copolymer of Synthesis Example 6 was used.
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 2 shows the results.
- Example 7 The same processing as in Example 1 was performed except that the copolymer of Synthesis Example 7 was used.
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 2 shows the results.
- Example 8 A process similar to that of Example 1 was performed except that the copolymer of Synthesis Example 8 was used.
- the coating amount of the starch and the solid content of the copolymer in the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 3 shows the results.
- Example 9 A process similar to that of Example 1 was performed except that the copolymer of Synthesis Example 9 was used.
- the coating amount of the starch and the solid content of the copolymer in the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 3 shows the results.
- Example 10 A process similar to that of Example 1 was performed except that the copolymer of Synthesis Example 10 was used.
- the coating amount of the starch and the solid content of the copolymer in the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 3 shows the results.
- Example 11 The same treatment as in Example 1 was performed, except that the treatment liquid was prepared so that the copolymer of Synthesis Example 10 was used and the solid content of starch was 14%.
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 2.2 g / m 2 (the coating amount of the copolymer was 0.32 g / m 2 ).
- Table 3 shows the results.
- Example 12 A process similar to that of Example 1 was performed except that the copolymer of Synthesis Example 11 was used.
- the coating amount of the starch and the solid content of the copolymer in the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Example 13 A process similar to that of Example 1 was performed except that the copolymer of Synthesis Example 12 was used.
- the coating amount of the starch and the solid content of the copolymer in the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ).
- Table 3 shows the results.
- Comparative Example 1 The same treatment as in Example 1 was performed except that only the starch was used without using the copolymer.
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.0 g / m 2 (the coating amount of the copolymer was 0.0 g / m 2 ).
- Table 4 shows the results.
- Comparative Example 2 The same treatment as in Example 1 was performed except that the copolymer of Comparative Synthesis Example 1 was used.
- the coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ). Table 4 shows the results.
- Comparative Example 3 The same treatment as in Example 1 was performed except that the copolymer of Comparative Synthesis Example 2 was used. The coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ). Table 4 shows the results. Comparative Example 4 The same treatment as in Example 1 was performed except that the copolymer of Comparative Synthesis Example 3 was used. The coating amount of the starch and the solid content of the copolymer of the obtained oil-resistant paper was 1.1 g / m 2 (the coating amount of the copolymer was 0.28 g / m 2 ). Table 4 shows the results.
- Example 14 A pulp slurry (pulp concentration: 2.5%) having a freeness of 600 cc (Canadian freeness) was prepared from wood bag pulp with 100% by weight of bagasse pulp using a disintegrator. To this pulp slurry, an alkyl ketene dimer (AKD), which is a kind of a sizing agent, was added in a concentration of 0.8% by weight based on the weight of the pulp. A pulp slurry was prepared by adding 1.0% by weight of solid content per weight. Using this pulp slurry, a paper plate weighing 7 g was prepared using an “automatic mold tester”. When a KIT test was performed on the obtained paper plate, the KIT value was 2. Table 5 shows the results.
- a pulp slurry (pulp concentration: 2.5%) having a freeness of 600 cc (Canadian freeness) was prepared from wood bag pulp with 100% by weight of bagasse pulp using a disintegrator.
- an alkyl ketene dimer (AKD) which is a kind of a
- Example 15 Instead of using the AKD of Example 14, cationized starch was used at a solids concentration of 1.0% by weight per pulp weight, and an aqueous copolymer dispersion was used at a solids concentration of 2.0% by weight per pulp weight.
- a paper plate was prepared. When the practical oil test 1 of the obtained paper plate was performed, the value was 3. Table 6 shows the results.
- Example 16 A paper plate was prepared in the same manner as in Example 15 except that the aqueous copolymer dispersion obtained in Synthesis Example 2 was used instead of the aqueous copolymer dispersion obtained in Synthesis Example 1. When the practical oil test 1 of the obtained paper plate was performed, the value was 5. Table 6 shows the results.
- Example 17 A paper plate was prepared in the same manner as in Example 15 except that the aqueous copolymer dispersion obtained in Synthesis Example 8 was used instead of the aqueous dispersion of copolymer obtained in Synthesis Example 1. When the practical oil test 1 of the obtained paper plate was performed, the value was 5. Table 6 shows the results.
- Comparative Example 5 A paper plate was prepared in the same manner as in Example 14, except that the aqueous copolymer dispersion obtained in Synthesis Example 1 was not added. When a KIT test was performed on the obtained paper plate, the KIT value was 0. Table 5 shows the results. Comparative Example 6 A paper plate was prepared in the same manner as in Example 14, except that after the AKD was added, the aqueous dispersion of the copolymer obtained in Comparative Synthesis Example 1 was added at a solid content concentration of 1% by weight per pulp weight. When a KIT test was performed on the obtained paper plate, the KIT value was 0. Table 5 shows the results.
- Comparative Example 7 A paper plate was prepared in the same manner as in Example 15, except that the aqueous copolymer dispersion obtained in Synthesis Example 1 was not added. The practical oil test 1 of the obtained paper plate had a value of 1. Table 6 shows the results.
- Test example 1 The oil-resistant papers in Examples 10, 11, 12, and Comparative Examples 1 and 2 were subjected to Practical Oil Test 1 and Practical Oil Test 2. Table 7 shows the results.
- the oil resistant agent of the present disclosure can be applied to paper used for food containers and food packaging materials.
- Examples of aspects of the present disclosure are as follows. [1] (A) a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, and (b) a non-fluorine having a repeating unit formed from an acrylic monomer having a hydrophilic group An oil-resistant agent for paper comprising a copolymer.
- R 1 is independently a hydrocarbon group having 7 to 40 carbon atoms
- X 1 is a hydrogen atom, a monovalent organic group or a halogen atom
- a group composed of at least one or more selected members (excluding a hydrocarbon group), k is 1-3.
- the oil-resistant agent for paper according to [1] which is a monomer represented by the formula: [3] In the acrylic monomer having a long-chain hydrocarbon group (a), X 1 is a hydrogen atom, a long-chain carbon number of the hydrocarbon group is 18 or more [1] or [2] as claimed in any one Oil resistant agent for paper.
- An acrylic monomer (a) having a long-chain hydrocarbon group, Equation (a1): CH 2 CC (—X 4 ) —C ( O) —Y 2 —R 2 [Wherein, R 2 is a hydrocarbon group having 7 to 40 carbon atoms; X 4 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 2 is —O— or —NH—.
- R 3 is each independently a hydrocarbon group having 7 to 40 carbon atoms
- X 5 is a hydrogen atom, a monovalent organic group or a halogen atom
- Y 3 is —O— or —NH—
- Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2.
- X 2 represents a hydrogen atom or a methyl group
- X 3 is a hydrogen atom or an unsaturated or saturated hydrocarbon group R having 1 to 22 carbon atoms, an alkylene group having 2 to 6 carbon atoms
- n is an integer of 1 to 90.
- the non-fluorinated copolymer is formed from a monomer (c) having an olefinic carbon-carbon double bond and an anionic or cationic donor other than the monomers (a) and (b).
- the oil-resistant agent for paper according to any one of [1] to [5], further comprising a repeating unit.
- the amount of the repeating unit formed from the acrylic monomer (a) having a long-chain hydrocarbon group is 30 to 90% by weight based on the copolymer, and the acrylic monomer (b) having a hydrophilic group
- the paper according to any one of [1] to [8], wherein the amount of the repeating unit formed from is 5 to 70% by weight based on the copolymer, and the non-fluorinated copolymer is a random copolymer. Oil resistant agent.
- the melting point or glass transition point of the non-fluorinated copolymer is 20 ° C.
- the oil-resistant agent for paper according to any one of [1] to [9].
- An oil-resistant paper having an oil-resistant layer containing the oil-resistant agent for paper according to any one of [1] to [11] and starch or modified starch on the surface of the paper.
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Abstract
Description
特許文献2(国際出願公開2013/008938号公報)は、1種又は2種以上の(メタ)アクリレート系モノマーと1種又は2種以上のビニル系モノマーとから形成され、ガラス転移点が-10℃~50℃である酸含有コポリマーを主成分とし、フィラーを含有する水性ニスを、秤量19~700g/m2の紙にフレキソ印刷法により塗工・乾燥して形成されるコート層を有する食品用包装紙を開示している。
特許文献3(特開2006-028697号公報)は、紙基材にアクリル系合成樹脂エマルジョンを塗工して耐油性合成樹脂層を形成した食品用耐油紙において、前記耐油性合成樹脂層が、紙基材表面に形成されたアンダーコート層と、表面層となるオーバーコート層を有し、前記アンダーコート層樹脂のガラス転移温度Tg1が-30~0℃、オーバーコート層樹脂のガラス転移温度Tg2が0~30℃である食品用耐油紙を開示している。
(a)炭素数7~40の長鎖炭化水素基を有するアクリル単量体から形成される繰り返し単位、および
(b)親水性基を有するアクリル単量体から形成される繰り返し単位
を有する非フッ素共重合体を含んでなる紙用耐油剤に関する。
紙用耐油剤は、水および/または有機溶媒、好ましくは水または水と有機溶媒の混合物(水性媒体)である液状媒体をも含有する。
本開示は、紙用耐油剤で処理されている耐油紙を提供する。紙の処理は、外添または内添である。耐油紙は、紙用耐油剤の外添処理方法により、紙用耐油剤および澱粉を含む耐油層を有する。あるいは耐油紙は、紙用耐油剤の内添処理方法により、紙用耐油剤を紙の内部に含む。
[1]
(a)炭素数7~40の長鎖炭化水素基を有するアクリル単量体から形成された繰り返し単位、および
(b)親水性基を有するアクリル単量体から形成された繰り返し単位
を有する非フッ素共重合体を含んでなる紙用耐油剤。
[2]
長鎖炭化水素基を有するアクリル単量体(a)が、式:
CH2=C(-X1)-C(=O)-Y1(R1)k
[式中、R1は、それぞれ独立的に、炭素数7~40の炭化水素基であり、
X1は、水素原子、一価の有機基またはハロゲン原子であり、
Y1は、2価~4価の炭素数1の炭化水素基、-C6H4-、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上で構成される基(但し、炭化水素基を除く)であり、
kは1~3である。]
で示される単量体である請求項1]に記載の紙用耐油剤。
[3]
長鎖炭化水素基を有するアクリル単量体(a)において、X1が水素原子であり、長鎖炭化水素基の炭素数が18~40である[1]または[2]に記載の紙用耐油剤。
[4]
長鎖炭化水素基を有するアクリル単量体(a)が、
(a1)式:
CH2=C(-X4)-C(=O)-Y2-R2
[式中、R2は、炭素数7~40の炭化水素基であり、
X4は、水素原子、一価の有機基またはハロゲン原子であり、
Y2は、-O-または-NH-である。]
で示されるアクリル単量体、および/または
(a2)式:
CH2=C(-X5)-C(=O)-Y3-Z(-Y4-R3)n
[式中、R3は、それぞれ独立的に、炭素数7~40の炭化水素基であり、
X5は、水素原子、一価の有機基またはハロゲン原子であり、
Y3は、-O-または-NH-であり、
Y4は、それぞれ独立的に、直接結合、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上で構成される基であり、
Zは、直接結合、あるいは2価または3価の炭素数1~5の炭化水素基であり、
nは、1または2である。]
で示されるアクリル単量体であり、
親水性基を有するアクリル単量体(b)が、式:
CH2=CX2C(=O)-O-(RO)n-X3 (b1)
および/または
CH2=CX2C(=O)-O-(RO)n-C(=O)CX2=CH2 (b2)
[式中、X2は、水素原子またはメチル基、
X3は、水素原子または炭素数1~22の不飽和または飽和の炭化水素基
Rは、炭素数2~6のアルキレン基、nは、1~90の整数である。]
で表わされる少なくとも1つのオキシアルキレン(メタ)アクリレートである、[1]~[3]のいずれかに記載の紙用耐油剤。
[5]
Y1またはY4は、-Y’-、-Y’-Y’-、-Y’-C(=O)-、-C(=O)-Y’-、-Y’-C(=O)-Y’-、-Y’-R’-、-Y’-R’-Y’-、-Y’-R’-Y’-C(=O)-、-Y’-R’-C(=O)-Y’-、-Y’-R’-Y’-C(=O)-Y’-、または-Y’-R’-Y’-R’-
[式中、Y’はそれぞれ独立して、直接結合、-O-、-NH-または-S(=O)2-であり、
R’は-(CH2)m-(mは1~5の整数である)、炭素数1~5の不飽和結合を有する直鎖状の炭化水素基、炭素数1~5の枝分かれ構造を有する炭化水素基、または-(CH2)l-C6H4-(CH2)l-(lはそれぞれ独立して0~5の整数であり-C6H4-はフェニレン基である)である。]
で示される基である[2]または[4]に記載の紙用耐油剤。
[6]
非フッ素共重合体が
単量体(a)および(b)以外の、オレフィン性炭素-炭素二重結合、およびアニオン性供与基またはカチオン性供与基を有する単量体(c)から形成される繰り返し単位
をさらに含む[1]~[5]のいずれかに記載の紙用耐油剤。
[7]
アニオン供与基がカルボキシル基、またはカチオン供与基がアミノ基である[6]に記載の紙用耐油剤。
[8]
長鎖炭化水素基を有するアクリル単量体(a)から形成される繰り返し単位の量が、共重合体に対して30~95重量%である[1]~[7]のいずれかに記載の紙用耐油剤。
[9]
長鎖炭化水素基を有するアクリル単量体(a)から形成される繰り返し単位の量が、共重合体に対して30~90重量%であり、親水性基を有するアクリル単量体(b)から形成される繰り返し単位の量が、共重合体に対して5~70重量%であり、アニオン性供与基またはカチオン性供与基を有する単量体(c)から形成される繰り返し単位の量は、非フッ素共重合体に対して、0.1~30重量%であり、
非フッ素共重合体がランダム共重合体である[1]~[8]のいずれかに記載の紙用耐油剤。
[10]
非フッ素共重合体の融点またはガラス転移点が20℃以上であるか、および/または非フッ素共重合体の動的粘弾性(複素粘性率)が、90℃において、10~5000Pa・sである[1]~[9]のいずれかに記載の紙用耐油剤。
[11]
水または水と有機溶媒の混合物である液状媒体をさらに含んでなる[1]~[10]のいずれかに記載の紙用耐油剤。
[12]
[1]~[11]のいずれかに記載の紙用耐油剤および澱粉または変性澱粉を含む耐油層を紙の表面に有する耐油紙。
[13]
耐油層における紙用耐油剤の固形分量が2g/m2以下である[12]に記載の耐油紙。
[14]
[1]~[11]のいずれかに記載の紙用耐油剤における非フッ素共重合体を紙の内部に含む耐油紙。
[15]
食品包装材または食品容器である[12]~[14]のいずれかに記載の耐油紙。
[16]
[1]~[11]のいずれかに記載の紙用耐油剤で紙を外添処理または内添処理により処理する紙の処理方法。
耐油剤は、紙に、高い耐油性および耐水性を付与する。
(a)炭素数7~40の長鎖炭化水素基を有するアクリル単量体から形成される繰り返し単位、および
(b)親水性基を有するアクリル単量体から形成される繰り返し単位を有する。
さらに、非フッ素共重合体は、単量体(a)および(b)に加えて、
(c)イオン供与基を有する単量体
によって形成されている繰り返し単位を有することが好ましい。
非フッ素共重合体は、単量体(a)、(b)および(c)に加えて、
(d)他の単量体
から形成される繰り返し単位を有していてもよい。
長鎖炭化水素基を有するアクリル単量体(a)は、炭素数7~40の長鎖炭化水素基を有する。炭素数7~40の長鎖炭化水素基は、炭素数7~40の直鎖状または分岐状の炭化水素基であることが好ましい。長鎖炭化水素基の炭素数は、10~40、例えば、12~30、特に15~30であることが好ましい。あるいは、長鎖炭化水素基の炭素数は、18~40であってよい。
CH2=C(-X1)-C(=O)-Y1(R1)k
[式中、R1は、それぞれ独立的に、炭素数7~40の炭化水素基であり、
X1は、水素原子、一価の有機基またはハロゲン原子であり、
Y1は、2価~4価の炭素数1の炭化水素基(特に、-CH2-、-CH=)、-C6H4-、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上で構成される基(但し、炭化水素基を除く)であり、
kは1~3である。]
で示される単量体であることが好ましい。
Y1は、炭素数1の炭化水素基、-C6H4-、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上によって構成される基(但し、炭化水素基を除く)であることが好ましい。炭素数1の炭化水素基の例として、-CH2-、枝分かれ構造を有する-CH=または枝分かれ構造を有する-C≡が挙げられる。
[式中、Y’は、直接結合、-O-、-NH-または-S(=O)2-であり、
R’は-(CH2)m-(mは1~5の整数である)または-C6H4-(フェニレン基)である。]
であってよい。
[式中、mは1~5の整数、特に2または4である。]
であることが好ましい。Y1は、-O-または-O-(CH2)m-NH-C(=O)-、特に-O-(CH2)m-NH-C(=O)-であることがより好ましい。
(a1)式:
CH2=C(-X4)-C(=O)-Y2-R2
[式中、R2は、炭素数7~40の炭化水素基であり、
X4は、水素原子、一価の有機基またはハロゲン原子であり、
Y2は、-O-または-NH-である。]
で示されるアクリル単量体、および
(a2)式:
CH2=C(-X5)-C(=O)-Y3-Z(-Y4-R3)n
[式中、R3は、それぞれ独立的に、炭素数7~40の炭化水素基であり、
X5は、水素原子、一価の有機基またはハロゲン原子であり、
Y3は、-O-または-NH-であり、
Y4は、それぞれ独立的に、直接結合、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上で構成される基であり、
Zは、2価または3価の炭素数1~5の炭化水素基であり、
nは、1または2である。]
で示されるアクリル単量体である。
アクリル単量体(a1)は、式:
CH2=C(-X4)-C(=O)-Y2-R2
[式中、R2は、炭素数7~40の炭化水素基であり、
X4は、水素原子、一価の有機基またはハロゲン原子であり、
Y2は、-O-または-NH-である。]
で示される化合物である。
R2は、脂肪族炭化水素基、特に飽和の脂肪族炭化水素基、特別にアルキル基であることが好ましい。R2において、炭化水素基の炭素数は、12~30、例えば16~26、特に18~22であることが好ましい。
X4は、水素原子、メチル基、フッ素原子を除くハロゲン、置換または非置換のベンジル基、置換または非置換のフェニル基であってよい。水素原子、メチル基または塩素原子であることが好ましい。
長鎖アクリルアミド単量体の好ましい具体例は、ステアリル(メタ)アクリルアミド、イコシル(メタ)アクリルアミド、ベヘニル(メタ)アクリルアミドである。
アクリル単量体(a2)は、アクリル単量体(a1)とは異なる単量体である。アクリル単量体(a2)は、-O-、-C(=O)-、-S(=O)2-、または-NH-から選ばれる少なくとも1つ以上で構成される基を有する(メタ)アクリレートまたは(メタ)アクリルアミドである。
アクリル単量体(a2)は、式:
CH2=C(-X5)-C(=O)-Y3-Z(-Y4-R3)n
[式中、R3は、それぞれ独立的に、炭素数7~40の炭化水素基であり、
X5は、水素原子、一価の有機基またはハロゲン原子であり、
Y3は、-O-または-NH-であり、
Y4は、それぞれ独立的に、直接結合、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上で構成される基であり、
Zは、直接結合、あるいは2価または3価の炭素数1~5の炭化水素基であり、
nは、1または2である。]
で示される化合物であってよい。
[式中、Y’はそれぞれ独立して、直接結合、-O-、-NH-または-S(=O)2-であり、
R’は-(CH2)m-(mは1~5の整数である)、炭素数1~5の不飽和結合を有する直鎖状の炭化水素基、炭素数1~5の枝分かれ構造を有する炭化水素基、または-(CH2)l-C6H4-(CH2)l-(lはそれぞれ独立して0~5の整数であり-C6H4-はフェニレン基である)である。]
であってよい。
[式中、mは1~5の整数である。]
である。
Zは直接結合でないことが好ましく、Y4およびZは同時に直接結合であることはない。
アクリル単量体(a2)は、CH2=C(-X5)-C(=O)-O-(CH2)m-NH-C(=O)-R3であることが特に好ましい。
あるいは、アクリル単量体(a2)は、側鎖にイソシアネート基を有する(メタ)アクリレート、例えば、2-メタクリロイルオキシエチルメタクリレートと長鎖アルキルアミンまたは長鎖アルキルアルコールを反応させることでも製造できる。長鎖アルキルアミンとしては例えば、ラウリルアミン、ミリスチルアミン、セチルアミン、ステアリルアミン、オレイルアミン、ベヘニルアミンなどがある。長鎖アルキルアルコールとしては例えば、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、オレイルアルコール、ベヘニルアルコールなどがある。
ステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート、ステアリルαクロロアクリレート、ベヘニルαクロロアクリレート;
ステアリル(メタ)アクリルアミド、ベヘニル(メタ)アクリルアミド;
[上記式中、nは7~40の数であり、mは1~5の数である。]
上記の化学式の化合物は、α位が水素原子であるアクリル化合物であるが、具体例は、α位がメチル基であるメタクル化合物およびα位が塩素原子であるαクロロアクリル化合物であってよい。
R12-C(=O)-NH-R13-O-R11
[式中、R11は、エチレン性不飽和重合性基を有する有機残基、
R12は、炭素数7~40の炭化水素基、
R13は、炭素数1~5の炭化水素基である。]
で示されるアミド基含有単量体であることが好ましい。
アミド基含有単量体の具体例としては、パルミチン酸アミドエチル(メタ)アクリレート、ステアリン酸アミドエチル(メタ)アクリレート、ベヘニン酸アミドエチル(メタ)アクリレート、ミリスチン酸アミドエチル(メタ)アクリレート、ラウリン酸アミドエチル(メタ)アクリレート、イソステアリン酸エチルアミド(メタ)アクリレート、オレイン酸エチルアミド(メタ)アクリレート、ターシャリーブチルシクロヘキシルカプロン酸アミドエチル(メタ)アクリレート、アダマンタンカルボン酸エチルアミド(メタ)アクリレート、ナフタレンカルボン酸アミドエチル(メタ)アクリレート、アントラセンカルボン酸アミドエチル(メタ)アクリレート、パルミチン酸アミドプロピル(メタ)アクリレート、ステアリン酸アミドプロピル(メタ)アクリレート、パルミチン酸アミドエチルビニルエーテル、ステアリン酸アミドエチルビニルエーテル、パルミチン酸アミドエチルアリルエーテル、ステアリン酸アミドエチルアリルエーテル、またはこれらの混合物が挙げられる。
親水性基を有するアクリル単量体(b)は、単量体(a)以外の単量体であって、親水性単量体である。親水性基は、オキシアルキレン基(アルキレン基の炭素数は2~6である。)であることが好ましい。特に、親水性基を有するアクリル単量体(b)は、ポリアルキレングリコールモノ(メタ)アクリレートおよび/またはポリアルキレングリコールジ(メタ)アクリレート、ポリアルキレングリコールモノ(メタ)アクリルアミドであることが好ましい。ポリアルキレングリコールモノ(メタ)アクリレートおよびポリアルキレングリコールジ(メタ)アクリレート、ポリアルキレングリコールモノ(メタ)アクリルアミドは、一般式:
CH2=CX2C(=O)-O-(RO)n-X3 (b1)
および
CH2=CX2C(=O)-O-(RO)n-C(=O)CX2=CH2 (b2)、
CH2=CX2C(=O)-NH-(RO)n-X3 (b3)
[式中、
X2は、各々独立に水素原子またはメチル基、
X3は、各々独立に水素原子または炭素数1~22の不飽和または飽和の炭化水素基
Rは、炭素数2~6のアルキレン基、
nは、1~90の整数
である。]
で示されるものであることが好ましい。nは、例えば1~50、特に1~30、特別に1~15あるいは2~15であってよい。あるいは、nは、例えば1であってよい。
Rは、直鎖または分岐のアルキレン基であってよく、例えば、式-(CH2)x-または-(CH2)x1-(CH(CH3))x2-[式中、x1およびx2は0~6、例えば2~5であり、x1およびx2の合計は1~6である。-(CH2)x1-と-(CH(CH3))x2-の順序は、記載の式に限定されず、ランダムであってもよい。]で示される基であってよい。
-(RO)n-において、Rは2種類以上(例えば、2~4種類、特に2種類)であってよく、-(RO)n-は、例えば、-(R1O)n1-と-(R2O)n2-[式中、R1とR2は、相互に異なって、炭素数2~6のアルキレン基であり、n1およびn2は、1以上の数であり、n1とn2の合計は2~90である。]の組み合わせであってよい。
CH2=CHCOO-CH2CH2O-H
CH2=CHCOO-CH2CH2CH2O-H
CH2=CHCOO-CH2CH(CH3)O-H
CH2=CHCOO-CH(CH3)CH2O-H
CH2=CHCOO-CH2CH2CH2CH2O-H
CH2=CHCOO-CH2CH2CH(CH3)O-H
CH2=CHCOO-CH2CH(CH3)CH2O-H
CH2=CHCOO-CH(CH3)CH2CH2O-H
CH2=CHCOO-CH2CH(CH2CH3)O-H
CH2=CHCOO-CH2C(CH3)2O-H
CH2=CHCOO-CH(CH2CH3)CH2O-H
CH2=CHCOO-C(CH3)2CH2O-H
CH2=CHCOO-CH(CH3)CH(CH3)O-H
CH2=CHCOO-C(CH3)(CH2CH3)O-H
CH2=CHCOO-(CH2CH2O)2-H
CH2=CHCOO-(CH2CH2O)4-H
CH2=CHCOO-(CH2CH2O)5-H
CH2=CHCOO-(CH2CH2O)6-H
CH2=CHCOO-(CH2CH2O)5-CH3
CH2=CHCOO-(CH2CH2O)9-CH3
CH2=CHCOO-(CH2CH2O)23-CH3
CH2=CHCOO-(CH2CH2O)90-CH3
CH2=CHCOO-(CH2CH(CH3)O)9-CH3
CH2=CHCOO-(CH2CH(CH3)O)12-CH3
CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H
CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3
CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9
CH2=CHCOO-(CH2CH2O)23-OOC(CH3)C=CH2
CH2=CHCOO-(CH2CH2O)20-(CH2CH(CH3)O)5-CH2-CH=CH2
CH2=C(CH3)COO-CH2CH2O-H
CH2=C(CH3)COO-CH2CH2CH2O-H
CH2=C(CH3)COO-CH2CH(CH3)O-H
CH2=C(CH3)COO-CH(CH3)CH2O-H
CH2=C(CH3)COO-CH2CH2CH2CH2O-H
CH2=C(CH3)COO-CH2CH2CH(CH3)O-H
CH2=C(CH3)COO-CH2CH(CH3)CH2O-H
CH2=C(CH3)COO-CH(CH3)CH2CH2O-H
CH2=C(CH3)COO-CH2CH(CH2CH3)O-H
CH2=C(CH3)COO-CH2C(CH3)2O-H
CH2=C(CH3)COO-CH(CH2CH3)CH2O-H
CH2=C(CH3)COO-C(CH3)2CH2O-H
CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H
CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H
CH2=C(CH3)COO-(CH2CH2O)2-H
CH2=C(CH3)COO-(CH2CH2O)4-H
CH2=C(CH3)COO-(CH2CH2O)5-H
CH2=C(CH3)COO-(CH2CH2O)6-H
CH2=C(CH3)COO-(CH2CH2O)9-H
CH2=C(CH3)COO-(CH2CH2O)5-CH3
CH2=C(CH3)COO-(CH2CH2O)9-CH3
CH2=C(CH3)COO-(CH2CH2O)23-CH3
CH2=C(CH3)COO-(CH2CH2O)90-CH3
CH2=C(CH3)COO-(CH2CH(CH3)O)9-H
CH2=C(CH3)COO-(CH2CH(CH3)O)12-CH3
CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H
CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3
CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9
CH2=C(CH3)COO-(CH2CH2O)23-OOC(CH3)C=CH2
CH2=C(CH3)COO-(CH2CH2O)20-(CH2CH(CH3)O)5-CH2-CH=CH2
CH2=CH-C(=O)-NH-CH2CH2CH2O-H
CH2=CH-C(=O)-NH-CH2CH(CH3)O-H
CH2=CH-C(=O)-NH-CH(CH3)CH2O-H
CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H
CH2=CH-C(=O)-NH-CH2CH2CH(CH3)O-H
CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H
CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H
CH2=CH-C(=O)-NH-CH2CH(CH2CH3)O-H
CH2=CH-C(=O)-NH-CH2C(CH3)2O-H
CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H
CH2=CH-C(=O)-NH-C(CH3)2CH2O-H
CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)O-H
CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)O-H
CH2=CH-C(=O)-NH-(CH2CH2O)2-H
CH2=CH-C(=O)-NH-(CH2CH2O)4-H
CH2=CH-C(=O)-NH-(CH2CH2O)5-H
CH2=CH-C(=O)-NH-(CH2CH2O)6-H
CH2=CH-C(=O)-NH-(CH2CH2O)9-H
CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3
CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3
CH2=CH-C(=O)-NH-(CH2CH2O)23-CH3
CH2=CH-C(=O)-NH-(CH2CH2O)90-CH3
CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3
CH2=CH-C(=O)-NH-(CH2CH(CH3)O)12-CH3
CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H
CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3
CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9
CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H
CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)O-H
CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H
CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H
CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)O-H
CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H
CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-H
CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)O-H
CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H
CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H
CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H
CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)O-H
CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)O-H
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)23-CH3
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)90-CH3
CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3
CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)12-CH3
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3
CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9
イオン供与基を有する単量体(c)は、単量体(a)および単量体(b)以外の単量体である。単量体(c)は、オレフィン性炭素―炭素二重結合およびイオン供与基を有する単量体であることが好ましい。イオン供与基は、アニオン供与基および/またはカチオン供与基である。
CH2=CHCOO-CH2CH2-N(CH3)2 およびその塩(例えば酢酸塩)
CH2=CHCOO-CH2CH2-N(CH2CH3)2 およびその塩(例えば酢酸塩)
CH2=C(CH3)COO-CH2CH2-N(CH3)2 およびその塩(例えば酢酸塩)
CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 およびその塩(例えば酢酸塩)
CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 およびその塩(例えば酢酸塩)
CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) およびその塩(例えば酢酸塩)
CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5)およびその塩(例えば酢酸塩)
CH2=CHCOO-CH2CH2-N+(CH3)3Cl-
CH2=CHCOO-CH2CH2-N+(-CH3)2(-CH2-C6H5)Cl-
CH2=C(CH3)COO-CH2CH2-N+(CH3)3Cl-
CH2=CHCOO-CH2CH(OH)CH2-N+(CH3)3Cl-
CH2=C(CH3)COO-CH2CH(OH)CH2-N+(CH3)3Cl-
CH2=C(CH3)COO-CH2CH(OH)CH2-N+(-CH2CH3)2(-CH2-C6H5)Cl-
CH2=C(CH3)COO-CH2CH2-N+(CH3)3Br-
CH2=C(CH3)COO-CH2CH2-N+(CH3)3I-
CH2=C(CH3)COO-CH2CH2-N+(CH3)3O-SO3CH3
CH2=C(CH3)COO-CH2CH2-N+(CH3)(-CH2-C6H5)2Br-
他の単量体(d)は、単量体(a)、(b)および(c)以外の単量体である。そのような他の単量体としては、エチレン、酢酸ビニル、塩化ビニル、フッ化ビニル、ハロゲン化ビニルスチン、α-メチルスチレン、p-メチルスチレン、ポリオキシアルキレンモノ(メタ)アクリレート、(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド、メチロール化(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、アルキルビニルエーテル、ハロゲン化アルキルビニルエーテル、アルキルビニルケトン、ブタジエン、イソプレン、クロロプレン、グリシジル(メタ)アクリレート、アジリジニル(メタ)アクリレート、ベンジル(メタ)アクリレート、イソシアネートエチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、短鎖アルキル(メタ)アクリレート、無水マレイン酸、ポリジメチルシロキサン基を有する(メタ)アクリレート、N-ビニルカルバゾールが挙げられる。
単量体(b)から形成される繰り返し単位(繰り返し単位(b))の量は、非フッ素共重合体に対して(または繰り返し単位(a)と繰り返し単位(b)の合計に対して)、5~70重量%または10~70重量%、好ましくは8~50重量%、より好ましくは10~40重量%であってよい。
単量体(c)から形成される繰り返し単位の量は、非フッ素共重合体に対して、0.1~30重量%、好ましくは0.5~20重量%、より好ましくは1~15重量%であってよい。
単量体(d)から形成される繰り返し単位の量は、非フッ素共重合体に対して、0~20重量%、例えば1~15重量%、特に2~10重量%であってよい。
本明細書において、「(メタ)アクリル」とは、アクリルまたはメタクリルを意味する。例えば、「(メタ)アクリレート」とは、アクリレートまたはメタクリレートを意味する。
非フッ素共重合体の融点またはガラス転移点は、好ましくは20℃以上、より好ましくは30℃以上、特に好ましくは35℃以上、例えば40℃以上である。
非フッ素共重合体の動的粘弾性(複素粘性率)は、90℃において、10~5000Pa・s、例えば20~3000Pa・s、特に50~1000Pa・sであることが好ましい。非フッ素共重合体の動的粘弾性(複素粘性率)は、70℃において、500~100000Pa・s、特に1000~50000Pa・sであることが好ましい。また、非フッ素共重合体の動的粘弾性(複素粘性率)は、80~90℃において、10~5000Pa・s、例えば20~3000Pa・s、特に50~1000Pa・sであることが好ましい。
本開示においては、重合(例えば、溶液重合または乳化重合、好ましくは溶液重合)後、水を加えてから脱溶剤して、重合体を水に分散させることが好ましい。乳化剤を加える必要なく、自己分散型の製品を製造することができる。
油溶性重合開始剤の具体例としては、2,2’-アゾビス(2-メチルプロピオニトリル)、2,2’-アゾビス(2-メチルブチロニトリル)、2,2’-アゾビス(2、4-ジメチルバレロニトリル)、2,2’-アゾビス(2、4-ジメチル4-メトキシバレロニトリル)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)、ジメチル2,2’-アゾビス(2-メチルプロピオネート)、2,2’-アゾビス(2-イソブチロニトリル)、ベンゾイルパーオキシド、ジ-第三級-ブチルパーオキシド、ラウリルパーオキシド、クメンヒドロパーオキシド、t-ブチルパーオキシピバレート、ジイソプロピルパーオキシジカーボネート、過ピバル酸t-ブチル等が好ましく挙げられる。
重合開始剤は単量体100重量部に対して、0.01~5重量部の範囲で用いられる。
溶液重合では、単量体を有機溶剤に溶解させ、窒素置換後、重合開始剤を添加して、例えば40~120℃の範囲で1~10時間、加熱撹拌する方法が採用される。重合開始剤は、一般に、油溶性重合開始剤であってよい。
ならびに
油溶性重合開始剤、例えば、2,2’-アゾビス(2-メチルプロピオニトリル)、2,2’-アゾビス(2-メチルブチロニトリル)、2,2’-アゾビス(2、4-ジメチルバレロニトリル)、2,2’-アゾビス(2、4-ジメチル4-メトキシバレロニトリル)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)、ジメチル2,2’-アゾビス(2-メチルプロピオネート)、2,2’-アゾビス(2-イソブチロニトリル)、ベンゾイルパーオキシド、ジ-第三級-ブチルパーオキシド、ラウリルパーオキシド、クメンヒドロパーオキシド、t-ブチルパーオキシピバレート、ジイソプロピルパーオキシジカーボネート、過ピバル酸t-ブチル
が用いられる。重合開始剤は単量体100重量部に対して、0.01~10重量部の範囲で用いられる。
耐油剤において、非フッ素共重合体の濃度は、例えば、0.01~50重量%であってよい。耐油剤は、乳化剤を含まないことが好ましい。
耐油剤は、従来既知の方法により被処理物に適用することができる。通常、耐油剤を有機溶剤または水に分散して希釈して、浸漬塗布、スプレー塗布、泡塗布などのような既知の方法により、被処理物の表面に付着させ、乾燥する方法が採られる(表面処理)。
被処理物の紙基材としては、紙、紙でできた容器、紙でできた成形体(例えばパルプモールド)などが挙げられる。
本開示の非フッ素共重合体は、紙基材に良好に付着する。
1つの塗布方式は、2本のゴムロールの間に紙を通して形成されるニップ部に塗布液(サイズ液)を供給し、ポンドと呼ばれる塗液溜りを作り、この塗液溜りに紙を通して紙の両面にサイズ液を塗布する、いわゆるポンド式ツーロールサイズプレスである。他の塗布方式は、サイズ液を表面転写型により塗布するゲートロール型、及び、ロッドメタリングサイズプレスである。ポンド式ツーロールサイズプレスにおいてサイズ液は紙の内部まで浸透しやすく、表面転写型においてサイズ液成分は紙の表面に留まりやすい。表面転写型は、ポンド式ツーロールサイズプレスと比べて、塗布層が紙の表面に留まりやすく、表面に形成される耐油層がポンド式ツーロールサイズプレスより多い。
本開示では、前者のポンド式2ロールサイズプレスを用いた場合でも紙に耐油性能を付与できる。
このように処理された紙は、室温または高温での簡単な乾燥後に、任意に、紙の性質に依存して300℃まで、例えば200℃まで、特に80℃~180℃の温度範囲をとり得る熱処理を伴うことで、優れた耐油性および耐水性を示す。
晒あるいは未晒高収率パルプ、新聞古紙、雑誌古紙、段ボール古紙あるいは脱墨古紙等の古紙パルプのいずれも使用することができる。また、上記パルプ原料と石綿、ポリアミド、ポリイミド、ポリエステル、ポリオレフィン、ポリビニルアルコール等の合成繊維との混合物も使用することができる。
必要により、澱粉、ポリビニルアルコール、染料、コーティングカラー、防滑剤等を用いて、サイズプレス、ゲートロールコーター、ビルブレードコーター、キャレンダー等によって、耐油剤を紙に塗布することができる。
内添においては、紙を形成するパルプ100重量部に対して、耐油剤の量が0.01~50重量部または0.01~30重量部、例えば0.01~10重量部、特に0.2~5.0重量部となるように、耐油剤をパルプと混合することが好ましい。
外添および内添において、澱粉および変性澱粉と非フッ素共重合体との重量比は、10:90~98:2であってよい。
以下において、部、%または比は、特記しない限り、重量部、重量%または重量比を表す。
非フッ素共重合体水分散液を約130℃のオーブンで30分間乾燥し、測定用サンプル共重合体を得た。共重合体の複素粘性率(Η*)を動的粘弾性測定装置RHEOSOL-G3000(株式会社UBM製)によって、昇温速度1℃/分で測定した。
重量平均分子量の測定
含フッ素共重合体の重量平均分子量は、GPC(ゲルパーミエーションクロマトグラフィー)により求めた(ポリスチレン換算)。
耐油性(KIT)
耐油性(KIT法)は、TAPPI T-559cm-02に従って測定した。KIT試験液はひまし油、トルエン、ヘプタンを表1の比率で混合した試験液である。表1に示す試験液1滴を紙の上におき、15秒後に油の浸透状態を観察した。浸透を示さないKIT試験液が与える耐油度の最高点を耐油性とした。KIT試験液の番号が高いほど耐油性が高い。
耐水性(Cobb値)は、JIS P 8140に従って測定した。
1センチメートルの水の高さを支える100平方センチメートルの紙により1分間に吸収される水の重量(g)を測定し、その数値を1平方メートルあたりの重量(g/m2)に換算した。
耐油性(実用油試験1)
得られた紙皿または処理紙に市販のオリーブオイルを約1g(処理紙は約0.1g)たらし、室温(20℃)で15分放置した後に、紙皿または処理紙の裏側の染込み具合を観察した。裏側の染込みの程度により、以下のように評価数値を設定した。
5:0-5%
4:6-20%
3:21-50%
2:51-75%
1:76-100%
耐油性(実用油試験2)
実用油試験1で、オリーブオイルをたらした処理紙または紙皿を70℃のオーブンに入れて7分後に取り出して染込み具合を観察した以外は実用油試験1と同じ方法で評価した。
撹拌装置、温度計、還流冷却器、滴下漏斗、窒素流入口および加熱装置を備えた容積500mlの反応器を用意し、溶媒のメチルエチルケトン(MEK)を100部添加した。続いて、撹拌下、ステアリルアクリレート(StA、融点:30℃)78部、ヒドロキシエチルアクリレート(HEA)16部、およびメタアクリル酸(MAA)6部からなる単量体(単量体計100部)、および開始剤のパーブチルPV(PV)1.2部をこの順に添加し、この混合物を65-75℃の窒素雰囲気下で12時間混合撹拌して共重合を行った。得られた共重合体含有溶液の固形分濃度は50重量%であった。得られた共重合体の分子量をゲルパーミエーションクロマトグラフィーで分析したところ、ポリスチレン換算の質量平均分子量は230,000であった。
後処理として、得られた共重合体溶液の50gに0.3%のNaOH水溶液142gを添加し、分散させた後、エバポレーターを用いて加熱しながら減圧下でMEKを留去し、乳白色の共重合水分散液(揮発性有機溶媒の含有量は1重量%以下)を得た。この水分散液にさらにイオン交換水を加えて固形分濃度15重量%である水分散液を得た。
この共重合体の融点は、48℃であった。
この共重合体の複素粘性率を測定した。結果を図1に示す。
この共重合体をクロロホルムに溶解し、PETフィルムにスピンコート後、風乾させた表面の接触角を測定すると、水に対する接触角は108°、n-ヘキサデカンに対する接触角は57~59°であった。
撹拌装置、温度計、還流冷却器、滴下漏斗、窒素流入口および加熱装置を備えた容積500mlの反応器を用意し、溶媒のメチルエチルケトン(MEK)を100部添加した。続いて、撹拌下、ステアリルアクリレート(StA、融点:30℃)78部、ヒドロキシエチルアクリレート(HEA)16部、およびジメチルアミノエチルメタクリレート(DM)6部からなる単量体(単量体計100部)、および開始剤のパーブチルPV(PV)1.2部をこの順に添加し、この混合物を65-75℃の窒素雰囲気下で12時間混合撹拌して共重合を行った。得られた共重合体含有溶液の固形分濃度は50重量%であった。
後処理として、得られた共重合体溶液の50gに0.4%の酢酸水溶液142gを添加し、分散させた後、エバポレーターを用いて加熱、減圧下でMEKを留去し、乳白色の共重合水分散液(揮発性有機溶媒の含有量は1重量%以下)を得た。この水分散液にさらにイオン交換水を加えて固形分濃度15重量%である水分散液を得た。
この共重合体をクロロホルムに溶解し、PETフィルムにスピンコート後、風乾させた表面の接触角を測定すると、水に対する接触角は106°、n-ヘキサデカンに対する接触角は62°であった。
合成例2のStAを60部、HEAを34部用いる他は、合成例2と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
合成例1のメタアクリル酸(MAA)に代えて、アクリル酸(AA)を6部用いる他は、合成例1と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
合成例1のヒドロキシルエチルアクリレート(HEA)に代えて、ヒドロキシルエチルメタアクリレート(HEMA)を16部用いる他は、合成例1と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
この共重合体をクロロホルムに溶解し、PETフィルムにスピンコート後、風乾させた表面の接触角を測定すると、水に対する接触角は102°、n-ヘキサデカンに対する接触角は48°であった。
合成例1のStAに代えて、ラウリルメタアクリレート(LMA、融点:-7℃)を78部用いる他は、合成例1と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
合成例1のStAに代えて、ステアリルメタアクリレート(StMA、融点:18℃)を78部用いる他は、合成例1と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
合成例1のStAに代えて、ステアリン酸アミドエチルアクリレート(C18AmEA、融点:70℃)を78部用いる他は、合成例1と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
合成例1のStA78部に代えて、合成例8のC18AmEAを39部、StAを39部用いる他は、合成例8と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
合成例8のMAAに代えて、DMを6部用いる他は、合成例8と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
この共重合体の融点は、64℃であった
この共重合体の複素粘性率を測定した。結果を図1に示す。
合成例10のHEAに代えて、ヒドロキシブチルアクリレート(HBA、Tg:-40℃)を16部用いる他は、合成例10と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
この共重合体の融点は、66℃であった。
この共重合体の複素粘性率を測定した。結果を図1に示す。
合成例11のC18AmEAを49部、HBAを27部用いる他は、合成例11と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
合成例1のStAに代えて、メチルメタアクリレート(MMA、融点:-48℃)を78部用いる他は、合成例1と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
比較合成例2
合成例2のHEAに代えて、N-ビニルピロリドン(NVP)を16部用いる他は、合成例1と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
比較合成例3
合成例1のStAに代えて、ターシャルブチルメタアクリレート(TBMA、融点:-60℃)を78部用いる他は、合成例1と同様に共重合と後処理を行い、固形分濃度15重量%である水分散体を得た。
実施例1
木材パルプとして、LBKP(広葉樹さらしクラフトパルプ)とNBKP(針葉樹さらしクラフトパルプ)の重量比率が、60重量%と40重量%で、かつ、パルプのろ水度が400ml(Canadian Standard Freeness)のパルプスラリーを調製し、このパルプスラリーに湿潤紙力増強剤、サイズ剤を添加して長網抄紙機により、紙密度が0.58g/cm3の坪量45g/m2の紙を外添処理(サイズプレス処理)の原紙として使用した。この原紙の耐油性(KIT値)は0、耐水性(Cobb値)は52g/m2であった。
合成例2の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表2に示す。
実施例3
合成例3の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表2に示す。
合成例4の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表2に示す。
実施例5
合成例5の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表2に示す。
合成例6の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表2に示す。
実施例7
合成例7の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表2に示す。
合成例8の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表3に示す。
合成例9の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表3に示す。
実施例10
合成例10の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表3に示す。
実施例11
合成例10の共重合体を用い、かつ、澱粉の固形分濃度が14%となるように処理液を調製した他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は2.2g/m2(共重合体の塗工量は0.32g/m2)であった。結果を表3に示す。
実施例12
合成例11の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表3に示す。
実施例13
合成例12の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表3に示す。
共重合体を使用せず、澱粉のみを用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.0g/m2(共重合体の塗工量は0.0g/m2)であった。結果を表4に示す。
比較例2
比較合成例1の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表4に示す。
比較合成例2の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表4に示す。
比較例4
比較合成例3の共重合体を用いる他は、実施例1と同様の処理を行った。得られた耐油紙の澱粉と共重合体の固形分の塗工量は1.1g/m2(共重合体の塗工量は0.28g/m2)であった。結果を表4に示す。
実施例14
木材パルプとして、バガスパルプ100重量%を離解機でろ水度が600cc(カナディアンフリーネス)のパルプスラリー(パルプ濃度2.5%)を調製した。このパルプスラリーにサイズ剤の1種であるアルキルケテンダイマー(AKD)をパルプ重量当たり固形分濃度で0.8重量%添加し、次いで、合成例1で得られた共重合体水分散液をパルプ重量当たり固形分濃度で1.0重量%添加し、パルプスラリーを調製した。このパルプスラリーを使用して、「自動モールド試験機」で重量が7gの紙皿を作成した。得られた紙皿のKIT試験を行うとKIT値が2であった。結果を表5に示す。
実施例14のAKDに変えて、カチオン化澱粉をパルプ重量当たり固形分濃度で1.0重量%用い、共重合体水分散液をパルプ重量当たり固形分濃度で2.0重量%で用いる他は、実施例14と同様に紙皿を作製した。得られた紙皿の実用油試験1を行うと値が3であった。結果を表6に示す。
実施例16
合成例1で得られた共重合体水分散液に代えて、合成例2で得られた共重合体水分散液を用いる他は、実施例15と同様に紙皿を作製した。得られた紙皿の実用油試験1を行うと値が5であった。結果を表6に示す。
合成例1で得られた共重合体水分散液に代えて、合成例8で得られた共重合体水分散液を用いる他は、実施例15と同様に紙皿を作製した。得られた紙皿の実用油試験1を行うと値が5であった。結果を表6に示す。
合成例1で得られた共重合体水分散液を添加しない他は、実施例14と同様に紙皿を作成した。得られた紙皿のKIT試験を行うとKIT値が0であった。結果を表5に示す。
比較例6
AKDを添加した後に、比較合成例1で得られた共重合体水分散液をパルプ重量当たり固形分濃度で1重量%添加した他は、実施例14と同様に紙皿を作成した。得られた紙皿のKIT試験を行うとKIT値が0であった。結果を表5に示す。
合成例1で得られた共重合体水分散液を添加しない他は、実施例15と同様に紙皿を作成した。得られた紙皿の実用油試験1の値は1であった。結果を表6に示す。
実施例10、実施例11、実施例12、比較例1および比較例2における耐油紙を実用油試験1および実用油試験2に付した。結果を表7に示す。
[1]
(a)炭素数7~40の長鎖炭化水素基を有するアクリル単量体から形成された繰り返し単位、および
(b)親水性基を有するアクリル単量体から形成された繰り返し単位
を有する非フッ素共重合体を含んでなる紙用耐油剤。
[2]
長鎖炭化水素基を有するアクリル単量体(a)が、式:
CH2=C(-X1)-C(=O)-Y1(R1)k
[式中、R1は、それぞれ独立的に、炭素数7~40の炭化水素基であり、
X1は、水素原子、一価の有機基またはハロゲン原子であり、
Y1は、2価~4価の炭素数1の炭化水素基、-C6H4-、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上で構成される基(但し、炭化水素基を除く)であり、
kは1~3である。]
で示される単量体である[1]に記載の紙用耐油剤。
[3]
長鎖炭化水素基を有するアクリル単量体(a)において、X1が水素原子であり、長鎖炭化水素基の炭素数が18以上である[1]または[2]のいずれかに記載の紙用耐油剤。
[4]
長鎖炭化水素基を有するアクリル単量体(a)が、
(a1)式:
CH2=C(-X4)-C(=O)-Y2-R2
[式中、R2は、炭素数7~40の炭化水素基であり、
X4は、水素原子、一価の有機基またはハロゲン原子であり、
Y2は、-O-または-NH-である。]
で示されるアクリル単量体、および/または
(a2)式:
CH2=C(-X5)-C(=O)-Y3-Z(-Y4-R3)n
[式中、R3は、それぞれ独立的に、炭素数7~40の炭化水素基であり、
X5は、水素原子、一価の有機基またはハロゲン原子であり、
Y3は、-O-または-NH-であり、
Y4は、それぞれ独立的に、直接結合、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上で構成される基であり、
Zは、直接結合、あるいは2価または3価の炭素数1~5の炭化水素基であり、
nは、1または2である。]
で示されるアクリル単量体であり、
親水性基を有するアクリル単量体(b)が、式:
CH2=CX2C(=O)-O-(RO)n-X3 (b1)
および/または
CH2=CX2C(=O)-O-(RO)n-C(=O)CX2=CH2 (b2)
[式中、X2は、水素原子またはメチル基、
X3は、水素原子または炭素数1~22の不飽和または飽和の炭化水素基
Rは、炭素数2~6のアルキレン基、nは、1~90の整数である。]
で表わされる少なくとも1つのオキシアルキレン(メタ)アクリレートである、[1]~[3]のいずれかに記載の紙用耐油剤。
[5]Y1またはY4は、-Y’-、-Y’-Y’-、-Y’-C(=O)-、-C(=O)-Y’-、-Y’-C(=O)-Y’-、-Y’-R’-、-Y’-R’-Y’-、-Y’-R’-Y’-C(=O)-、-Y’-R’-C(=O)-Y’-、-Y’-R’-Y’-C(=O)-Y’-、または-Y’-R’-Y’-R’-
[式中、Y’はそれぞれ独立して、直接結合、-O-、-NH-または-S(=O)2-であり、
R’は-(CH2)m-(mは1~5の整数である)、炭素数1~5の不飽和結合を有する直鎖状の炭化水素基、炭素数1~5の枝分かれ構造を有する炭化水素基、または-(CH2)l-C6H4-(CH2)l-(lはそれぞれ独立して0~5の整数であり-C6H4-はフェニレン基である)である。]
で示される基である[2]または[4]のいずれかに記載の紙用耐油剤。
[6]
非フッ素共重合体が
単量体(a)および(b)以外の、オレフィン性炭素-炭素二重結合、およびアニオン性供与基またはカチオン性供与基を有する単量体(c)から形成される繰り返し単位
をさらに含む[1]~[5]のいずれかに記載の紙用耐油剤。
[7]
アニオン供与基がカルボキシル基、またはカチオン供与基がアミノ基である[6]に記載の紙用耐油剤。
[8]
長鎖炭化水素基を有するアクリル単量体(a)から形成される繰り返し単位の量が、共重合体に対して30~95重量%である[1]~[7]のいずれかに記載の紙用耐油剤。
[9]
長鎖炭化水素基を有するアクリル単量体(a)から形成される繰り返し単位の量が、共重合体に対して30~90重量%であり、親水性基を有するアクリル単量体(b)から形成される繰り返し単位の量が、共重合体に対して5~70重量%であり、非フッ素共重合体がランダム共重合体である[1]~[8]のいずれかに記載の紙用耐油剤。
[10]
非フッ素共重合体の融点またはガラス転移点が20℃以上であるか、および/または非フッ素共重合体の動的粘弾性(複素粘性率)が、90℃において、10~5000Pa・sである[1]~[9]のいずれかに記載の紙用耐油剤。
[11]
水または水と有機溶媒の混合物である液状媒体をさらに含んでなる[1]~[10]のいずれかに記載の紙用耐油剤。
[12]
[1]~[11]のいずれかに記載の紙用耐油剤および澱粉または変性澱粉を含む耐油層を紙の表面に有する耐油紙。
[13]
耐油層における紙用耐油剤の固形分量が2g/m2以下である[12]に記載の耐油紙。
[14]
[1]~[11]のいずれかに記載の紙用耐油剤を紙の内部に含む耐油紙。
[15]
食品包装材または食品容器である[12]~[14]のいずれかに記載の耐油紙。
[16]
[1]~[11]のいずれかに記載の紙用耐油剤で紙を外添処理または内添処理により処理する紙の処理方法。
Claims (16)
- (a)炭素数7~40の長鎖炭化水素基を有するアクリル単量体から形成された繰り返し単位、および
(b)親水性基を有するアクリル単量体から形成された繰り返し単位
を有する非フッ素共重合体を含んでなる紙用耐油剤。 - 長鎖炭化水素基を有するアクリル単量体(a)が、式:
CH2=C(-X1)-C(=O)-Y1(R1)k
[式中、R1は、それぞれ独立的に、炭素数7~40の炭化水素基であり、
X1は、水素原子、一価の有機基またはハロゲン原子であり、
Y1は、2価~4価の炭素数1の炭化水素基、-C6H4-、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上で構成される基(但し、炭化水素基を除く)であり、
kは1~3である。]
で示される単量体である請求項1に記載の紙用耐油剤。 - 長鎖炭化水素基を有するアクリル単量体(a)において、X1が水素原子であり、長鎖炭化水素基の炭素数が18~40である請求項1または2に記載の紙用耐油剤。
- 長鎖炭化水素基を有するアクリル単量体(a)が、
(a1)式:
CH2=C(-X4)-C(=O)-Y2-R2
[式中、R2は、炭素数7~40の炭化水素基であり、
X4は、水素原子、一価の有機基またはハロゲン原子であり、
Y2は、-O-または-NH-である。]
で示されるアクリル単量体、および/または
(a2)式:
CH2=C(-X5)-C(=O)-Y3-Z(-Y4-R3)n
[式中、R3は、それぞれ独立的に、炭素数7~40の炭化水素基であり、
X5は、水素原子、一価の有機基またはハロゲン原子であり、
Y3は、-O-または-NH-であり、
Y4は、それぞれ独立的に、直接結合、-O-、-C(=O)-、-S(=O)2-または-NH-から選ばれる少なくとも1つ以上で構成される基であり、
Zは、直接結合、あるいは2価または3価の炭素数1~5の炭化水素基であり、
nは、1または2である。]
で示されるアクリル単量体であり、
親水性基を有するアクリル単量体(b)が、式:
CH2=CX2C(=O)-O-(RO)n-X3 (b1)
および/または
CH2=CX2C(=O)-O-(RO)n-C(=O)CX2=CH2 (b2)
[式中、X2は、水素原子またはメチル基、
X3は、水素原子または炭素数1~22の不飽和または飽和の炭化水素基
Rは、炭素数2~6のアルキレン基、nは、1~90の整数である。]
で表わされる少なくとも1つのオキシアルキレン(メタ)アクリレートである、請求項1~3のいずれかに記載の紙用耐油剤。 - Y1またはY4は、-Y’-、-Y’-Y’-、-Y’-C(=O)-、-C(=O)-Y’-、-Y’-C(=O)-Y’-、-Y’-R’-、-Y’-R’-Y’-、-Y’-R’-Y’-C(=O)-、-Y’-R’-C(=O)-Y’-、-Y’-R’-Y’-C(=O)-Y’-、または-Y’-R’-Y’-R’-
[式中、Y’はそれぞれ独立して、直接結合、-O-、-NH-または-S(=O)2-であり、
R’は-(CH2)m-(mは1~5の整数である)、炭素数1~5の不飽和結合を有する直鎖状の炭化水素基、炭素数1~5の枝分かれ構造を有する炭化水素基、または-(CH2)l-C6H4-(CH2)l-(lはそれぞれ独立して0~5の整数であり-C6H4-はフェニレン基である)である。]
で示される基である請求項2または4に記載の紙用耐油剤。 - 非フッ素共重合体が
単量体(a)および(b)以外の、オレフィン性炭素-炭素二重結合、およびアニオン性供与基またはカチオン性供与基を有する単量体(c)から形成される繰り返し単位
をさらに含む請求項1~5のいずれかに記載の紙用耐油剤。 - アニオン供与基がカルボキシル基、またはカチオン供与基がアミノ基である請求項6に記載の紙用耐油剤。
- 長鎖炭化水素基を有するアクリル単量体(a)から形成される繰り返し単位の量が、共重合体に対して30~95重量%である請求項1~7のいずれかに記載の紙用耐油剤。
- 長鎖炭化水素基を有するアクリル単量体(a)から形成される繰り返し単位の量が、共重合体に対して30~90重量%であり、親水性基を有するアクリル単量体(b)から形成される繰り返し単位の量が、共重合体に対して5~70重量%であり、アニオン性供与基またはカチオン性供与基を有する単量体(c)から形成される繰り返し単位の量は、非フッ素共重合体に対して、0.1~30重量%であり、非フッ素共重合体がランダム共重合体である請求項1~8のいずれかに記載の紙用耐油剤。
- 非フッ素共重合体の融点またはガラス転移点が20℃以上であるか、および/または非フッ素共重合体の動的粘弾性(複素粘性率)が、90℃において、10~5000Pa・sである請求項1~9のいずれかに記載の紙用耐油剤。
- 水または水と有機溶媒の混合物である液状媒体をさらに含んでなる請求項1~10のいずれかに記載の紙用耐油剤。
- 請求項1~11のいずれかに記載の紙用耐油剤および澱粉または変性澱粉を含む耐油層を紙の表面に有する耐油紙。
- 耐油層における紙用耐油剤の固形分量が2g/m2以下である請求項12に記載の耐油紙。
- 請求項1~11のいずれかに記載の紙用耐油剤における非フッ素共重合体を紙の内部に含む耐油紙。
- 食品包装材または食品容器である請求項12~14のいずれかに記載の耐油紙。
- 請求項1~11のいずれかに記載の紙用耐油剤で紙を外添処理または内添処理により処理する紙の処理方法。
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Also Published As
Publication number | Publication date |
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CN112513370A (zh) | 2021-03-16 |
JPWO2020054856A1 (ja) | 2021-03-11 |
EP3851578B1 (en) | 2024-05-29 |
EP3851578A1 (en) | 2021-07-21 |
EP3851578A4 (en) | 2022-06-01 |
US11851822B2 (en) | 2023-12-26 |
US20210164165A1 (en) | 2021-06-03 |
JP7157349B2 (ja) | 2022-10-20 |
TWI752348B (zh) | 2022-01-11 |
TW202030399A (zh) | 2020-08-16 |
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