Water- and oil-resistant agent composition, method for producing the same, article, and water- and oil-resistant paper

Abstract

Provided is a water- and oil-resistant agent composition that can give an article excellent in practical oil-resistance.　Provided is a water- and oil-resistant agent composition including: a fluorine-containing polymer consisting of a unit based on monomer (a) below and a unit based on monomer (b) below; a polyglycerol fatty acid ester; and an aqueous medium.　Monomer (a): a compound represented by CH2=CH-Rf (wherein Rf represents a perfluoroalkyl group having 1-8 carbon atoms).　Monomer (b): a monomer copolymerizable with the monomer (a).

Description

[Technical Field]

[0001] The present invention relates to a water- and oil-proofing composition, a method for producing the same, an article, and water- and oil-proof paper. [Background technology]

[0002] Water- and oil-resistant compositions that impart water resistance and oil resistance to substrates such as paper are known. Treating pulp or paper with the water- and oil-resistant composition produces water- and oil-resistant paper. Methods for treating pulp or paper with the water- and oil-resistant composition include, for example, a method of applying or impregnating the paper with the water- and oil-resistant composition (external addition), and a method of making paper from a pulp slurry containing the water- and oil-resistant composition (internal addition).

[0003] Known water- and oil-resistant compositions include those containing a fluorine-containing polymer having units based on a (meth)acrylate having a perfluoroalkyl group. However, the ester bond in the (meth)acrylate-based unit is easily cleaved by hydrolysis with an alkali or the like. As a result, the perfluoroalkyl group is lost from the fluorine-containing polymer, which can reduce the water resistance and oil resistance.

[0004] Incidentally, as a fluorine-containing polymer that does not have a unit based on a (meth)acrylate having a perfluoroalkyl group, a fluorine-containing polymer having a unit based on (perfluoroalkyl)ethylene is known. Patent Document 1 describes a dispersion containing a fluorine-containing polymer having units based on (perfluoroalkyl)ethylene and an aqueous medium, and also specifically describes examples in which (perfluoroalkyl)ethylene is copolymerized with vinyl acetate, vinyl stearate, vinyl pivalate, etc. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2019 / 138680 Summary of the Invention [Problem to be solved by the invention]

[0006] According to the studies of the present inventors, by treating pulp or paper with the dispersion liquid of Patent Document 1, it is possible to obtain waterproof and oil-resistant paper whose water- and oil-resistant properties are resistant to deterioration by alkalis, etc. However, this waterproof and oil-resistant paper may not have sufficient oil resistance under practical use conditions (hereinafter also referred to as "practical oil resistance").

[0007] The present invention provides a water- and oil-proofing composition that can provide an article having excellent practical oil resistance, a method for producing the same, an article having excellent practical oil resistance, and water- and oil-proof paper. [Means for solving the problem]

[0008] The present invention has the following aspects. [1] A water- and oil-resistant composition comprising a fluorine-containing polymer comprising units based on the following monomer (a) and units based on the following monomer (b), a polyglycerol fatty acid ester, and an aqueous medium: Monomer (a): A compound represented by the following formula (1): CH2=CH-R f (1) However, R f is a perfluoroalkyl group having 1 to 8 carbon atoms. Monomer (b): A monomer copolymerizable with the monomer (a). [2] The water- and oil-resistant composition according to [1], wherein the content of the polyglycerol fatty acid ester is 2 to 8 parts by mass per 100 parts by mass of the fluoropolymer. [3] The water- and oil-resistant composition according to [1] or [2], wherein the polyglycerol fatty acid ester has an HLB value of 10 to 18. [4] The water- and oil-resistant agent composition according to any one of [1] to [3], wherein the proportion of units based on the monomer (a) is 15 to 40 mol % based on all units constituting the fluorine-containing polymer.

[0009] [5] The water- and oil-resistant agent composition according to any one of [1] to [4], wherein at least a part of the monomer (b) is the following monomer (b1): Monomer (b1): A compound represented by the following formula (2) or (3) and having a molecular weight of 45 to 350. CH2=CH-Q (2) CH2=CHCH2-Q (3) Here, Q is a halogen atom or an organic group in which the bond terminal atom is an oxygen atom, a nitrogen atom, or a sulfur atom. [6] In the formula (2) or (3), Q is a fluorine atom, a chlorine atom, -OR 4 , -OC(=O)R 4 , -NHR 4 , -NR 4 R 5 , -SR 4 or a nitrogen-containing heterocyclic group in which a nitrogen atom constituting the ring is a bond terminal atom. (However, R 4 and R 5 are each independently an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms forming a ring, an aryl group, or a heterocyclic group. [7] The water- and oil-resistant composition according to [5] or [6], wherein the monomer (b1) is a vinyl carboxylic acid ester, an allyl carboxylic acid ester, an alkyl vinyl ether, an alkyl allyl ether, a hydroxyalkyl vinyl ether, a hydroxyalkyl allyl ether, a vinyl halide, or an allyl halide. [8] The water- and oil-resistant agent composition according to any one of [5] to [7], wherein the proportion of units based on the monomer (b1) is 60 to 85 mol % based on all units constituting the fluorine-containing polymer. [9] R in the formula (1) f The water- and oil-resistant agent composition according to any one of [1] to [8], wherein is a perfluoroalkyl group having 1 to 6 carbon atoms.

[0010]

[10] A method for producing a water- and oil-resistant agent composition, comprising polymerizing a monomer component comprising the following monomer (a) and the following monomer (b) in an emulsion containing a polyglycerol fatty acid ester, an aqueous medium, and a polymerization initiator: Monomer (a): A compound represented by the following formula (1): CH2=CH-R f (1) However, R f is a perfluoroalkyl group having 1 to 8 carbon atoms. Monomer (b): A monomer copolymerizable with the monomer (a).

[11] The method for producing a water- and oil-resistant agent composition according to

[10] , wherein the content of the polyglycerol fatty acid ester is 2 to 8 parts by mass per 100 parts by mass of the monomer component.

[12] The method for producing the water- and oil-resistant agent composition according to

[10] or

[11] , wherein the proportion of the monomer (a) relative to the total monomer components is 15 to 40 mol %.

[13] An article treated with the water- and oil-resistant agent composition according to any one of [1] to [9].

[14] A waterproof and oil-resistant paper obtained by treating pulp or paper with the waterproof and oil-resistant agent composition according to any one of [1] to [9]. [Effects of the Invention]

[0011] According to the water- and oil-proofing composition of the present invention, an article having excellent practical oil resistance can be obtained. According to the method for producing a water- and oil-resistant agent composition of the present invention, it is possible to produce a water- and oil-resistant agent composition that can give an article having excellent practical oil resistance. The article and water- and oil-resistant paper of the present invention have excellent practical oil resistance. DETAILED DESCRIPTION OF THE INVENTION

[0012] The meanings and definitions of terms used in the present invention are as follows. The term "unit based on a monomer" is a general term for an atomic group formed directly by polymerizing one monomer molecule, and an atomic group obtained by chemically converting a part of the atomic group. "(Meth)acrylate" is a general term for acrylate and methacrylate. Similarly, "(meth)acryloyl" is a general term for acryloyl and methacryloyl. The number average molecular weight (hereinafter also referred to as "Mn") of the polymer is a molecular weight in terms of polymethyl methacrylate obtained by measuring by gel permeation chromatography (hereinafter also referred to as "GPC") using a calibration curve prepared using standard polymethyl methacrylate samples. The solid content concentration is calculated by (solid content mass / sample mass) x 100, where the mass of the sample before heating is the sample mass and the mass of the sample after drying for 4 hours in a convection dryer at 120°C is the solid content mass.

[0013] [Water- and oil-resistant composition] The water- and oil-resistant composition of the present invention (hereinafter also referred to as "the composition") contains a specific fluorine-containing polymer (hereinafter also referred to as "polymer A"), a polyglycerol fatty acid ester, and an aqueous medium. The polymer A is preferably dispersed in the aqueous medium as emulsified particles. The present composition may contain a medium other than an aqueous medium, if necessary. The present composition may contain surfactants other than the polyglycerol fatty acid ester, if necessary. The composition may contain other ingredients as needed. The present composition encompasses a dispersion obtained by the method for producing the water- and oil-resistant agent composition of the present invention described below, i.e., a dispersion obtained by polymerizing the monomer component in an emulsion containing the monomer component, a polyglycerol fatty acid ester, an aqueous medium, and a polymerization initiator (hereinafter also referred to as "dispersion (D1)"), and a dispersion obtained by further diluting the dispersion (D1) with any aqueous medium for treating articles, etc. (hereinafter also referred to as "dispersion (D2)").

[0014] (Polymer A) Polymer A is composed of units based on monomer (a) (hereinafter also referred to as "units (a)") and units based on monomer (b) (hereinafter also referred to as "units (b)"). Monomer (a): A compound represented by the following formula (1): CH2=CH-R f (1) However, R f is a perfluoroalkyl group having 1 to 8 carbon atoms. Monomer (b): A monomer copolymerizable with monomer (a).

[0015] In the monomer (a), R fThe number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 4 to 6, and particularly preferably 6, in terms of a good conversion rate to polymer A, availability of raw materials, and ease of handling. R f is preferably linear.

[0016] Examples of monomer (a) include CH2=CH-CF3, CH2=CH-CF2CF3, CH2=CH-CF2CF2CF3, CH2=CH-CF(CF3)2, CH2=CH-(CF2)3CF3, CH2=CH-CF2CF(CF3)2, CH2=CH-C(CF3)3, CH2=CH-(CF2)4CF3, CH2=CH-CF2CF2CF(CF3)2, CH2=CH-(CF2)5CF3, CH2=CH-(CF2)5CF(CF3)2, and CH2=CH-(CF2)7CF3. As the monomer (a), CH2=CH-CF3, CH2=CH-CF2CF3, CH2=CH-CF(CF3)2, CH2=CH-(CF2)3CF3 and CH2=CH-(CF2)5CF3 are preferred, CH2=CH-CF3, CH2=CH-CF2CF3, CH2=CH-(CF2)3CF3 and CH2=CH-(CF2)5CF3 are more preferred, and CH2=CH-(CF2)3CF3 and CH2=CH-(CF2)5CF3 are even more preferred. Two or more types of monomer (a) may be used in combination.

[0017] The monomer (b) may be any monomer as long as it is copolymerizable with the monomer (a). In view of ease of copolymerization with the monomer (a), it is preferred that at least a part of the monomer (b) is the monomer (b1). Monomer (b1): A compound represented by the following formula (2) or (3) and having a molecular weight of 45 to 350. CH2=CH-Q (2) CH2=CHCH2-Q (3) Here, Q is a halogen atom or an organic group in which the bond terminal atom is an oxygen atom, a nitrogen atom, or a sulfur atom.

[0018] The molecular weight of the monomer (b1) is the Mn value obtained by GPC measurement for compounds for which a molecular weight distribution can be obtained by GPC measurement, and is the formula weight calculated from the structural formula for compounds for which a molecular weight distribution cannot be obtained by GPC measurement. The molecular weight of the monomer (b1) is more preferably 50 to 300, and even more preferably 55 to 150, in that it is possible to introduce a functional group that improves adhesion to the substrate without excessively lowering the mass ratio of the monomer (a) in order to maintain oil resistance.

[0019] Examples of organic groups in which the bond terminal atom is an oxygen atom, a nitrogen atom, or a sulfur atom include -OR 4 , -OC(=O)R 4 , -NHR 4 , -NR 4 R 5 , -SR 4 and nitrogen-containing heterocyclic groups in which the nitrogen atom constituting the ring is the bond terminal atom. 4 and R 5 are each independently an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The alkyl group has, for example, 1 to 22 carbon atoms. The cycloalkyl group has, for example, 3 to 8 carbon atoms forming a ring. The organic group in Q may have a reactive group such as a hydroxy group, a carboxy group, an amino group, or an alkylamino group, or a halogen atom, and may also have a linking group such as an ether oxygen atom, a carbonyloxy group, or a carbonyl group at a site other than the bond terminal. Furthermore, it may have a polymerizable carbon-carbon double bond. A hydroxy group is preferred as the reactive group. It is preferred that the organic group in Q does not have a polymerizable carbon-carbon double bond. Q is preferably a halogen atom, -OR because it is easily copolymerizable with the monomer (a) and has good adhesion to the substrate. 4 , -OC(=O)R 4 is preferred, and a fluorine atom, a chlorine atom, or —OC(═O)R 4 is more preferable. 4 is the same as above.

[0020] The compound represented by formula (2) is preferably a vinyl carboxylate, a vinyl ether, or a vinyl halide. As the vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether are preferred. The compound represented by formula (3) is preferably a carboxylic acid allyl ester, an allyl ether, or an allyl halide. As the allyl ether, alkyl allyl ether and hydroxyalkyl allyl ether are preferred.

[0021] The number of carbon atoms in the acyl group in the vinyl carboxylic acid ester or allyl carboxylic acid ester is preferably 24 or less, more preferably 2 to 6. It is also preferable to use a vinyl carboxylic acid ester or allyl carboxylic acid ester having an acyl group with 2 to 6 carbon atoms in combination with a vinyl carboxylic acid ester or allyl carboxylic acid ester having an acyl group with 10 to 22 carbon atoms. The alkyl or hydroxyalkyl in the alkyl vinyl ether, hydroxyalkyl vinyl ether, alkyl allyl ether, and hydroxyalkyl allyl ether preferably has 2 to 6 carbon atoms.

[0022] Examples of vinyl carboxylate esters include vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl chloroacetate, and divinyl adipate. Of the vinyl carboxylate esters, vinyl acetate is particularly preferred because it allows the production of articles with excellent oil resistance.

[0023] Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, chloropropyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether.

[0024] Examples of the carboxylic acid allyl ester include allyl acetate and diallyl adipate. Examples of allyl ethers include allyl ethyl ether, diallyl ether, 1,3-diallyloxy-2-propanol, and ethylene glycol monoallyl ether.

[0025] Examples of vinyl halides include vinyl chloride and vinyl fluoride. Examples of the allyl halide include allyl chloride and allyl fluoride. Other examples of the compound represented by formula (2) or formula (3) include N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and ethyl vinyl sulfide.

[0026] As the monomer (b1), vinyl carboxylate esters, allyl carboxylate esters, alkyl vinyl ethers, alkyl allyl ethers, hydroxyalkyl vinyl ethers, hydroxyalkyl allyl ethers, vinyl halides and allyl halides are preferred, as they have good copolymerizability with the monomer (a) and can give articles with excellent oil resistance, and vinyl carboxylate esters and vinyl halides are more preferred. Specific examples of the monomer (b1) include vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl chloroacetate, ethyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, ethylene glycol monoallyl ether, vinyl chloride, and vinyl fluoride, and vinyl acetate is more preferred, as these monomers can provide articles with excellent oil resistance.

[0027] In polymer A, at least a portion of the units (b) may be units based on a monomer (b) other than the monomer (b1). The monomer (b) other than the monomer (b1) will hereinafter be referred to as a monomer (b2).

[0028] Examples of the monomer (b2) include olefins, halogenated olefins other than vinyl halides, alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, fluoroalkyl (meth)acrylates, and perfluoro(alkyl vinyl ethers). Specific examples include ethylene, propylene, vinylidene chloride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, tetrafluoroethylene, methyl (meth)acrylate, ethyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, N-methylolacrylamide, 2-perfluorohexylethyl (meth)acrylate, CF2=CFOCF3, CF2=CFOCF2CF3, CF2=CFOCF2CF2CF3, CF2=CFOCF2CF2CF2CF3, and CF2=CFOCF2CF(CF3)OCF2CF2CF3.

[0029] Monomer (b2) is preferably a (meth)acrylate. However, since polymer A can obtain an article whose water resistance and oil resistance are less likely to be reduced by alkali or the like, it is preferable that it does not contain a unit based on a (meth)acrylate having a perfluoroalkyl group. Therefore, monomer (b2) is preferably a (meth)acrylate that does not contain a fluorine atom. Examples of (meth)acrylates that do not contain a fluorine atom include methyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate. n-Butyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate are preferred because they tend to lower the glass transition temperature of polymer A and improve film-forming properties, and lauryl (meth)acrylate, stearyl (meth)acrylate and behenyl (meth)acrylate are preferred because they tend to improve the water resistance of the article.

[0030] A polymer in which at least a portion of the units (b) are units based on the monomer (b1) is preferred as the polymer A. Examples of the polymer in which at least a portion of the units (b) are units based on the monomer (b1) include a polymer having only units based on the monomer (b1) as the units (b), and a polymer having units based on the monomer (b1) and units based on the monomer (b2). The polymer A may have units based on two or more types of monomer (b1). When the polymer A has units based on the monomer (b2), it may have units based on two or more types of monomer (b2).

[0031] The proportion of units (a) relative to all units constituting polymer A (i.e., the sum of units (a) and units (b)) is preferably 15 to 40 mol %, more preferably 20 to 38 mol %, and even more preferably 25 to 35 mol %. Articles obtained using this composition have better water resistance and oil resistance. When the proportion of units (a) is equal to or less than the upper limit, the conversion rate in the polymerization reaction of polymer A tends to be higher.

[0032] When at least a portion of the units (b) are units based on the monomer (b1), the proportion of the units based on the monomer (b1) to all units constituting the polymer A is preferably 60 to 85 mol%, more preferably 62 to 80 mol%, and even more preferably 65 to 75 mol%. When the proportion of the units based on the monomer (b1) is equal to or greater than the lower limit, the conversion rate in the polymerization reaction of the polymer A tends to be higher. When the proportion of the units based on the monomer (b1) is equal to or less than the upper limit, the water resistance and oil resistance of articles obtained using the composition are superior.

[0033] The proportion of units based on monomer (b2) to all units constituting polymer A is preferably 25% by mass or less, more preferably 12% by mass or less, even more preferably 10% by mass or less, and may be 0% by mass. When the proportion of units based on monomer (b2) is equal to or less than the upper limit, an article can be obtained that is even less susceptible to deterioration in water resistance and oil resistance due to alkalis, etc.

[0034] The ratio of each unit is: 1 It can be calculated from the reaction rate of each monomer component by H-NMR and gas chromatography. When the conversion rate of the monomer components to Polymer A is high (for example, 90% or more) during the production of Polymer A, the proportion of each unit may be calculated based on the amount of the monomer components charged. The conversion rate is calculated from the theoretical mass of polymer A calculated from the amounts of raw materials charged during the production of polymer A and the actual mass of polymer A produced by multiplying the actual mass by the theoretical mass by 100.

[0035] The Mn of polymer A is preferably 10,000 or more, more preferably 11,000 or more, and even more preferably 12,000 or more. The Mn of polymer A is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. When the Mn of polymer A is at least the above lower limit, the water resistance and oil resistance of an article obtained using the composition are more excellent. When the Mn of polymer A is at most the above upper limit, the water dispersibility of polymer A is more excellent.

[0036] (Polyglycerol fatty acid ester) The polyglycerol fatty acid ester contributes to improving the practical oil resistance and the dispersion stability of polymer A in the present composition.

[0037] The polyglycerol fatty acid ester is an ester of polyglycerol and a fatty acid. The average degree of polymerization of polyglycerol is preferably 6 to 15, more preferably 8 to 12. When the average degree of polymerization is within the above range, the HLB of the polyglycerol fatty acid ester can be easily adjusted to the preferred range described below. Examples of polyglycerin include tetraglycerin (average degree of polymerization 4), hexaglycerin (average degree of polymerization 6), and decaglycerin (average degree of polymerization 10). The average degree of polymerization is determined using the hydroxyl value (mgKOH / g) according to JIS K 1557-1: 2009. Specifically, when 56.1×1000 / hydroxyl value=A, the average degree of polymerization can be calculated using the formula {(2×A−18.0) / (74.1−A)}.

[0038] The fatty acids may be saturated or unsaturated, and may be straight-chain or branched. The number of carbon atoms in the fatty acid is preferably 6 to 22, more preferably 8 to 18. When the number of carbon atoms in the fatty acid is within the above range, the HLB of the polyglycerol fatty acid ester can be easily adjusted to fall within the preferred range described below.

[0039] The molar ratio of polyglycerin to fatty acid (polyglycerin: fatty acid) in the polyglycerin fatty acid ester is preferably 15:1 to 2:1, more preferably 12:1 to 8:1. When the amount of polyglycerin is 8 to 12 moles per mole of carboxylic acid, it is easy to set the HLB within the preferred range described below.

[0040] Examples of polyglycerin fatty acid esters include tetraglyceryl dilaurate, tetraglyceryl dimyristate, tetraglyceryl dipalmitate, tetraglyceryl distearate, tetraglyceryl dibehenate, tetraglyceryl trilaurate, tetraglyceryl trimyristate, tetraglyceryl tripalmitate, tetraglyceryl tristearate, tetraglyceryl tribehenate, tetraglyceryl tetralaurate, tetraglyceryl tetramyristate, tetraglyceryl tetrapalmitate, and tetraglyceryl tetrastearate. Laglyceryl, Tetraglyceryl Tetrabehenate, Hexaglyceryl Dilaurate, Hexaglyceryl Dimyristate, Hexaglyceryl Dipalmitate, Hexaglyceryl Distearate, Hexaglyceryl Dibehenate, Hexaglyceryl Trilaurate, Hexaglyceryl Trimyristate, Hexaglyceryl Tripalmitate, Hexaglyceryl Tristearate, Hexaglyceryl Tribehenate, Hexaglyceryl Tetralaurate, Hexaglyceryl Tetramyristate, Hexaglyceryl Tetrapalmitate, Tetrastearic Acid Hexaglyceryl, Hexaglyceryl Tetrabehenate, Hexaglyceryl Pentalaurate, Hexaglyceryl Pentamyrstate, Hexaglyceryl Pentapalmitate, Hexaglyceryl Pentastearate, Hexaglyceryl Pentabehenate, Decaglyceryl Monolaurate, Decaglyceryl Monomyristate, Decaglyceryl Monopalmitate, Decaglyceryl Monostearate, Decaglyceryl Monobehenate, Decaglyceryl Dilaurate, Decaglyceryl Dimyristate, Decaglyceryl Dipalmitate, Decaglyceryl Distearate Lyceryl, Decaglyceryl Dibehenate, Decaglyceryl Trilaurate, Decaglyceryl Trimyristate, Decaglyceryl Tripalmitate, Decaglyceryl Tristearate, Decaglyceryl Tribehenate, Decaglyceryl Tetralaurate, Decaglyceryl Tetramyristate, Decaglyceryl Tetrapalmitate, Decaglyceryl Tetrastearate, Decaglyceryl Tetrabehenate, Decaglyceryl Pentalaurate, Decaglyceryl Pentamyrstate, Decaglyceryl Pentapalmitate, Decaglyceryl PentastearateExamples include decaglyceryl pentabehenate, decaglyceryl heptalaurate, decaglyceryl heptamyrstate, decaglyceryl heptapalmitate, decaglyceryl heptastearate, decaglyceryl heptabehenate, decaglyceryl octalaurate, decaglyceryl octamyrstate, decaglyceryl octapalmitate, decaglyceryl octastearate, and decaglyceryl octabehenate. Decaglyceryl monolaurate and decaglyceryl monostearate are more preferred because they provide articles obtained from the composition with superior practical oil resistance and dispersion stability of polymer A in the composition. Two or more types of polyglycerol fatty acid esters may be used.

[0041] The HLB of the polyglycerol fatty acid ester is preferably 10 to 18, more preferably 12 to 17. When the HLB of the polyglycerol fatty acid ester is within the above range, the practical oil resistance of the article obtained from the composition and the dispersion stability of polymer A in the composition are excellent. HLB is measured by the Griffin method.

[0042] (aqueous medium) Aqueous media include water and water containing a water-soluble organic solvent. The water-soluble organic solvent is an organic solvent that is miscible with water in any ratio, and is preferably at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, polyglycerols, and aprotic polar solvents. Examples of alcohols include t-butanol and propylene glycol. Examples of ether alcohols include 3-methoxymethylbutanol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol. Examples of polyglycerin include the same polyglycerin as in the polyglycerin fatty acid ester. Examples of aprotic polar solvents include N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (hereinafter also referred to as "THF"), acetonitrile, acetone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-3-methyl-1-butanol, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. When the liquid medium is an aqueous medium, the water-soluble organic solvent is preferably an ether alcohol, and more preferably dipropylene glycol, tripropylene glycol, or dipropylene glycol monomethyl ether, from the viewpoint of improving the compatibility between the polymer A and the aqueous medium and facilitating the formation of a uniform film on the article. When the aqueous medium is water containing water-soluble organic solvents, the total content of the water-soluble organic solvents is preferably 1 to 80 parts by mass, more preferably 5 to 60 parts by mass, per 100 parts by mass of water.

[0043] (medium other than aqueous medium) Examples of media other than the aqueous media include water-insoluble media. Examples of water-insoluble media include glycols, glycol ethers (excluding ether alcohols), hydrocarbons, ketones, esters, and halogenated compounds other than ethers (excluding ether alcohols and glycol ethers). Two or more of these media may be used. Examples of the glycol or glycol ether include diethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. Examples of the hydrocarbons include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Examples of aliphatic hydrocarbons include pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, and hexadecane. Examples of alicyclic hydrocarbons include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. Examples of the ketone include methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, and methyl isobutyl ketone. Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, and methyl propionate. An example of the ether is diisopropyl ether. Examples of the halogen compound include halogenated hydrocarbons and halogenated ethers. Examples of halogenated hydrocarbons include hydrochlorofluorocarbons, hydrofluorocarbons, and hydrobromocarbons. Examples of halogenated ethers include hydrofluoroethers. Examples of hydrofluoroethers include separated hydrofluoroethers and non-separated hydrofluoroethers. Separated hydrofluoroethers are compounds in which a perfluoroalkyl group or a perfluoroalkylene group and an alkyl group or an alkylene group are bonded via an etheric oxygen atom. Non-separated hydrofluoroethers are hydrofluoroethers containing a partially fluorinated alkyl group or alkylene group. When a medium other than an aqueous medium is contained, the content of the medium other than an aqueous medium is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, per 100 parts by mass of polymer A.

[0044] (Other surfactants) As the other surfactant, a surfactant having no fluorine atom is preferred. Examples of other surfactants include anionic surfactants, nonionic surfactants (excluding polyglycerol fatty acid esters), cationic surfactants, and amphoteric surfactants.

[0045] Examples of nonionic surfactants include surfactants described in paragraphs

[0067] to

[0095] of JP-A-2009-215370. 1 ~s 6 (However, polyglycerin fatty acid esters are excluded.) Surfactants 1 As the alkyl ether, polyoxyethylene alkyl ether is preferred. Surfactants 2 As the surfactant, acetylene glycol ethylene oxide adduct is preferred. 3 As the nonionic surfactant, an ethylene oxide propylene oxide polymer is preferred. Two or more types of nonionic surfactants may be used in combination.

[0046] Examples of cationic surfactants include surfactants described in paragraphs

[0096] to

[0100] of JP-A-2009-215370. 7 Examples include: Surfactants 7 As the ammonium salt, an ammonium salt in which one or more hydrogen atoms bonded to the nitrogen atom are substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene chain having a hydroxyl group at the end is preferred, and the ammonium salt represented by the following formula (s 71 ) represented by the compound (s 71 ) is more preferred. [(R 21 )4N + ]·X - (s 71 ) 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 terminal hydroxyl group. 21 may be the same or different, but the four R 21 is not a hydrogen atom at the same time. X - is the counter ion. X - As the cation, chloride ion, ethyl sulfate ion, or acetate ion is preferred. compound(s) 71 ) include, for example, monostearyl trimethyl ammonium chloride, monostearyl dimethyl monoethyl ammonium ethyl sulfate, mono(stearyl) monomethyl di(polyethylene glycol) ammonium chloride, di(tallow alkyl) dimethyl ammonium chloride, and dimethyl monococonut amine acetate. Two or more cationic surfactants may be used in combination.

[0047] Examples of amphoteric surfactants include surfactants described in paragraphs

[0101] to

[0102] of JP-A-2009-215370. 8 These may be used alone or in combination of two or more.

[0048] (Other ingredients) The other components may be added to the dispersion (D1) or to the dispersion (D2). Examples of other components that can be added to the dispersion (D1) include resins other than the polymer A, adhesives, crosslinking agents, catalysts, organic fillers, inorganic fillers, supports, preservatives, flocculants, buffers, bactericides, biocides, sequestering agents, hydrophobizing agents, surfactants, antifoaming agents, and volatile organic solvents. Examples of other components to be added to the dispersion (D2) include, as co-additives for external addition described below, paper strength agents (various starches, resins, etc.), sizing agents, penetrating agents, antifoaming agents, chelating agents, dyes, pigments, dyes, binders, acids, alkalis, alginates, and aluminum sulfate, and examples of co-additives for internal addition described below include coagulants, retention agents, sizing agents, paper strength agents, pigments, dyes, and pH adjusters. Two or more of the other components may be used. The same component as that added to the dispersion liquid (D1) or a different component that causes the same effect may be added to the dispersion liquid (D2). Examples of other components are not limited to these.

[0049] When the present composition contains a crosslinking agent, the adhesion to the substrate tends to be improved. As the crosslinking agent, an isocyanate-based crosslinking agent, a methylol-based crosslinking agent, a carbodiimide-based crosslinking agent, and an oxazoline-based crosslinking agent are preferred. Examples of the isocyanate crosslinking agent include an aromatic block type isocyanate crosslinking agent, an aliphatic block type isocyanate crosslinking agent, an aromatic unblocked type isocyanate crosslinking agent, and an aliphatic unblocked type isocyanate crosslinking agent. The isocyanate crosslinking agent is preferably a water-dispersible type emulsified with a surfactant, or a self-water-dispersible type having a hydrophilic group.

[0050] Examples of methylol-based crosslinking agents include condensates or pre-condensates of urea or melamine with formaldehyde, methylol-dihydroxyethylene-urea and derivatives thereof, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, dicyandiamide-formaldehyde condensates, methylol-carbamate, methylol-(meth)acrylamide, and polymers thereof.

[0051] The carbodiimide crosslinking agent is a polymer having a carbodiimide group in the molecule, and is a crosslinking agent that exhibits excellent reactivity with carboxyl groups, amino groups, and active hydrogen groups of the substrate. The oxazoline-based crosslinking agent is a polymer having an oxazoline group in the molecule, and is a crosslinking agent that exhibits excellent reactivity with carboxy groups of the substrate and the like.

[0052] Other crosslinking agents include, for example, divinyl sulfone, polyamide and its cationic derivatives, polyamine and its cationic derivatives, epoxy derivatives such as diglycidyl glycerol, halide derivatives such as (epoxy-2,3-propyl)trimethylammonium chloride and N-methyl-N-(epoxy-2,3-propyl)morpholinium chloride, pyridinium salts of chloromethyl ether of ethylene glycol, polyamine-polyamide-epichlorohydrin resins, polyvinyl alcohol or its derivatives, polyacrylamide or its derivatives, and glyoxal resin-based wrinkle inhibitors.

[0053] When the present composition contains a methylol-based crosslinking agent or a glyoxal resin-based wrinkle preventative, it is preferable to contain a catalyst as an additive. Preferred catalysts include, for example, inorganic amine salts and organic amine salts. Examples of inorganic amine salts include ammonium chloride. Examples of organic amine salts include amino alcohol hydrochlorides and semicarbazide hydrochloride. Examples of amino alcohol hydrochlorides include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride, and 2-amino-2-methylpropanol hydrochloride.

[0054] (proportion of each ingredient) The content of the polyglycerol fatty acid ester is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, and even more preferably 4 to 7 parts by mass, relative to 100 parts by mass of polymer A. When the content of the polyglycerol fatty acid ester is within the above range, the practical oil resistance of an article obtained using the present composition is superior.

[0055] The content of the aqueous medium can be appropriately selected depending on the desired solid content of the composition. The solid content concentration of the present composition is preferably from 20 to 70 mass %, more preferably from 30 to 60 mass %, when the composition is in the form of dispersion (D1) (immediately after the production of the present composition). When the composition is a dispersion (D2) (when the composition is used to treat an article), the solid content concentration of the composition is preferably from 0.1 to 7 mass %, more preferably from 0.2 to 5 mass %.

[0056] The content of the other surfactant is preferably 6 parts by mass or less, and more preferably 3 parts by mass or less, per 100 parts by mass of polymer A. When the content of the surfactant is equal to or less than the upper limit, adverse effects of the surfactant on the water resistance and oil resistance of an article obtained using the present composition can be reduced. The content of the other surfactant may be 0 parts by mass.

[0057] The content of the crosslinking agent in the present composition is preferably 1 to 50 parts by mass per 100 parts by mass of polymer A when used to treat a substrate such as paper.

[0058] (Mechanism of action) In the present composition described above, since polymer A has units (a), it is possible to obtain articles (waterproof and oilproof paper, etc.) whose water resistance and oil resistance are resistant to deterioration by alkalis and the like. Furthermore, since the present composition contains the polyglycerol fatty acid ester together with polymer A, it has excellent practical oil resistance.

[0059] [Method for producing water- and oil-resistant agent composition] This composition can be produced, for example, by polymerizing the monomer components consisting of monomer (a) and monomer (b) in an emulsion containing a polyglycerol fatty acid ester, an aqueous medium, and a polymerization initiator. This method improves the conversion of the monomer components to polymer A and also increases the number-average molecular weight of the resulting polymer A. The emulsion may contain other surfactants (excluding polyglycerol fatty acid esters) as needed.

[0060] The proportion of the monomer (a) relative to the total monomer components (i.e., the sum of the monomers (a) and (b)) is preferably 15 to 40 mol%, more preferably 20 to 38 mol%, and even more preferably 25 to 35 mol%. When the proportion of the monomer (a) is equal to or greater than the lower limit, the water resistance and oil resistance of the article obtained using the composition are superior. When the proportion of the monomer (a) is equal to or less than the upper limit, the conversion rate in the polymerization reaction of polymer A tends to be higher.

[0061] When at least a portion of the monomer (b) is the monomer (b1), the proportion of the monomer (b1) relative to the total monomer components is preferably 60 to 85 mol%, more preferably 62 to 80 mol%, and even more preferably 65 to 75 mol%. When the proportion of the monomer (b1) is equal to or greater than the lower limit, the conversion rate in the polymerization reaction tends to be higher. When the proportion of the monomer (b1) is equal to or less than the upper limit, the water resistance and oil resistance of the resulting article are better.

[0062] The proportion of the monomer (b2) relative to the total monomer components is preferably 25% by mass or less, more preferably 12% by mass or less, even more preferably 10% by mass or less, and may be 0% by mass. When the proportion of the monomer (b2) is equal to or less than the upper limit, an article can be obtained that is less susceptible to deterioration in water resistance and oil resistance due to alkalis, etc.

[0063] Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, and an ionic polymerization initiator, with a radical polymerization initiator being preferred. Examples of the radical polymerization initiator include an azo-based polymerization initiator, a peroxide-based polymerization initiator, and a redox-based initiator, which are used depending on the polymerization temperature. Azo-based compounds are preferred as the radical polymerization initiator, and salts of azo-based compounds are more preferred. The polymerization temperature is preferably 20 to 150°C. 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, per 100 parts by mass of the monomer component.

[0064] A molecular weight modifier may be used when polymerizing the monomer components. Examples of the molecular weight modifier include aromatic compounds, mercapto alcohols, mercaptocarboxylic acids, and alkyl mercaptans, and more preferably mercaptocarboxylic acids or alkyl mercaptans. Examples of the molecular weight modifier include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dimer (CH═C(Ph)CHC(CH)Ph, where Ph is a phenyl group). The amount of the molecular weight modifier added is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and may be 0 parts by mass, per 100 parts by mass of the monomer component.

[0065] The emulsion can be prepared by mixing an aqueous medium, a monomer component, and, if necessary, other surfactants, dispersing the mixture using a homogenizer, a high-pressure emulsifier, or the like, and then adding a polymerization initiator. The concentration of the monomer component in the emulsion is preferably 20 to 60% by mass, more preferably 30 to 50% 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 polymer A during polymerization of the monomer component can be improved, and the molecular weight of polymer A can be sufficiently increased.

[0066] The content of the polyglycerol fatty acid ester in the emulsion is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, and even more preferably 4 to 7 parts by mass, per 100 parts by mass of the monomer component. If the content of the polyglycerol fatty acid ester is within the above range, the practical oil resistance of an article obtained using the composition will be superior, and if it is equal to or greater than the above lower limit, the dispersion stability of the emulsion will be superior.

[0067] The content of the other surfactant in the emulsion is preferably 6 parts by mass or less, more preferably 3 parts by mass or less, per 100 parts by mass of the monomer component. When the content of the other surfactant is equal to or less than the upper limit, adverse effects of the other surfactant on the water resistance and oil resistance of the article obtained using the composition can be reduced. The content of the other surfactant may be 0 parts by mass.

[0068] The dispersion of polymer A obtained by polymerizing the monomer components in the emulsion may be used as the present composition as is, or may be used as the present composition after diluting with an aqueous medium to adjust the solid content concentration. Other components may also be added to the present composition.

[0069] The conversion rate of the monomer component to polymer A at the end of polymerization is preferably 80% or more, more preferably 90% or more. By increasing the conversion rate, the molecular weight of polymer A also increases, and the water resistance and oil resistance of waterproof and oil-resistant paper and the like made using this composition also improve. Furthermore, by achieving a high conversion rate, performance degradation due to residual monomers is suppressed, and the amount of fluorine atoms contained in polymer A increases, resulting in good water resistance and oil resistance. To achieve a conversion rate of 80% or more, it is preferable to optimize the emulsion composition and polymerization time.

[0070] The composition can be applied to the treatment of various substrates and to the production of water- and oil-resistant paper, which will be described later.

[0071] (Mechanism of action) In the manufacturing method of the present invention described above, a monomer component containing the monomer (a) is polymerized, and therefore a water- and oil-resistant agent composition can be produced that can provide an article whose water resistance and oil resistance are resistant to deterioration by alkalis, etc. Furthermore, in the production method of the present invention, since the monomer components are polymerized in an emulsion, it is possible to increase the molecular weight of the polymer A. As a result, it is possible to produce a waterproof and oil-proof agent composition that can be used to produce waterproof and oil-proof paper and the like that has excellent water resistance and oil resistance. Furthermore, in the production method of the present invention, since the emulsion contains a polyglycerol fatty acid ester, it is possible to produce a water- and oil-resistant agent composition that can give articles having excellent practical oil resistance.

[0072] However, the method for producing the present composition is not limited to the above method. For example, the present composition may be produced by polymerizing the above monomer components to obtain polymer A, and then mixing the obtained polymer A with a polyglycerol fatty acid ester and an aqueous medium. In this case, polymer A can be obtained by a conventionally known method such as emulsion polymerization, solution polymerization, or bulk polymerization.

[0073] [Goods] The articles of the present invention are treated with the present compositions. The article of the present invention can be obtained by treating a substrate with the present composition. By treating a substrate with the present composition, an article having water and oil resistance can be obtained.

[0074] Examples of substrates include paper substrates (paper, paperboard, molded pulp, synthetic paper using synthetic fibers as at least a part of the raw material, and related products), woven or nonwoven fabrics based on cellulose or regenerated cellulose, woven or nonwoven fabrics based on natural or artificial fibers (cotton, cellulose acetate, wool, silk, etc.), woven or nonwoven fabrics based on artificial or synthetic fibers (polyamide fibers, polyester fibers, polyolefin fibers, polyurethane fibers, polyacrylonitrile fibers, etc.), leather, artificial leather, resins, plastic materials such as films, glass, wood, metal, concrete, stone, tile, ceramics, brick, and painted surfaces.

[0075] The treatment method includes applying or impregnating the composition onto a substrate, drying the substrate in an environment of 60°C or higher, and optionally heat treating the substrate. By performing drying, heat treatment, etc., it is possible to impart better water resistance and oil resistance to the substrate.

[0076] As for the article, water-resistant and oil-resistant paper and water-resistant and oil-resistant pulp mold are preferred because the present composition is suitable for treating paper substrates.

[0077] The article of the present invention has excellent practical oil resistance because it has been treated with the present composition.

[0078] [Water-resistant and oil-resistant paper] The water-resistant and oil-resistant paper of the present invention is made from pulp or paper treated with the present composition. Methods for producing waterproof and oil-resistant paper include a method in which the present composition is applied to or impregnated into a paper base material (external addition), and a method in which a pulp slurry containing the present composition is made into paper (internal addition). In the external addition process and internal addition process, the present composition may be used after being diluted with water or an aqueous medium. The solid content concentration of the present composition used in the manufacturing method of waterproof and greaseproof paper is preferably 10 to 30 mass %, more preferably 20 to 25 mass %.

[0079] (External additive processing) The paper base material can be made by dispersing pulp in water and using one type of pulp slurry alone or two or more types mixed at any blending ratio, beating, adding chemicals, and then papering using a wire. Examples of the form include a continuous long web, cut sheets, and molded products (containers, etc.) obtained using a pulp molding machine. The basis weight is, for example, 10 to 500 g / m. 2 That's fine too.

[0080] Specific examples of raw materials for pulp include wood such as conifers and broad-leaved trees, herbs such as bagasse, rice straw, bamboo, reeds, and palm husks, and waste paper. Pulp made from wood and herbs is called fresh pulp, and pulp made from waste paper is called recycled pulp. Fresh pulp is called by different names depending on the production method, such as kraft pulp (KP), sulfite pulp (SP), soda pulp, mechanical pulp (MP), thermomechanical pulp (TMP), and chemithermomechanical pulp (CTMP). Fresh pulp may be subjected to one or more bleaching treatments, as needed. The recycled pulp may be produced by carrying out one of the processes of defibration, dedusting, deinking and bleaching, or by combining a plurality of these processes, as required.

[0081] The paper base material may contain sizing agents, fixing agents, dry strength agents, wet strength agents, aluminum sulfate, retention aids, dyes, pigments, fillers, etc., within the range that does not impair the effects of the present invention.

[0082] The composition may also include a co-agent. Examples of co-additives used in external additive processing include paper strength agents (various starches, resins, etc.), sizing agents, penetrating agents, antifoaming agents, chelating agents, dyes, pigments, dyes, binders, acids, alkalis, alginates, and aluminum sulfate.

[0083] The application or impregnation of the composition may be carried out at any stage after papermaking, such as at the size press stage after papermaking, wet pressing, and pre-drying, or at a stage using a coater after the size press. The composition may be applied using a coating machine. Examples of the coating machine include a size press, a coater, and a printing machine. Examples of the size press include a two-roll size press, a film transfer size press, and a calendar size press. 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, and a short dwell blade coater. Examples of the printing press include a gravure printing press, a flexographic printing press, and an offset printing press.

[0084] After the paper substrate is coated or impregnated with the composition, it is dried. The drying method may be a method of drying with 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.

[0085] (Inner additive processing) The pulp slurry comprises water and pulp dispersed in the water. The raw material for the pulp is the same as that described above for the external additive process. The pulp slurry may be produced by disintegrating dry pulp using a disintegrator, or by diluting wet pulp produced in a pulp manufacturing facility. One type of pulp slurry may be used alone, or two or more types may be mixed at any desired ratio. The concentration of pulp in the pulp slurry is preferably 0.1 to 10% by mass.

[0086] The composition may be added at any stage before the pulp slurry is fed onto the wire of the paper machine. Other additives may be added to the pulp slurry. Examples of the additives used in the internal addition process include coagulants, retention aids, sizing agents, paper strength agents, pigments, dyes, and pH adjusters.

[0087] A paper machine can be used to make paper from the pulp slurry. The paper machine may be any machine capable of dewatering the pulp slurry on a wire. The paper machine may be a continuous paper machine such as a Fourdrinier paper machine, or a batch-type pulp molding machine. A batch-type pulp molding machine is, for example, a machine that dewaters the pulp slurry using a molding frame formed from a wire to produce a molded body.

[0088] The water- and oil-resistant paper of the present invention is made from pulp or paper treated with the present composition, and therefore has excellent practical oil resistance. [Example]

[0089] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. The room temperature is 25 ± 5°C. "Part" means "part by mass". Examples 1 to 8 are examples, and Examples 9 to 14 are comparative examples.

[0090] (Solid content concentration) The sample (fluorine-containing polymer dispersion) obtained in the examples described below was heated in an intake type oven (convection dryer) heated to 120°C for 4 hours. The solid content concentration (measured) (mass %) was determined by dividing the mass of the solid obtained after heating (solid content mass) by the mass of the sample before heating. The solid content concentration (theory) was calculated from the solid content concentration and the usage amount of the raw materials used in each example.

[0091] (Composition of fluorine-containing polymer) The composition of the fluorine-containing polymer (the ratio of each monomer unit to all the units constituting the fluorine-containing polymer) (mol %) was calculated based on the charged amount of the monomer components.

[0092] (Molecular weight) (Recovery of fluorine-containing polymer) 6 g of the fluorine-containing polymer dispersion obtained in each example was dropped into 60 g of a mixed solution of 6 g of hexane and 54 g of 2-butanol, and stirred to precipitate a solid. After centrifuging at 3000 rpm for 5 minutes, the obtained solid was separated. 30 g of isopropyl alcohol denatured alcohol (manufactured by Imazu Co., Ltd., product name: 95% IPA denatured alcohol) and 30 g of ion-exchanged water were added to the separated solid and stirred well. After centrifuging at 3000 rpm for 5 minutes, the obtained solid was separated from the supernatant and vacuum dried at 35°C overnight to obtain a fluorine-containing polymer.

[0093] (Measurement of Mn) The recovered fluorine-containing polymer was dissolved in a mixed medium of fluorine-containing medium (AK-225, product name of AGC) / THF = 6 / 4 (volume ratio) to form a solution with a solid content concentration of 0.5 mass %, passed through a 0.2 μm filter, and used as an analysis sample. For the analysis sample, the number average molecular weight (Mn) was measured by GPC measurement. The measurement conditions are as follows. Apparatus: Tosoh HLC-8320GPC Column: Polymer Laboratories, MIXED-C 300 x 7.5 mm 5 μm Mobile phase: AK-225 / THF=6 / 4 (volume ratio) mixed medium, Flow rate: 1.0mL / min, Oven temperature: 37℃, Sample concentration: 1.0% by mass Injection volume: 50μL, Detector: RI (refractive index detector), Molecular weight standards: polymethyl methacrylate (Mn = 2136000, 955000, 569000, 332800, 121600, 67400, 31110, 13300, 7360, 1950, 1010, and 550).

[0094] (Oil resistance: TAPPI KIT) The test paper was evaluated for oil resistance (kit method) using a test liquid (kit test liquid) made by mixing castor oil, toluene, and heptane in the ratios (volume %) shown in Table 1, according to the following method in accordance with TAPPI KIT-559cm-02. At room temperature, the test paper was placed on a clean, flat, black surface, and a drop of the test liquid with the higher kit number was dropped onto the test paper from a height of 13 mm. After 15 seconds, the dropped test liquid was removed with clean blotting paper, and the condition of the surface of the test paper that had come into contact with the test liquid was visually observed. The first (highest) kit number at which no trace of the dropped liquid remained on the surface of the test paper was used as an index of oil resistance. The higher the number, the better the oil resistance. Grade 4 or higher was considered ○ (pass).

[0095] [Table 1]

[0096] (Water resistance: Stöckicht size) The test paper was measured for sizing degree (seconds) by the Stockigt method in accordance with JIS P 8122:2004. The longer the sizing degree, the better the water resistance. A sizing degree of 7 seconds or more was rated as ○ (pass).

[0097] (Practical oil resistance: soybean oil test) The test paper was cut to a size of 5 cm x 5 cm. The cut test paper was then folded in four, unfolded, and placed on a horizontal table. Approximately 0.5 mL of soybean oil was dropped near the center of the test paper. The test paper with the dropped soybean oil was then placed in an environmental test chamber and held at 60°C for 1 or 2 hours. After that, the test paper was removed from the environmental test chamber and the soybean oil on the test paper was removed. The degree of soybean oil absorption onto the test paper was then visually observed and rated on a six-point scale as shown in Table 2. The higher the number, the better the practical oil resistance. This test uses general-purpose vegetable edible oils and fats, allowing for evaluation of oil resistance under practical usage conditions.

[0098] [Table 2]

[0099] The raw materials used in the examples below are as follows: (Monomer (a)) C6OLF: CH2=CH-(CF2)5CF3 (Tokyo Chemical Industry Co., Ltd.). (Monomer (b)) VAC: vinyl acetate (Tokyo Chemical Industry Co., Ltd.). VP: vinyl pivalate (Tokyo Chemical Industry Co., Ltd.). NVP: N-vinyl-2-pyrrolidone.

[0100] (Polyglycerol fatty acid ester) D1-50SV: Decaglyceryl monostearate (Nikko Chemicals product name, NIKKOL Decaglyn 1-50SV, HLB value 15). D1-L: Decaglyceryl monolaurate (Nikko Chemicals product name, NIKKOL Decaglyn 1-L, HLB value 15.5).

[0101] (Other surfactants) E430: 10% by mass aqueous solution of polyoxyethylene oleyl ether (approximately 30 moles of ethylene oxide adduct, Kao Corporation product name, Emulgen 430). P204: Ethylene oxide-propylene oxide polymer (oxyethylene group content 40% by mass, average molecular weight 3330, NOF Corporation product name, Pronon #204). SFY420: 10% by mass dipropylene glycol solution of acetylene glycol ethylene oxide adduct (number of moles of ethylene oxide added: 1.3 moles, product name: Surfynol 420, manufactured by Nissin Chemical Industry Co., Ltd.). <Cationic surfactants> LQ1863: 63% by mass solution of monostearyltrimethylammonium chloride in water and isopropyl alcohol (Lion Specialty Chemicals product name, Lipocard 18-63).

[0102] (medium) Water: Ion-exchanged water. DPG: dipropylene glycol. (Polymerization initiator) VA-061A: 20% by mass aqueous solution of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (product name: VA-061, Fujifilm Wako Pure Chemical Industries, Ltd.) acetate (VA-061:acetic acid = 1:0.8 (mass ratio)).

[0103] (Example 1) <Preparation of Fluoropolymer Dispersion> A 30 mL vial was charged with 66.7 parts of C6OLF, 33.3 parts of VAC, 3.0 parts of D1-50SV, 82.5 parts of water, and 17.5 parts of DPG to obtain a mixture. The resulting mixture was stirred with a homogenizer to obtain an emulsion. The entire emulsion was transferred to an ampoule, and 5.0 parts of VA061A was added. The gas phase of the ampoule was replaced with nitrogen, and polymerization was carried out at 45°C for 72 hours to obtain a fluoropolymer dispersion. Table 3 shows the solids concentration, fluoropolymer composition, and Mw of the resulting fluoropolymer dispersion.

[0104] <Preparation of test paper 1 (external addition)> The obtained fluoropolymer dispersion was diluted with water to prepare a treatment liquid having a solid content concentration of about 2% by mass. The treatment liquid was applied to a size press using a basis weight of 40 g / m 2The coating amount of the treatment liquid was adjusted so that the mass of the fluorine-containing polymer per unit area of ​​the resulting test paper was about 0.2 g / m. 2 or about 0.6 g / m 2 Table 3 shows the evaluation results of the obtained test papers.

[0105] (Example 2) <Preparation of test paper 2 (internal addition)> Pulp with a mass ratio (LBKP / NBKP) of hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP) of 5 / 5 and a post-filtration water volume of 550 mLc.sf was dispersed in water so that the solid content of the stock was 1.0 mass%, and the fluoropolymer dispersion prepared in Example 1 was further blended to prepare a stock. This stock was hand-made on a paper machine to a basis weight after drying of about 80 g / cm. 2 The paper was made so that the paper was sized to meet the above criteria, and dried at 100°C for 60 seconds using a drum dryer to obtain a test paper. Csf is a unit that indicates the amount of water when water-dispersed pulp with a Canadian Standard Freeness of 1000 mL is filtered through a specified filter. The amount of the fluoropolymer dispersion to be blended is such that the mass of the fluoropolymer per unit area of ​​the resulting test paper is about 80 g / m 2 The amount was set so that the mass of the fluoropolymer relative to the dry mass of the pulp was about 0.3% by mass. Table 5 shows the evaluation results of the obtained test papers.

[0106] (Examples 3 to 14) Fluorine-containing polymer dispersions were prepared and test papers were produced in the same manner as in Example 1, except for using the raw materials shown in Tables 3 and 4. Tables 3 and 4 show the solids concentrations of the obtained fluoropolymer dispersions, the compositions and Mw of the fluoropolymers, and the evaluation results of the obtained test papers.

[0107] [Table 3]

[0108] [Table 4]

[0109] [Table 5]

[0110] The test papers obtained using the fluoropolymer dispersions of Examples 1 to 8 were excellent in practical oil resistance and also had good water resistance. On the other hand, the test papers obtained using the fluoropolymer dispersions of Examples 9 to 14 containing other surfactants instead of the polyglycerol fatty acid ester had good oil resistance measured by the kit method but poor practical oil resistance. [Industrial Applicability]

[0111] The water- and oil-proofing composition of the present invention is useful as a water- and oil-proofing agent for paper, a surface treatment agent for glass and resin products, a water- and oil-repellent agent, an antifouling agent, a release agent, etc. The waterproof and oil-resistant paper using the waterproof and oil-proofing composition of the present invention is useful as a food packaging container, food packaging paper, stain-proof sheet, etc. The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2020-088235, filed on May 20, 2020, are hereby incorporated by reference as part of the disclosure of the specification of the present invention.

Claims

1. The present invention relates to a fluorine-containing polymer comprising a unit based on the following monomer (a) and a unit based on the following monomer (b), at least one polyglycerol fatty acid ester selected from the group consisting of decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monopalmitate, decaglyceryl monostearate, and decaglyceryl monobehenate, and an aqueous medium, At least a part of the monomer (b) is the following monomer (b1): the proportion of units based on the monomer (a) is 15 to 40 mol % based on all units constituting the fluorine-containing polymer, the proportion of units based on the monomer (b1) is 60 to 85 mol % based on all units constituting the fluorine-containing polymer, A water- and oil-proofing agent composition for pulp or paper, wherein the content of the polyglycerol fatty acid ester is 2 to 8 parts by mass per 100 parts by mass of the fluorine-containing polymer. Monomer (a): A compound represented by the following formula (1): CH ２ =CH-R ｆ (1) However, R ｆ is a perfluoroalkyl group having 4 to 6 carbon atoms. Monomer (b): A monomer copolymerizable with the monomer (a). Monomer (b1): vinyl acetate.

2. a monomer component comprising the following monomer (a) and the following monomer (b), at least one polyglycerol fatty acid ester selected from the group consisting of decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monopalmitate, decaglyceryl monostearate, and decaglyceryl monobehenate, an aqueous medium, and a polymerization initiator; At least a part of the monomer (b) is the following monomer (b1): the ratio of the monomer (a) to the total monomer components is 15 to 40 mol %, the proportion of the monomer (b1) relative to the total monomer components is 60 to 85 mol %, A method for producing a water- and oil-proofing agent composition for pulp or paper, wherein the content of the polyglycerol fatty acid ester is 2 to 8 parts by mass per 100 parts by mass of the monomer component. Monomer (a): A compound represented by the following formula (1): CH ２ =CH-R ｆ (1) However, R ｆ is a perfluoroalkyl group having 4 to 6 carbon atoms. Monomer (b): A monomer copolymerizable with the monomer (a). Monomer (b1): vinyl acetate.

3. 2. A waterproof and oil-resistant paper obtained by treating pulp or paper with the waterproof and oil-resistant composition according to claim 1.

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