Classifications

• • 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
  • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine 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
  • 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
  • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
  • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
  • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
• • 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
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • 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
  • C08F2810/00—Chemical modification of a polymer

Definitions

• the present invention relates to a polymer, a method for producing the same, a water and oil resistant composition, an article, and a water and oil resistant paper.
• a water and oil resistant composition that imparts water resistance and oil resistance to a base material such as paper is known.
• Treatment of pulp or paper with a water and oil resistant composition gives a water and oil resistant paper.
• Examples of the method for treating pulp or paper with the water and oil resistant composition include a method of applying or impregnating the paper with the water and oil resistant composition (external addition work) and a method of making a pulp slurry containing the water and oil resistant composition. There is (internal addition work).
• Patent Document 1 describes a water- and oil-resistant composition in which a fluorine-containing copolymer is dispersed in an aqueous medium.
• the fluorine-containing copolymer of Patent Document 1 has 60 to 98% by mass of a unit based on a monomer having a perfluoroalkyl group having 6 or less carbon atoms and 1 to 20% by mass of a unit based on a monomer having an oxyalkylene group.
• % And a unit based on a monomer having a dialkylamino group is contained in an amount of 1 to 30% by mass.
• the fluorine-containing copolymer of Patent Document 1 uses (meth) acrylate as a monomer, and the ester bond in (meth) acrylate is easily cleaved by hydrolysis with alkali or the like or photolysis with ultraviolet rays. Therefore, the perfluoroalkyl group and the like may be lost from the fluorine-containing copolymer, and the water resistance and oil resistance may decrease.
• fluorine-containing copolymers having no unit based on (meth) acrylate having a perfluoroalkyl group are known as fluorine-containing copolymers having no unit based on (meth) acrylate having a perfluoroalkyl group.
• a fluorine-containing copolymer having a (perfluoroalkyl) vinyl unit, a vinyl acetate unit, and a vinyl alcohol unit (Patent Document 2).
• Patent Documents 3 to 4 A fluorine-containing copolymer having a (perfluoroalkyl) vinyl unit and a vinyl acetate unit
• the fluorine-containing copolymer of Patent Document 2 has a small content of (perfluoroalkyl) vinyl unit and is water-soluble. Therefore, when the substrate is treated with the composition containing this fluorine-containing copolymer, it is water resistant. Insufficient properties and oil resistance.
• the fluorine-containing copolymers of Patent Documents 3 and 4 have a high content of (perfluoroalkyl) vinyl units, when the substrate is treated with the composition containing this fluorine-containing copolymer, water resistance and oil resistance are obtained. Insufficient sex.
• a polymer which can be dissolved or dispersed in a liquid medium and can obtain a water-resistant and oil-resistant paper having excellent water resistance and oil resistance, a manufacturing method thereof, a water- and oil-resistant paper having excellent water resistance and oil resistance, and the like can be obtained.
• a water and oil resistant composition, an article having excellent water resistance and oil resistance, and a water and oil resistant paper are provided.
• the present invention is as follows. ⁇ 1> A polymer having the following unit a and at least the unit b among the following unit b and the following unit c.
• the ratio of the unit a to all the units constituting the polymer is 28 to 70 mol%, and the total ratio of the unit b and the unit c is 30 to 72 mol%.
• Unit a A unit represented by the following equation 1. -(CH 2- CHR f ) -Equation 1 However, R f is a perfluoroalkyl group having 1 to 8 carbon atoms.
• Unit b A unit represented by the following equation 2.
• R is an alkyl group having 1 to 4 carbon atoms.
• ⁇ 2> The polymer of ⁇ 1>, wherein the ratio of the unit a to the total number of moles of the unit a and the unit b is 20 to 70 mol%.
• ⁇ 3> The polymer of ⁇ 1> or ⁇ 2> having a number average molecular weight of 9,000 or more.
• ⁇ 7> The method for producing the polymer of ⁇ 6>, wherein the recovered polymer is purified and saponified.
• ⁇ 8> The method for producing a polymer according to any one of ⁇ 4> to ⁇ 7>, wherein the unit based on the monomer c is saponified in the presence of a fluorine-containing medium.
• ⁇ 9> A water and oil resistant composition containing the polymer according to any one of ⁇ 1> to ⁇ 3> and a liquid medium.
• ⁇ 10> The water and oil resistant agent composition of ⁇ 9> for paper.
• ⁇ 11> An article treated with the water and oil resistant composition of ⁇ 9>.
• ⁇ 12> A water and oil resistant paper containing the polymer according to any one of ⁇ 1> to ⁇ 3>.
• ⁇ 13> The water-resistant and oil-resistant paper of ⁇ 12>, which has a fluorine atom content of 0.01 to 2.0 g / m 2 .
• the polymer of the present invention can be dissolved or dispersed in a liquid medium. Further, according to the polymer of the present invention, water-resistant and oil-resistant paper having excellent water resistance and oil resistance can be obtained. According to the method for producing a polymer of the present invention, it is possible to produce a polymer which can be dissolved or dispersed in a liquid medium and can obtain water-resistant and oil-resistant paper having excellent water resistance and oil resistance. According to the water and oil resistant composition of the present invention, a water and oil resistant paper having excellent water resistance and oil resistance can be obtained.
• the article of the present invention is excellent in water resistance and oil resistance.
• the water and oil resistant paper of the present invention is excellent in water resistance and oil resistance.
• the meanings and definitions of the terms in the present invention are as follows.
• the "unit based on a monomer” is a general term for an atomic group directly formed by polymerizing one molecule of a monomer and an atomic group obtained by chemically converting a part of the atomic group.
• a "unit based on a monomer” is also simply referred to as a "monomer unit”.
• “(Meta) acrylate” is a general term for acrylate and methacrylate.
• (meth) acryloyloxy group is a general term for acryloyloxy group and metaacryloyloxy group.
• the solid content concentration is calculated by solid content mass / sample mass ⁇ 100, where the mass of the sample before heating is the sample mass and the mass after drying the sample in a convection dryer at 120 ° C. for 4 hours is the solid content mass.
• Mn number average molecular weight
• Mw mass average molecular weight
• the polymer of the present invention (hereinafter, also referred to as “polymer A”) has a unit a and a unit b.
• the polymer A may further have a unit c.
• the polymer A may further have another unit (hereinafter, referred to as “unit d”).
• Unit a A unit represented by the following equation 1. -(CH 2- CHR f ) -Equation 1 However, R f is a perfluoroalkyl group having 1 to 8 carbon atoms.
• Unit b A unit represented by the following equation 2. -(CH 2- CH (OH))-Equation 2
• R is an alkyl group having 1 to 4 carbon atoms.
• the carbon number of R f in the unit a is preferably 4 to 6, and particularly preferably 6 from the viewpoint of being excellent in water resistance and oil resistance of water and oil resistant paper using the composition containing the polymer A.
• R f may be linear or branched, and is preferably linear.
• CF 3 , CF 2 CF 3 , CF (CF 3 ) 2 , CF 2 CF 2 CF 3 and CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 are preferable, and CF 3 and CF 2 CF 3 are preferable.
• CF 2 CF 2 CF 2 CF 3 and CF 2 CF 2 CF 2 CF 2 CF 3 are more preferable, and CF 2 CF 2 CF 2 CF 3 and CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 are further preferable.
• preferable are preferable.
• the unit a is typically a unit based on the monomer a.
• the carbon number of R is preferably 1 to 2 and particularly preferably 1 from the viewpoint of being excellent in water resistance and oil resistance of water and oil resistant paper using the composition containing the polymer A. That is, it is particularly preferable that R is a methyl group. R may be linear or branched, and is preferably linear.
• the unit c is typically a unit based on the monomer c.
• Monomer c A compound represented by the following formula 5.
• R is an alkyl group having 1 to 4 carbon atoms.
• the monomer c is a carboxylic acid vinyl ester having an alkyl group having 1 to 4 carbon atoms.
• Examples of the monomer c include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl pivalate. Two or more types of monomer c may be used in combination.
• the unit d is a unit based on the monomer a and another monomer copolymerizable with the monomer c (hereinafter, referred to as “monomer d”).
• the monomer d may be a compound having two or more polymerization-reactive carbon-carbon double bonds.
• the number of polymerization-reactive carbon-carbon double bonds in the other monomer is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.
• a compound having a vinyl group or an allyl group is preferable because it is easily copolymerized with the monomer a and the monomer c.
• Examples of the monomer d include vinyl halides having 8 or more carbon atoms, carboxylic acid allyl esters, vinyl ethers, allyl ethers, vinyl halides, olefins, (meth) acrylates, (meth) acrylamides, and halogenated substances other than vinyl halides. Examples thereof include, but are not limited to, olefins and the like.
• vinyl carboxylic acid esters having 8 or more carbon atoms include vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl octylate, vinyl monochloroacetate, and the like.
• examples thereof include divinyl adipate, vinyl methacrylate, vinyl crotonate, and vinyl cinnate.
• examples of the carboxylic acid allyl ester include allyl acetate and diallyl adipate.
• Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, and chloropropyl vinyl ether. Examples thereof include cyclohexyl vinyl ether, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether.
• Examples of the allyl ether include allyl ethyl ether, diallyl ether, and 1,3-diallyloxy-2-propanol.
• Examples of vinyl halides include vinyl chloride and vinyl fluoride.
• Examples of the olefin include ethylene and propylene.
• Examples of the (meth) acrylate include alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, aromatic (meth) acrylate, aliphatic cyclic (meth) acrylate, and (meth) acrylic acid.
• Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
• Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyoxyethylene. Examples thereof include glycol mono (meth) acrylate, polyoxypropylene glycol mono (meth) acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth) acrylate.
• Examples of the aromatic (meth) acrylate include phenyl (meth) acrylate, benzyl (meth) acrylate, and pentafluorophenyl (meth) acrylate.
• Examples of the aliphatic cyclic (meth) acrylate include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.
• Examples of the (meth) acrylate other than the above include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N, N. -Dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate can be mentioned.
• Examples of (meth) acrylamide include alkyl (meth) acrylamide, hydroxyalkyl (meth) acrylamide, and (meth) acrylamide in which nitrogen atoms form a heterocyclic structure.
• Examples of the alkyl (meth) acrylamide include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N, N-diisopropylacrylamide, and the like.
• Examples of the hydroxyalkyl (meth) acrylamide include N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, and N- (4-hydroxybutyl) (meth) acrylamide.
• Examples of the (meth) acrylamide in which the nitrogen atom forms a heterocyclic structure include N- (meth) acryloyl morpholine and N- (meth) acryloyl piperidine.
• monomer d examples include, but are not limited to, N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and ethyl vinyl sulfide.
• the ratio of the unit a is 28 to 70 mol%, preferably 30 to 45 mol%, and more preferably 32 to 40 mol% with respect to all the units constituting the polymer A.
• the ratio of the unit a is equal to or higher than the lower limit of the above range, the conversion rate of the monomer component to the polymer A can be improved and the molecular weight of the polymer A can be increased during the polymerization of the monomer component. Further, it is easy to make the polymer A soluble in an organic solvent even though the ratio of the unit b to the total of the unit b and the unit c is high. In addition, it is excellent in water resistance and oil resistance of water and oil resistant paper using the composition containing the polymer A. When the ratio of the unit a is not more than the upper limit of the above range, the conversion rate to the polymer A can be improved and the molecular weight of the polymer A can be increased.
• the total ratio of the unit b and the unit c is 30 to 72 mol%, preferably 35 to 70 mol%, and more preferably 40 to 68 mol% with respect to all the units constituting the polymer A.
• the total ratio of the unit b and the unit c is equal to or greater than the lower limit of the above range, the conversion rate to the polymer A can be improved and the molecular weight of the polymer A can be increased.
• the polymer A can be dissolved in an organic solvent even though the ratio of the unit b to the total of the unit b and the unit c is high. Easy to do. In addition, it is excellent in water resistance and oil resistance of water and oil resistant paper using the composition containing the polymer A.
• the ratio of the unit b is 45 mol% or more, preferably 75 mol% or more, more preferably 95 mol% or more, and may be 100 mol% with respect to the total of the unit b and the unit c.
• the ratio of the unit b to the total of the unit b and the unit c is equal to or higher than the lower limit, the water resistance and oil resistance of the water-resistant and oil-resistant paper using the composition containing the polymer A are excellent.
• the unit b is a saponified unit c, and the ratio of the unit b to the total of the unit b and the unit c corresponds to the degree of saponification.
• the ratio of the number of moles of the unit a is preferably 20 to 70 mol%, more preferably 25 to 45 mol%, and even more preferably 30 to 40 mol% with respect to the total number of moles of the unit a and the unit b. If it is within the above range, it is easily dissolved in an organic solvent.
• the total ratio of the unit a, the unit b, and the unit c is preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass with respect to all the units constituting the polymer A. Within the above range, the conversion rate of the monomer component to the polymer A can be improved during the polymerization of the monomer component, and the molecular weight of the polymer A can also be increased. In addition, it is excellent in water resistance and oil resistance of water and oil resistant paper using the composition containing the polymer A.
• the ratio of each unit can be calculated by, for example, 1 1 H-NMR or 13 C-NMR.
• the Mn of the polymer A is preferably 9,000 or more, more preferably 10,000 or more, and even more preferably 11,000 or more.
• the Mn of the polymer A is preferably 100,000 or less, more preferably 80,000 or less, still more preferably 50,000 or less.
• Mn of the polymer A is not more than the lower limit of the above range, the water resistance and oil resistance of the water-resistant and oil-resistant paper using the composition containing the polymer A are further excellent.
• the solubility of the polymer A in the organic solvent is further excellent, and the viscosity of the solution of the polymer A can be lowered.
• the Mn of the polymer A is preferably 9,000 to 100,000, more preferably 10,000 to 80,000, and even more preferably 11,000 to 50,000. When the Mn of the polymer A is within the above range, the water resistance and oil resistance of the water-resistant and oil-resistant paper using the composition containing the polymer A are further excellent.
• the Mw of the polymer A is preferably 9,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more.
• the Mw of the polymer A is preferably 150,000 or less, more preferably 120,000 or less, still more preferably 100,000 or less.
• the Mw of the polymer A is not less than the lower limit of the above range, the water resistance and oil resistance of the water-resistant and oil-resistant paper using the composition containing the polymer A are further excellent.
• the solubility of the polymer A in the organic solvent is further excellent, and the viscosity of the solution of the polymer A can be lowered.
• the Mw of the polymer A is preferably 9,000 to 150,000, more preferably 15,000 to 120,000, still more preferably 20,000 to 100,000. When the Mw of the polymer A is within the above range, the water resistance and oil resistance of the water-resistant and oil-resistant paper using the composition containing the polymer A are further excellent.
• the polymer A does not contain the polymer A having a molecular weight of 1,000 or less, or if it contains the polymer A, the ratio thereof is preferably 1% or less with respect to the entire polymer A. It is more preferable that the polymer A does not contain the polymer A having a molecular weight of 1,000 or less. When the polymer A having a molecular weight of 1,000 or less is contained, the ratio thereof is more preferably 1% or less with respect to the entire polymer A. If the polymer A does not contain the polymer A having a molecular weight of 1,000 or less, or if the polymer A contains the polymer A within the above range, the water resistance of the water resistant oil resistant paper or the like using the composition containing the polymer A And the oil resistance is further excellent.
• the ratio of the polymer A having a molecular weight of 1,000 or less to the entire polymer A is such that the molecular weight of the polymer A with respect to the peak area of the entire polymer A is 1,000 in the chart obtained by measuring the molecular weight of the polymer A by GPC measurement. It can be calculated as the ratio (%) of the peak area of the following part.
• the polymer A described above has a unit a and at least a unit b among the unit b and the unit c, the ratio of the unit a to all the units is 28 to 70 mol%, and the unit b and the unit c Since the total ratio is 30 to 72 mol% and the ratio of the unit b to the total of the unit b and the unit c is 45 mol% or more, it can be dissolved or dispersed in a liquid medium. In addition, it is excellent in water resistance and oil resistance of water and oil resistant paper using the composition containing the polymer A.
• the polymer A can be produced, for example, by the following production method.
• the following monomer a and the following monomer c are contained, and the ratio of the monomer a to the entire monomer component is 28 to 70 mol%, and the ratio of the monomer c is 30 to 72 mol%.
• a polymer obtained by polymerizing a monomer component in the presence of a polymerization initiator and having a unit based on the monomer a and a unit based on the monomer c hereinafter, also referred to as “polymer B”).
• the polymer A can be produced by saponifying the unit based on the monomer c so that the degree of saponification is 45 mol% or more and converting it into the unit b.
• the unit b may be converted into a part or all of the units based on the monomer c.
• Monomer a A compound represented by the following formula 4.
• CH 2 CH-R f formula 4
• Monomer c A compound represented by the following formula 5.
• the monomer component may further contain other monomers.
• the ratio of the monomer a to the entire monomer component is 28 to 70 mol%, preferably 30 to 45 mol%, and more preferably 32 to 40 mol%.
• the ratio of the monomer a is not less than the lower limit of the above range, the conversion rate of the monomer component to the polymer B can be improved and the molecular weight of the polymer B can be increased during the polymerization of the monomer component.
• it is excellent in water resistance and oil resistance of water and oil resistant paper using a composition containing polymer A.
• the ratio of the monomer a is not more than the upper limit of the above range, the conversion rate to the polymer B can be improved and the molecular weight of the polymer B can be increased.
• the ratio of the monomer c to the entire monomer component is 30 to 72 mol%, preferably 35 to 70 mol%, and more preferably 40 to 68 mol%.
• the proportion of the monomer c is not less than the lower limit of the above range, the conversion rate to the polymer B can be improved and the molecular weight of the polymer B can be increased.
• the ratio of the monomer c is not more than the upper limit of the above range, the polymer A can be easily dissolved in an organic solvent even though the ratio of the unit b to the total of the unit b and the unit c is high. In addition, it is excellent in water resistance and oil resistance of water and oil resistant paper using the composition containing the polymer A.
• the total ratio of the monomer a and the monomer c to the entire monomer component is preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.
• the conversion rate of the monomer component to the polymer B can be improved and the molecular weight of the polymer B can be increased during the polymerization of the monomer component.
• it is excellent in water resistance and oil resistance of water and oil resistant paper using the composition containing the polymer A.
• the polymerization initiator examples include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, and an ionic polymerization initiator, and a radical polymerization initiator is preferable.
• a radical polymerization initiator for example, an azo-based polymerization initiator, a peroxide-based polymerization initiator, and a redox-based polymerization initiator are used depending on the polymerization temperature.
• an azo compound is preferable, and a salt of the azo compound is more preferable.
• the amount of the polymerization initiator added is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the monomer component.
• the polymerization temperature is preferably 20 to 150 ° C, more preferably 40 to 90 ° C.
• a molecular weight modifier When polymerizing the monomer component, a molecular weight modifier may be used.
• the molecular weight adjusting agent for example, an aromatic compound, a mercapto alcohol, a mercaptocarboxylic acid, and an alkyl mercaptan are preferable, and a mercaptocarboxylic acid or an alkyl mercaptan is more preferable.
• the amount of the molecular weight adjusting agent added is preferably 0 to 5 parts by mass, more preferably 0 to 2 parts by mass with respect to 100 parts by mass of the monomer component.
• Examples of the polymerization method include an emulsion polymerization method, a solution polymerization method, and bulk polymerization. Of these, the emulsion polymerization method is preferable.
• the conversion rate of the monomer component to the polymer B can be improved and the molecular weight of the polymer B can be increased without using a liquid medium other than the aqueous medium. it can.
• the monomer component is polymerized in an emulsion containing a monomer component, an aqueous medium, an emulsifier, and a polymerization initiator.
• aqueous medium include the same as the aqueous medium in the water and oil resistant agent composition described later.
• emulsifier include the same emulsifiers in the water and oil resistant composition described later.
• the emulsion can be prepared by mixing an aqueous medium, a monomer component and an emulsifier, dispersing them with a homogenizer, a high-pressure emulsifier or the like, and then adding a polymerization initiator.
• the temperature at which the mixed solution is emulsified is, for example, 20 to 150 ° C.
• the concentration of the monomer component in the emulsion is preferably 40 to 70% by mass, more preferably 45 to 60% by mass. When the concentration of the monomer component in the emulsion is within the above range, the conversion rate of the monomer component to the polymer B can be improved during the polymerization of the monomer component, and the molecular weight of the polymer B can be improved. Can be high enough.
• the content of the emulsifier in the emulsion is preferably 1 to 6 parts by mass with respect to 100 parts by mass of the monomer component.
• the content of the emulsifier is at least the lower limit of the above range, the dispersion stability of the emulsion is excellent.
• the content of the emulsifier is not more than the upper limit of the above range, there is little adverse effect on the water resistance and oil resistance of the water-resistant and oil-resistant paper using the composition containing the polymer A.
• the temperature of the emulsion may be raised to the above-mentioned polymerization temperature.
• the polymerization time is, for example, 4 to 120 hours.
• the conversion rate of the monomer component to the polymer B at the end of the polymerization is preferably 80% or more, more preferably 90% or more. By increasing the conversion rate, the molecular weight of the polymer B is also increased, and the water resistance and oil resistance of the water-resistant and oil-resistant paper using the composition containing the polymer A are also improved.
• Examples of the method for setting the conversion rate to 80% or more include a method of optimizing the emulsification composition, a method of optimizing the polymerization time, and a molar ratio (a / c) of the monomer a to the monomer c at the time of polymerization. There is a method of optimization.
• the molar ratio (a / c) of the monomer a to the monomer c at the time of polymerization is preferably 28/72 to 70/30, and 30/70 to 50/50 in terms of setting the conversion rate to 80% or more. Is more preferable.
• An emulsion of polymer B is obtained by polymerizing into a monomer component in an emulsion.
• the emulsion may be subjected to the saponification step as it is, or the polymer B may be recovered from the emulsion and the recovered polymer B may be subjected to the saponification step.
• the method for recovering the polymer B is not particularly limited, and a known method can be appropriately adopted. For example, as shown in Examples described later, there is a method in which an emulsion is dropped onto a mixed medium of 2-butanol and hexane to precipitate the polymer B, and solid-liquid separation is performed.
• the polymer B may be purified before the recovered polymer B is subjected to the saponification step.
• the purification method include a method of washing the polymer B with water and a polar solvent other than water.
• the temperature of the water is preferably 20 to 70 ° C, more preferably 40 to 60 ° C.
• the amount of water used is, for example, 6 to 20 times the mass ratio of the polymer B.
• a polar solvent in which the polymer B does not dissolve or swell and has a relatively low boiling point is preferable in terms of workability, and a protic polar solvent is more preferable.
• protic polar solvents include t-butanol and isopropyl alcohol.
• the temperature of the polar solvent is not particularly limited, but is, for example, 20 to 30 ° C.
• the amount of the polar solvent other than water used is, for example, 6 to 20 times the mass ratio of the polymer B.
• the washing time is, for example, 5 to 40 minutes.
• the saponification method is not particularly limited, and a known saponification method can be adopted.
• a method of contacting the polymer B with an alkaline compound in the presence of an aqueous medium can be mentioned.
• the aqueous medium the same medium as the aqueous medium in the water and oil resistant agent composition described later can be used.
• the amount of the aqueous medium used is, for example, 200 to 5000 parts by mass with respect to 100 parts by mass of the polymer B.
• the alkaline compound include sodium hydroxide and potassium hydroxide.
• the amount of the alkaline compound used is, for example, 0.2 to 35 parts by mass with respect to 100 parts by mass of the polymer B as the amount of the active ingredient.
• the concentration is preferably 5 to 60% by mass, more preferably 10 to 50% by mass.
• the saponification time can be adjusted according to the concentration of the alkaline compound used.
• the unit based on the monomer c is preferably saponified in the presence of a fluorinated medium. Since the polymer B can be dispersed well in the fluorine-containing medium, the unit based on the monomer c can be efficiently saponified by the presence of the fluorine-containing medium.
• a fluorine-containing medium for example, the polymer B and the fluorine-containing medium are mixed to obtain a dispersion, and an aqueous medium and an alkaline compound are added to the dispersion. Then react.
• fluorine-containing medium examples include 1H-tridecafluorohexane (AGC product name, Asahiclean AC-2000, hereinafter referred to as "AC-2000”), 1,1,1,2,2,3,3. 4,4,5,5,6,6-tridecafluorooctane (AGC product name, Asahiclean AC-6000, hereinafter referred to as "AC-6000”), 1,1,2,2-tetrafluoro- 1- (2,2,2-trifluoroethoxy) ethane (AGC product name, Asahiclean AE-3000, hereinafter referred to as "AE-3000”), dichloropentafluoropropane (AGC product name, Asahiclean AK-) 225, hereinafter referred to as "AK-225"), 1, 1, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane (AGC) Product name, Cytop CT-solv100E), 1-methoxyn
• the reaction temperature for saponifying the unit based on the monomer c is preferably 5 to 80 ° C, more preferably 20 to 70 ° C.
• the reaction time can be set according to the desired degree of saponification and varies depending on the reaction temperature, but is, for example, 5 minutes to 48 hours, and further 30 minutes to 30 hours.
• the reaction can be completed, for example, by a method of neutralizing the alkaline compound, a method of washing the alkaline compound with an aqueous medium, or the like. After completion of the reaction, if necessary, the aqueous medium or the like is removed from the reaction solution to recover the polymer A.
• the degree of saponification is 45 mol% or more, preferably 75 mol% or more, more preferably 95 mol% or more, and may be 100 mol%.
• the saponification degree is at least the above lower limit value, the water resistance and oil resistance of water and oil resistant paper using the composition containing the polymer A are excellent.
• the water and oil resistant agent composition of the present invention contains the polymer A and a liquid medium.
• the liquid medium include an aqueous medium, a non-aqueous medium, and a mixed medium thereof.
• the composition is preferably a polymer dispersion containing the polymer A, the aqueous medium, and the emulsifier.
• the composition is preferably a polymer solution containing the polymer A and the non-aqueous medium or the mixed medium.
• the emulsifier in the polymer solution is typically 0.3 parts by mass or less with respect to 100 parts by mass of the polymer A.
• the present composition also means a dispersion obtained by the method for producing the polymer A of the present invention, and a dispersion obtained by further diluting the dispersion in order to treat the substrate.
• the composition may contain other components, if necessary.
• aqueous medium examples include water or a mixed medium of water and a water-soluble organic solvent.
• the water-soluble organic solvent is an organic solvent that can be miscible with water in an arbitrary ratio.
• the water-soluble organic solvent at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols and aprotic polar solvents is preferable.
• the alcohol include t-butanol and propylene glycol.
• the ether alcohol examples include 3-methoxymethylbutanol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol.
• aprotic polar solvent examples include N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (hereinafter referred to as "THF"), acetonitrile, and acetone.
• THF tetrahydrofuran
• acetonitrile examples include N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (hereinafter referred to as "THF"), acetonitrile, and acetone.
• THF tetrahydrofuran
• the non-aqueous medium is a liquid medium that does not contain the above-mentioned aqueous medium, and is typically an organic solvent other than the water-soluble organic solvent.
• the non-aqueous medium is not particularly limited as long as it can dissolve the polymer A, and for example, a ketone that does not contain the aqueous medium, a compound having an amide bond, and an ether bond that does not contain the aqueous medium. Examples thereof include compounds having no hydroxyl group and fluorine-containing media.
• Examples of the ketone that does not contain the aqueous medium include methyl ethyl ketone and methyl isobutyl ketone.
• Examples of the compound having an amide bond include dimethylacetamide, 3-methoxy-dimethylpropanamide, 3-butoxydimethylpropaneamide, and methylpyrrolidone.
• Examples of the compound that does not contain the aqueous medium and has an ether bond and no hydroxyl group include diethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
• the fluorine-containing medium the same compounds as those listed in the above item of water and oil resistant composition can be used.
• As the non-aqueous medium two or more kinds may be used.
• the mixing medium may be a mixing medium in which the polymer A is soluble and a non-aqueous medium and an aqueous medium that is optionally miscible with the non-aqueous medium are combined.
• the non-aqueous medium constituting the mixing medium the above-mentioned compound can be used, and a fluorine-containing medium or the above-mentioned ketone compound is preferable.
• the fluorine-containing medium in the mixed medium AK-225, AE-3000, AC-6000, and AC-2000 are preferable.
• the ketone compound methyl isobutyl ketone is preferable.
• the above compounds can be used, a water-soluble organic solvent is preferable, an aprotic polar solvent is more preferable, and THF, acetone, N, N-dimethylformamide is further preferable.
• a combination of a fluorine-containing medium and an aprotic polar solvent, or a combination of a fluorine-containing medium and the above-mentioned ketone compound is preferable, and a mixed medium of AK-225 and THF is more preferable.
• the ratio of the fluorine-containing medium in the mixing medium is preferably 30 to 70% by volume, more preferably 40 to 60% by volume, based on the total mass of the mixing medium. When the ratio of the fluorine-containing medium in the mixed medium is within the above range, the polymer A is easily dissolved, which is preferable.
• the above ratio is a value at room temperature (25 ⁇ 5 ° C.).
• the emulsifier is a surfactant having both hydrophilic and hydrophobic moieties.
• Examples of the emulsifier include anionic emulsifier, nonionic emulsifier, cationic emulsifier and amphoteric emulsifier.
• the emulsifier is preferably a non-fluorine-based emulsifier that does not have a fluorine atom.
• the nonionic emulsifier alone, the nonionic emulsifier in combination with the cationic or amphoteric emulsifier, or the anionic emulsifier alone.
• the ratio of the nonionic emulsifier to the cationic emulsifier is preferably 100/0 to 40/60 (mass ratio), more preferably 97/3 to 40/60 (mass ratio).
• the total amount of the emulsifier with respect to 100 parts by mass of the polymer A can be 5 parts by mass or less, so that the water and oil resistant paper using this composition derived from the emulsifier can be used. It is possible to reduce adverse effects on water resistance and oil resistance.
• nonionic emulsifier examples include the surfactants s1 to s6 described in paragraphs [0067] to [0595] of JP-A-2009-215370.
• the surfactant s1 is a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, a polyoxyalkylene monoalkapolyenyl ether, or a polyoxyalkylene monopolyfluoroalkyl ether.
• a polyoxyethylene alkyl ether is preferable.
• Surfactant s2 is a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.
• an acetylene glycol ethylene oxide adduct is preferable as a nonionic emulsifier.
• the surfactant s3 is a compound in which a polyoxyethylene chain and a polyoxyalkylene chain in which two or more oxyalkylenes having three or more carbon atoms are continuously connected are linked and both ends are hydroxyl groups.
• an ethylene oxide propylene oxide polymer is preferable.
• One type of nonionic emulsifier may be used alone, or two or more types may be used in combination.
• cationic emulsifier examples include the surfactant s7 described in paragraphs [0996] to [0100] of JP-A-2009-215370.
• Surfactant s7 is a substituted ammonium salt form cationic emulsifier.
• the surfactant s7 is preferably an ammonium salt in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group or a polyoxyalkylene chain having a hydroxyl group at the end, and is represented by the following formula s71.
• Compound s71 is more preferable. [(R 21 ) 4 N + ] ⁇ X - formula s71.
• R 21 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a polyoxyalkylene chain having a hydroxyl group at the end. ..
• the four R 21s may be the same or different, but the four R 21s are not hydrogen atoms at the same time.
• X - is a counterion. As X ⁇ , chloride ion, ethyl sulfate ion, or acetate ion is preferable.
• Examples of the compound s71 include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono (stearyl) monomethyldi (polyethylene glycol) ammonium chloride, monofluorohexyltrimethylammonium chloride, and di (beef alkyl) dimethylammonium chloride. , Dimethylmonococonutamine acetate.
• One type of cationic emulsifier may be used alone, or two or more types may be used in combination.
• amphoteric emulsifier examples include the surfactant s8 described in paragraphs [0101] to [0102] of JP2009-215370A. One of these may be used, or two or more thereof may be used in combination.
• the surfactant s8 is alanine, imidazolinium betaine, amide betaine or betaine acetate.
• Other components may be added to the dispersion obtained by the method for producing the polymer A of the present invention, or the dispersion may be added to a further diluted dispersion.
• examples of other components added to the dispersion obtained by the method for producing the polymer A of the present invention include resins other than the polymer A, sizing agents, cross-linking agents, catalysts, organic fillers, inorganic fillers, and supports. Examples include agents, retainers, flocculants, buffers, bactericides, biocides, metal ion sequestering agents, hydrophobic agents, surfactants, defoaming agents and volatile organic solvents.
• components to be added to the dispersion liquid obtained by further diluting the above dispersion liquid for treating the base material include, for example, a paper strength enhancer (various starches, resins, etc.) as a concomitant agent for external addition work described later.
• a paper strength enhancer variant starches, resins, etc.
• examples include sizing agents, penetrants, defoaming agents, chelating agents, dyes, pigments, dyes, binders, acids, alkalis, alginates, and sulfuric acid bands.
• agents, paper strength enhancers, pigments, dyes, and pH adjusters Two or more kinds of other components may be used.
• the same type of component added to the dispersion liquid obtained by the method for producing the polymer A or a component causing the same action, and another type of component was further diluted with the dispersion liquid in order to further treat the substrate. It may be added to the dispersion. Examples of other components are not limited to these.
• the adhesiveness to the substrate is likely to be improved.
• a cross-linking agent an isocyanate-based cross-linking agent, a methylol-based cross-linking agent, a carbodiimide-based cross-linking agent, and an oxazoline-based cross-linking agent are preferable.
• the isocyanate-based cross-linking agent include an aromatic block-type isocyanate-based cross-linking agent, an aliphatic block-type isocyanate-based cross-linking agent, an aromatic non-block type isocyanate-based cross-linking agent, and an aliphatic non-block type isocyanate-based cross-linking agent.
• the isocyanate-based cross-linking agent is preferably an aqueous dispersion type emulsified with a surfactant or a self-aqueous dispersion type having a hydrophilic group.
• methylol-based cross-linking agent examples include a condensate or precondensate of urea or melamine and formaldehyde, methylol-dihydroxyethylene-urea and its derivatives, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, and dicyandiamide.
• -Formaldehyde condensates, methylol-carbamate, methylol- (meth) acrylamide, and polymers thereof.
• the carbodiimide-based cross-linking agent is a polymer having a carbodiimide group in the molecule, and is a cross-linking agent that exhibits excellent reactivity with a carboxy group, an amino group, and an active hydrogen group of a base material or the like.
• the oxazoline-based cross-linking agent is a polymer having an oxazoline group in the molecule, and is a cross-linking agent that exhibits excellent reactivity with a carboxy group such as a base material.
• cross-linking agents include, for example, divinyl sulfone, polyamide and its cationic derivative, polyamine and its cationic derivative, epoxy derivative such as diglycidyl glycerol, (epoxy-2,3-propyl) trimethylammonium chloride, N-methyl-N. -Halide derivatives such as (epoxy-2,3-propyl) morpholinium chloride, pyridinium salt of chloromethyl ether of ethylene glycol, polyamine-polyamide-epicrohydrin resin, polyvinyl alcohol or its derivative, polyacrylamide or its derivative, glyoxal resin Examples include anti-wrinkle agents.
• catalysts include, for example, inorganic amine salts and organic amine salts.
• inorganic amine salt include ammonium chloride.
• organic amine salt include aminoalcohol hydrochloride and semicarbazide hydrochloride.
• amino alcohol hydrochloride include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanol hydrochloride, and 2-amino-2-methylpropanol hydrochloride.
• the solid content concentration of the present composition obtained when the polymer A is produced by the production method of the present invention is preferably 25 to 70% by mass, more preferably 30 to 60% by mass.
• the content of the emulsifier of the present composition obtained when the polymer A is produced by the production method of the present invention is preferably 1 to 6 parts by mass with respect to 100 parts by mass of the polymer A.
• the solid content concentration when the present composition is used for treating a base material such as paper is, for example, 0.1 to 10% by mass, preferably 0.3 to 5% by mass, more preferably 0.8 to 3% by mass. preferable.
• the concentration of the cross-linking agent in the composition is preferably 0.1 to 3% by mass.
• the polymer A has a unit a and at least a unit b of the unit b and the unit c, and the ratio of the unit a to all the units is 28 to 70 mol%, the unit b. Since the total ratio of the unit c to the unit c is 30 to 72 mol% and the ratio of the unit b to the total of the unit b and the unit c is 45 mol% or more, the water-resistant and oil-resistant paper using the present composition, etc. Has excellent water resistance and oil resistance. Further, in the present composition, the solubility or dispersibility of the polymer A in the liquid medium is also good.
• the article of the present invention is an article processed using the present composition.
• Articles treated with this composition include, for example, fibers, textile fabrics, textile braids, non-woven fabrics, glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resins.
• Examples include molded products, porous resins, and porous fibers.
• the porous resin is used, for example, as a filter.
• Examples of the material of the porous resin include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene.
• Examples of the material of the porous fiber include glass fiber, cellulose nanofiber, carbon fiber, and cellulose acetate.
• Examples of the treatment method include a method in which the composition is applied or impregnated into an article by a known coating method and then dried.
• the water and oil resistant paper of the present invention contains the polymer A.
• the content of the polymer A is preferably 0.01 to 3.0 g / m 2 and 0.1 to 1.5 g / m 2 as the mass of the polymer A per unit area of the water-resistant and oil-resistant paper of the present invention. More preferred. When the content of the polymer A is at least the lower limit of the above range, the water resistance and the oil resistance are more excellent. When the content of the polymer A is not more than the upper limit of the above range, it is more excellent in air permeability or water vapor permeability.
• the content of the polymer A can be calculated from the fluorine atom content of the water-resistant and oil-resistant paper. Details are as described in Examples described later.
• the fluorine atom content of the water-resistant and oil-resistant paper is determined by the pyrohydrolysis combustion method. The specific measurement procedure is as shown in Examples described later.
• the fluorine atom content is preferably 0.01 to 2.0 g / m 2 and more preferably 0.6 to 1.0 g / m 2 as the mass of fluorine atoms per unit area of the water-resistant and oil-resistant paper of the present invention.
• the fluorine atom content is at least the lower limit of the above range, the water resistance and oil resistance are more excellent.
• the fluorine atom content is not more than the upper limit of the above range, it is more excellent in air permeability or water vapor permeability.
• Examples of the method for producing water- and oil-resistant paper include a method of applying or impregnating the composition to a paper base material (external addition work) or a method of making a pulp slurry containing the present composition (internal addition work).
• the present composition may be diluted with water or an aqueous medium before use.
• the paper base material one type of pulp slurry in which pulp is dispersed in water is used alone, or two or more types are mixed at an arbitrary mixing ratio, beaten, and a chemical is added, and then the paper is prepared using a wire.
• Examples of the form include a continuous long web-shaped one, a single-wafered one obtained by cutting the web-shaped one, and a molded body (container, etc.) obtained by a pulp molding machine.
• the basis weight of the paper base material is, for example, 10 g / m 2 to 500 g / m 2 .
• the raw material for pulp include wood such as softwood and hardwood; herbs such as bagasse, rice straw, bamboo, reeds, and palms; and used paper.
• pulp made from wood and herbs is called fresh pulp
• pulp made from used paper is called recycled pulp.
• Fresh pulp is called by different names depending on the production method. Examples of the name of fresh pulp include kraft pulp (KP), sulfite pulp (SP), soda pulp, mechanical pulp (MP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP) and the like.
• KP kraft pulp
• SP sulfite pulp
• MP mechanical pulp
• TMP thermomechanical pulp
• CMP chemithermomechanical pulp
• the fresh pulp one or a plurality of bleached pulps may be used as needed.
• the recycled pulp if necessary, one of the steps of desorption, dust removal, deinking, and bleaching may be performed, or a pulp produced by combining a plurality of steps may be used.
• the paper base material may contain a sizing agent, a fixing agent, a dry paper strength agent, a wet paper strength agent, a sulfate band, a yield improver, a dye, a pigment, a filler, etc., as long as the effects of the present invention are not impaired.
• the coating or impregnation of the present composition may be carried out at any stage after papermaking, may be at the stage of papermaking, wet pressing and size pressing after passing through the pre-stage dryer, and the stage of using a coater after the size pressing. It may be.
• a coating machine may be used for coating the composition.
• the coating machine include a size press machine, a coater, a printing machine and the like.
• the size press machine include a two-roll size press machine, a film transfer size press machine, and a calender size press machine.
• Examples of the coater include a roll coater, an air knife coater, a die coater, a blade coater, a bar coater, a bill blade coater, a short dwell blade coater, and the like.
• the printing machine include a gravure printing machine, a flexographic printing machine, an offset printing machine and the like.
• the drying method may be a method of drying by heat or a method of drying without applying heat (air drying).
• the drying temperature is preferably 20 to 300 ° C, more preferably 20 to 250 ° C.
• Pulp slurry contains water and pulp dispersed in water.
• the raw material of the pulp is the same as that described for the external addition work.
• the pulp slurry may be produced by dissociating dry pulp with a dissociator, or may be used by diluting wet pulp produced in a pulp production facility.
• One type of pulp slurry is used alone, or two or more types are mixed at an arbitrary blending ratio.
• the concentration of pulp in the pulp slurry is preferably 0.1 to 10% by mass.
• this composition may be carried out at any stage before the pulp slurry is supplied onto the wire of the paper machine.
• a paper machine can be used to make pulp slurry.
• the paper machine may be any device capable of dehydrating the pulp slurry on the wire.
• the paper machine may be a continuous paper machine such as a long net paper machine, or a batch type pulp molding machine or the like.
• the batch type pulp molding machine is, for example, an apparatus for producing a molded product by dehydrating a pulp slurry using a molding frame formed of wires.
• the water- and oil-resistant paper of the present invention is pulp or paper treated with the present composition, it is excellent in water resistance and oil resistance.
• Examples 1 to 9 are examples, and examples 10 to 27 are comparative examples.
• Room temperature is a temperature of 25 ⁇ 5 ° C.
• Solid content concentration The sample (emulsified liquid) was heated in an intake oven (convection dryer) heated to 120 ° C. for 4 hours.
• the solid content concentration was determined by dividing the mass of the solid obtained after heating (mass of solid content) by the mass of the sample before heating.
• Conversion rate From the theoretical value of the solid content concentration of the polymer emulsion calculated from the amount of raw materials used in each example and the measured value of the solid content concentration of the polymer emulsion, the weight of the monomer component is calculated by the measured value / theoretical value ⁇ 100. The conversion rate to coalescence was calculated. A conversion rate of 90% or more was defined as A (good), 80% or more and less than 90% was defined as B (possible), and a conversion rate of less than 80% was defined as C (impossible).
• the molecular weights of the polymers (FV1) to (FV9), (1b), (2b), (3b-1) and (3b-2) were measured by the following procedure. Other polymers did not dissolve in the mixing medium described below and could not be measured.
• the number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by GPC measurement.
• the saponification degree was calculated by (1- (Y / X)) ⁇ 100.
• the fluorine atom content of the treated paper was determined by the pyrohydrolysis combustion method according to the method described in JP-A-2009-215370.
• the pyrohydrolysis combustion method is described in Analytical Chemistry Vol. 26, No. 10. This method is based on the quartz tube oxygen combustion gas collection method described in "Quantification of Fluorine in Fluorine-Containing Organic Compounds" (1977, published by Japan Society for Analytical Chemistry), pp. 721 to 723.
• the polymer content of the treated paper that is, the amount of the polymer adhering to the treated paper (g / m 2 ) was calculated from the fluorine atom content of the polymer and the fluorine atom content of the treated paper. ..
• the fluorine atom content of the polymer was calculated from the amount of the monomer used in the production of the polymer.
• the polymer content (g) of the treated paper is due to the difference in mass of the paper before and after coating. / M 2 ) was estimated.
• test solution for the treated paper, use a test solution (kit test solution) in which castor oil, toluene, and heptane are mixed at the ratio (volume%) shown in Table 1, and use the following method according to TAPPI KIT-559 cm-02 to achieve oil resistance (oil resistance).
• kit test solution in which castor oil, toluene, and heptane are mixed at the ratio (volume%) shown in Table 1, and use the following method according to TAPPI KIT-559 cm-02 to achieve oil resistance (oil resistance).
• the kit method was evaluated. Under room temperature conditions, the treated paper was placed on a clean, flat black surface and one drop of test solution with a large kit number was dropped onto the test paper from a height of 13 mm. After 15 seconds, the test solution dropped with a clean absorbent paper was removed, and the state of the surface of the paper with which the test solution came into contact was visually observed.
• the first and highest kit number at which no traces of droplets dropped on the surface of the paper were left was used as an index of oil resistance. The higher the number, the higher the oil resistance. If the kit number has a numerical value after the decimal point, it means that the evaluation is higher than the kit number by the numerical value after the decimal point.
• the oil resistance is preferably 5 or more, and particularly preferably 7 or more.
• the treated paper was measured in size (seconds) by the Stekiht method according to JIS P 8122: 2004. The longer the size, the higher the water resistance.
• the degree of sizing is preferably 5 seconds or more, and particularly preferably 10 seconds or more.
• E430 Polyoxyethylene oleyl ether (addition of about 30 mol of ethylene oxide, Kao product name, Emargen 430)
• P204 Ethylene oxide / propylene oxide polymer (oxyethylene group content 40% by mass, NOF product name, pronon # 204)
• AQ18-63 63% by mass water of monostearyltrimethylammonium chloride and isopropyl alcohol solution (Lion product name, Lipocard 18-63)
• SFY485 acetylene glycol ethylene oxide adduct (30 moles of ethylene oxide adduct, product name of Nissin Chemical Industry Co., Ltd., Surfinol 485)
• VA-061A 2,2'-azobis [2- (2-imidazolin-2-yl) propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA-061) and an 80% by mass aqueous acetic acid solution in a mass ratio of 1: 1.
• DBPO Benzoyl peroxide
• the viscosity was adjusted by diluting the mixture concentration with methanol from 80% by mass stepwise to 70% by mass, 60% by mass, and then 50% by mass.
• the temperature was raised to 65 ° C. during the polymerization.
• the reaction was mixed with 200 g of methanol. Then, it was distilled to remove unreacted VAC from the reaction solution to obtain polymers (polymers before saponification (FV7) and (FV8)).
• TFE tetrafluoroethylene
• 2.0 g of the polymer, 0.5 mL of concentrated sulfuric acid, 50 mL of ethanol, and 1 mL of water were placed in a 100 mL flask, and the mixture was heated and stirred at 90 ° C. to hydrolyze the t-butyl group of TBVE and convert it into a hydroxyl group.
• This reaction system became a uniform solution 3 to 4 hours after stirring.
• the reaction was carried out at 90 ° C. for a total of 12 hours to obtain a reaction solution.
• the obtained reaction solution was added dropwise to water to precipitate a polymer.
• the obtained polymer was washed with water and then vacuum dried at 40 ° C. to isolate 1.42 g of a white polymer (polymer (FV9)).
• polymer (FV9) 97 mol% or more of t-butyl groups of TBVE used by hydrolysis were converted into hydroxyl groups.
• the obtained alkaline gel was pulverized, and 50 minutes after the pulverization, the reaction was terminated by neutralizing with 0.6 mL of a 70 mass% acetic acid aqueous solution in 50 g of methanol. After completion of the reaction, the medium was evaporated under reduced pressure and dried at 40 ° C. under reduced pressure for 1 hour to obtain a solid. The solid was washed with water, filtered, and then dried again at 40 ° C. to obtain a polymer (saponified polymer (7b) or (8b)).
• Table 2 shows the amounts of the monomer, medium, emulsifier, and polymerization initiator used in Production Examples (1a) to (6a), the molar ratio of C6OLF to VAC at the time of polymerization, and the monomer with respect to 100% by mass of the emulsion.
• the concentration of the component, the solid content concentration of the emulsion, the conversion rate of the polymer, and the molecular weight (Mn, Mw) are shown.
• Table 3 shows the amounts of the monomer, the medium, and the polymerization initiator used in Production Examples (7a) and (8a), the molar ratio of C6OLF and VAC at the time of polymerization, the conversion rate of the polymer, and the molecular weight (Mn, Mw).
• Table 4 shows the saponified polymers (FV1) to (FV8) before saponification, and the polymers (1b), (2b), (3b-1), (3b-2), (4b) to (8b). The saponification conditions when obtained are shown.
• the molecular weights (Mn, Mw) of the polymers used in Examples 1 to 27 described later are shown regardless of the presence or absence of saponification.
• the molecular weights of the polymers (4b) to (8b) and EVAL were not measured because they were insoluble in the mixed medium of AK-225 / THF.
• the prepared treatment liquid is coated on a bleached non-sized paper having a basis weight of 40 g / m 2 with a bar coat, and then left at room temperature overnight, and the mixed medium contained in the treatment liquid is contained. Was volatilized. It was then dried at 105 ° C. for 60 seconds.
• the polymers (8b) shown in Examples 13 to 15 of Table 5 were diluted with water to prepare a treatment solution having the concentration shown in Table 5.
• the prepared treatment liquid was coated on bleached unsized paper having a basis weight of 40 g / m 2 with a bar coat, and dried at 105 ° C. for 60 seconds.
• the prepared treatment liquid was coated on bleached unsized paper having a basis weight of 40 g / m 2 with a bar coat, and then left overnight at room temperature to volatilize the mixed medium contained in the treatment liquid. It was then dried at 105 ° C. for 60 seconds.
• Example 19 To 95 parts by mass of water, 5 parts by mass of polyvinyl alcohol (Kuraray Poval PVA-117 manufactured by Kuraray Co., Ltd.) (hereinafter, also referred to as “PVA”) was added, the temperature was raised to 95 ° C. with stirring, and the mixture was held for 1 hour. The mixture was cooled to room temperature to obtain a PVA aqueous solution having a concentration of 5% by mass. An aqueous solution obtained by further diluting the PVA aqueous solution with water to the concentration shown in the PVA pretreatment column of Table 5 was prepared as the pretreatment solution.
• PVA polyvinyl alcohol
• This pretreatment liquid was coated with a bar coat on unbleached size paper having a basis weight of 40 g / m 2 so that the amount of PVA shown in the coating amount column of Table 5 adhered. It was then dried at 105 ° C. for 60 seconds.
• the prepared treatment liquid was coated on a paper subjected to PVA pretreatment with a bar coat, and then left overnight at room temperature to volatilize the mixed medium contained in the treatment liquid. It was then dried at 105 ° C. for 60 seconds.
• the prepared treatment liquid is coated on bleached size paper having a basis weight of 40 g / m 2 with a bar coat, and then the coated bleached size paper is left overnight at room temperature, and the mixed medium contained in the treatment liquid is contained. Was volatilized. It was then dried at 105 ° C. for 60 seconds.
• Examples 25-27 5 parts by mass of EVAL was added to 95 parts by mass of water, the temperature was raised to 95 ° C. with stirring, and the temperature was maintained for 1 hour.
• the mixture was cooled to room temperature to obtain an EVAL aqueous solution having a concentration of 5% by mass.
• the EVAL aqueous solution was further diluted with water to the concentration shown in Table 5 to prepare a treatment solution.
• the prepared treatment liquid was coated on bleached unsized paper having a basis weight of 40 g / m 2 with a bar coat, and then dried at 105 ° C. for 60 seconds.
• Table 5 shows the polymer content (g / m 2 ), fluorine atom content (g / m 2 ), water resistance and oil resistance of the treated papers of Examples 1 to 27.
• the polymers (1b), (2b) and (3b-1) used in Examples 1 to 9 were dissolved in a liquid medium.
• the treated paper was excellent in oil resistance and water resistance.
• the polymer (3b-2) of Examples 10 to 12 in which the ratio (saponification degree) of the unit b to the total of the unit b and the unit c is less than 45 mol% the treated paper is inferior in oil resistance and water resistance.
• the polymers (4b) to (7b) having a unit a content of 0.25 to 25 mol% were not dissolved in the mixed medium of AK-225 and THF or in water.
• the polymers (8b) of Examples 13 to 15 having a unit a content of 0.05 mol% were dissolved in water, but the treated paper was inferior in oil resistance and water resistance.
• the treated paper was inferior in oil resistance and water resistance.
• the oil resistance and water resistance were improved as compared with Examples 16 to 18, but inferior to those of Examples 1 to 9.
• the polymer (FV9) of Examples 22 to 24 having a TFE unit instead of the unit a was dissolved in a mixed medium of AK-225 and THF, but the treated paper was inferior in oil resistance and water resistance. ..
• EVAL of Examples 25 to 27 containing no fluorine at all the treated paper was inferior in oil resistance and water resistance.
• the polymer of the present invention and a composition containing the same are useful as a water and oil resistant agent, a surface treatment agent for glass, resin products and the like, a water and oil repellent, an antifouling treatment agent, a release agent and the like.
• the water and oil resistant paper of the present invention is useful as a food packaging container, a food packaging paper, an antifouling sheet, and the like.

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• 2020
  • 2020-03-11 JP JP2021509015A patent/JP7359202B2/ja active Active
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