Fluorine-based polymer, surface treatment agent, method for manufacturing textile products, and textile products

Abstract

A fluorine polymer according to the present disclosure has excellent water repellency as a result of comprising a structural unit that is derived from a fluorine-containing polymerizable monomer represented by general formula (A) and a structural unit that is derived from a cyclic hydrocarbon-containing monomer represented by general formula (B).

Description

[Technical Field]

[0001] The present application discloses a fluorine-based polymer, a surface treatment agent, a method for producing a textile product, and the textile product. [Background technology]

[0002] Fluorine-based surface treatment agents containing compounds having a long-chain fluoroalkyl group have been known as surface treatment agents used to provide water repellency to substrate surfaces, etc. For example, by treating a fiber substrate with the fluorine-based surface treatment agent, a fiber product having excellent water repellency can be obtained.

[0003] On the other hand, when long-chain fluoroalkyl compounds are used as fluorine-based surface treatment agents, there are concerns about the environmental impact. In particular, when the carbon number of the long-chain fluoroalkyl group is large, the environmental impact is large. Therefore, perfluorooctanesulfonic acid (C8H 17 SO2F (hereinafter abbreviated as PFOS) and perfluorooctanoic acid (C7H 15 These are being replaced by fluorine-based surface treatment agents with perfluoroalkyl groups containing six or fewer carbon atoms, which do not generate long-chain fluoroalkyl compounds such as perfluoroalkanesulfonic acids and perfluoroalkanoic acids with more than eight carbon atoms.

[0004] As examples of fluorine-based surface treatment agents having a perfluoroalkyl group with 6 or less carbon atoms, Patent Documents 1 and 2 disclose copolymers containing, as a copolymerization component, a (meth)acrylate having a perfluoroalkyl group with 6 or less carbon atoms. However, these fluorine-based surface treatment agents contain substances derived from tetrafluoroethylene (hereinafter abbreviated as TFE), and may contain PFOA, which is generated during the manufacturing process of the fluorine-based surface treatment agent, as well as substances of very high concern specified in the European REACH regulation. Therefore, the surface treatment imposes a large burden on the environment and there are concerns about accumulation in the human body.

[0005] On the other hand, it has also been proposed to use, as a fluorine-based surface treatment agent, a fluorine-based polymer derived from hexafluoropropylene oxide (hereinafter abbreviated as HFPO), which has no environmental impact, instead of a fluorine-based polymer derived from TFE. For example, Patent Document 3 discloses a fluorine-containing polymer for masonry treatment, which contains a copolymer containing a fluorine-containing (meth)acrylate having a fluoroalkyl group, a fluoroalkenyl group, or a fluoroether group as a copolymerization component. However, the effectiveness of a fluorine-containing polymer containing a fluorine-containing acrylate having a fluoroether group is unclear. Furthermore, when a fluorine-based polymer derived from HFPO is used, its crystallinity is low, making it difficult to achieve high water repellency like that of a fluorine-based surface treatment agent derived from TFE. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2002 / 083809 [Patent Document 2] International Publication No. 2004 / 035708 [Patent Document 3] International Publication No. 2008 / 143093 Summary of the Invention [Problem to be solved by the invention]

[0007] As described above, there is a need for new fluorine-based polymers that have excellent water repellency. [Means for solving the problem]

[0008] As one of the means for solving the above problems, the present application provides: A structural unit derived from a fluorine-containing polymerizable monomer represented by the following general formula (A), A structural unit derived from a cyclic hydrocarbon-containing monomer represented by the following general formula (B), Fluorine-based polymer comprising Disclose.

[0009] [ka] In general formula (A), Rf 1 is a perfluoroalkyl group having 1 to 3 carbon atoms, Rf 2 and Rf 3 are each independently a perfluoroalkylene group having 1 to 3 carbon atoms, R 1 is hydrogen, a methyl group or chlorine, X 1 is -O(R 2 )O-, -NH(R 2 )O- or -NH-, and R 2 is a linear, branched or cyclic aliphatic hydrocarbon group having 2 to 6 carbon atoms, n is an integer from 6 to 60.

[0010] [ka] In general formula (B), R 3 is hydrogen, a methyl group or chlorine, Y 1 -COO-, -O-, -COO(R 4 )-, -COO(R 4 )O-, -CONH-, -CONHCO-, or -COOR 4 is a group represented by NHCO-, and R 4 is a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, X 2 represents a cyclic hydrocarbon group having 4 to 30 carbon atoms which may have a substituent, m is 0 or 1.

[0011] The fluorine-based polymer of the present disclosure may have structural units derived from at least one monomer (C) selected from vinyl halides and vinylidene halides.

[0012] The fluorine-based polymer of the present disclosure may have a structural unit derived from a (meth)acrylate ester monomer represented by the following general formula (D).

[0013] [ka] In general formula (D), R 5 is chlorine, bromine, iodine, hydrogen or a methyl group, Y 2 -COO-, -CONH-, -CONHCO-, -COOR 6 is a group represented by NHCO-, and R 6 is a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, X 3 is a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0014] The fluorine-based polymer of the present disclosure may have a structural unit derived from a crosslinkable monomer represented by the following general formula (E).

[0015] [ka] In general formula (E), R 7 is hydrogen or a methyl group, R 8 is a single bond or a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, Z is a group represented by -COO- or -CONH-, R 8 If is a single bond, X 4 is a hydroxyl group, an acetyl group, an epoxy group, a chloromethyl group, an amino group, a carboxyl group, a vinyl group, or an acryloyl group, R 8 is a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, X 4 is a hydroxyl group, an acetyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a vinyl group, or an acryloyl group.

[0016] In the fluorine-containing polymer of the present disclosure, the fluorine-containing polymerizable monomer may be represented by the following general formula (A1).

[0017] [ka]

[0018] In the fluorine-based polymer of the present disclosure, the cyclic hydrocarbon-containing monomer may contain a cyclic aliphatic group having at least two rings, or an alkyl group to which a cyclic aliphatic group having at least two rings is bonded.

[0019] In the fluorine-based polymer of the present disclosure, the cyclic hydrocarbon-containing monomer may be at least one selected from the group consisting of isobornyl(meth)acrylate, norbornyl(meth)acrylate, dicyclopentadienyl(meth)acrylate, adamantyl(meth)acrylate, 2-methyl-2-adamantyl(meth)acrylate, and 2-ethyl-2-adamantyl(meth)acrylate.

[0020] In addition, as one of the means for solving the above problems, the present application provides: A surface treatment agent containing the fluoropolymer of the present disclosure. Disclose.

[0021] The surface treatment agent of the present disclosure may contain at least one of waxes, silicones, and a crosslinking agent.

[0022] The surface treatment agent of the present disclosure may be used as at least one of a water repellent, a water- and oil-repellent, a water-repellent and antifouling agent, and a water-, oil-, and antifouling agent.

[0023] The fluorine-based polymer of the present disclosure may be used, for example, to impart water repellency to a fiber substrate when producing a fiber product. A method for producing a textile product, comprising contacting a textile substrate with a treatment liquid containing the fluoropolymer of the present disclosure. Disclose.

[0024] In addition, as one of the means for solving the above problems, the present application provides: A textile product to which the fluoropolymer of the present disclosure is attached. Disclose. [Effects of the Invention]

[0025] The fluoropolymer of the present disclosure has excellent water repellency. DETAILED DESCRIPTION OF THE INVENTION

[0026] 1. Fluorine-based polymers The fluorine-based polymer according to this embodiment comprises a structural unit derived from a fluorine-containing polymerizable monomer represented by the following general formula (A) and a structural unit derived from a cyclic hydrocarbon-containing monomer represented by the following general formula (B):

[0027] 1.1 Monomer (A) The fluorine-containing polymer according to this embodiment comprises a structural unit derived from a fluorine-containing polymerizable monomer (monomer (A)) represented by the following general formula (A): The monomer (A) may be used singly or in combination of two or more.

[0028] [ka]

[0029] In general formula (A), Rf 1 Rf is a perfluoroalkyl group having 1 to 3 carbon atoms. 1 The carbon number of Rf may be 2 to 3. 1 When the number of carbon atoms is 3, even better water repellency is likely to be exhibited. The monomer (A) may be, for example, one having a perfluoroalkyl group derived from hexafluoropropylene oxide (HFPO).

[0030] In general formula (A), Rf 2 and Rf 3 Rf are each independently a perfluoroalkylene group having 1 to 3 carbon atoms. 2 and Rf 3 The carbon number of each of Rf may be 2 to 3. 2 The carbon number is 3, and Rf 3 When the number of carbon atoms is 2, more excellent water repellency is likely to be exhibited.

[0031] In general formula (A), R 1 is hydrogen, a methyl group or chlorine.

[0032] In general formula (A), X 1 is -O(R 2 )O-, -NH(R 2 )O- or -NH-, and R 2 is a linear, branched or cyclic aliphatic hydrocarbon group having 2 to 6 carbon atoms. 2 When the number of carbon atoms is 2 or more and 4 or less, more excellent water repellency is likely to be exhibited.

[0033] In general formula (A), n is an integer of 6 to 60. It becomes difficult to ensure water repellency if n exceeds 60. n is preferably 7 or more and preferably 45 or less.

[0034] In the fluoropolymer according to this embodiment, the monomer (A) may be represented by the following general formula (A1): In this case, the fluoropolymer is likely to have even better water repellency, and is also likely to have excellent oil repellency and stain resistance.

[0035] [ka]

[0036] The content of the structural units derived from the monomer (A) in the fluoropolymer is not particularly limited. For example, the fluoropolymer may contain 15% by mass or more and 60% by mass or less of the structural units derived from the monomer (A). The lower limit is preferably 20% by mass or more. If the structural units derived from the monomer (A) in the fluoropolymer are too few, sufficient water repellency may not be exhibited. On the other hand, if the structural units derived from the monomer (A) in the fluoropolymer are too many, polymerization may be hindered, resulting in a decrease in performance.

[0037] As mentioned above, the monomer (A) has Rf 1 , Rf 2 , Rf 3 Rf has a perfluoroalkyl group or perfluoroalkylene group having 1 to 3 carbon atoms, and has a structure in which a plurality of these are linked via ether bonds. 1 , Rf 2 , Rf 3 Compared with tetrafluoroethylene (TFE)-based monomers, which are a type of fluorine-based monomer, fluoropolymers do not contain environmentally hazardous substances such as PFOA and have a smaller environmental impact. On the other hand, when a monomer (A) having repeating ether bonds is polymerized as described above, the crystallinity of the polymerized fluoropolymer tends to be low, and many hydrophilic groups are contained in the polymer structure. Therefore, fluoropolymers composed only of monomer (A) are unlikely to exhibit excellent water repellency, and have conventionally only been used for the purpose of imparting antifouling properties to the surfaces of display panels, etc. In contrast, in the fluoropolymer of the present embodiment, copolymerization of the following monomer (B) with monomer (A) enhances the crystallinity of the fluoropolymer, which is believed to enable the fluoropolymer to exhibit excellent water repellency.

[0038] 1.2 Monomer (B) The fluorine-based polymer according to this embodiment comprises a structural unit derived from a cyclic hydrocarbon-containing monomer (monomer (B)) represented by the following general formula (B): Only one type of monomer (B) may be used alone, or two or more types may be used in combination.

[0039] [ka]

[0040] In general formula (B), R 3 is hydrogen, a methyl group or chlorine. In particular, R 3 When is hydrogen or a methyl group, and particularly when is a methyl group, more excellent water repellency is likely to be exhibited.

[0041] In general formula (B), Y 1 -COO-, -O-, -COO(R 4 )-, -COO(R 4 )O-, -CONH-, -CONHCO-, or -COOR 4 is a group represented by NHCO-, and R 4 is a straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0042] In general formula (B), X 2 is a cyclic hydrocarbon group having 4 to 30 carbon atoms, which may have a substituent. Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged ring groups. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group has 4 to 30 carbon atoms, and preferably 6 to 20 carbon atoms. The cyclic hydrocarbon group has more preferably 15 or less, and particularly preferably 12 or less carbon atoms. Examples of the cyclic hydrocarbon group include cyclic aliphatic groups having 4 to 20 carbon atoms, and particularly 5 to 12 carbon atoms, aromatic groups having 4 to 20 carbon atoms, and aromatic aliphatic groups having 6 to 20 carbon atoms. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, and phenyl groups.

[0043] In the present application, examples of the "substituent" include chain groups such as linear or branched hydrocarbon groups. Alternatively, other substituents may be used as long as the desired effect is achieved. Examples of the "substituent" include at least one selected from the group consisting of deuterium, a cyano group, a halogen group, a nitro group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, a halogenated linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms. The substituent may preferably be at least one selected from the group consisting of deuterium, a cyano group, a halogen group, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a halogenated linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an alkylaryl group having 7 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsilyl group having 1 to 12 carbon atoms, an arylsilyl group having 6 to 18 carbon atoms, and an aryloxy group having 6 to 12 carbon atoms.

[0044] In this application, X 2 is a substituted cyclic hydrocarbon group having 4 to 30 carbon atoms, 2 The number of carbon atoms excluding the carbon atoms of the substituent is 4 or more and 30 or less. That is, X 2 In the formula (I), a part of the cyclic hydrocarbon group having 4 to 30 carbon atoms may be substituted with a substituent.

[0045] In general formula (B), m is 0 or 1. In particular, when m is 1, even better water repellency is likely to be exhibited.

[0046] The monomer (B) is preferably one whose homopolymer has a high glass transition temperature (Tg). For example, the monomer (B) may be one capable of forming a homopolymer having a Tg of preferably 50°C or higher, more preferably 80°C or higher. This makes it easier for the fluoropolymer to exhibit even better water repellency. The monomer (B) may or may not contain fluorine, but it is preferable that it does not contain fluorine.

[0047] Furthermore, when the monomer (B) is a compound having a ring strain structure, which includes a cyclic aliphatic group having at least two rings or an alkyl group to which a cyclic aliphatic group having at least two rings is bonded, the fluoropolymer is likely to have excellent oil repellency and stain resistance in addition to water repellency.

[0048] Specific examples of the monomer (B) include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2 2-methyl-2-adamantyl(meth)acrylate, 2-ethyl-2-adamantyl(meth)acrylate, bicyclo[3.3.1]non-9-yl(meth)acrylate, styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether. In particular, when the monomer (B) is at least one selected from the group consisting of isobornyl(meth)acrylate, norbornyl(meth)acrylate, dicyclopentadienyl(meth)acrylate, adamantyl(meth)acrylate, 2-methyl-2-adamantyl(meth)acrylate, and 2-ethyl-2-adamantyl(meth)acrylate, the fluorine-based polymer is likely to have excellent oil repellency and stain resistance in addition to water repellency. In the present application, the term "(meth)acrylate" means an acrylate, a methacrylate, or a mixture thereof.

[0049] The content of the structural units derived from the monomer (B) in the fluoropolymer is not particularly limited. For example, the fluoropolymer may contain 20% by mass or more and 60% by mass or less of the structural units derived from the monomer (B). The upper limit is preferably 50% by mass or less. If the structural units derived from the monomer (B) in the fluoropolymer are too few, sufficient water repellency may not be exhibited. On the other hand, if the structural units derived from the monomer (B) in the fluoropolymer are too many, the adhesion to the treated material (e.g., fiber substrate) may decrease, and durability (e.g., washing durability) may decrease.

[0050] 1.3 Other monomers The fluorine-based polymer according to this embodiment may have structural units derived from other monomers in addition to the structural units derived from the above-mentioned monomers (A) and (B). An example of a monomer that can constitute the other structural units will be described below.

[0051] 1.3.1 Monomer (C) The fluoropolymer according to this embodiment may comprise structural units derived from at least one monomer (C) selected from vinyl halides and vinylidene halides. The monomer (C) may be used singly or in combination of two or more. A fluoropolymer comprising structural units derived from the monomer (C) is likely to have excellent water repellency, oil repellency, and stain resistance.

[0052] Examples of the halogen constituting the monomer (C) include fluorine and chlorine.

[0053] The content of the structural units derived from the monomer (C) in the fluoropolymer is not particularly limited, and at least a portion of the remainder, excluding the structural units derived from the monomers (A) and (B), may be composed of structural units derived from the monomer (C). Specifically, the fluoropolymer may contain 40% by mass or less of structural units derived from the monomer (C). The upper limit is preferably 30% by mass or less. The lower limit is not particularly limited and may be 0% by mass or 5% by mass or more. If the amount of the monomer (C) in the fluoropolymer is too large, the polymerization reaction may not proceed normally, resulting in the formation of a large amount of homopolymer, which may result in a decrease in antifouling properties and a decrease in emulsion stability.

[0054] 1.3.2 Monomer (D) The fluoropolymer according to this embodiment may comprise a structural unit derived from a (meth)acrylate ester monomer (monomer (D)) represented by the following general formula (D): Only one type of monomer (D) may be used alone, or two or more types may be used in combination. A fluoropolymer comprising a structural unit derived from monomer (D) is likely to have excellent oil repellency and stain resistance in addition to water repellency.

[0055] [ka]

[0056] In general formula (D), R 5 is chlorine, bromine, iodine, hydrogen, or a methyl group. In particular, when it is chlorine, bromine, iodine, or a methyl group, the fluorine-based polymer is likely to have even more excellent oil repellency and stain resistance in addition to water repellency.

[0057] In general formula (D), Y 2 -COO-, -CONH-, -CONHCO-, -COOR 6 is a group represented by NHCO-, and R 6 is a straight-chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0058] In general formula (D), X 3 is a straight-chain or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms. Straight-chain hydrocarbon groups are particularly likely to exhibit high performance. The straight-chain or branched hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 28 carbon atoms, and more preferably 1 to 22 carbon atoms. X 3 is preferably a saturated aliphatic hydrocarbon group, particularly an alkyl group.

[0059] Particularly preferred specific examples of the monomer (D) include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, t-butyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, etc. Among these, stearyl (meth)acrylate and behenyl (meth)acrylate are particularly preferred.

[0060] The content of the structural units derived from the monomer (D) in the fluoropolymer is not particularly limited, and at least a portion of the remainder, excluding the structural units derived from the monomers (A) and (B), may be composed of structural units derived from the monomer (D). Specifically, the fluoropolymer may contain 15% by mass or less of structural units derived from the monomer (D). The lower limit is not particularly limited, and may be 0% by mass or 5% by mass or more. In this case, the water repellency of the fluoropolymer is likely to be further improved.

[0061] 1.3.3 Monomer (E) The fluorine-based polymer according to this embodiment may comprise a structural unit derived from a crosslinkable monomer (monomer (E)) represented by the following general formula (E): Only one type of monomer (E) may be used alone, or two or more types may be used in combination. A fluorine-based polymer comprising a structural unit derived from monomer (E) is likely to have excellent oil repellency and stain resistance in addition to water repellency, and also tends to have improved durability (washing durability, friction durability) of the water repellency, oil repellency, and stain resistance.

[0062] [ka]

[0063] In general formula (E), R 7 is hydrogen or a methyl group. 8is a single bond or a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms. Furthermore, Z is a group represented by -COO- or -CONH-. X 4 Regarding R 8 The cases are divided according to the type of R 8 If is a single bond, X 4 is a hydroxyl group, an acetyl group, an epoxy group, a chloromethyl group, an amino group, a carboxyl group, a vinyl group, or an acryloyl group, and R 8 is a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, X 4 is a hydroxyl group, an acetyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a vinyl group, or an acryloyl group.

[0064] Monomer (E) may be a compound having at least two olefinic carbon-carbon double bonds (preferably (meth)acrylate groups), or a compound having at least one olefinic carbon-carbon double bond and at least one reactive group. Examples of monomer (E) include, but are not limited to, diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0065] The content of the structural units derived from the monomer (E) in the fluoropolymer is not particularly limited, and at least a portion of the remainder, excluding the structural units derived from the monomers (A) and (B), may be composed of structural units derived from the monomer (E). Specifically, the fluoropolymer may contain 10% by mass or less of the structural units derived from the monomer (E). The lower limit is not particularly limited, and may be 0% by mass or 5% by mass or more. In this case, the durability (washing durability, friction durability) of the fluoropolymer is likely to be further improved.

[0066] 1.4 Molecular weight of fluoropolymers The fluoropolymer according to this embodiment is obtained by polymerizing at least the above-described monomers (A) and (B). The molecular weight of the fluoropolymer is not particularly limited. The fluoropolymer may have a weight average molecular weight of, for example, 5,000 or more and 1,000,000 or less. The lower limit is preferably 20,000 or more, and the upper limit is preferably 300,000 or less.

[0067] 1.5 Polymerization conditions The polymerization conditions for obtaining a fluoropolymer are not particularly limited, but the polymer can be produced by radical polymerization, preferably in a solvent. Specifically, for example, the monomers (A) and (B), optionally at least one of the monomers (C) to (E), and a polymerization initiator are added to a solvent to initiate the polymerization reaction, thereby polymerizing each component. The solvent for the polymerization reaction is preferably at least one of an organic solvent and water, and an organic solvent and water may be mixed as needed. When the solvent for the polymerization reaction contains water, a non-fluoropolymer can be obtained by emulsion or dispersion polymerization. The polymerization temperature is preferably 20°C to 150°C. If the temperature is below 20°C, polymerization tends to be insufficient compared to temperatures within the above range, while if the temperature exceeds 150°C, control of the reaction heat may be difficult. Components that can be used together with the monomers during polymerization will be described later.

[0068] 2. Polymer composition The polymer composition may contain 5% by mass or more and 60% by mass or less of a fluoropolymer. The lower limit is preferably 20% by mass or more, and the upper limit is preferably 40% by mass or less. If the content of the fluoropolymer is low, there is a risk that water repellency and the like may decrease. If the content is too high, it may become difficult to control the reaction. For example, the polymer composition may be used as a surface treatment agent as described below, or may be diluted with water or the like and then used for the surface treatment as described below. In addition to the fluoropolymer, the polymer composition may contain a solvent (organic solvent or water), an emulsifying dispersant, and other components.

[0069] 2.1 Organic solvents Examples of the organic solvent include fluorine-based solvents and organic solvents made of compounds containing no fluorine atoms.

[0070] The fluorine-containing solvent is not particularly limited, and any solvent made of a fluorine-containing compound can be used as long as it is liquid under atmospheric pressure (1 atm) at a temperature of 25° C. When a mixture of two or more fluorine-containing compounds is used as the fluorine-containing solvent, each fluorine-containing compound may be liquid or solid under atmospheric pressure at a temperature of 25° C., as long as the mixture is liquid under atmospheric pressure at a temperature of 25° C.

[0071] Examples of fluorine-based solvents include hydrofluorocarbons such as 1,1,1,3,3-pentafluorobutane and 1,1,2,2,3,3,4-heptafluorocyclopentane; hydrofluoroolefins such as HFO-1233zd (cis-1-chloro-3,3,3-trifluoropropene) and HCFO-1233yd (1-chloro-2,3,3-trifluoro-1-propene); and HFE- and hydrofluoroethers such as 1,347pcf, 1,1,1,2,3,4,4,5,5,5-decafluoro-2-trifluoromethyl-3-methoxypentane, 1-methoxy-1,1,2,2,3,3,3-heptafluoropropane, 1-methoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane, and 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane. These fluorine-based solvents can be used alone or in combination of two or more.

[0072] The polymer composition may contain an organic solvent made of a compound that does not contain a fluorine atom. The organic solvent is usually liquid at a temperature of 25°C under atmospheric pressure (1 atm).

[0073] The organic solvent made of a compound that does not contain a fluorine atom is not particularly limited, and at least one selected from the group consisting of alcohols, ketones, ethers, esters, glycol ethers, and hydrocarbons can be used.

[0074] Examples of alcohols include methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, tertiary amyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, benzyl alcohol, phenethyl alcohol, 2,3-butanediol, 2-methyl-1,2-propanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, benzyl alcohol, and phenethyl alcohol.

[0075] Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone.

[0076] Examples of ethers include tertiary butyl methyl ether and dibenzyl ether.

[0077] Examples of esters include n-butyl acetate, isoamyl acetate, 2-ethylhexyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, vinyl acetate, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monobutyl ether acetate.

[0078] Examples of glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-i-butyl ether, ethylene glycol mono-n-hexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol mono-i-propyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol mono-i-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-i-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-i-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-i-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-i-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-i-butyl ether, tripropylene glycol monomethyl ether, 3-methoxybutanol, 3-methoxy-3-methyl-1-butanol, and the like.

[0079] Examples of hydrocarbons include nonane, decane, decene, undecane, undecene, dodecane, dodecene, tridecane, tetradecane, pentadecane, menthane, bicyclohexyl, cyclododecane, 2,2,4,4,6,8,8-heptamethylnonane, cyclohexane, liquid paraffin, isoparaffin, toluene, xylene, and ethylbenzene.

[0080] The above organic solvents can be used alone or in combination of two or more.

[0081] It is preferable to use an organic solvent that does not unnecessarily damage the material to be treated, such as swelling or whitening. From the viewpoint of reducing residues on the material to be treated, the boiling point of the organic solvent under atmospheric pressure is preferably 250°C or lower, more preferably 200°C or lower, and even more preferably 150°C or lower.

[0082] The content of the organic solvent in the polymer composition is not particularly limited and may be any amount, but is preferably an amount that does not cause the polymer composition to exhibit a flash point.

[0083] 2.2 Emulsifying and dispersing agents When a fluoropolymer is obtained by emulsion or dispersion polymerization, an emulsifying dispersant may be used in the polymerization reaction. Examples of such emulsifying dispersants include amines and surfactants. In this application, "emulsion dispersion" means "at least one of emulsification and dispersion," and is not limited to emulsion, but may also be a dispersion other than emulsion, or a mixture of emulsion and dispersion other than emulsion.

[0084] Examples of amines include linear or branched monoalkylamines having 8 to 24 carbon atoms, linear or branched dialkylamines having 1 to 24 carbon atoms, and linear or branched trialkylamines having 1 to 24 carbon atoms, and from the viewpoint of water repellency and stain resistance, linear or branched trialkylamines having 1 to 24 carbon atoms are preferred. One type of amine may be used alone, or two or more types may be used in combination.

[0085] The content of the amines is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the monomers to be polymerized.

[0086] As the surfactant, it is preferable to use a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or the like.

[0087] Examples of cationic surfactants include monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, monoalkylamine acetates having 8 to 24 carbon atoms, dialkylamine acetates having 8 to 24 carbon atoms, and alkylimidazoline quaternary salts having 8 to 24 carbon atoms. Among these, from the viewpoints of emulsion dispersibility and processing stability, monoalkyltrimethylammonium salts having 12 to 18 carbon atoms and dialkyldimethylammonium salts having 12 to 18 carbon atoms are preferred.

[0088] The content of the cationic surfactant is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the monomers to be polymerized.

[0089] These cationic surfactants may be used alone or in combination of two or more.

[0090] Examples of nonionic surfactants include a compound (F1) represented by the following general formula (I-1) (hereinafter also referred to as "compound (F1)"), having an HLB value of 5.0 to 19.0; a compound (F2) represented by the following general formula (II-1) (hereinafter also referred to as "compound (F2)"), having an HLB value of 5.0 to 19.0; a compound (F3) (hereinafter also referred to as "compound (F3)"), in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, having an HLB value of 5.0 to 19.0; and alkylene oxide adducts other than compounds (F1) to (F3). Hereinafter, compounds (F1) to (F3) are collectively referred to as "component (F)." Since component (F) has one or more polymerizable unsaturated groups in its molecule, it can be copolymerized with the above-mentioned monomers.

[0091] [ka] In formula (I-1), R9 represents a hydrogen atom or a methyl group, and X 5 represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 3 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0092] [ka] In formula (II-1), R 10 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and Y 4 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0093] The HLB value of the (F) component is 5.0 to 19.0. Here, from the viewpoint of the storage stability of the surface treatment agent, it is more preferable to use two or more (F) components having different HLB values ​​in combination. That is, it is preferable that the HLB value of a mixture of two or more (F) components is within the range of 5.0 to 19.0.

[0094] In the compound (F1), in the general formula (I-1), R 9 is a hydrogen atom or a methyl group. A methyl group is particularly preferred. X 5 is a linear or branched alkylene group having 1 to 6 carbon atoms. In particular, a linear alkylene group having 2 to 3 carbon atoms is more preferred. Y 3 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 3 The type, combination and number of alkyleneoxy groups in may be appropriately selected so as to fall within the above HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure.

[0095] The compound (F1) is preferably a compound represented by the following general formula (I-2).

[0096] [ka] In formula (I-2), R 9represents a hydrogen atom or a methyl group, and X 5 represents a linear or branched alkylene group having 1 to 6 carbon atoms; A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and q can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 80 is preferred. When q is 2 or more, q A 1 The O's may be the same or different.

[0097] In the compound represented by the above general formula (I-2), R 9 is a hydrogen atom or a methyl group, and is more preferably a methyl group. 5 A is a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 2 to 3 carbon atoms. 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. 1 The types and combinations of O and the number q can be appropriately selected so as to fall within the above HLB range. From the viewpoint of emulsion dispersion stability, q is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When q is 2 or more, q A 1 O may be the same or different. 1 When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0098] The compound represented by the general formula (I-2) can be obtained by a conventionally known method, and is not particularly limited. It can also be easily obtained from commercial products, such as "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0099] In the compound (F2), in the above general formula (II-1), R 10is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, and examples thereof include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group. In terms of the emulsion dispersion stability of the fluoropolymer according to this embodiment, R 10 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

[0100] Y 4 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 4 The type, combination, and number of alkyleneoxy groups in (I) can be appropriately selected so as to fall within the above HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure. From the viewpoint of emulsion dispersion stability, the alkyleneoxy group is preferably an ethyleneoxy group.

[0101] The compound (F2) is preferably a compound represented by the following general formula (II-2).

[0102] [ka] In formula (II-2), R 10 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and A 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and r can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 50 is preferred. When r is 2 or more, r A 2 The O's may be the same or different.

[0103] R in the compound represented by the above general formula (II-2) 10 represents R in the above general formula (II-1). 10 The same can be mentioned.

[0104] A 2O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsion dispersion stability, A 2 The types and combinations of O and the number of r can be appropriately selected so as to fall within the above HLB range. 2 O is more preferably an ethyleneoxy group, and r is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and even more preferably an integer of 8 to 14. When r is 2 or more, r A 2 O may be the same or different. 2 When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0105] The compound represented by the general formula (II-2) can be synthesized by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group by a conventionally known method, and the method is not particularly limited. For example, the compound can be synthesized by adding a predetermined amount of alkylene oxide under pressure at 120 to 170°C using an alkali catalyst such as caustic soda or caustic potassium.

[0106] Phenols having the corresponding unsaturated hydrocarbon group include pure products or mixtures produced industrially, as well as pure products or mixtures extracted and purified from plants, etc. Examples include 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc., which are extracted from cashew nut shells and are collectively known as cardanol.

[0107] Compound (F3) is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group, and has an HLB value of 5.0 to 19.0. Examples of the fat or oil having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids that may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoleidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion dispersion stability, alkylene oxide adducts of triglycerides of fatty acids containing at least one hydroxy unsaturated fatty acid are preferred, alkylene oxide adducts of castor oil (triglycerides of fatty acids containing ricinoleic acid) having 2 to 4 carbon atoms are more preferred, and ethylene oxide adducts of castor oil are even more preferred. Furthermore, the number of moles of alkylene oxide added can be appropriately selected so as to fall within the above-mentioned HLB range, and from the viewpoint of emulsion dispersion stability, 20 to 50 moles are more preferred, and 25 to 45 moles are even more preferred. Furthermore, when two or more types of alkylene oxides are used, they can have a block addition structure or a random addition structure.

[0108] Compound (F3) can be synthesized by adding an alkylene oxide to a fat or oil having a hydroxyl group and a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to a triglyceride of a fatty acid containing ricinoleic acid, i.e., castor oil, using an alkali catalyst such as caustic soda or caustic potassium under pressure at 120 to 170°C.

[0109] When component (F) is used in producing the fluoropolymer according to this embodiment, the amount is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of structural units derived from the monomers (A) to (E). If the amount exceeds 20% by mass, the water repellency and stain resistance tend to be insufficient. If the amount is less than 0.01% by mass, the emulsion dispersion stability of the fluoropolymer tends to be insufficient.

[0110] Examples of alkylene oxide adducts other than component (F) include alkylene oxide adducts of alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and oils, and polypropylene glycol.

[0111] Examples of alcohols include linear or branched alcohols or alkenols having 8 to 24 carbon atoms, and acetylene alcohols represented by the following general formula (W).

[0112] [ka] In formula (W), R 85 and R 86 each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms.

[0113] Examples of polycyclic phenols include monohydric phenols such as phenol and naphthol, which may have a hydrocarbon group having 1 to 12 carbon atoms, or their styrene (styrene, α-methylstyrene, vinyltoluene) adducts or benzyl chloride reaction products. Examples of amines used to obtain alkylene oxide adducts other than component (F) include linear or branched aliphatic amines having 8 to 44 carbon atoms.

[0114] Examples of amides include linear or branched fatty acid amides having 8 to 44 carbon atoms.

[0115] Examples of fatty acids include straight-chain or branched-chain fatty acids having 8 to 24 carbon atoms.

[0116] Examples of polyhydric alcohol fatty acid esters include condensation reaction products of polyhydric alcohols and linear or branched fatty acids having 8 to 24 carbon atoms.

[0117] Examples of fats and oils include vegetable fats and oils, animal fats and oils, vegetable waxes, animal waxes, mineral waxes, and hardened oils.

[0118] When alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, oils and fats, and alkylene oxide adducts of polypropylene glycol are used as the nonionic surfactant, among these, from the viewpoints of having little effect on water repellency and soil resistance, having little effect on light fastness, and improving the emulsion dispersibility of the copolymer, linear or branched alcohols or alkenols having 8 to 24 carbon atoms and acetylene alcohols represented by the above general formula (W) are preferred, and linear or branched alcohols having 8 to 24 carbon atoms and acetylene alcohols represented by the above general formula (W) are more preferred.

[0119] Examples of the alkylene oxide in the alkylene oxide adduct other than component (F) include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, epichlorohydrin, etc. From the viewpoints of having little effect on water repellency and soil resistance and improving the emulsion dispersibility of the copolymer, ethylene oxide and 1,2-propylene oxide are preferred as the alkylene oxide, and ethylene oxide is more preferred.

[0120] The number of moles of alkylene oxide added in the alkylene oxide adduct other than component (F) is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50. When the number of moles of alkylene oxide added is within the above range, high levels of water repellency, soil resistance, and product stability are likely to be obtained. Note that if the number of moles of alkylene oxide added is less than 1 mole, product stability, water repellency, and soil resistance tend to decrease, while if it exceeds 200 moles, water repellency and soil resistance tend to decrease.

[0121] When alkylene oxide adducts of alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and oils, and polypropylene glycol are used as alkylene oxide adducts other than component (F), if the HLB of the nonionic surfactant is 5 to 19, a better aqueous dispersion of the fluorine-based polymer of the present embodiment can be obtained.

[0122] When an alkylene oxide adduct other than component (F) is used as the nonionic surfactant, the content of the alkylene oxide adduct other than component (F) is preferably 0.01 to 20 mass %, more preferably 0.1 to 10 mass %, based on the total amount of monomers to be polymerized.

[0123] The following components can also be used as nonionic surfactants. For example, as a nonionic surfactant other than component (F), an ester obtained by reacting a polyhydric alcohol having 3 to 6 carbon atoms and 2 to 5 hydroxyl groups with a fatty acid having 8 to 22 carbon atoms may be used. Here, the origin of the fatty acid having 8 to 22 carbon atoms is not particularly limited, and the fatty acid may be saturated or unsaturated. The structure of the fatty acid is also not particularly limited, and may be linear, branched, or have a hydroxyl group. Examples of polyhydric alcohols having 3 to 6 carbon atoms and 2 to 5 hydroxyl groups include glycerin, diglycerin, triglycerin, sorbitan, pentaerythritol, propylene glycol, and glucoside.

[0124] These nonionic surfactants may be used alone or in combination of two or more.

[0125] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaines, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0126] The content of the amphoteric surfactant is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of monomers to be polymerized.

[0127] These amphoteric surfactants may be used alone or in combination of two or more.

[0128] From the viewpoints of emulsion dispersion stability, water repellency, and antifouling properties, the emulsifying dispersant preferably uses at least one of a cationic surfactant, an amphoteric surfactant, and an amine in combination with a nonionic surfactant. In this case, from the viewpoints of emulsion dispersion stability, water repellency, and antifouling properties, the content of the at least one of a cationic surfactant, an amphoteric surfactant, and an amine is preferably 3 to 27% by mass based on the total content of the cationic surfactant, the amphoteric surfactant, and the amine, and the nonionic surfactant.

[0129] 2.3 Other ingredients The polymer composition may optionally further contain at least one additive selected from the group consisting of initiators, chain transfer agents, and polymerization inhibitors added during polymer polymerization, emulsifiers added as components when used as surface treatment agents (described below), and other additives. The other additives may be any additives that do not alter the properties of the polymer composition. For example, the polymer composition may further contain one or more of waxes, silicones, crosslinking agents, other water repellents, antibacterial agents, deodorizers (deodorizers), flame retardants, antistatic agents, softeners, and wrinkle inhibitors. These additives may be present together with the monomers, etc., before polymerization of the fluoropolymer, or may be added additionally during or after polymerization of the fluoropolymer.

[0130] The initiator may be selected from known polymerization initiators such as azo-based, peroxide-based, and redox-based initiators. The amount of the initiator may be determined taking into consideration the molecular weight of the polymer. The amount of the initiator may be, for example, 0.1 to 10 parts by mass per 100 parts by mass of the fluoropolymer.

[0131] The chain transfer agent may be added, for example, for the purpose of adjusting the molecular weight in the polymerization reaction. Examples of the chain transfer agent that may be used include dodecyl mercaptan and t-butyl alcohol. The amount of the chain transfer agent is not particularly limited. For example, it may be 5 parts by mass or less per 100 parts by mass of the fluoropolymer. If the amount of the chain transfer agent is too large, the molecular weight may decrease significantly, which may make it difficult to efficiently produce a fluoropolymer having excellent water repellency, etc.

[0132] On the other hand, a polymerization inhibitor may be added for the purpose of adjusting the molecular weight of the fluorine-based polymer. The type of polymerization inhibitor is not particularly limited.

[0133] The emulsifier may be added, for example, to further improve dispersion stability. Known emulsifiers, such as glycolic acid, may be used as the emulsifier. The amount of the emulsifier is not particularly limited. For example, it is desirable that the amount be 10 parts by mass or less per 100 parts by mass of the fluoropolymer.

[0134] The polymer composition may contain, as additives, one or more of waxes, silicones, crosslinking agents, other water repellents, antibacterial agents, deodorizing agents (deodorizers), flame retardants, antistatic agents, softening agents, and wrinkle-resistant agents.

[0135] Examples of waxes include low-molecular-weight polyolefins such as polyethylene and polypropylene; vegetable waxes such as carnauba wax, rice wax, candelilla wax, and jojoba oil; animal waxes such as beeswax; mineral and petroleum waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax; ester waxes of higher fatty acids and higher alcohols such as stearyl stearate and behenyl behenate; ester waxes of higher fatty acids and monohydric or polyhydric lower alcohols such as butyl stearate, propyl oleate, monostearate glyceride, distearate glyceride, and pentaerythritol tetrabehenate; ester waxes of higher fatty acids and polyhydric alcohol polymers such as diethylene glycol monostearate, dipropylene glycol distearate, distearate diglyceride, and tetrastearate triglyceride; and higher sorbitan fatty acid ester waxes such as sorbitan monostearate. Paraffin wax is preferred from the viewpoint of water repellency. The waxes can be used alone or in combination of two or more.

[0136] The content of waxes in the polymer composition is not particularly limited. For example, the ratio of the mass P (solid content) of the fluoropolymer to the mass W of the waxes is preferably P:W=99.5:0.5 to 60:40, and more preferably 99:1 to 85:15.

[0137] Examples of silicones include modified silicones that do not have a functional group that can react with an isocyanate group, such as long-chain alkyl-modified silicone, long-chain alkyl-aralkyl-modified silicone, and higher fatty acid amide-modified silicone.

[0138] As the modified silicone, an organo-modified silicone represented by the following general formula (1) can be used.

[0139] [ka] In formula (1), R 20 , R 21 and R 22 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 4 carbon atoms; R 23 represents a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or a saturated hydrocarbon group having 3 to 40 carbon atoms; R 30 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 40 carbon atoms and an aromatic ring, or a saturated hydrocarbon group having 3 to 40 carbon atoms; a represents an integer of 0 or more; b represents an integer of 1 or more; (a+b) is 10 to 200; when a is 2 or more, multiple R 20 and R 21 may be the same or different, and when b is 2 or more, there are multiple R 22 and R 23 may be the same or different.

[0140] In the organo-modified silicone, the alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, and cycloheptyl groups, as well as groups in which some or all of the hydrogen atoms bonded to these groups have been substituted with halogen atoms, amino groups, cyano groups, or the like.

[0141] Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a naphthyl group, and groups in which some or all of the hydrogen atoms bonded to these groups have been substituted with halogen atoms, amino groups, cyano groups, or the like.

[0142] The alkoxyl group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. In these groups, some or all of the hydrogen atoms may be substituted with a halogen atom, an amino group, a cyano group, or the like. R 20 , R 21 and R 22 are each independently preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0143] Examples of the hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring include an aralkyl group having 8 to 40 carbon atoms and a group represented by the following general formula (2) or (3).

[0144] [ka] In formula (2), R 40 represents an alkylene group having 2 to 6 carbon atoms, and R 41 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and c represents an integer of 0 to 3. When c is 2 or 3, multiple R41 may be the same or different.

[0145] The alkylene group may be linear or branched.

[0146] [ka] In formula (3), R 42 represents an alkylene group having 2 to 6 carbon atoms, and R 43 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and d represents an integer of 0 to 3. When d is 2 or 3, multiple R 43 may be the same or different.

[0147] The alkylene group may be linear or branched.

[0148] Examples of the aralkyl group having 8 to 40 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylethyl group, etc. Among these, the phenylethyl group and the phenylpropyl group are preferred in terms of ease of industrial production and availability.

[0149] In the group represented by the general formula (2), R 40 is preferably an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, and more preferably 0.

[0150] In the group represented by the general formula (3), R 42 is preferably an alkylene group having 2 to 4 carbon atoms, and d is preferably 0 or 1, and more preferably 0.

[0151] As the hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, the aralkyl group having 8 to 40 carbon atoms and the group represented by the general formula (2) are preferred in that they are easy to produce industrially and are readily available, and the aralkyl group having 8 to 40 carbon atoms is more preferred in that it can improve the water repellency and stain resistance of the resulting textile product.

[0152] The saturated hydrocarbon group having 3 to 40 carbon atoms may be linear or branched. Examples of the saturated hydrocarbon group having 3 to 40 carbon atoms include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, stearyl, tricosyl, lignoceryl (tetracosyl), cellotyl (hexacosyl), monthyl (octacosyl), melissyl (triacontane), and dotriacontane. As the saturated hydrocarbon group having 3 to 40 carbon atoms, an alkyl group having 8 to 30 carbon atoms is preferred, and an alkyl group having 12 to 28 carbon atoms is more preferred, in terms of improving the water repellency and stain resistance of the resulting textile product.

[0153] In organo-modified silicones, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 40 carbon atoms and an aromatic ring, or a saturated hydrocarbon group having 3 to 40 carbon atoms.

[0154] Examples of the hydrocarbon group having 6 to 40 carbon atoms and having an aromatic ring include an aralkyl group having 6 to 40 carbon atoms and a group represented by the general formula (2) or (3). Examples of the aralkyl group having 6 to 40 carbon atoms include a phenyl group, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, and a naphthylethyl group. Of these, the phenylethyl group and the phenylpropyl group are preferred because they are easy to produce industrially and readily available.

[0155] R is easy to manufacture industrially and is readily available. 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0156] In the organo-modified silicone, a is an integer of equal to or greater than 0. From the viewpoints of ease of industrial production, ease of availability, and superior peel strength of the resulting textile product against resin coatings, a is preferably equal to or less than 40, and more preferably equal to or less than 30.

[0157] In the organo-modified silicone, (a+b) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a+b) is preferably 20 to 100, and more preferably 40 to 60. When (a+b) is within the above range, the silicone itself tends to be easier to produce and handle.

[0158] Organo-modified silicones can be synthesized by conventional methods, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an aromatic compound and / or an α-olefin having a vinyl group.

[0159] Examples of the silicone having a SiH group include methylhydrogensilicone and a copolymer of dimethylsiloxane and methylhydrogensiloxane, each having a degree of polymerization of 10 to 200. Among these, methylhydrogensilicone is preferred because it is easy to produce industrially and is readily available.

[0160] The aromatic compound having a vinyl group is represented by the formula (1) R 23In the above formula, the aromatic compound is a compound from which a hydrocarbon group having an aromatic ring and 8 to 40 carbon atoms is derived. Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

[0161] The above α-olefin is represented by R in the above general formula (1). 23 In the above formula, it is a compound from which a saturated hydrocarbon group having 3 to 40 carbon atoms is derived. Examples of α-olefins include α-olefins having 3 to 40 carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene.

[0162] The hydrosilylation reaction may be carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group and the α-olefin in a stepwise or all at once, if necessary, in the presence of a catalyst.

[0163] The amounts of the SiH group-containing silicone, the vinyl group-containing aromatic compound, and the α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone, etc.

[0164] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, with platinum compounds being preferred, such as platinum(IV) chloride.

[0165] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200° C., preferably 50 to 150° C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150° C.

[0166] The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may also be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0167] Commercially available modified silicones can be used. For example, long-chain alkyl-modified silicones include KF-412, KF-413, KF-414, KF-415, KF-4003, KF-4701, KF-4917, KF-7235B, and X-22-7322 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BELSILCDM3526VP, BELSILCM7026VP, and BELSILSDM5055VP (all manufactured by Wacker Asahi Kasei Silicones). Long-chain alkyl-aralkyl-modified silicones include X-22-1877 (manufactured by Shin-Etsu Chemical Co., Ltd.). Higher fatty acid amide-modified silicones include KF-3935 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0168] The content of silicones in the polymer composition, expressed as the ratio of the mass P (solid content) of the fluoropolymer to the mass S of the silicones, is preferably P:S=99.5:0.5 to 60:40, more preferably 99:1 to 85:15.

[0169] Examples of the crosslinking agent include melamine resin, glyoxal resin, and compounds having one or more isocyanate groups or blocked isocyanate groups. The crosslinking agents can be used alone or in combination of two or more.

[0170] For example, when fibers are used as the treated material, softeners can be added to make the textile product feel smooth to the touch. Any known softener can be used without limitation. Preferably, dimethyl silicone, hydrogen silicone, amino-modified silicone, fatty acid amide, polyether-modified silicone, etc. can be used. The content of the softener may be, for example, 0.5 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the polymer composition.

[0171] The penetrating agent may be added to assist the penetration of the fluoropolymer, for example, when the material to be treated has a high density and it is difficult to penetrate the fluoropolymer into the interior thereof. Any known penetrating agent may be used without limitation. From the viewpoint of easily maintaining water repellency, etc., preferred penetrating agents include glycols such as butyl diglycol and monoethylene glycol, isopropyl alcohol, butyl cellosolve, and alcohol solvents such as higher alcohols and lower alcohols. The content of the penetrating agent may be, for example, 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the polymer composition.

[0172] The antistatic agent may be any known antistatic agent. Cationic polymers such as stearyl trimethyl ammonium methyl sulfate, lauryl triethyl ammonium methyl sulfate, octyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, stearyl ethyl dimethyl ammonium chloride, and lauryl trimethyl ammonium chloride, phosphate ester compounds, and guanidine hydrochloride compounds may be preferably used. The content of the antistatic agent may be, for example, 0.1 to 5 parts by mass per 100 parts by mass of the polymer composition.

[0173] 3. Surface treatment agents The surface treatment agent according to this embodiment is characterized by containing the above-mentioned fluoropolymer. The surface treatment agent according to this embodiment may contain, for example, 5% by mass or more and 60% by mass or less of the above-mentioned fluoropolymer. If the amount of fluoropolymer in the surface treatment agent is too small, it may be difficult to achieve water repellency, etc. On the other hand, if the proportion of fluoropolymer in the surface treatment agent is too high, it may have an adverse effect on the treated material. For example, if the treated material is a fibrous substrate, it may feel hard to the touch after surface treatment.

[0174] 3.1 Components other than fluorine-based polymers The surface treatment agent according to this embodiment may contain other components in addition to the fluoropolymer. As described above, the surface treatment agent according to this embodiment may be the polymer composition described above as is, or may be diluted with water or the like. In addition to the fluoropolymer, the surface treatment agent may contain, for example, a surfactant, a leveling agent, a surface treatment agent, a solvent, and optionally other components. Examples of other components include the remainders of the components used in the polymerization reaction, such as initiators, chain transfer agents, polymerization inhibitors, and emulsification aids, as well as the additives described above. As described above, examples of additives include one or more of waxes, silicones, crosslinking agents, other water repellents, antibacterial agents, deodorizers (deodorizers), flame retardants, antistatic agents, softeners and anti-wrinkle agents, and antifoaming agents. In particular, when the surface treatment agent according to this embodiment contains at least one of waxes, silicones, and crosslinking agents, it is likely to exhibit even higher performance.

[0175] 3.2 Application The surface treatment agent according to this embodiment can impart sufficient water repellency to a substrate by treating the substrate. Furthermore, depending on the components contained in the surface treatment agent, it can also impart oil repellency and antifouling properties to the substrate. In other words, the surface treatment agent according to this embodiment can be used as at least one of a water repellent, a water- and oil-repellent, a water- and oil-repellent antifouling agent, and a water-, oil-, and stain-resistant agent.

[0176] Examples of substrates that can be treated with the surface treatment agent (for example, water repellent agent) according to this embodiment include fibers, leather, glass, metals, resins, and stone materials.

[0177] 4. Manufacturing methods for textile products The technology of the present disclosure also has an aspect as a method for producing a textile product. That is, the method for producing a textile product according to this embodiment includes contacting a textile substrate with the treatment liquid containing the above-described fluorine-based polymer.

[0178] 4.1 Processing solution The treatment liquid containing a fluoropolymer may be the same as the above-mentioned polymer composition or surface treatment agent containing a solvent, i.e., a fluoropolymer dispersed in a solvent such as water.

[0179] 4.2 Fiber substrate The fibrous substrate to be treated with the treatment solution is not particularly limited, but examples thereof include natural plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fiber, carbon fiber, and metal fiber; and mixed fibers thereof.

[0180] 4.3 Contact method The method for contacting the fiber substrate with the treatment solution can be a known method such as immersion, spraying, atomization, or coating. When the surface treatment agent contains a solvent or water, it is preferable to dry the surface treatment agent at 10 to 200°C for 10 seconds to several days to remove the solvent or water after contacting the fiber substrate. A heat treatment may then be performed. The conditions for the heat treatment are not particularly limited, but the heat treatment temperature may be 120°C or higher and 200°C or lower, and the heat treatment time may be 10 seconds or higher and 300 seconds or lower, for example.

[0181] 4.4 Amount of Grant The amount of treatment liquid applied to the fibrous substrate may be adjusted depending on the required level of water repellency. For example, the amount of fluoropolymer applied is preferably adjusted to 0.01 to 10 g, more preferably 0.05 to 5 g, per 100 g of fibrous substrate. If the amount of fluoropolymer applied is too small, the textile product may not exhibit sufficient water repellency, while if the amount of fluoropolymer applied is too large, the texture of the textile product may become rough and hard.

[0182] 5. Textile products The technology of the present disclosure also has an aspect of a textile product to which a fluoropolymer is attached. That is, the textile product according to this embodiment can be obtained by treating a textile substrate with a treatment liquid containing the fluoropolymer of this embodiment described above, thereby adhering the fluoropolymer to the textile substrate. The form of attachment of the fluoropolymer in the textile product is not particularly limited. For example, the textile product according to this embodiment may have a coating containing the fluoropolymer on its surface. In particular, it is preferable that the entire surface of the textile product is covered with the coating. The textile product according to this embodiment can exhibit sufficient water-repellent properties even when used outdoors for a long period of time. Furthermore, the textile product according to this embodiment can reduce environmental impact by using the fluoropolymer as the water-repellent component. [Example]

[0183] The present invention will be further explained below with reference to examples, but the present invention is not limited to these examples in any way.

[0184] 1. Preparation of fluoropolymer composition 1.1 Manufacturing Example 1 In an autoclave, component (A), component (B), surfactant, acid, organic solvent, chain transfer agent, and water listed in Table 1 below were mixed and stirred, and then emulsified and dispersed by ultrasonic irradiation at 45°C for 5 minutes. The atmosphere inside the autoclave was replaced with nitrogen, and the reaction vessel was sealed. Then, the initiator 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the reaction was carried out at 60°C for 4 hours, obtaining an emulsified dispersion containing a fluoropolymer as a fluoropolymer composition. The content of each of the above components is as listed in Table 1-1 below.

[0185] 1.2 Manufacturing Examples 2 to 26 An emulsified dispersion containing a fluoropolymer was obtained as a fluoropolymer composition in the same manner as in Production Example 1, except that the components and amounts thereof shown in Tables 1-1 to 1-3 below were used.

[0186] The components shown in Tables 1-1 to 1-3 are generally available. For example, among the components in Tables 1-1 to 1-3, component (A) (fluorine-containing polymerizable monomer) is a commercially available product manufactured by Nicca Chemical Co., Ltd. Specifically, the monomer (A) is represented by the following general formula (A), and Rf 1 is a perfluoroalkyl group having 3 carbon atoms, and Rf 2 is a perfluoroalkylene group having 3 carbon atoms, and Rf 3 is a perfluoroalkylene group having 2 carbon atoms, and R 1 is hydrogen and X 1 is -O(R 2 )O-, and R 2 has 2, 3 or 4 carbon atoms, and n is 7, 28, 43, 60 or 73.

[0187] [ka]

[0188] Furthermore, among the components in Tables 1-1 to 1-3 below, industrial products were used for isobornyl methacrylate, which is component (B) (cyclic hydrocarbon-containing monomer), vinyl chloride, which is component (C), polyoxyethylene alkyl ether, which is a nonionic surfactant, stearyltrimethylammonium chloride, which is a cationic surfactant, tripropylene glycol, which is an organic solvent, dodecyl mercaptan, which is a chain transfer agent, and 2,2'-azobis(2-methylpropionamidine) dihydrochloride, which is an initiator.

[0189] 1.3 Manufacturing Example 27 Components (A) and (B) listed in Table 1 below, along with Novec 7200 (1-methoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane) manufactured by 3M, were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, and mixed uniformly while heating and flowing nitrogen. After purging with nitrogen, the mixture was heated to 75°C. After adding the initiator azobisisobutyronitrile, the mixture was reacted at 75°C for 6 hours to obtain a solvent-based fluorine-based polymer composition. The content of each of the above components is as listed in Tables 1-3 below.

[0190] 1.4 Manufacturing Example 28 A solvent-based fluorine-based polymer composition was obtained in the same manner as in Production Example 27, except that the components and amounts thereof shown in Table 1-3 below were used.

[0191] [Table 1-1]

[0192] [Table 1-2]

[0193] [Table 1-3]

[0194] 2. Preparation of organo-modified silicone emulsion dispersion (Preparation Example 1) A reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet, and dropping funnel was charged with 63.2 g of methyl hydrogen silicone with a SiH group equivalent weight of 63.2 g / mol and a degree of polymerization of 50. Nitrogen was introduced, and the mixture was heated to 65°C while mixing until homogeneous. A hydrosilylation catalyst, a solution of platinum(IV) chloride in ethylene glycol monobutyl ether and toluene, was added to the reaction system to achieve a platinum concentration of 5 ppm. When the reaction temperature reached 120°C, 168.3 g of 1 mole of 1-dodecene was added dropwise, and the reaction was continued at 120°C for 6 hours. Completion of the addition reaction was confirmed by FT-IR analysis of the resulting organo-modified silicone, confirming the disappearance of the absorption spectrum derived from the SiH group of the methyl hydrogen silicone. Thus, a compound represented by the following general formula (L-1) was obtained: a1 = 0, a2 = 50, R = 0. 222 is a methyl group, R 223 is a dodecyl group, R 230 , R 231 , R 232 , R 233 , R 234 and R 235 An organo-modified silicone was obtained in which the methyl group was used. 3 parts by mass of an ethylene oxide 9-mol adduct of a branched higher alcohol having 12 to 14 carbon atoms was added to 20 parts by mass of the obtained organo-modified silicone and mixed. 77 parts by mass of water was then added little by little while mixing, and the mixture was emulsified and dispersed in water to obtain an organo-modified silicone emulsion dispersion containing 20% ​​by mass of the organo-modified silicone.

[0195] [ka]

[0196] 3. Preparation of Wax Dispersion (Preparation Example 2) A high-pressure reactor was charged with 150 g of paraffin wax (melting point 69°C, penetration 12 (25°C)), 350 g of pure water, 8.5 g of polyoxyethylene stearyl ether (HLB=10.7), and 6.5 g of polyoxyalkylene branched decyl ether (HLB=14.7), and sealed. The contents of the reactor were then heated to 110-120°C with stirring. The contents of the reactor were then emulsified and dispersed for 30 minutes while maintaining high pressure, yielding an aqueous paraffin wax emulsion. The wax content was further adjusted to 30% by mass with pure water, yielding a wax emulsion.

[0197] 4. Preparation of surface treatment agent and preparation of evaluation samples 4.1 Reference examples 1~9, Example 10 to 12, Reference Examples 13 and 14, Examples 15 to 22, Reference Example 23 ~25 and Comparative Examples 1 to 4 The emulsified dispersions of the fluorine-containing polymer compositions obtained in Production Examples 1 to 26, the emulsified dispersions obtained in Preparation Examples 1 and 2, NK Assist FU (manufactured by Nicca Chemical Co., Ltd., an isocyanate-based crosslinking agent), and water were mixed to obtain the compositions (parts by mass) shown in Tables 2-1 to 2-3 below to obtain surface treatment agents. Three types of fabric were immersed in the mixture: PET 100% Tricot Car seat (hereinafter referred to as PET fabric) to confirm its performance for use as a car seat, and 100% PET Dewspo and Nylon Rib (hereinafter referred to as NYLON fabric) to confirm its performance for use as a clothing material. At this time, the pressure of the mangle was adjusted, and for car seat applications, the pickup was adjusted to approximately 60%, and then the fabric was dried in a mini tenter at 150°C for 300 seconds and heat-treated at 160°C for 30 seconds.For clothing applications, the pickup was adjusted to approximately 50%, and then the fabric was dried in a mini tenter at 180°C for 60 seconds and heat-treated at 180°C for 30 seconds to obtain a sample for evaluation.

[0198] 4.2 reference Example 26 and Comparative Example 5 The solvent-based fluoropolymer compositions obtained in Production Examples 27 and 28 and a solvent (Novec 7200) were mixed to obtain the compositions (parts by mass) shown in Table 3 below, to obtain surface treatment agents. Commercially available glass plates (12 cm × 7.5 cm) and aluminum plates (15 cm × 7.0 cm) were used as substrates (materials to be treated). First, they were pre-cleaned with acetone to remove surface residues. Next, the obtained surface treatment agent was coated onto the surface of the substrate (application amount: 5 ml for glass plate, 6 ml for aluminum plate), and then dried at room temperature to obtain samples for evaluation.

[0199] 5. Evaluation Method The evaluation samples obtained as described above were subjected to the following evaluations.

[0200] 5.1 Evaluation of stain resistance (oil repellency) Reference examples 1~9, Example 10 to 12, Reference Examples 13 and 14, Examples 15 to 22, Reference Example 23 After placing the samples obtained in Comparative Examples 1 to 25 and Comparative Examples 1 to 4 flat, three 5 mm diameter droplets of n-tetradecane (AATCC TM118-Oil Repellency: Grade 4 Determination Reagent for Hydrocarbon Resistance Test) with a surface tension of 26 dyne / cm were dropped onto the samples. After 30 seconds, the state of the three droplets was visually observed and rated based on the grading criteria in Table 4 below. In Tables 2-1 to 2-3 below, "A / 1, B / 2" means that there was one droplet of rating A and two droplets of rating B. The same applies to the evaluation of IPA repellency below.

[0201] 5.2 Evaluation of IPA repellency (water repellency) Reference examples 1~9, Example 10 to 12, Reference Examples 13 and 14, Examples 15 to 22, Reference Example 23 After placing the samples obtained in 1 to 25 and Comparative Examples 1 to 4 flat, three 5 mm diameter droplets of a water:IPA (60:40) mixture with a surface tension of 26.6 dyne / cm were dropped onto the samples. After 30 seconds, the state of the three droplets was visually observed and judged based on the criteria in Table 4 below.

[0202] 5.3 Evaluation of initial water repellency by spray method Reference examples 1~9,Example 10 to 12, Reference Examples 13 and 14, Examples 15 to 22, Reference Example 23 The spray water repellency of the samples obtained in 1 to 25 and Comparative Examples 1 to 4 was evaluated using a test method in accordance with the standard of AATCC TM22-2017. Good spray water repellency was rated as "5", and poor spray water repellency was rated as "1".

[0203] 5.4 Evaluation of oil repellency Reference examples 1~9, Example 10 to 12, Reference Examples 13 and 14, Examples 15 to 22, Reference Example 23 The oil repellency of the samples obtained in Examples 1 to 25 and Comparative Examples 1 to 4 was evaluated using a test method in accordance with the standard of AATCC TM118-2013. Good oil repellency was rated as "3," and poor oil repellency was rated as "0."

[0204] 5.5 Evaluation of spray water and oil repellency after washing The samples obtained in Examples 10, 21, and 22 were washed five times (L-5) in accordance with the standard of AATCC TM135-2018, and spray water repellency and oil repellency after tumble drying were evaluated.

[0205] 5.6 Contact angle evaluation reference For the samples obtained in Example 26 and Comparative Example 5, the sliding angle of water from the sample surface was measured using a simple automatic contact angle meter, sliding angle model DSA25T, manufactured by KRUSS. Measurements were taken at three random points, and the average value was calculated. The amount of water dropped was 20 μL for evaluation.

[0206] [Table 2-1]

[0207] [Table 2-2]

[0208] [Table 2-3]

[0209] [Table 3]

[0210] [Table 4]

[0211] [Table 5]

[0212] As is clear from the results shown in Tables 2-1 to 2-3, Reference examples 1~9, Example 10 to 12, Reference Examples 13 and 14, Examples 15 to 22, Reference Example 23 The surface treatment agents of Comparative Examples 1 to 25 were able to impart excellent stain resistance, IPA (water repellency), spray water repellency, and oil repellency to the fibrous substrate, which was the treated material, regardless of the type of fibrous substrate. On the other hand, the surface treatment agents of Comparative Examples 1 to 4 were unable to impart sufficient performance to any of stain resistance, IPA (water repellency), spray water repellency, and oil repellency.

[0213] As is evident from the results shown in Table 3, reference The surface treatment agent of Example 26 was able to impart superior water repellency to the treated materials, that is, glass plate and aluminum plate, compared to the surface treatment agent of Comparative Example 5.

[0214] As is clear from the results shown in Table 5, the spray water repellency and oil repellency after washing were superior to those of Example 10 in Examples 21 and 22 in which a non-fluorine-containing crosslinkable monomer was copolymerized.

[0215] As described above, all simple modifications and variations of the present invention can be easily implemented by a person skilled in the art, and all such modifications and variations are included within the scope of the present invention.

Claims

1. A structural unit derived from a fluorine-containing polymerizable monomer represented by the following general formula (A), A structural unit derived from a cyclic hydrocarbon-containing monomer represented by the following general formula (B), Equipped with a structural unit derived from at least one monomer (C) selected from vinyl halide and vinylidene halide, and A structural unit derived from a crosslinkable monomer represented by the following general formula (E): Fluorine-based polymer comprising one or both of the following: 【Chemistry 1】 In general formula (A), Rf １ is a perfluoroalkyl group having 1 to 3 carbon atoms, Rf ２ and Rf ３ are each independently a perfluoroalkylene group having 1 to 3 carbon atoms, R １ is hydrogen, a methyl group or chlorine, X １ is -O(R ２ ) O-, -NH(R ２ ) is a group represented by —O— or —NH—, and R ２ is a linear, branched or cyclic aliphatic hydrocarbon group having 2 to 6 carbon atoms, n is an integer from 6 to 60. 【Chemistry 2】 In general formula (B), R ３ is hydrogen, a methyl group or chlorine, Y １ is -COO-, -O-, -COO(R ４ ) -, -COO(R ４ ) O—, —CONH—, —CONHCO—, or —COOR ４ is a group represented by NHCO—, and R ４ is a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, X ２ represents a cyclic hydrocarbon group having 4 to 30 carbon atoms which may have a substituent, m is 0 or 1. 【Transformation 3】 In general formula (E), R ７ is hydrogen or a methyl group, R ８ is a single bond or a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, Z is a group represented by —COO— or —CONH—, R ８ is a single bond, X ４ is a hydroxyl group, an acetyl group, an epoxy group, a chloromethyl group, an amino group, a carboxyl group, a vinyl group, or an acryloyl group, R ８ is a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, X ４ is a hydroxyl group, an acetyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a vinyl group, or an acryloyl group.

2. A structural unit derived from a (meth)acrylate ester monomer represented by the following general formula (D): The fluorine-based polymer of claim 1 , comprising: 【Chemistry 4】 In general formula (D), R ５ is chlorine, bromine, iodine, hydrogen or a methyl group, Y ２ represents -COO-, -CONH-, -CONHCO-, or -COOR ６ is a group represented by NHCO—, and R ６ is a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, X ３ is a straight-chain or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms.

3. The fluorine-containing polymerizable monomer is represented by the following general formula (A1): The fluorine-containing polymer according to claim 1 . 【Transformation 5】

4. the cyclic hydrocarbon-containing monomer contains a cyclic aliphatic group having at least two rings or an alkyl group to which a cyclic aliphatic group having at least two rings is bonded; The fluorine-containing polymer according to claim 1 .

5. the cyclic hydrocarbon-containing monomer is at least one selected from the group consisting of isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate; The fluorine-containing polymer according to claim 4.

6. The fluorine-based polymer according to any one of claims 1 to 5 is contained. Surface treatment agent.

7. comprising at least one of waxes, silicones, and crosslinkers; The surface treatment agent according to claim 6.

8. It is used as at least one of a water repellent, a water- and oil-repellent, a water-repellent and antifouling agent, and a water-, oil-repellent and antifouling agent, The surface treatment agent according to claim 6.

9. contacting a fibrous substrate with a treatment liquid containing the fluorine-based polymer according to any one of claims 1 to 5; A method for producing a textile product, comprising:

10. A fluorine-based polymer according to any one of claims 1 to 5 attached thereto. Textile products.

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