WO2011027877A1 - Water and oil resistant agent for paper, treatment process and paper - Google Patents

Water and oil resistant agent for paper, treatment process and paper Download PDF

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Publication number
WO2011027877A1
WO2011027877A1 PCT/JP2010/065191 JP2010065191W WO2011027877A1 WO 2011027877 A1 WO2011027877 A1 WO 2011027877A1 JP 2010065191 W JP2010065191 W JP 2010065191W WO 2011027877 A1 WO2011027877 A1 WO 2011027877A1
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WO
WIPO (PCT)
Prior art keywords
paper
water
group
oil resistant
monomer
Prior art date
Application number
PCT/JP2010/065191
Other languages
French (fr)
Inventor
Eiji Masuda
Michio Matsuda
Kayo Kusumi
Tetsuya Uehara
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to EP10755005.5A priority Critical patent/EP2473673B1/en
Priority to US13/393,431 priority patent/US9249540B2/en
Priority to KR1020127005420A priority patent/KR101330384B1/en
Priority to JP2012526269A priority patent/JP5413508B2/en
Priority to CA 2771339 priority patent/CA2771339C/en
Priority to CN201080038806.XA priority patent/CN102575435B/en
Publication of WO2011027877A1 publication Critical patent/WO2011027877A1/en
Priority to ZA2012/01321A priority patent/ZA201201321B/en

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

  • the present invention is related to a water and oil resistant agent for paper, a treatment process by the agent and the treated paper therewith.
  • copolymer composition comprising a long chain C6-C12 polyfluoroalkyl group
  • Rf group (hereinafter called as "Rf group") has been utilized previously as the water and oil resistant agent for paper.
  • a paper-treatment agent comprising, as an essential component, a fluorine-containing copolymer having a short chain Rf, specified polymer units and a high molecular weight can exhibit a superior water and oil resistance.
  • a paper-treatment agent comprising, as an essential component, a fluorine-containing copolymer having a short chain Rf, specified polymer units and a high molecular weight can exhibit a superior water and oil resistance.
  • the subject of the invention is related to a water and oil resistant agent for paper comprising a fluorine-containing copolymer comprising the repeating units derived from: (a) a fluorine-containing monomer having a fluoroalkyi group represented by the general formula:
  • X represents a hydrogen atom, a linear or branched to C 2 i alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group wherein X 1 and X 2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a cyano group, a linear or branched C 1 -C 21 fluoroalkyi group, a substituted or non-substituted benzyl group, or a substituted or non-substituted phenyl group;
  • Y is -O- or -NH-
  • Z is a C 1 -C 10 aliphatic group, a C 6 -C 10 aromatic or cyclic aliphatic group,
  • Z 1 is a hydrogen atom or an acetyl group, a -(CH 2 )m-S02-(CH 2 )n- group or a -(CH 2 ) m -S-(CH 2 )n- group wherein m is 1-10 and n is 0-
  • Rf is a C C 6 linear or branched fluoroalkyi group, (b) a hydrophilic monomer, and
  • a weight average molecular weight of the fluorine-containing copolymer is 100,000 or more.
  • the weight average molecular weight is determined by the gel permeation chromatography measurement in terms of a molecular weight of polymethyl methacrylate.
  • the subject of the present invention is related to a process for treating a paper with the above-described water and oil resistant agent, and it is also related to a water and oil resistant paper obtained thereby.
  • the present invention provides the water and oil resistant agent comprising a fluorine- containing copolymer, which agent affords the superior water and oil resistance to the paper.
  • the present invention provides the process for the paper treatment by the water and oil resistant agent and the water and oil resistive paper obtained by utilizing the water and oil resistant agent.
  • the composition of the fluorine-containing copolymer has a great influence on the water and oil resistance of the water and oil resistant agent.
  • the fluorine-containing copolymer used in the present invention is explained as follows.
  • the fluorine-containing monomer (a) may be substituted by a halogen atom etc. at its a- position. Therefore, X in the formula (1 ) may be a hydrogen atom, a linear or branched Ci to C 2 i alky!
  • the Rf group is preferably a perfluoroalkyi group.
  • the carbon number of the Rf group may be 1-6, especially 4-6, and typically 6.
  • the examples of the Rf group are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , - C(CF 3 ) 3 , -(CF 2 ) 4 CF 3 , -(CF 2 ) 2 CF(CF 3 ) 2 , - CF 2 C(CF 3 ) 3 , -CF(CF 3 )CF 2 CF 2 CF 3 , -( CF 2 ) 5 CF 3 and -( CF 2 ) 3 CF(CF 3 ) 2 etc.
  • -( CF 2 ) 5 CF 3 is preferable.
  • Non-limiting examples of the fluorine-containing monomer (a) are exemplified as follows:
  • Rf is a fluoroalkyi group of C r C 6 , preferably C 4 -C 6 .
  • the fluoroalkyi group (Rf) in the fluorine-containing monomer (a) may be, preferably a perfluoroalkyl group, and most preferably a C 4 -C 6 perfluoroalkyl group.
  • the fluorine-containing monomer (a) may be a mixture of two or more types of monomers.
  • the amount of the fluorine-containing monomer (a) may be 40-90 wt%, more preferably 45-85 wt%, most preferably 60-85 wt% based on the fluorine-containing copolymer.
  • the hydrophilic monomer (b) is at least one oxyaikylene (meth)acrylate, preferably represented by the general formulas:
  • X 1 is a hydrogen atom or a methyl group
  • X 2 is a hydrogen atom or a saturated or unsaturated C 1 -C 22 hydrocarbon group
  • R is a C 2 -C 6 alkylene group
  • n is an integer of 1-90
  • polyoxyalkylene (meth)acrylate and/or 2-hydroxyethyl (meth)acrylate are exemplified.
  • the oxyaikylene group is preferably C2 - C6, more preferably C2 - C4.
  • the average polymerization degree of oxyalylene groups in the polyoxyalkylene group may be 2 to 20, preferably 2 to 10.
  • CH 2 C(CH 3 )-C
  • the oxyaikylene (meth) acrylate may be preferably (b1 ) ⁇ -hydroxy-polyoxyalkylene (meth) acrylate and/or (b2) 2-hydroxyethyl (meth) acrylate.
  • the monomer (c) is a compound having an anion-donating group and a carbon-carbon double bond.
  • the anion-donating group may be a carboxyl group or a sulfonic acid group.
  • the monomer (c) may be preferably at least one selected from the group consisting of (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic cid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrene sulfonic aicd, vinylbenzene sulfonic acid, acrylamide-tert-butylsulfonic acid, and salts thereof.
  • the especially preferable monomer (c) is (meth)acrylic acid.
  • the amount of the monomer (a) may be 40 - 90 wt% preferably 60 - 85 wt%, the amount of the monomer (b) may be 2 - 50 wt%, preferably 5- 35 wt%, and the amount of the monomer (c ) may be 0.1 - 30 wt%, preferably 1 - 15 wt%
  • the hydrophilic monomer (b) preferably comprises (b1) ⁇ -hydroxy-polyoxyethylene (meth)acrylate and/or (b2) 2-hydroxyethyl (meth)acrylate, and the wt% range of the monomer (b) is equal to the sum amount of (b1 ) and (b2).
  • both the composition of the fluorine-containing copolymer and the molecular weight of the fluorine-containing copolymer greatly influence the water and oil resistance.
  • the weight average molecular weight of the fluorine-containing copolymer of the present invention is 100,000 or more, preferably, 100,000 to 3,000,000, and further preferably 120,000 to 2,000,000. When the molecular weight is in these ranges, satisfactory water and oil resistance and viscosity properties are obtained.
  • the first preferable embodiment of the monomer composition for the fluorine-containing copolymer comprises at least one fluorine-containing monomer (a) wherein Rf represents a perfluoroalkyl group having 4 - 6 carbon atoms, the hydrophilic monomer (b) containing at least one of ⁇ -hydroxy-polyoxyalkylene (meth)acrylate (b1 ) and/or 2-hydroxyethyl (meth)acrylate (b2) and
  • the anion donating group-containing monomer (c) selected from the group consisting of (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid.
  • the hydrophilic monomer (b) is ⁇ -hydroxy-polyoxyalkylene (meth)acrylate (b1) and/or 2- hydroxyethyl (meth)acrylate (b2)
  • the anion donating group-containing monomer (c) is (meth)acrylic acid.
  • (meth)acryiate (b ) (the average polymerization degree of polyoxyethylene is 2 to 10) and/or 2-hydroxyethyl (meth)acrylate (b2), and the anion donating group containing monomer (c) is (meth)acrylic acid, the weight ratio of (a) : (b) : (c) is 60 - 85: 5 - 35: 1-15, and the weight average molecular weight of the obtained fluorine-containing polymer is 120,000 to 2,000,000.
  • the present invention also relates to a process for a water and oil resistant treatment of a paper, which process comprises a step of applying the water and oil resistant agent of the present invention to the surface of the paper.
  • This treatment process is hereinafter called as "surface application process".
  • the present invention also relates to a process for a water and oil resistant treatment of a paper, which process comprises a step of applying the water and oil resistant agent of the present invention to the whole of the paper including its internal parts.
  • This treatment process is hereinafter called as "internal application process".
  • the water and oil resistant agent of the present invention comprising a fluorine-containing copolymer is applied in the papermaking step from pulp.
  • the present invention also relates to a water and oil resistant paper treated by the water and oil resistant agent of the present invention.
  • the present invention also relates to a paper obtained by the surface application process and the internal application process.
  • the production of the fluorine-containing copolymer of the present invention can be carried out by polymerizing monomers (a), (b) (or (b1 ) and/or (b2)) and (c) in a liquid medium.
  • the liquid medium is preferably water soluble or water dispersible solvent.
  • the liquid medium may be a mixture comprising the water soluble or water dispersible solvent.
  • the monomer and the liquid medium preferably are in a form of a solution wherein the monomer is disolved in the liquid medium.
  • the polymerization may be a solution polymerization or an emulsion polymerization, preferably a solution
  • the monomer (c) (an anion donating group) may be neutralized with a base (such as an aqueous solution of inorganic or organic base) after conducting the copolymerization; or the copolymerization may be carried out using the monomer (c) neutralized with the base in advance.
  • a base such as an aqueous solution of inorganic or organic base
  • the copolymerization may be carried out using the monomer (c) neutralized with the base in advance.
  • triethenolamine etc. are preferable from the view point of the improvement of the dispersing stability of the obtained fluorine-containing copolymer in the aqueous medium.
  • the polymer mixture after copolymerization may be, if necessary, diluted by adding the liquid medium (for example, water or an aqueous solution containing inorganic or organic bases).
  • the liquid medium for example, water or an aqueous solution containing inorganic or organic bases.
  • ketones for example, acetone or methyl ethyl ketone
  • alcohols for example, methanol, ethanol and isopropanol
  • ethers for example, methyl or ethyl ether of ethylene glycol or propylene glycol, acetate ester thereof, tetrahydrofuran and dioxane
  • acetonitrile for example,
  • methyl ethyl ketone (MEK), N-methyl-2-pyrollidone (NMP), a mixture of N- methyl-2-pyrollidone and acetone, isopropanol or methanol is preferable as a solvent.
  • the total monomer concentration in the solution may be in the range of 20 - 70 wt%, preferably, 40 - 60 wt%.
  • the copolymerization may be carried out using at least one initiator in the range of 0.1 - 3.0 wt% based on the total weight of the monomers.
  • the following initiators may be used: peroxides such as benzoyl peroxide, lauroyl peroxide, succinyl peroxide and ter- butyl peroxypivalate, or azo-compounds such as 2, 2-azobis-isobutylonitrile, 4, 4-azobis (4-cyanopentanoic acid) and azodicarbonamide.
  • a chain transfer agent may be used for controlling the molecular weight of the copolymer.
  • alkylmercaptan dodecylmercaptan, laury!mercaptan, stearylmercaptan, etc.
  • aminoethanethiol mercaptoethanol, thioglycollic acid, and 2- mercaptopropionic acid etc.
  • the amount of the chain transfer agent used may be in a range of 0.05 - 1 parts by weight based on 100 parts by weight of the total monomers in the copolymerization.
  • the copolymerization can be carried out in the range between 40 °C and the boiling point of the reaction mixture.
  • the dilution step may be carried out by adding a liquid medium, for example, water or an aqueous solution of a strong or moderate inorganic or organic base into the organic solution of fluorine-containing copolymer in organic solvent.
  • a liquid medium for example, water or an aqueous solution of a strong or moderate inorganic or organic base
  • the above described bases are exemplified as such a base usable for the dilution step.
  • the amount of the aqueous solution and the concentration of the base are preferable to be sufficiently enough firstly to neutralize the carboxylic acid group or the sulfonic acid group, and secondly to attain the solid concentration of the fluorine-containing copolymer of 5 - 35 wt%, preferably 15 - 25 wt% in the final copolymer solution.
  • the amount of base in the range of 0.1 - 5 eq., preferably 0.5 -3 eq. based on the monomer (c).
  • the paper to which the water and oil resistant agent comprising the fluorine-containing copolymer of the present invention is to be applied can be produced by the conventional paper making method. Both the internal application process and the surface application process may be used. In the internal application process, the treating agent is added to the pulp slurry before paper making, and in the surface application process, the treating agent is added to the paper after paper making. In case of applying the water and oil resistant agent of the present invention to the surface of the paper (surface application process), it is preferable to use the water and oil resistant agent in such amount that the weight ratio of the fluorine atoms is in the range of 0.005 - 0.6 wt%, preferably 0.01 - 0.4 wt% based on the weight of the paper.
  • the water and oil resistant agent in case of applying the water and oil resistant agent to the whole paper including its internal parts, it is preferable to use the water and oil resistant agent in such amount that the weight ratio of the fluorine atoms is in the range of 0.01 - 1.0 wt%, especially, 0.02 - 0.6 wt% based on the weight of the pulp.
  • the paper substrate thus treated exhibits a superior oil and water resistance after heat treatment at room temperature or at high temperature, or if necessary depending on the nature of the paper substrate, by accompanying a heat treatment which can be at a higher temperature of at most 300 °C, for example, at most 200 °C.
  • the paper substrate treated by the process of the present invention is exemplified as follows: a raw paper for plaster board, a coated raw paper, a wood-containing paper, a general liner and a flute, a neutral white role paper, a neutral liner, an anti-corrosion liner, a paper combined with metal and a kraft paper, etc.
  • the following paper substrate are further exemplified: a neutral paper for printing and writing, a neutral coated raw paper, a neutral paper for PPC, a neutral heat-sensitive paper, a neutral pressure-sensitive paper, a neutral paper for ink-jet, and a neutral paper for information industry.
  • Other papers such as a mold paper formed by molding, especially, a molded paper vessel, are exemplified.
  • a pulp-molded vessel can be produced by the process described in the JP9-183429A.
  • the following materials can be utilized as a starting pulp materials for paper: a bleached or unbleached chemical pulp such as a kraft pulp or a sulfite pulp, a bleached or unbleached high-yield pulp such as a grand pulp, a mechanical pulp or a thermo- mechanical pulp, and a waste pulp such as a waste paper of newspaper, magazine, cardboard or deinked paper, etc.
  • a bleached or unbleached chemical pulp such as a kraft pulp or a sulfite pulp
  • a bleached or unbleached high-yield pulp such as a grand pulp
  • a mechanical pulp or a thermo- mechanical pulp a waste pulp
  • waste pulp such as a waste paper of newspaper, magazine, cardboard or deinked paper, etc.
  • synthetic fibers such as polyamide, polyimide, polyester, polyolefin and polyvinylalcohol, etc.
  • a size agent in addition to the water and oil resistant agent, can be added optionally to improve the water resistance of the paper.
  • the examples of the size agent are a cationic size agent, an anionic size agent and a rosin size agent (for example, an acidic rosin size agent, a neutral rosin size agent).
  • a styrene-acrylic acid copolymer, alkenylsuccinic anhydride and an alkylketene dimer are preferable.
  • the amount of the size agent may be 0.001 - 5 wt% based on the amount of the pulp.
  • a paper strengthening agent such as starch, various modified starch, caroboxymethyl- cellulose, polyamidepolyamine-epichlorohydrin (PEA), polydiallyldimethylammonium chloride (poly-DADMAC) and polyamide etc., a retention aid, a dyestuff, a fluorescent dyestuff, a filler, a pigment, a slime-controlling agent, an anti-slipping agent, a deformer, etc.
  • the paper-treatment agents can be applied to the paper by means of a size press, coating (a gate roll coater, a bill blade coater and a bar coater, etc.).
  • aqueous dispersion The stability of the dispersion of fluorine-containing copolymer in water (aqueous dispersion) was observed as follows: An aqueous dispersion having a solid content being adjusted to 20 wt% was left standing for seven days at room temperature in 110ml clear glass sample pot, and its dispersion state was visually observed by eyes whether a sedimentation or a coagulation occurred or not. The evaluation was summarized as follows: “Good” stands for absence of sedimentation or coagulation; “Fair” stands for fractional sedimentation or aggregation; "Poor” stands for large sedimentation or coagulation.
  • the test consists of measuring the weight (g) of the water absorbed in one minute by the paper having 1 m 2 area and supporting 1 cm height of water.
  • the oil resistance was measured according to the TAPPI T-559 cm-02 method. A drop of the test oil shown in Table 1 was placed on the paper, then, the infiltration state of the oil was observed after 15 seconds. The maximum point of an oil resistance given by the oil having no infiltration was assigned to be an oil resistance of the paper.
  • This test is particularly useful to verify the anti-grease paper suitability for the pet-food packaging. Briefly, this test implies the contact in standardized conditions of the petfood with the paper specimen to be tested.
  • the pet-food with the trademark
  • the roll speed is 50 - 60 cm/sec. during the creasing.
  • the first crease is formed along the line connecting the centers of the facing two edges, and the second crease is formed on the opposite side of the paper.
  • the creased specimen is placed on the grid to cover the grid surface completely.
  • a metal ring having an internal diameter equal to 7.2 cm and height equal to 2.5 cm is placed in the middle of the specimen.
  • C6FA 2-hydroxyethyl methacrylate
  • MAA methacrylic acid
  • the copolymerization was carried out by following the same procedure as Synthesis Example 1 except that lauryimercaptane (L-SH) in 0.1 parts was additionally charged as the chain transfer agent and the initiator was replaced by tert-butyl peroxypivalate in 0.5 parts, to give a solution (S2) containing the copolymer.
  • the solid content of the solution (S2) was 50 wt%.
  • the weight average molecular weight was 150,000 in terms of the molecular weight of polymethyl methacrylate.
  • the solid content of the solution (S3) was 50 wt%.
  • the weight average molecular weight was 500,000 in terms of the molecular weight of polymethyl
  • the copolymerization was carried out by following the same procedure as Synthesis Example 1 except that itaconic acid (IA) was used in 5 parts instead of methacrylic acid (MAA).
  • the solid content of the solution (S4) obtained was 50 wt%.
  • the weight average molecular weight was 180,000 in terms of the molecular weight of polymethyl methacrylate.
  • the copolymerization was carried out by following the same procedure as Synthesis Example 1 except that laurylmercaptane (L-SH) in 0.3 parts was additionally charged as the chain transfer agent.
  • the obtained solid content of the solution (R1 ) containing the copolymer was 50 wt%.
  • the weight average molecular weight was 50,000 in terms of the molecular weight of polymethyl methacrylate.
  • the copolymerization was carried out by following the same procedure as Synthesis Example 1 except that laurylmercaptane (L-SH) in 1.0 part was additionally charged as a chain transfer agent.
  • L-SH laurylmercaptane
  • the obtained solid content of the solution (R2) containing the copolymer was 50 wt%.
  • the weight average molecular weight was 10,000 in terms of the molecular weight of polymethyl methacrylate.
  • Example 2 except that itaconic acid (IA) was used in 5 parts instead of methacrylic acid (MAA).
  • the obtained solid content of the solution (R3) containing the copolymer was 50 wt%.
  • the weight average molecular weight was 45,000 in terms of the molecular weight of polymethyl methacrylate.
  • Preparation Example 1 A pale yellow aqueous dispersion containing fluorine-containing copolymer (the content of the volatile organic solvent being less than 1 wt%) was obtained by the following sequential procedures: Adding 1.2 g of an aqueous 23 % ammonia solution and 90 g of an ion-exchanged water to the solution (S1) containing the fluorine-containing copolymer obtained in Synthesis Example 1 , preparation of an emulsified dispersion and
  • aqueous dispersion (SD1 ) having a solid content of 20 wt%.
  • Preparation Example 1 was carried out except that 1.3 g of diethanolamine as a base was used, to give an aqueous dispersions (SD4) having a solid content of 20 wt%.
  • SD4 aqueous dispersions having a solid content of 20 wt%.
  • the dispersion stability of the SD4 was measured, and the obtained results are shown in Table 3.
  • a paper to be tested was produced by using a test paper machine installed in the
  • the types of pulp used were LBKP (Leaf Bleached Kraft Pulp) and NBKP (Needle Bleached Kraft Pulp), and their ratio was 6/4 (L/N) and the freeness of the pulp was 400 ml (Canadian Standard Freeness).
  • a cationic starch Stayloc 400 (produced by Tate and Lyle) was added in 2 wt% based on the dried pulp weight, and further a size agent Hereon 70 (produced by Hercules corp.) was added in 0.0375 wt% based on the dried pulp weight.
  • a paper was produced from the pulp slurry by using a fourdrinire machine. The basis weight of the paper obtained was 60 g/cm 2 and the thickness was 0.01 mm. The water resistance (Cobb value) was 80 g/cm 2 , and the oil resistance (Kit value) was 0.
  • the water and oil resistant paper (treated paper) was produced in following to the procedure described below using, as an water and oil resistant agent, the aqueous dispersion solution (SD1) containing the fluorine-containing copolymer obtained in Preparation Example 1
  • the aqueous dispersion solution (SD1) containing the fluorine-containing copolymer obtained in Preparation Example 1 was diluted to adjust the solid content to 0.2 wt% to give the water and oil resistant composition.
  • the paper prepared above was dipped in the water and oil resistant composition for 5 minutes and dried at 115 °C for 70 seconds to obtain a raw paper for test.
  • the aqueous dispersion solutions (SD2 - SD4) containing the fluorine-containing copolymer obtained in Preparation Examples 2 - 4 the water and oil resistant compositions were obtained by diluting the aqueous dispersion solutions (SD2 - SD4) to adjust the solid content to 0.2 wt%.
  • the Kit Test and the Cobb Test were carried out in the same way as Example 1. The obtained results are shown in Table 3.
  • Example 1 - 3 the water and oil resistant compositions were obtained by diluting the aqueous dispersion solutions (RD1 - RD3) to adjust the solid content to 0.2 wt%. Using each composition, the Kit Test and the Cobb Test were carried out in the same way as the Example 1. The obtained results are shown in Table 3. Table 3 (Evaluation results in the surface application process: Examples 1 - 4)
  • aqueous dispersion (875 g) containing a 0.5 wt% mixture of 40 parts of a beaten LBKP (Leaf Bleached Kraft Pulp) and 60 parts of a beaten NBKP (Needle Bleached Kraft Pulp) having a freeness of 450 ml (Canadian Standard Freeness) was introduced under stirring into the flask, then, 3.06 g of an aqueous solution containing 1 wt% of the cationic starch (SB GUM-POSIT300 produced by SANGUAN WONGSE IND. CO., LTD) was added and the stirring was continued for 1 minuets, then 1.31 g of an aqueous solution containing 1 wt% of polyamidoamine-epichlorohydrin (WS-4020 produced by Japan
  • the resultant pulp slurry was made into paper with a standard hand papermaking machine described in J IS P8222 (The hand papermaking machine was modified to give a paper having a size of 25 cm x 25 cm).
  • the resultant wet paper was pressed between filter paper sheets under a pressure of 3.5 kg/cm 2 so as to sufficiently absorb water contained in the paper.
  • the paper was dried over a drum drier (115°C x 70 seconds) to obtain a water and oil resistant paper.
  • the basis weight of the resultant paper was 70 g/m 2 .
  • the water resistance (Cobb value) of this hand sheet paper was 100 g/m 2 or more, and the oil resistance (Kit value) was 0, and the oil resistance (AGR) was 100.
  • Example 5 The same procedures in Example 5 were carried out except that the aqueous dispersions (SD2 and SD3) containing the fluorine-containing copolymer were used instead of the aqueous dispersion (SD1) containing the fluorine-containing copolymer in the Example 5.
  • SD2 and SD3 aqueous dispersions containing the fluorine-containing copolymer were used instead of the aqueous dispersion (SD1) containing the fluorine-containing copolymer in the Example 5.
  • SD1 aqueous dispersion
  • Example 5 The same procedures as in Example 5 were carried out except that the aqueous dispersions (RD1 - RD3) containing the fluorine-containing copolymer were used instead of the aqueous dispersion (SD1 ) containing the fluorine-containing copolymer in Example 5.
  • the water resistance and the oil resistance of the obtained water and oil resistant papers were evaluated, and these results are shown in Table 4.

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Abstract

Disclosed is a water and oil resistant agent comprising a fluorine-containing copolymer obtained by copolymerizing a (meth)acrylate monomer having a fluoroalkyl group having 1 - 6 carbon atoms, which agent affords a superior water and oil resistance to a paper. The invention also discloses a process for treating a paper by the water and oil resistant agent and a treated paper thereby.

Description

DESCRIPTION
WATER AND OIL RESISTANT AGENT FOR PAPER,
TREATMENT PROCESS AND PAPER
CROSS REFERENCE TO RELATED APPLICATIONS
This application has priority from US Application No. 61/238997 filed September 1 , 2009, disclosures of which are incorporated herein by reference. TECHNICAL FIELD
The present invention is related to a water and oil resistant agent for paper, a treatment process by the agent and the treated paper therewith.
BACKGROUND ART
The copolymer composition comprising a long chain C6-C12 polyfluoroalkyl group
(hereinafter called as "Rf group") has been utilized previously as the water and oil resistant agent for paper.
On the other hand, US EPA (United State Environment Protection Agency) pointed out that the long chain Rf group produces perfluoro-octanoic acid (hereinafter called as "PFOA") which might cause an influence on the environment.
Therefore, many efforts have been made to develop a water and oil resistant agent for paper by using a fluorine-containing copolymer having a short chain Rf group. The water resistance and the oil resistance, however, tend to decrease along with the decrease of the carbon number of the Rf group, and the water and oil resistance is not satisfactory. So, further improvements have to be made to provide a paper having an enough water and oil resistance.
Sugimoto et. al. (WO2009/057716), for example, proposed the water and oil resistant agent for paper comprising a fluorine-containing copolymer which contains, as essential polymer units, a fluorine-containing (meth)acrylate monomer having a Ci.C6 Rf group, a polyalkylene glycol (meth)acrylate monomer and itaconic acid. The water and oil resistance of this agent has been improved fairy well. A further improvement, however, is still required to attain usual properties of the copolymer having a long chain Rf group.
DISCLOSURE OF INVENTION
We, the inventors, surprisingly discovered that a paper-treatment agent comprising, as an essential component, a fluorine-containing copolymer having a short chain Rf, specified polymer units and a high molecular weight can exhibit a superior water and oil resistance. Thus, the present invention has been completed.
That is, the subject of the invention is related to a water and oil resistant agent for paper comprising a fluorine-containing copolymer comprising the repeating units derived from: (a) a fluorine-containing monomer having a fluoroalkyi group represented by the general formula:
CH2=C(-X)-C(=0)-Y-Z-Rf (1)
wherein X represents a hydrogen atom, a linear or branched to C2i alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX1X2 group wherein X1 and X2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a cyano group, a linear or branched C1-C21 fluoroalkyi group, a substituted or non-substituted benzyl group, or a substituted or non-substituted phenyl group;
Y is -O- or -NH-;
Z is a C1-C10 aliphatic group, a C6-C10 aromatic or cyclic aliphatic group,
a -CH2CH2N(R1)S02- group wherein R1 is a C C4 alkyl group,
a ^CH2CH(OZ1) CH2- group wherein Z1 is a hydrogen atom or an acetyl group, a -(CH2)m-S02-(CH2)n- group or a -(CH2)m-S-(CH2)n- group wherein m is 1-10 and n is 0-
10, and
Rf is a C C6 linear or branched fluoroalkyi group, (b) a hydrophilic monomer, and
(c) a monomer having an anion-donating group,
wherein a weight average molecular weight of the fluorine-containing copolymer is 100,000 or more. The weight average molecular weight is determined by the gel permeation chromatography measurement in terms of a molecular weight of polymethyl methacrylate.
The subject of the present invention is related to a process for treating a paper with the above-described water and oil resistant agent, and it is also related to a water and oil resistant paper obtained thereby.
EFFECT OF THE INVENTION
The present invention provides the water and oil resistant agent comprising a fluorine- containing copolymer, which agent affords the superior water and oil resistance to the paper. The present invention provides the process for the paper treatment by the water and oil resistant agent and the water and oil resistive paper obtained by utilizing the water and oil resistant agent.
MODE FOR CARRYING OUT THE INVENTION
In the present invention, the composition of the fluorine-containing copolymer has a great influence on the water and oil resistance of the water and oil resistant agent. The fluorine-containing copolymer used in the present invention is explained as follows. The fluorine-containing monomer (a) may be substituted by a halogen atom etc. at its a- position. Therefore, X in the formula (1 ) may be a hydrogen atom, a linear or branched Ci to C2i alky! group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX1X2 group wherein X1 and X2are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a cyano group, a linear or branched C1-C21 fluoroalkyl group, a substituted or non-substituted benzyl group, or a substituted or non-substituted phenyl group. In the formula (1 ), the Rf group is preferably a perfluoroalkyi group. The carbon number of the Rf group may be 1-6, especially 4-6, and typically 6. The examples of the Rf group are -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, -CF2CF(CF3)2, - C(CF3)3, -(CF2)4 CF3, -(CF2)2CF(CF3)2, - CF2C(CF3)3, -CF(CF3)CF2CF2CF3, -( CF2)5 CF3 and -( CF2)3CF(CF3)2 etc. Especially, -( CF2)5 CF3 is preferable.
Non-limiting examples of the fluorine-containing monomer (a) are exemplified as follows:
CH2=C( -H)-C(=0)-0-(CH2)2-Rf
CH2=C( -H)-C(=0)-0-C6H4-Rf
CH2=C( -CI)-C(=0)-0-(CH2)2-Rf
CH2=C( -H)-C(=0)-0-(CH2)2N(-CH3)S02-Rf
CH2=C( -H)-C(=0)-0-(CH2)2N(-C2H5) S02-Rf
CH2=C( -H)-C(=0)-0-CH2CH(-OH) CH2-Rf
CH2=C( -H)-C(=0)-0-CH2CH(-OCOCH3) CH2-Rf
CH2=C( -H)-C(=0)-0-(CH2)2-S-Rf
CH2=C( -H)-C(=0)-0-(CH2)2-S-(CH2)2-Rf
CH2=C( -H)-C(=0)-0-(CH2)3-S02-Rf
CH2=C( -H)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf
CH2=C( -H)-C(=0)-NH-(CH2)2-Rf
CH2=C( -CH3)-C(=0)-0-(CH2)2-S-Rf
CH2=C( -CH3)-C(=0)-0-(CH2)2-S-(CH2)2-Rf
CH2=C( -CH3)-C(=0)-0-(CH2)3-S02-Rf
CH2=C( -CH3)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf
CH2=C( -CH3)-C(=0)-NH-(CH2)2-Rf
CH2=C( -F)-C(=0)-0-(CH2)2-S-Rf
CH2=C( -F)-C(=0)-0-(CH2)2-S-(CH2)2-Rf
CH2=C( -F)-C(=0)-0-(CH2)2-S02-Rf
CH2=C( -F)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf
CH2=C( -F)-C(=0)-NH-(CH2)2-Rf CH2=C(-CI)-C(=0)-0-(CH2)2-S-Rf
CH2=C(-CI)-C(=0)-0-(CH2)2-S-(CH2)2-Rf
CH2=C(-CI)-C(=0)-0-(CH2)2-S02-Rf
CH2=C(-CI)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf CH2=C(-CI)-C(=0)-NH-(CH2)2-Rf
CH2=C(-CF3)-C(=0)-0-(CH2)2-S-Rf
CH2=C(-CF3)-C(=0)-0-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF3)-C(=0)-0-(CH2)2-S02-Rf
CH2=C(-CF3)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf CH2=C(-CF3)-C(=0)-NH-(CH2)2-Rf
CH2=C(-CF2H)-C(=0)-0-(CH2)2-S-Rf
CH2=C(-CF2H)-C(=0)-0-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF2H )-C(=0)-0-(CH2)2-S02-Rf
CH2=C(-CF2H )-C(=0)-0-(CH2)2-S02-(CH2)2-Rf CH2=C(-CF2H )-C(=0)-NH-(CH2)2-Rf
CH2=C(-CN)-C(=0)-0-(CH2)2-S-Rf
CH2=C(-CN)-C(=0)-0-(CH2)2-S-(CH2)2-Rf
CH2=C(-CN )-C(=0)-0-(CH2)2-S02-Rf
CH2=C(-CN )-C(=0)-0-(CH2)2-S02-(CH2)2-Rf CH2=C(-CN )-C(=0)-NH-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=0)-0-(CH2)2-S-Rf
CH2=C(-CF2CF3)-C(=0)-0-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF2CF3 )-C(=0)-0-(CH2)2-S02-Rf
CH2=C(-CF2CF3 )-C(=0)-0-(CH2)2-S02-(CH2)2-Rf CH2=C(-CF2CF3 )-C(=0)-NH-(CH2)2-Rf
CH2=C(-F)-C(=0)-0-(CH2)3-S-Rf
CH2=C(-F)-C(=0)-0-(CH2)3-S-(CH2)2-Rf
CH2=C(-F)-C(=0)-0-(CH2)3-S02-Rf
CH2=C(-F)-C(=0)-0-(CH2)3-S02-(CH2)2-Rf CH2=C(-F)-C(=0)-NH-(CH2)3-Rf
CH2=C(-CI)-C(=0)-0-(CH2)3-S-Rf
CH2=C(-C[)-C(=0)-0-(CH2)3-S-(CH2)2-Rf
CH2=C(-CI)-C(=0)-0-(CH2)3-S02-Rf
CH2=C(-CI)-C(=0)-0-(CH2)3-S02-(CH2)2-Rf
CH2=C(-CF3)-C(=0)-0-(CH2)3-S-Rf
CH2=C(-CF3)-C(=0)-0-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF3)-C(=0)-0-(CH2)3-S02-Rf
CH2=C(-CF3)-C(=0)-0-(CH2)3-S02-(CH2)2-Rf
CH2=C(-CF2H)-C(=0)-0-(CH2)3-S-Rf
CH2=C(-CF2H)-C(=0)-0-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF2H )-C(=0)-0-(CH2)3-S02-Rf
CH2=C(-CF2H )-C(=0)-0-(CH2)3-S02-(CH2)2-Rf
CH2=C(-CN)-C(=0)-0-(CH2)3-S-Rf
CH2=C(-CN)-C(=0)-0-(CH2)3-S-(CH2)2-Rf
CH2=C(-CN)-C(=0)-0-(CH2)3-S02-Rf
CH2=C(-CN)-C(=0)-0-(CH2)3-S02-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=0)-0-(CH2)3-S-Rf
CH2=C(-CF2CF3)-C(=0)-0-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF2CF3 )-C(=0)-0-(CH2)3-S02-Rf
CH2=C(-CF2CF3 )-C(=0)-0-(CH2)2-S02-(CH2)2-Rf
wherein Rf is a fluoroalkyi group of CrC6, preferably C4-C6.
The fluoroalkyi group (Rf) in the fluorine-containing monomer (a) may be, preferably a perfluoroalkyl group, and most preferably a C4-C6 perfluoroalkyl group.
The fluorine-containing monomer (a) may be a mixture of two or more types of monomers. The amount of the fluorine-containing monomer (a) may be 40-90 wt%, more preferably 45-85 wt%, most preferably 60-85 wt% based on the fluorine-containing copolymer. The hydrophilic monomer (b) is at least one oxyaikylene (meth)acrylate, preferably represented by the general formulas:
CH2=CX1C(=0)-0-(RO)n-X2 (2a)
and
CH2=CX1C(=0)-0-(RO)n-C(=0)CX1=CH2 (2b)
wherein X1 is a hydrogen atom or a methyl group;
X2 is a hydrogen atom or a saturated or unsaturated C1-C22 hydrocarbon group;
R is a C2-C6 alkylene group; and
n is an integer of 1-90,
wherein polyoxyalkylene (meth)acrylate and/or 2-hydroxyethyl (meth)acrylate are exemplified.
The oxyaikylene group is preferably C2 - C6, more preferably C2 - C4. The average polymerization degree of oxyalylene groups in the polyoxyalkylene group may be 2 to 20, preferably 2 to 10.
The following compounds are exemplified as the oxyaikylene (meth)acrylate:
CH2=CH-C(=0)-0-CH2CH2OH, CH2=C(CH3)-C(=0)-0-CH2CH2OH, CH2=CH-C(=0)-0- (CH2CH20)2H, CH2=CH-C(=0)-0-(CH2CH20)3H, CH2=CH-C(=0)-0-(CH2CH20)1 , H, CH2=CH-C(=0)-0-(CH2CH20)12H, CH2=C(CH3)-C(=0)-0-(CH2CH20)2H, CH2=C(CH3)-
Figure imgf000008_0001
(CH2CH20)i2H, CH2=CH-C(=0)-0-(CH2)2-OCH3, CH2=CH-C(=0)-0-(CH )2-OCH2CH3, CH2=C(CH3)-C(=0)-0-(CH2)2-OCH3, CH2=C(CH3)-C(=0)-0-(CH2)2-OCH2CH3, CH2=CH- C(=0)-0-(CH2CH20)C(=0)-CH=CH2, CH2=CH-C(=0)-0-(CH2CH20)2C(=0)-CH=CH2, CH2=C(CH3)-C(=0)-0-(CH2CH20)C(=0)-CH=CH2, CH2=C(CH3)-C(=0)-0-
(CH2CH20)2C(=0)-CH=CH2.
The oxyaikylene (meth) acrylate may be preferably (b1 ) ω-hydroxy-polyoxyalkylene (meth) acrylate and/or (b2) 2-hydroxyethyl (meth) acrylate. The monomer (c) is a compound having an anion-donating group and a carbon-carbon double bond. The anion-donating group may be a carboxyl group or a sulfonic acid group. The monomer (c) may be preferably at least one selected from the group consisting of (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic cid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrene sulfonic aicd, vinylbenzene sulfonic acid, acrylamide-tert-butylsulfonic acid, and salts thereof. The especially preferable monomer (c) is (meth)acrylic acid.
In the fluorine-containing copolymer, the amount of the monomer (a) may be 40 - 90 wt% preferably 60 - 85 wt%, the amount of the monomer (b) may be 2 - 50 wt%, preferably 5- 35 wt%, and the amount of the monomer (c ) may be 0.1 - 30 wt%, preferably 1 - 15 wt% The hydrophilic monomer (b) preferably comprises (b1) ω-hydroxy-polyoxyethylene (meth)acrylate and/or (b2) 2-hydroxyethyl (meth)acrylate, and the wt% range of the monomer (b) is equal to the sum amount of (b1 ) and (b2). That is, the ratio in wt% among monomers (a), (b1 ), (b2) and (c) may be preferably in the range of (a) : (b1 ) : (b2) : (c) = 60- 85: 1- 15: 5- 20: 1-15.
In the present invention, both the composition of the fluorine-containing copolymer and the molecular weight of the fluorine-containing copolymer greatly influence the water and oil resistance. The weight average molecular weight of the fluorine-containing copolymer of the present invention is 100,000 or more, preferably, 100,000 to 3,000,000, and further preferably 120,000 to 2,000,000. When the molecular weight is in these ranges, satisfactory water and oil resistance and viscosity properties are obtained.
The preferable embodiments of the fluorine-containing copolymer of the present invention are described below:
The first preferable embodiment of the monomer composition for the fluorine-containing copolymer comprises at least one fluorine-containing monomer (a) wherein Rf represents a perfluoroalkyl group having 4 - 6 carbon atoms, the hydrophilic monomer (b) containing at least one of ω-hydroxy-polyoxyalkylene (meth)acrylate (b1 ) and/or 2-hydroxyethyl (meth)acrylate (b2) and
the anion donating group-containing monomer (c) selected from the group consisting of (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid.
Specifically is exemplified the embodiment wherein the fluorine-containing monomer (a) is F(CF2)4CH2CH2OCOCH=CH2 , F(CF2)6CH2CH2OCOCH=CH2 or a mixture thereof, the hydrophilic monomer (b) is ω-hydroxy-polyoxyalkylene (meth)acrylate (b1) and/or 2- hydroxyethyl (meth)acrylate (b2), and the anion donating group-containing monomer (c) is (meth)acrylic acid.
Further specifically is exemplified the embodiment wherein the fluorine-containing monomer (a) is F(CF2)4CH2CH2OCOCH=CH2 , F(CF2)6CH2CH2OCOCH=CH2 or a mixture thereof, the hydrophilic monomer (b) is ω-hydroxy-polyoxyethylene
(meth)acryiate (b ) (the average polymerization degree of polyoxyethylene is 2 to 10) and/or 2-hydroxyethyl (meth)acrylate (b2), and the anion donating group containing monomer (c) is (meth)acrylic acid, the weight ratio of (a) : (b) : (c) is 60 - 85: 5 - 35: 1-15, and the weight average molecular weight of the obtained fluorine-containing polymer is 120,000 to 2,000,000.
The present invention also relates to a process for a water and oil resistant treatment of a paper, which process comprises a step of applying the water and oil resistant agent of the present invention to the surface of the paper. This treatment process is hereinafter called as "surface application process". In this process, it is preferable to apply the water and oil resistant agent comprising a fluorine-containing copolymer in such amount that the weight ratio of the fluorine atoms to the paper is 0.005 to 0.6 wt%.
The present invention also relates to a process for a water and oil resistant treatment of a paper, which process comprises a step of applying the water and oil resistant agent of the present invention to the whole of the paper including its internal parts. This treatment process is hereinafter called as "internal application process". In this process, the water and oil resistant agent of the present invention comprising a fluorine-containing copolymer is applied in the papermaking step from pulp. Specifically, it is preferable to apply the water and oil resistant agent in such amount that the weight ratio of the fluorine atoms to the paper is 0.01 to 1.0 wt%.
The present invention also relates to a water and oil resistant paper treated by the water and oil resistant agent of the present invention.
The present invention also relates to a paper obtained by the surface application process and the internal application process.
The production of the fluorine-containing copolymer of the present invention can be carried out by polymerizing monomers (a), (b) (or (b1 ) and/or (b2)) and (c) in a liquid medium. The liquid medium is preferably water soluble or water dispersible solvent. The liquid medium may be a mixture comprising the water soluble or water dispersible solvent. The monomer and the liquid medium preferably are in a form of a solution wherein the monomer is disolved in the liquid medium. The polymerization may be a solution polymerization or an emulsion polymerization, preferably a solution
polymerization in view of stability of polymerization reaction.
In this invention, the monomer (c) (an anion donating group) may be neutralized with a base (such as an aqueous solution of inorganic or organic base) after conducting the copolymerization; or the copolymerization may be carried out using the monomer (c) neutralized with the base in advance. When the monomers are polymerized after the monomer (c) is neutralized with the base in advance, the neutralization with a basic aqueous solution after copolymerization is not necessary. 65191
11
As the inorganic or organic bases, the followings are exemplified:
sodium hydroxide, potassium hydroxide, ammonia, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-sec-butylamine, ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-aminomethyl-1 ,3-propanediol, 2-amino- 2-hydroxymethyl-1 ,3-propanediol, bis (hydroxymethyl) methylaminomethane, tris
(hydroxymethyl) aminomethane, lysine, and arginine, etc. Among these bases, sodium hydroxide, potassium hydroxide, ammonia, triethylamine, diethanolamine and
triethenolamine etc. are preferable from the view point of the improvement of the dispersing stability of the obtained fluorine-containing copolymer in the aqueous medium.
The polymer mixture after copolymerization may be, if necessary, diluted by adding the liquid medium (for example, water or an aqueous solution containing inorganic or organic bases).
As non-limiting examples of the water-soluble or water-dispersible organic solvents utilized in copolymerization, the followings are exemplified: ketones (for example, acetone or methyl ethyl ketone), alcohols (for example, methanol, ethanol and isopropanol), ethers (for example, methyl or ethyl ether of ethylene glycol or propylene glycol, acetate ester thereof, tetrahydrofuran and dioxane), acetonitrile,
dimethylformamide, N-methyl-2-pyrollidone, butyllactone and dimethylsulfoxide, etc. Among them, methyl ethyl ketone (MEK), N-methyl-2-pyrollidone (NMP), a mixture of N- methyl-2-pyrollidone and acetone, isopropanol or methanol is preferable as a solvent. The total monomer concentration in the solution may be in the range of 20 - 70 wt%, preferably, 40 - 60 wt%.
The copolymerization may be carried out using at least one initiator in the range of 0.1 - 3.0 wt% based on the total weight of the monomers. The following initiators may be used: peroxides such as benzoyl peroxide, lauroyl peroxide, succinyl peroxide and ter- butyl peroxypivalate, or azo-compounds such as 2, 2-azobis-isobutylonitrile, 4, 4-azobis (4-cyanopentanoic acid) and azodicarbonamide.
A chain transfer agent may be used for controlling the molecular weight of the copolymer. As the chain transfer agent, alkylmercaptan (dodecylmercaptan, laury!mercaptan, stearylmercaptan, etc.), aminoethanethiol, mercaptoethanol, thioglycollic acid, and 2- mercaptopropionic acid etc. are preferably exemplified. The amount of the chain transfer agent used may be in a range of 0.05 - 1 parts by weight based on 100 parts by weight of the total monomers in the copolymerization. The copolymerization can be carried out in the range between 40 °C and the boiling point of the reaction mixture. The dilution step may be carried out by adding a liquid medium, for example, water or an aqueous solution of a strong or moderate inorganic or organic base into the organic solution of fluorine-containing copolymer in organic solvent. The above described bases are exemplified as such a base usable for the dilution step.
Among them, sodium hydroxide and ammonia are preferably used. The amount of the aqueous solution and the concentration of the base are preferable to be sufficiently enough firstly to neutralize the carboxylic acid group or the sulfonic acid group, and secondly to attain the solid concentration of the fluorine-containing copolymer of 5 - 35 wt%, preferably 15 - 25 wt% in the final copolymer solution. In order to neutralize the carboxylic acid group and the sulfonic acid group, it is advantageous to make the amount of base in the range of 0.1 - 5 eq., preferably 0.5 -3 eq. based on the monomer (c).
The paper to which the water and oil resistant agent comprising the fluorine-containing copolymer of the present invention is to be applied can be produced by the conventional paper making method. Both the internal application process and the surface application process may be used. In the internal application process, the treating agent is added to the pulp slurry before paper making, and in the surface application process, the treating agent is added to the paper after paper making. In case of applying the water and oil resistant agent of the present invention to the surface of the paper (surface application process), it is preferable to use the water and oil resistant agent in such amount that the weight ratio of the fluorine atoms is in the range of 0.005 - 0.6 wt%, preferably 0.01 - 0.4 wt% based on the weight of the paper. On the other hand, in case of applying the water and oil resistant agent to the whole paper including its internal parts, it is preferable to use the water and oil resistant agent in such amount that the weight ratio of the fluorine atoms is in the range of 0.01 - 1.0 wt%, especially, 0.02 - 0.6 wt% based on the weight of the pulp.
The paper substrate thus treated exhibits a superior oil and water resistance after heat treatment at room temperature or at high temperature, or if necessary depending on the nature of the paper substrate, by accompanying a heat treatment which can be at a higher temperature of at most 300 °C, for example, at most 200 °C.
The paper substrate treated by the process of the present invention is exemplified as follows: a raw paper for plaster board, a coated raw paper, a wood-containing paper, a general liner and a flute, a neutral white role paper, a neutral liner, an anti-corrosion liner, a paper combined with metal and a kraft paper, etc. The following paper substrate are further exemplified: a neutral paper for printing and writing, a neutral coated raw paper, a neutral paper for PPC, a neutral heat-sensitive paper, a neutral pressure-sensitive paper, a neutral paper for ink-jet, and a neutral paper for information industry. Other papers such as a mold paper formed by molding, especially, a molded paper vessel, are exemplified. A pulp-molded vessel can be produced by the process described in the JP9-183429A.
The following materials can be utilized as a starting pulp materials for paper: a bleached or unbleached chemical pulp such as a kraft pulp or a sulfite pulp, a bleached or unbleached high-yield pulp such as a grand pulp, a mechanical pulp or a thermo- mechanical pulp, and a waste pulp such as a waste paper of newspaper, magazine, cardboard or deinked paper, etc. The mixtures may be also utilized between the pulp materials above mentioned and any one of synthetic fibers such as polyamide, polyimide, polyester, polyolefin and polyvinylalcohol, etc.
When the surface application process and the internal application process are applied, a size agent, in addition to the water and oil resistant agent, can be added optionally to improve the water resistance of the paper. The examples of the size agent are a cationic size agent, an anionic size agent and a rosin size agent (for example, an acidic rosin size agent, a neutral rosin size agent). Among them, a styrene-acrylic acid copolymer, alkenylsuccinic anhydride and an alkylketene dimer are preferable. The amount of the size agent may be 0.001 - 5 wt% based on the amount of the pulp.
If necessary, other agents generally added to the paper-treatment agent may be used: a paper strengthening agent such as starch, various modified starch, caroboxymethyl- cellulose, polyamidepolyamine-epichlorohydrin (PEA), polydiallyldimethylammonium chloride (poly-DADMAC) and polyamide etc., a retention aid, a dyestuff, a fluorescent dyestuff, a filler, a pigment, a slime-controlling agent, an anti-slipping agent, a deformer, etc. In the surface application process, the paper-treatment agents can be applied to the paper by means of a size press, coating (a gate roll coater, a bill blade coater and a bar coater, etc.).
The followings are examples which specifically explain the present invention. These examples are for the explanation of the present invention, but do not limit the present invention. The terms "parts" and "%" read, if not specified, "parts by weight" and "weight %", respectively.
The testing methods used in the examples are described as follows:
"Viscosity"
A viscosity of a solution was measured using a rotary viscometer at a controlled solution temperature of 25 °C. "Stability test"
The stability of the dispersion of fluorine-containing copolymer in water (aqueous dispersion) was observed as follows: An aqueous dispersion having a solid content being adjusted to 20 wt% was left standing for seven days at room temperature in 110ml clear glass sample pot, and its dispersion state was visually observed by eyes whether a sedimentation or a coagulation occurred or not. The evaluation was summarized as follows: "Good" stands for absence of sedimentation or coagulation; "Fair" stands for fractional sedimentation or aggregation; "Poor" stands for large sedimentation or coagulation.
"Water resistance test: Cobb test (JIS P8 40)"
The test consists of measuring the weight (g) of the water absorbed in one minute by the paper having 1 m2 area and supporting 1 cm height of water.
"Oil resistance test (Kit Test)"
The oil resistance was measured according to the TAPPI T-559 cm-02 method. A drop of the test oil shown in Table 1 was placed on the paper, then, the infiltration state of the oil was observed after 15 seconds. The maximum point of an oil resistance given by the oil having no infiltration was assigned to be an oil resistance of the paper.
Table 1
Degree of oil Caster oil Toluene n-Heptane
resistance
1 100 0 0
2 90 5 5
3 80 10 10
4 70 15 15
5 60 20 20
6 50 25 25
7 40 30 30
8 30 35 35
9 20 40 40
10 10 45 45
11 0 50 50
12 0 45 55
"AGR (Aggressive-grease Resistance) Test"
This test is particularly useful to verify the anti-grease paper suitability for the pet-food packaging. Briefly, this test implies the contact in standardized conditions of the petfood with the paper specimen to be tested. The pet-food with the trademark
Sciencediet (produced by Hill's corp.) was used as the pet-food for testing. The petfood is finely milled in a mixer. An anti-grease paper specimen, having 10 x 10 cm sizes, is cut out to be tested, and placed over a coated paper sheet on which a grid of 100 small squares is printed, having a surface exactly equal to that of specimen to be tested. Before fitting the position on the grid, the specimen is slightly creased. First of all, the specimen is folded back along the line connecting the centers of the facing two edges, and the crease is reinforced by a proper roll (weight: 2450+110 g; diameter: 8 cm; width: 7 cm) covered with a rubber layer with 0.6 cm thickness and having a controlled hardness. The roll speed is 50 - 60 cm/sec. during the creasing. The first crease is formed along the line connecting the centers of the facing two edges, and the second crease is formed on the opposite side of the paper. The creased specimen is placed on the grid to cover the grid surface completely. A metal ring having an internal diameter equal to 7.2 cm and height equal to 2.5 cm is placed in the middle of the specimen.
Then 36 g of milled pet-food are taken, which are homogeneously paced inside the ring on the paper specimen to be tested. A weight equal to 1.5 kg, cylinder-shaped, having lower surface smooth as that of the ring, is then placed on the milled pet-food applied to the paper specimen. The whole is put in a stove at 60 °C and 50% humidity for 24 hours. This time elapsed, the weight and the pet-food are removed and the specimen surface is tested to find fat stains, which would witness the occurred fat penetration. The test result is expressed in terms of percentage of stained surface. To have a significant result, the test is carried out on at least 4 specimens subjected to the same treatment and the final result is the average of the 4 tests.
Synthesis Example 1
Hundred (100) parts by weight of methyl ethyl ketone (MEK) as a solvent was introduced into a 500 ml reaction vessel equipped with a stirrer, a thermometer, a refluxing condenser, a dropping funnel, a nitrogen gas inlet and a heater. Then, under stirring, a monomer consisting of 77 parts of F(CF2)6CH2CH20COCH=CH2 (hereinafter called as "C6FA"), 13 parts of 2-hydroxyethyl methacrylate (HE A), 5 parts of ω-hydroxy- polyoxyethyleneacrylate (BLEMMERR AE-200 produced by NOF: the average degree of polymerization of the polyoxyethylene group = 4.5) and 5 parts of methacrylic acid (MAA) (the total amount of monomer is 100 parts), and an initiator, 4,4'-azobis (4- cyanopentanoic acid) (0.5 parts) were added in these sequences to obtain a mixture, which was further stirred for 12 hrs. under the nitrogen atmosphere at 70 °C to complete the copolymerization, thereby giving a solution (S1). The solid concentration of the obtained solution containing the copolymer (S1) was 50 wt%. The molecular weight of the obtained fluorine-containing copolymer was measured by the gel permeation chromatography, and the weight average molecular weight was 500,000 in terms of the molecular weight of polymethyl methacrylate. Synthesis Example 2
The copolymerization was carried out by following the same procedure as Synthesis Example 1 except that lauryimercaptane (L-SH) in 0.1 parts was additionally charged as the chain transfer agent and the initiator was replaced by tert-butyl peroxypivalate in 0.5 parts, to give a solution (S2) containing the copolymer. The solid content of the solution (S2) was 50 wt%. The weight average molecular weight was 150,000 in terms of the molecular weight of polymethyl methacrylate.
Synthesis Example 3
The copolymerization was carried out by following the same procedure as Synthesis Example 1 except that the amount of F(CF2)6CH2CH2OCOCH=CH2 (C6FA) was 74 parts, the amount of 2-hydroxyethyl methacrylate (HEMA) was 16 parts, and the initiator was replaced by tert-butyl perpivalate in 0.5 parts, to give a solution (S3) containing the copolymer. The solid content of the solution (S3) was 50 wt%. The weight average molecular weight was 500,000 in terms of the molecular weight of polymethyl
methacrylate.
Synthesis Example 4
The copolymerization was carried out by following the same procedure as Synthesis Example 1 except that itaconic acid (IA) was used in 5 parts instead of methacrylic acid (MAA). The solid content of the solution (S4) obtained was 50 wt%. The weight average molecular weight was 180,000 in terms of the molecular weight of polymethyl methacrylate.
Comparative Synthesis Example 1 0 065191
19
The copolymerization was carried out by following the same procedure as Synthesis Example 1 except that laurylmercaptane (L-SH) in 0.3 parts was additionally charged as the chain transfer agent. The obtained solid content of the solution (R1 ) containing the copolymer was 50 wt%. The weight average molecular weight was 50,000 in terms of the molecular weight of polymethyl methacrylate.
Comparative Synthesis Example 2
The copolymerization was carried out by following the same procedure as Synthesis Example 1 except that laurylmercaptane (L-SH) in 1.0 part was additionally charged as a chain transfer agent. The obtained solid content of the solution (R2) containing the copolymer was 50 wt%. The weight average molecular weight was 10,000 in terms of the molecular weight of polymethyl methacrylate.
Comparative Synthesis Example 3
The copolymerization was carried out following the same procedure as Synthesis
Example 2 except that itaconic acid (IA) was used in 5 parts instead of methacrylic acid (MAA). The obtained solid content of the solution (R3) containing the copolymer was 50 wt%. The weight average molecular weight was 45,000 in terms of the molecular weight of polymethyl methacrylate.
The results of the viscosity measurement of the solutions obtained in Synthesis
Examples 1 - 4 and in Comparative Synthetic Examples 1 - 3 are shown in Table 2.
Figure imgf000020_0001
Preparation Example 1 A pale yellow aqueous dispersion containing fluorine-containing copolymer (the content of the volatile organic solvent being less than 1 wt%) was obtained by the following sequential procedures: Adding 1.2 g of an aqueous 23 % ammonia solution and 90 g of an ion-exchanged water to the solution (S1) containing the fluorine-containing copolymer obtained in Synthesis Example 1 , preparation of an emulsified dispersion and
evaporating MEK under reduced pressure by heating. To this aqueous dispersion is further added the ion-exchanged water to obtain an aqueous dispersion (SD1 ) having a solid content of 20 wt%.
The dispersion stability of the SD1 obtained was evaluated in the above described method, and the obtained results are shown in Table 3.
Preparation Examples 2 and 3
As to the solutions (S2 and S3) obtained in Synthesis Examples 2 and 3, the same procedures as Preparation Example 1 were carried out except that 6.0 g of an aqueous 10 wt% sodium hydroxide solution as a base and 85 g of ion-exchange water were used, to give an aqueous dispersions (SD2 and SD3) having a solid content of 20 wt%. The dispersion stability of the SD2 and SD3 were measured, and the obtained results are shown in Table 3. Preparation Example 4
As to the solution (S4) obtained in Synthesis Example 4, the same procedure as
Preparation Example 1 was carried out except that 1.3 g of diethanolamine as a base was used, to give an aqueous dispersions (SD4) having a solid content of 20 wt%. The dispersion stability of the SD4 was measured, and the obtained results are shown in Table 3.
Comparative Preparation Examples 1 and 2
As to the solutions (R1 and R2) obtained in Comparative Synthesis Examples land 2, the same procedures as Preparation Example 1 were carried out, to give an aqueous 10 065191
21 dispersions (RD1 and RD2) having a solid content of 20 wt%. The dispersion stabilities of the RD1 and RD2 were measured, and the obtained results are shown in Table 3.
Comparative Preparation Example 3
As to the solution (R3) obtained in Comparative Synthesis Example 3, the same procedure as Preparation Example 1 was carried out except that 1.3 g of diethanolamine was used as the base, to give an aqueous dispersion (RD3) having a solid content of 20 wt%. The dispersion stability of the RD3 was measured, and the obtained results are shown in Table 3.
Example 1 (Evaluation in the surface application process)
Preparation of a paper to be tested
A paper to be tested was produced by using a test paper machine installed in the
Western Michigan University in U.S.A. The production process is shown below.
The types of pulp used were LBKP (Leaf Bleached Kraft Pulp) and NBKP (Needle Bleached Kraft Pulp), and their ratio was 6/4 (L/N) and the freeness of the pulp was 400 ml (Canadian Standard Freeness).
In slurry of the pulp having a concentration of about 2 %, a cationic starch Stayloc 400 (produced by Tate and Lyle) was added in 2 wt% based on the dried pulp weight, and further a size agent Hereon 70 (produced by Hercules corp.) was added in 0.0375 wt% based on the dried pulp weight. A paper was produced from the pulp slurry by using a fourdrinire machine. The basis weight of the paper obtained was 60 g/cm2 and the thickness was 0.01 mm. The water resistance (Cobb value) was 80 g/cm2, and the oil resistance (Kit value) was 0.
The water and oil resistant paper (treated paper) was produced in following to the procedure described below using, as an water and oil resistant agent, the aqueous dispersion solution (SD1) containing the fluorine-containing copolymer obtained in Preparation Example 1 The aqueous dispersion solution (SD1) containing the fluorine-containing copolymer obtained in Preparation Example 1 was diluted to adjust the solid content to 0.2 wt% to give the water and oil resistant composition.
The paper prepared above was dipped in the water and oil resistant composition for 5 minutes and dried at 115 °C for 70 seconds to obtain a raw paper for test.
Using the raw paper obtained above as the testing paper, the Kit Test and the Cobb Test mentioned above were carried out. The obtained results are shown in Table 3. Examples 2 - 4 (Evaluation in the surface application process)
Using, as water and oil resistant agents, the aqueous dispersion solutions (SD2 - SD4) containing the fluorine-containing copolymer obtained in Preparation Examples 2 - 4, the water and oil resistant compositions were obtained by diluting the aqueous dispersion solutions (SD2 - SD4) to adjust the solid content to 0.2 wt%. Using each composition, the Kit Test and the Cobb Test were carried out in the same way as Example 1. The obtained results are shown in Table 3.
Comparative Examples 1 - 3 (Evaluation in the surface application process)
Using, as water and oil resistant agents, the aqueous dispersion solutions (RD1 - RD3) containing the fluorine-containing copolymer obtained in Comparative Preparation
Examples 1 - 3, the water and oil resistant compositions were obtained by diluting the aqueous dispersion solutions (RD1 - RD3) to adjust the solid content to 0.2 wt%. Using each composition, the Kit Test and the Cobb Test were carried out in the same way as the Example 1. The obtained results are shown in Table 3. Table 3 (Evaluation results in the surface application process: Examples 1 - 4)
- Exp.1 Exp.2 Exp. 3 Exp. 4
Fluorine-c Copolymer solution No. S1 S2 S3 S4 ontaining
C6FA 77 77 74 77 Copolymer
HEMA 13 13 16 13 Solution Monomer comp.
AE-200 5 5 5 5 (parts by weight)
MAA 5 5 5 -
IA - - - 5
Chain transfer agent (L-SH) (parts by
0 0.1 0 0 weight)
Molecular weight of
Mw 500,000 150,000 500,000 180,000 copolymer
Aqueous Aqueous dispersion No. SD1 SD2 SD3 SD4 Dispersion Oil resistance: Kit value 8 8 8 7
Water resistance: Cobb value (g/m2) 25 25 25 27
Dispersion stability Good Good Good Good
Table 3 (continued) (Evaluation results in the surface application process:
Comparative Examples 1 - 3)
- Comp. Comp. Comp.
Exp.1 Exp.2 Exp. 3
Fluorine-c Copolymer solution No. R1 R2 R3
ontaining
C6FA 77 77 77
Copolymer
HEMA 13 13 13
Solution Monomer comp.
AE-200 5 5 5
(parts by weight)
MAA 5 5 -
IA - - 5
Chain transfer agent (L-SH) (parts
0.3 1 0.1
by weight)
Molecular weight of
Mw 50,000 10,000 45,000
copolymer
Aqueous Aqueous dispersion No. RD1 RD2 RD3
Dispersion Oil resistance: Kit value 8 9 9
Water resistance: Cobb value (g/m2) 50 76 25
Dispersion stability Good Poor Poor
From the results of Table 3, it is understood that the oil resistance, the water resistance and the dispersion stability of Examples 1 - 4 are all good, whereas in Comparative Examples 1 and 2, the water resistance is poor, and in Comparative Examples 2 and 3, the dispersion stability is poor.
Example 5 (Evaluation in the internal application process)
An aqueous dispersion (875 g) containing a 0.5 wt% mixture of 40 parts of a beaten LBKP (Leaf Bleached Kraft Pulp) and 60 parts of a beaten NBKP (Needle Bleached Kraft Pulp) having a freeness of 450 ml (Canadian Standard Freeness) was introduced under stirring into the flask, then, 3.06 g of an aqueous solution containing 1 wt% of the cationic starch (SB GUM-POSIT300 produced by SANGUAN WONGSE IND. CO., LTD) was added and the stirring was continued for 1 minuets, then 1.31 g of an aqueous solution containing 1 wt% of polyamidoamine-epichlorohydrin (WS-4020 produced by Japan
PMC Co., Ltd., a paper strengthening agent in wet condition) was added and the stirring was continued for 1 minuets, then 1.31 g of the diluted aqueous dispersion (SD1) containing 1 wt% of the fluorine-containing copolymer was added and the stirring was continued for 1 minuets.
The resultant pulp slurry was made into paper with a standard hand papermaking machine described in J IS P8222 (The hand papermaking machine was modified to give a paper having a size of 25 cm x 25 cm).
The resultant wet paper was pressed between filter paper sheets under a pressure of 3.5 kg/cm2 so as to sufficiently absorb water contained in the paper. The paper was dried over a drum drier (115°C x 70 seconds) to obtain a water and oil resistant paper.
The basis weight of the resultant paper was 70 g/m2. The water resistance (Cobb value) of this hand sheet paper was 100 g/m2 or more, and the oil resistance (Kit value) was 0, and the oil resistance (AGR) was 100.
Examples 6 and 7 (Evaluation in the internal application process)
The same procedures in Example 5 were carried out except that the aqueous dispersions (SD2 and SD3) containing the fluorine-containing copolymer were used instead of the aqueous dispersion (SD1) containing the fluorine-containing copolymer in the Example 5. The water resistance and the oil resistance of the obtained water and oil resistant papers were evaluated, and these results are shown in Table 4.
Comparative Examples 4 - 6 (Evaluation in the internal application process)
The same procedures as in Example 5 were carried out except that the aqueous dispersions (RD1 - RD3) containing the fluorine-containing copolymer were used instead of the aqueous dispersion (SD1 ) containing the fluorine-containing copolymer in Example 5. The water resistance and the oil resistance of the obtained water and oil resistant papers were evaluated, and these results are shown in Table 4.
Exp. 5 Exp. 6 Exp. 7
Fluorine-con Copolymer solution No. S1 S2 S3
taining
C6FA 77 77 74
Copolymer
HEMA 13 13 16
Solution Monomer comp.
AE-200 5 5 5
(parts by weight)
MAA 5 5 5
IA - - -
Chain transfer agent (L-SH) (parts
0 0.1 0
by weight)
Molecular weight
Mw 500,000 150,000 500,000
of copolymer
Aqueous Aqueous dispersion No. SD1 SD2 SD3
Dispersion Oil resistance: Kit value 8 8 8
Oil resistance: AGR value 10 8 10
Water resistance: Cobb value 25 25 25
(g/m2)
Dispersion stability Good Good Good Table 4 (continued) (Evaluation results in the Internal application process:
Comparative Examples 4 - 6)
- Comp. Exp. Comp. Comp.
4 Exp. 5 Exp. 6
Fluorine-c Copolymer solution No. R1 R2 R3
ontaining
C6FA 77 77 77
Copolymer
HEMA 13 13 13
Solution Monomer comp.
AE-200 5 5 5
(parts by weight)
MAA 5 5 -
IA - - 5
Chain transfer agent (L-SH) (parts
0.3 1 0.1 by weight)
Molecular weight of
Mw 50,000 10,000 45,000
copolymer
Aqueous Aqueous dispersion No. RD1 RD2 RD3
Dispersion Oil resistance: Kit value 8 9 9
Oil resistance: AGR value 10 15 35
Water resistance: Cobb value (g/m2) 50 76 25
Dispersion stability Good Poor Poor
From the results of Table 4, it is understood that the oil resistance, the water resistance and the dispersion stability of Examples 5 - 7 are all good, whereas in Comparative Examples 4 and 5, the water resistance is poor, and in the comparative Examples 5 and
6, the dispersion stability is poor.

Claims

1. A water and oil resistant agent for paper comprising a fluorine-containing copolymer comprising the repeating units derived from:
(a) a fluorine-containing monomer having a fluoroalkyl group represented by the general formula:
CH2=C(-X)-C(=0)-Y-Z-Rf (1)
wherein X represents a hydrogen atom, a linear or branched Ci to C2 alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX X2 group wherein X1 and X2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a cyano group, a linear or branched C C2i fluoroalkyl group, a substituted or non-substituted benzyl group, or a substituted or non-substituted phenyl group;
Y is -O- or -NH-;
Z is a C C10 aliphatic group, a C6-Cio aromatic or cyclic aliphatic group, a - CH2CH2N(R )S02- group wherein R1 is a C C4 alkyl group,
a -CH2CH(OZ1) CH2- group wherein Z is a hydrogen atom or an acetyl group), a -(CH2)m-S02-(CH2)n- group or a -(CH2)m-S-(CH2)n- group wherein m is 1-10 and n is 0-
10, and
Rf is a Ci-C6 linear or branched fluoroalkyl group,
(b) a hydrophilic monomer, and
(c) a monomer having an anion-donating group,
wherein a weight average molecular weight of the fluorine-containing copolymer is 100,000 or more. 2. The water and oil resistant agent for paper claimed in claim 1 , wherein the fluoroalkyl group (Rf group) in the monomer (a) is a perfluoroalkyi group.
3. The water and oil resistant agent for paper claimed in claim 1 , wherein the fluoroalkyl group (Rf group) in the monomer (a) is the perfluoroalkyi group having 4 to 6 carbon atoms.
4. The water and oil resistant agent for paper claimed in claim 1 , wherein the monomer (b) is at least one oxyalkylene (meth)acrylate represented by the general formulas:
CH2=CX1C(=0)-0-(RO)n-X2 (2a)
and
CH2=CX1C(=0)-0-(RO)n-C(=0)CX1=CH2 (2b)
wherein X1 is a hydrogen atom or a methyl group;
X2 is a hydrogen atom or a saturated or unsaturated Ci-C22 hydrocarbon group;
R is a C2-C6 alkylene group; and
n is an integer of 1-90.
5. The water and oil resistant agent for paper claimed in claim 4, wherein the oxyalkylene (meth)acrylate is at least one selected from (b1) ω-hydroxypolyoxyalkylene (meth)acrylate and/or (b2) 2-hydroxyethyl (meth)acrylate.
6. The water and oil resistant agent for paper claimed in claim 1 , wherein the monomer (c) is a compound having an anion-donating group and a carbon-carbon double bond.
7. The water and oil resistant agent for paper claimed in claim 1 , wherein the anion- donating group is a carboxylic acid group or a sulfonic acid group. 8. The water and oil resistant agent for paper claimed in claim 1 , wherein the monomer (c) is at least one selected from the group consisting of (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic cid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrene sulfonic aicd, vinylbenzene sulfonic acid, acrylamide-tert- butylsulfonic acid, and salts thereof.
9. The water and oil resistant agent for paper claimed in claim 1 , wherein the amount of the monomer (a) is 40 - 90 wt%, the amount of the monomer (b) is 2 - 50 wt% and the amount of the monomer (c ) is 0.1 - 30 wt% based on the fluorine-containing polymer.
10. The water and oil resistant agent for paper claimed in claim 1 , wherein the weight average molecular weight of the fluorine-containing copolymer is 100,000 to 3,000,000.
11. The water and oil resistant agent for paper claimed in claim 1 , wherein the weight average molecular weight of the fluorine-containing copolymer is 120,000 to 2,000,000.
12. The water and oil resistant agent for paper claimed in claim 1 , wherein the monomer (a) is at least one fluorine-containing monomer wherein Rf in the general formula (1) represents a perfluoroalkyl group having 4 to 6 carbon atoms,
the monomer (b) is (b1) ω-hydroxy-pbiyoxyalkylene (meth)acrylate and/or (b2) 2- hydroxyethyl (meth)acrylate and
the monomer (c) is at least one selected from the group consisting of (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. 13. The water and oil resistant agent for paper claimed in claim 1 , wherein the monomer (a) is F(CF2)4CH2CH2OCOCH=CH2 , F(CF2)6CH2CH2OCOCH=CH2 or a mixture thereof,
the monomer (b) is (b1) ω-hydroxy-polyoxyethylene (meth)acrylate and/or (b2) 2- hydroxyethyl (meth)acrylate and
the monomer (c) is (meth)acrylic acid.
14. The water and oil resistant agent for paper claimed in claim 13, wherein the weight ratio of (a) : (b) : (c) is 60 - 85: 5 - 35: 1-15, and the weight average molecular weight of the obtained fluorine-containing polymer is 120,000 to 2,000,000.
15. The water and oil resistant agent for paper claimed in claim 1 , wherein the monomer (a) is F(CF2)4CH2CH2OCOCH=CH2 or F(CF2)6CH2CH2OCOCH=CH2 or the mixture thereof, the monomer (b) comprises ω-hydroxy-polyoxyethylene (meth)acrylate (b1 ) and 2-hydroxyethyl (meth)acrylate (b2) and the monomer (c) is methacrylic acid.
16. The water and oil resistant agent for paper claimed in claim 15, wherein the weight ratios of (a): (b1): (b2): (c) are 60- 85: 1- 15: 5- 20: 1-15, and the weight average molecular weight of the obtained fluorine-containing polymer is 120,000 to 2,000,000.
17. A process for a water and oil resistant treatment of a paper, wherein the process comprises a step of applying the water and oil resistant agent claimed in any one of claims 1 - 6 to the surface of the paper. 8. The process claimed in claim 17, wherein the process uses the water and oil resistant agent in such amount that the weight ratio of the fluorine atoms is in the range of 0.005 - 0.6 wt% based on the weight of the paper.
19. The process for the water and oil resistant treatment of a paper, wherein the process comprises a step of applying the water and oil resistant agent claimed in any one of claims 1 - 16 to the whole paper including its internal parts.
20. The process claimed in claim 19, wherein the step of applying the water and oil resistant agent to the whole paper is a step of applying the water and oil resistant agent at a paper making stage with pulp.
21. The process claimed in claim 20, wherein the water and oil resistant agent is used in such amount that the weight ratio of the fluorine atoms is in the range of 0.01 - 1.0 wt% based on the weight of the pulp.
22. A treated paper which is treated with the water and oil resistant agent claimed in any one of the claims 1 - 16.
23. The treated paper which is obtained by the process claimed in claim 17.
24. The treated paper which is obtained by the process claimed in claim 19.
PCT/JP2010/065191 2009-09-01 2010-08-31 Water and oil resistant agent for paper, treatment process and paper WO2011027877A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013109530A1 (en) 2012-01-17 2013-07-25 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
EP2826918A4 (en) * 2012-03-16 2015-08-12 Daikin Ind Ltd Water-resistant/oil-resistant agent for paper
EP3150684A4 (en) * 2014-05-28 2017-11-29 Daikin Industries, Ltd. Masonry treatment composition
US10829576B2 (en) 2016-04-27 2020-11-10 AGC Inc. Liquid repellent composition, method for its production, and method for producing oil resistant paper

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012117709A1 (en) 2011-02-28 2012-09-07 日東電工株式会社 Oil-repellant ventilation filter
JP6037643B2 (en) * 2012-04-06 2016-12-07 日東電工株式会社 Breathable film with oil repellency
JP2017078227A (en) * 2014-02-25 2017-04-27 旭硝子株式会社 Oil-proof agent composition for pulp slurry addition, manufacturing method of oil-proof paper and oil-proof paper
JP2018053372A (en) * 2015-02-06 2018-04-05 旭硝子株式会社 Method for producing oil-resistant paper
JP2018109242A (en) * 2015-05-13 2018-07-12 旭硝子株式会社 Oil-resistant paper and method for producing oil-resistant paper
KR101666835B1 (en) * 2015-06-15 2016-10-17 주식회사 자연닮 Eco-friendly and water-soluble food wrapping paper with a moisture-proof, oil resistance, water resistance and heat-sealing by multi-layer coating technology and method of preparing the same
US10745860B2 (en) 2015-12-16 2020-08-18 The Coca-Cola Company System and methods for reducing edge wicking of a paperboard comprising fruit fiber and compositions produced thereby
CN105862506B (en) * 2016-06-01 2017-10-10 万邦特种材料股份有限公司 A kind of grease proofing forming paper production technology
KR102330283B1 (en) * 2017-08-18 2021-11-24 주식회사 케이티앤지 Cigarette filter wrapping paper and cigarette comprising the same
CN107619451A (en) * 2017-09-20 2018-01-23 开翊新材料科技（上海）有限公司 It is a kind of for the fluorinated copolymers of waterproof and oilproof paper and its preparation method of emulsion
JP6994343B2 (en) * 2017-10-06 2022-01-14 明成化学工業株式会社 Oil-resistant paper and oil-resistant paper manufacturing method
JP7185124B2 (en) 2017-12-28 2022-12-07 ダイキン工業株式会社 Pulp molded product and its manufacturing method
WO2023169485A1 (en) 2022-03-10 2023-09-14 北京马普新材料有限公司 Copolymer, treatment agent, and preparation method therefor and use thereof
CN114953678A (en) * 2022-06-08 2022-08-30 嘉兴星越包装材料有限公司 Vehicle lamp drying agent package and oil-proof and water-proof treatment method for paper

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3491169A (en) * 1966-07-22 1970-01-20 Du Pont Oil and water repellent
JPH09183429A (en) 1995-12-27 1997-07-15 Fuji Corn Seisakusho:Kk Oilproof and waterproof simple food container
EP1942225A1 (en) * 2005-09-21 2008-07-09 Daikin Industries, Ltd. Treatment for paper and method for treatment of paper
WO2009057716A1 (en) 2007-11-01 2009-05-07 Asahi Glass Company, Limited Fluorinated copolymer, water-proof and oil-proof agent composition, and their production methods

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2926770B2 (en) * 1989-06-21 1999-07-28 ダイキン工業株式会社 New copolymer
US5143991A (en) * 1989-06-21 1992-09-01 Daikin Industries, Ltd. Copolymer desoiling agent
JPH07116266B2 (en) * 1990-07-09 1995-12-13 ダイキン工業株式会社 New copolymer and antifouling agent
DE4027594A1 (en) * 1990-08-31 1992-03-05 Herberts Gmbh WATER-DUMBABLE COPOLYMER, THEIR PRODUCTION AND USE, AND AQUEOUS COATING AGENTS
US5183839A (en) * 1990-12-17 1993-02-02 Allied-Signal Inc. Fluoropolymers and fluoropolymer coatings
JP2854567B2 (en) * 1996-11-22 1999-02-03 ダイキン工業株式会社 Antifouling agent
US6465591B1 (en) * 2000-04-24 2002-10-15 Avery Dennison Corporation Acrylic emulsion coating for films, paper and rubber
AU2001283381A1 (en) * 2000-08-18 2002-03-04 3M Innovative Properties Company Fluoroalkyl (meth)acrylate copolymer coating compositions
GB0119728D0 (en) * 2001-08-14 2001-10-03 Avecia Bv Aqueous crosslinkable coating compositions
AU2003242307A1 (en) * 2002-06-13 2003-12-31 Daikin Industries, Ltd. Copolymer, paper-treating agent, and processed paper
JP4329559B2 (en) * 2003-05-02 2009-09-09 ダイキン工業株式会社 Surface treatment agent comprising fluorine-containing polymer
JP4655041B2 (en) * 2004-06-25 2011-03-23 ダイキン工業株式会社 Soil release agent containing fluorine-containing copolymer and method for producing the same
CN1687180A (en) * 2005-03-18 2005-10-26 上海瀛正科技有限公司 Method for preparing super branched polyacrylate fluorine and application in finishing agent for textile
US7754836B2 (en) * 2005-09-01 2010-07-13 Daikin Industries, Ltd. Water and oil repellent composition and treatment method
EP1961775A4 (en) * 2005-12-15 2010-09-01 Asahi Glass Co Ltd Fluorine-containing polymer, negative photosensitive composition and partition wall
JP5351023B2 (en) * 2006-08-25 2013-11-27 クラリアント ファイナンス （ビーブイアイ） リミティド Oil repellency, water repellency and soil repellency perfluoroalkylethyl methacrylate copolymer
JP5315663B2 (en) * 2007-10-22 2013-10-16 ユニマテック株式会社 Water and oil repellent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3491169A (en) * 1966-07-22 1970-01-20 Du Pont Oil and water repellent
JPH09183429A (en) 1995-12-27 1997-07-15 Fuji Corn Seisakusho:Kk Oilproof and waterproof simple food container
EP1942225A1 (en) * 2005-09-21 2008-07-09 Daikin Industries, Ltd. Treatment for paper and method for treatment of paper
WO2009057716A1 (en) 2007-11-01 2009-05-07 Asahi Glass Company, Limited Fluorinated copolymer, water-proof and oil-proof agent composition, and their production methods
EP2206735A1 (en) * 2007-11-01 2010-07-14 Asahi Glass Company, Limited Fluorinated copolymer, water-proof and oil-proof agent composition, and their production methods

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013109530A1 (en) 2012-01-17 2013-07-25 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
US8771470B2 (en) 2012-01-17 2014-07-08 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
US20140290883A1 (en) * 2012-01-17 2014-10-02 Agc Chemicals Americas, Inc. Method Of Preparing A Treated Article And Treated Article Formed Therefrom
JP2015507103A (en) * 2012-01-17 2015-03-05 エージーシー ケミカルズ アメリカズ，インコーポレイテッド Method for preparing treated articles and treated articles produced thereby
US9133584B2 (en) 2012-01-17 2015-09-15 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
US9499943B2 (en) 2012-01-17 2016-11-22 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
EP2826918A4 (en) * 2012-03-16 2015-08-12 Daikin Ind Ltd Water-resistant/oil-resistant agent for paper
EP3150684A4 (en) * 2014-05-28 2017-11-29 Daikin Industries, Ltd. Masonry treatment composition
US10829576B2 (en) 2016-04-27 2020-11-10 AGC Inc. Liquid repellent composition, method for its production, and method for producing oil resistant paper

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