Polymers, methods for producing polymers, water-repellent and oil-repellent compositions and articles

Abstract

The present invention provides: a polymer that allows the production of an article having excellent water- and oil-repellency; a method for producing the polymer; a water- and oil-repellent composition comprising the polymer; and an article having excellent water- and oil-repellency.　The polymer according to the present invention has a unit (a) represented by formula (1) and a unit (b) represented by formula (2), wherein: the proportion of the unit (a) with respect to the total of the unit (a) and the unit (b) is 20-60 mol%; and the proportion of the unit (b) with respect to the total of the unit (a) and the unit (b) is 40-80 mol%.　Formula (1): -(CH2-CHRf)-; Formula (2): -(CH2-CH-(O-C(=O)NH-Rd))-, where Rf is a perfluoroalkyl group with having 1-8 carbons, and　Rd is an alkyl group having 6-24 carbons.

Description

[Technical Field]

[0001] This invention relates to polymers, methods for producing polymers, water-repellent and oil-repellent compositions, and articles. [Background technology]

[0002] Water and oil repellency is sometimes imparted to the surface of articles such as textile products. Conventionally, water and oil repellent compositions containing fluorine-containing polymers having units based on (meth)acrylates with perfluoroalkyl groups have been used for water and oil repellency treatment of articles. However, the ester bonds in the (meth)acrylate-based units are easily cleaved by hydrolysis with alkalis, etc. As a result, the perfluoroalkyl groups may be lost from the fluorine-containing polymer, and the water and oil repellency of the article may decrease.

[0003] As a water-repellent and oil-repellent composition that can obtain articles whose water-repellent and oil-repellent properties are not easily reduced by alkalis, etc., a water-repellent and oil-repellent composition containing a fluorine-containing polymer that does not have units based on (meth)acrylate having a perfluoroalkyl group has been proposed. As a fluorine-containing polymer that does not have units based on (meth)acrylate having a perfluoroalkyl group, there is a fluorine-containing polymer that has units based on (perfluoroalkyl)ethylene.

[0004] Patent Document 1 discloses a dispersion containing a polymer that includes units based on (perfluoroalkyl)ethylene. It also discloses various monomers that can polymerize with (perfluoroalkyl)ethylene, such as vinyl stearate, vinyl chloride, and 4-hydroxybutyl vinyl ether. Example 10 of the examples discloses a copolymer of (perfluorohexyl)ethylene (49.8 mol%) and vinyl stearate. Example 29 discloses a copolymer of (perfluorohexyl)ethylene (40 mol%), vinyl acetate, and vinyl chloride.

[0005] Patent Document 2 discloses a surface treatment agent composition containing a fluorine-containing polymer having a unit based on a fluorine-containing olefin and a unit based on a hydrocarbon vinyl. As the hydrocarbon vinyl, vinyl stearate is disclosed. Further, as optional monomers, non-fluorine non-crosslinkable monomers such as vinyl halide and vinyl alkyl ether, and non-fluorine crosslinkable monomers are disclosed. In Example 18, a copolymer of (perfluorohexyl)ethylene (15 mol%) and vinyl stearate is disclosed.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, in articles treated with a water and oil repellent composition containing the fluorine-containing polymer disclosed in each of Examples of Patent Documents 1 and 2, the water repellency is insufficient. The present invention provides a polymer from which an article excellent in water and oil repellency can be obtained, a method for producing the polymer, a water and oil repellent composition containing the polymer, and an article excellent in water and oil repellency.

Means for Solving the Problems

[0008] The present invention has the following aspects. [1] A polymer; the polymer has the following unit (a) and the following unit (b); the ratio of the unit (a) is 20 to 60 mol% with respect to the total of the unit (a) and the unit (b); the ratio of the unit (b) is 40 to 80 mol% with respect to the total of the unit (a) and the unit (b). Unit (a): A unit represented by the following formula (1). -(CH2-CHR f)- (1) However, R f These are perfluoroalkyl groups having 1 to 8 carbon atoms. Unit (b): The unit represented by the following formula (2). -(CH2-CH-(OC(=O)NH-R d ))- (2) However, R d These are alkyl groups with 6 to 24 carbon atoms. [2] The polymer according to [1], wherein the sum of unit (a) and unit (b) is 50 mol% or more of the total units of the polymer. [3] The polymer according to [1] or [2], wherein the number average molecular weight is 1,000 to 20,000. [4] A method for producing a polymer, comprising polymerizing a monomer component containing the following monomer (a) and the following monomer (c), wherein the proportion of monomer (a) to the sum of monomer (a) and monomer (c) is 20 to 60 mol%, and the proportion of monomer (c) is 40 to 80 mol%, in the presence of a polymerization initiator; saponifying the unit (c) of a polymer (A) having a unit (a) based on monomer (a) and a unit (c) based on monomer (c); and then reacting the hydroxyl group of the polymer (B) obtained by saponifying the unit (c) of polymer (A) with the following compound (d). Monomer (a): A compound represented by the following formula (3). CH2=CH-R f (3) However, R f These are perfluoroalkyl groups having 1 to 8 carbon atoms. Monomer (c): A compound represented by the following formula (4). CH2=CH-OC(=O)R (4) However, R is an alkyl group having 1 to 4 carbon atoms. Compound (d): A compound represented by the following formula (5). O=C=NR d (5) However, R d These are alkyl groups with 6 to 24 carbon atoms. [5] The manufacturing method according to [4], wherein the total ratio of monomer (a) and monomer (c) is 50 mol% or more with respect to the total monomers in the monomer component. [6] The manufacturing method according to [4] or [5], wherein the polymerization is solution polymerization. A water-repellent and oil-repellent composition comprising a polymer described in any of [7][1] to [3] and a liquid medium. An article treated with the water-repellent and oil-repellent composition described in [8][7]. [Effects of the Invention]

[0009] According to the polymer of the present invention and the water-repellent and oil-repellent composition containing the polymer, articles with excellent water-repellent and oil-repellent properties can be obtained. According to the polymer manufacturing method of the present invention, it is possible to produce polymers that yield articles with excellent water-repellent and oil-repellent properties. The articles of the present invention exhibit excellent water-repellent and oil-repellent properties. [Modes for carrying out the invention]

[0010] The following terms used in this specification and in the claims are defined as follows: A "unit" is a general term for atomic groups that are directly formed by the polymerization of one monomer molecule, and atomic groups that are obtained by chemically transforming a part of that atomic group. A "monomer-based unit" refers to an atomic group that is directly formed by the polymerization of one monomer molecule. A "monomer" refers to a compound that has a polymerizable carbon-carbon double bond. "(Meth)acrylate" is a general term for acrylates and methacrylates. The solid content concentration is calculated by dividing the sample mass by the sample mass (the mass of the sample before heating) and the solid content mass (the mass of the sample after drying it in a convection dryer at 120°C for 4 hours), and then multiplying by 100. The number average molecular weight (hereinafter referred to as "Mn") and the mass average molecular weight (hereinafter referred to as "Mw") of the polymer are the molecular weights in terms of polymethyl methacrylate obtained by measurement with gel permeation chromatography (hereinafter referred to as "GPC") using a calibration curve prepared with a standard polymethyl methacrylate sample. The "~" indicating a numerical range means that the numerical values described before and after it are included as the lower limit value and the upper limit value. The various numerical ranges disclosed in this specification can be combined arbitrarily with their lower limit values and upper limit values to form new numerical ranges.

[0011] <Polymer> The polymer of the present invention (hereinafter also referred to as "polymer (C)") has the following unit (a) and the following unit (b). Polymer (C) may further have another unit (e) other than unit (a) and unit (b).

[0012] Unit (a): A unit represented by the following formula (1). -(CH2-CHR f )- (1) However, R f is a perfluoroalkyl group having 1 to 8 carbon atoms.

[0013] Unit (b): A unit represented by the following formula (2). -(CH2-CH-(O-C(=O)NH-R d ))- (2) However, R d is an alkyl group having 6 to 24 carbon atoms.

[0014] In polymer (C), the proportion of unit (a) is 20 to 60 mol% based on the total of unit (a) and unit (b). The proportion of unit (b) is 40 to 80 mol% based on the total of unit (a) and unit (b). Hereinafter, some examples of polymer (C) will be described. However, the following description is a disclosure of representative examples of the invention, and the present invention is not limited to the following disclosure.

[0015] (Unit (a)) R in unit (a) f R is a perfluoroalkyl group having 1 to 8 carbon atoms. f The number of carbon atoms is preferably 4 to 6, and particularly preferably 6, from the viewpoint that articles using the water-repellent and oil-repellent composition containing the polymer (C) exhibit superior water-repellent and oil-repellent properties. R f It may be linear or branched. f It is preferable that it be in a linear chain.

[0016] R f Preferably, CF3, CF2CF3, CF(CF3)2, CF2CF2CF2CF3, and CF2CF2CF2CF2CF2CF3 are preferred, more preferably CF3, CF2CF3, CF2CF2CF2CF3, and CF2CF2CF2CF2CF2CF3 are preferred, and even more preferably CF2CF2CF2CF3 and CF2CF2CF2CF2CF2CF3 are preferred.

[0017] The unit (a) is typically a unit based on monomer (a). Monomer (a): A compound represented by the following formula (3). CH2=CH-R f (3) However, R f R in equation (1) above is f It is the same as R. f R is a perfluoroalkyl group having 1 to 8 carbon atoms. f Details and preferred embodiments are shown in formula (1) R f This is the same as what was explained earlier. Monomer (a) may be used alone or in combination of two or more types.

[0018] (Unit (b)) R in unit (b) d R is an alkyl group having 6 to 24 carbon atoms. d The number of carbon atoms is preferably 12 to 22, and more preferably 14 to 18, from the viewpoint that articles using the water-repellent and oil-repellent composition containing the polymer (C) have superior water repellency. R dIt may be linear or branched. d It is preferable that it be in a linear chain.

[0019] R d As for the polymer (C), articles using a water-repellent and oil-repellent composition containing polymer (C) exhibit superior water repellency, so dodecyl group (lauryl group), tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group (cetyl group), heptadecyl group, octadecyl group (stearyl group), nonadecyl group, eicosyl group, hencoisyl group, docosyl group (behenyl group), and tricosyl group are preferred, lauryl group, cetyl group, stearyl group, and behenyl group are more preferred, and cetyl group and stearyl group are even more preferred.

[0020] As will be described later, unit (b) is typically obtained by chemically transforming unit (c), which is based on monomer (c), by reacting it with compound (d) after saponification. Monomer (c): A compound represented by the following formula (4). CH2=CH-OC(=O)R (4)

[0021] In monomer (c), R is an alkyl group having 1 to 4 carbon atoms. The number of carbon atoms in R is preferably 1, as this allows for good copolymerization with unit (a) and is easily saponified in the manufacturing method described later. In other words, monomer (c) is preferably vinyl acetate. R may be linear or branched. R is preferably linear. Monomer (c) may be used alone or in combination of two or more types.

[0022] Compound (d): A compound represented by the following formula (5). O=C=NR d (5) However, R d R in equation (2) above is d It is the same as R. d R is an alkyl group having 6 to 24 carbon atoms. d Details and preferred embodiments are shown in formula (2) R dThis is the same as what was explained earlier. Compound (d) may be used alone or in combination of two or more compounds.

[0023] (Unit: e) Unit (e) is typically a unit (e) based on a monomer other than monomer (a) and monomer (c) that is copolymerizable with monomer (a) and monomer (c) (hereinafter referred to as "monomer (e)"). Monomer (e) may be a compound having two or more polymerization-reactive carbon-carbon double bonds. The number of polymerization-reactive carbon-carbon double bonds in monomer (e) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. As monomer (e), a compound having a vinyl group or an allyl group is preferred because it readily copolymerizes with monomer (a) and monomer (c).

[0024] Examples of monomer(e) include vinyl carboxylates, allyl carboxylates, vinyl ethers, allyl ethers, vinyl halides, olefins, (meth)acrylates, (meth)acrylamides, and halogenated olefins other than vinyl halides. However, monomer(e) is not limited to these examples. Monomer (e) may be used alone or in combination of two or more types.

[0025] Examples of vinyl carboxylates having 8 or more carbon atoms include vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl octoate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotate, and vinyl cinnamate. Examples of allyl carboxylic acid esters include allyl acetate and diallyl adipate.

[0026] Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, chloropropyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether. Examples of allyl ethers include allyl ethyl ether, diallyl ether, and 1,3-diallyloxy-2-propanol. Examples of vinyl halides include vinyl chloride and vinyl fluoride. Examples of olefins include ethylene and propylene.

[0027] Examples of (meth)acrylates include alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, aromatic (meth)acrylates, aliphatic cyclic (meth)acrylates, and (meth)acrylic acid. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyoxyethylene glycol mono(meth)acrylate, polyoxypropylene glycol mono(meth)acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth)acrylate. Examples of aromatic (meth)acrylates include phenyl (meth)acrylate, benzyl (meth)acrylate, and pentafluorophenyl (meth)acrylate. Examples of aliphatic cyclic (meth)acrylates include cyclohexyl (meth)acrylate and isobornyl (meth)acrylate. Other (meth)acrylates besides those mentioned above include, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-diisopropylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate.

[0028] Examples of (meth)acrylamides include alkyl(meth)acrylamides, hydroxyalkyl(meth)acrylamides, and (meth)acrylamides in which the nitrogen atom forms a heterocyclic structure. Examples of alkyl(meth)acrylamides include N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N,N-diisopropylacrylamide, N-(n-butyl)(meth)acrylamide, N-(t-butyl)(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N-lauryl(meth)acrylamide, N-stearyl(meth)acrylamide, N-behenyl(meth)acrylamide, and N,N-dimethylaminoethyl(meth)acrylamide. Examples of hydroxyalkyl(meth)acrylamides include N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, and N-(4-hydroxybutyl)(meth)acrylamide. Examples of (meth)acrylamides in which the nitrogen atom forms a heterocyclic structure include N-(meth)acryloylmorpholine and N-(meth)acryloylpiperidine.

[0029] Examples of halogenated olefins other than vinyl halogenates include vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, trifluorochloroethylene, CF2=CFOCF3, CF2=CFOCF2CF3, CF2=CFOCF2CF2CF3, CF2=CFOCF2CF2CF2CF3, and CF2=CFOCF2CF(CF3)OCF2CF2CF3.

[0030] Other examples of monomer(e) include, for example, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and ethyl vinyl sulfide. However, other examples of monomer(e) are not limited to these examples.

[0031] (Composition of polymer (C)) The proportion of unit (a) is 20 to 60 mol%, preferably 25 to 55 mol%, and more preferably 30 to 50 mol%, relative to the sum of unit (a) and unit (b). If the proportion of unit (a) is above the lower limit of the above range, articles using the water- and oil-repellent composition of the present invention can exhibit better oil repellency. If the proportion of unit (a) is below the upper limit of the above range, polymer (C) can be easily synthesized with a good polymerization yield. Therefore, articles using the water- and oil-repellent composition of the present invention are more likely to exhibit better water- and oil-repellent properties.

[0032] The proportion of unit (b) is 40 to 80 mol%, preferably 45 to 75 mol%, and more preferably 50 to 70 mol%, relative to the sum of unit (a) and unit (b). If the proportion of unit (b) is above the lower limit of the above range, polymer (C) can be easily synthesized with a good polymerization yield. Therefore, articles using the water-repellent and oil-repellent composition of the present invention tend to exhibit better water repellency. If the proportion of unit (b) is below the upper limit of the above range, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties.

[0033] The total ratio of unit (a) and unit (b) is preferably 50 mol% or more, more preferably 60 to 100 mol%, even more preferably 60 to 98 mol%, and even more preferably 70 to 95 mol% relative to the total units of polymer (C). If the total ratio of unit (a) and unit (b) is above the lower limit of the above range, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties. If the total ratio of unit (a) and unit (b) is below the upper limit of the above range, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better oil-repellent properties.

[0034] The proportion of each unit is, 1 The reaction rates of each monomer component can be calculated by 1H-NMR and gas chromatography. When polymer (C) is produced, if the conversion rate of monomer components to polymer (A) is high (e.g., 90% or more), the proportion of each unit may be calculated based on the amount of monomer component charged.

[0035] (Properties) The Mn of polymer (C) is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more. The Mn of polymer (C) is preferably 20,000 or less, more preferably 18,000 or less, and even more preferably 15,000 or less. If the Mn of polymer (C) is equal to or greater than the lower limit, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better oil-repellent properties. If the Mn of polymer (C) is equal to or less than the upper limit, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties. The Mn of polymer (C) is preferably 1,000 to 20,000, more preferably 2,000 to 18,000, and even more preferably 3,000 to 15,000. If the Mn of polymer (C) is within the above range, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties.

[0036] The Mw of polymer (C) is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. The Mw of polymer (C) is preferably 100,000 or less, more preferably 60,000 or less, and even more preferably 40,000 or less. If the Mw of polymer (C) is equal to or greater than the lower limit, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better oil-repellent properties. If the Mw of polymer (C) is equal to or less than the upper limit, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties. The Mw of polymer (C) is preferably 5,000 to 100,000, more preferably 8,000 to 60,000, and even more preferably 10,000 to 40,000. If the Mw of polymer (C) is within the above range, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties. The Mn and Mw values ​​of polymer (C) are obtained using a measurement sample prepared by the method described in "Step 3" of the Examples below. If it is difficult to prepare a measurement sample by Step 3, the sample preparation conditions and GPC measurement conditions may be changed as appropriate.

[0037] (Mechanism of action) The polymer (C) described above contains 20 mol% or more of units (a) having perfluoroalkyl groups with 1 to 8 carbon atoms, thus exhibiting excellent water and oil repellency. Furthermore, polymer (C) contains 40 mol% or more of units (b) having alkyl groups with 6 to 24 carbon atoms, thus exhibiting excellent water repellency.

[0038] <Method for producing polymer (C)> Polymer (C) can be produced, for example, by the following manufacturing method. A method for producing a polymer, comprising: polymerizing monomer components containing the following monomer (a) and monomer (c), wherein the proportion of monomer (a) to the total of monomer (a) and monomer (c) is 20 to 60 mol%, and the proportion of monomer (c) is 40 to 80 mol%, in the presence of a polymerization initiator; saponifying the unit (c) of a polymer (A) having a unit (a) based on monomer (a) and a unit (c) based on monomer (c); and then reacting the hydroxyl group of polymer (B) obtained by saponifying the unit (c) of polymer (A) with the following compound (d).

[0039] Monomer (a): A compound represented by the following formula (3). CH2=CH-Rf (3) Monomer (c): A compound represented by the following formula (4). CH2=CH-OC(=O)R (4) Compound (d): A compound represented by the following formula (5). O=C=NR d (5) However, R f , R, R d This is the same as what was explained in the section on <polymers>.

[0040] (monomer components) The monomeric component includes monomer (a) and monomer (c). The monomeric component may further include monomer (e). Details and preferred embodiments of each monomer are the same as those described in the <Polymers> section.

[0041] The proportion of monomer (a) is 20 to 60 mol%, preferably 25 to 55 mol%, and more preferably 30 to 50 mol%, relative to the total of monomers (a) and monomer (c). If the proportion of monomer (a) is above the lower limit of the above range, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties. If the proportion of monomer (a) is below the upper limit of the above range, the polymerization yield will be good. Therefore, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties.

[0042] The proportion of monomer (c) is 40 to 80 mol%, preferably 45 to 75 mol%, and more preferably 50 to 70 mol%, relative to the total of monomer (a) and monomer (c). If the proportion of monomer (c) is above the lower limit of the above range, the polymerization yield will be good. Therefore, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water repellency. If the proportion of monomer (c) is below the upper limit of the above range, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties.

[0043] The total ratio of monomer (a) and monomer (c) is preferably 50 mol% or more, more preferably 60 to 100 mol%, even more preferably 60 to 98 mol%, and even more preferably 70 to 95 mol% relative to the total monomers in the monomer component. If the total ratio of monomer (a) and monomer (c) is above the lower limit of the above range, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better water-repellent and oil-repellent properties. If the total ratio of monomer (a) and monomer (c) is below the upper limit of the above range, articles using the water-repellent and oil-repellent composition of the present invention can exhibit better oil-repellent properties.

[0044] (polymerization) Polymerization of monomeric components in the presence of a polymerization initiator yields a polymer (A) having units (a) based on monomer (a) and units (c) based on monomer (c).

[0045] Examples of polymerization initiators include thermal polymerization initiators, photopolymerization initiators, radiation polymerization initiators, radical polymerization initiators, and ionic polymerization initiators. Among these, radical polymerization initiators are preferred. Examples of radical polymerization initiators include azo polymerization initiators, peroxide polymerization initiators, and redox initiators, which are used depending on the polymerization temperature. Azo compounds are preferred as radical polymerization initiators, and salts of azo compounds are more preferred.

[0046] The amount of polymerization initiator added is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of monomer component. The polymerization temperature is preferably 20 to 150°C, and more preferably 40 to 90°C. The polymerization time also varies depending on the reaction temperature, but can be, for example, 5 to 144 hours. The polymerization time is preferably 12 to 86 hours. Polymerization is preferably carried out in an inert atmosphere such as nitrogen.

[0047] When polymerizing monomer components, molecular weight modifiers may be used. Preferred molecular weight modifiers include aromatic compounds, mercapto alcohols, mercaptocarboxylic acids, and alkyl mercaptans, with mercaptocarboxylic acids and alkyl mercaptans being more preferred. More specifically, examples include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dima (CH2=C(Ph)CH2C(CH3)2Ph, where Ph is a phenyl group). The amount of molecular weight adjusting agent added is preferably 0 to 5 parts by mass, and more preferably 0 to 2 parts by mass, per 100 parts by mass of monomer component.

[0048] Polymerization methods include, for example, solution polymerization, emulsion polymerization, and bulk polymerization. Among these, solution polymerization and emulsion polymerization are preferred, with solution polymerization being particularly preferred. In solution polymerization, monomer components can be polymerized without using emulsifiers, making it easy to remove water before reacting polymer (B) and compound (d). Therefore, the reaction between polymer (B) and compound (d) proceeds easily.

[0049] For solution polymerization, it is preferable to use a mixed medium consisting of a fluorine-containing medium and a medium that can form an azeotrope with water (hereinafter sometimes referred to as "azeotropic medium"). Using a mixed medium containing a fluorine-containing medium makes it easier to ensure the solubility of polymer (A) obtained by polymerization. Furthermore, using a mixed medium containing an azeotropic medium makes it easier to remove water before reacting polymer (B) with compound (d).

[0050] Examples of fluorine-containing media include 1H-tridecafluorohexane (AGC product name, AsahiClean AC-2000, hereinafter referred to as "AC-2000"), 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane (AGC product name, AsahiClean AC-6000, hereinafter referred to as "AC-6000"), and 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy) Tan (AGC product name, Asahi Clean AE-3000, hereinafter referred to as "AE-3000"), dichloropentafluoropropane (AGC product name, Asahi Clean AK-225, hereinafter referred to as "AK-225"), 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (AGC product name, Cytop CT-solv100E), 1-methoxynonafluorobutane (3M Japan product name, Novec 7100), 1-ethoxynonafluorobutane (3M Japan product name, Novec 7200), 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)pentane (3M Japan product name, Novec 7600), 2H,3H-perfluoropentane (Mitsui DuPont Fluorochemicals product name, Vertr Examples include elXF), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1-nonanol, hexafluorobenzene, hexafluoro-2-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, and 1H,1H,7H-dodecafluoro-1-heptanol. It is preferable to dehydrate fluorine-containing media before use.

[0051] Examples of azeotropic media include methyl isobutyl ketone, toluene, and methyl ethyl ketone. Among these, methyl isobutyl ketone is preferred because it has a high water content in the azeotropic mixture and provides better dehydration efficiency.

[0052] The proportion of the fluorine-containing medium in the mixed medium is preferably 50 to 90% by mass, and more preferably 60 to 80% by mass. If the proportion of the fluorine-containing medium is above the lower limit of the above range, the monomer components dissolve more easily. If the proportion of the fluorine-containing medium is below the upper limit of the above range, the resulting polymer dissolves more easily.

[0053] The proportion of the azeotropic medium in the mixed medium is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass. If the proportion of the azeotropic medium is above the lower limit of the above range, polymer (A) dissolves more easily. If the proportion of the azeotropic medium is below the upper limit of the above range, monomer components dissolve more easily.

[0054] In emulsion polymerization, for example, monomer components are polymerized in an emulsion containing monomer components, an aqueous medium, an emulsifier, and a polymerization initiator. Examples of aqueous media include water; and mixed media of water and water-soluble organic solvents. A water-soluble organic solvent is an organic solvent that can be miscible with water in any proportion. Preferably, the water-soluble organic solvent is at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents. When the aqueous medium contains a water-soluble organic solvent, the proportion of the water-soluble organic solvent is preferably 1 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of water.

[0055] Emulsifiers are surfactants that have both hydrophilic and hydrophobic parts. Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers. Non-fluorinated emulsifiers that do not contain fluorine atoms are preferred. Details of the emulsifiers will be explained later in the section on <Water- and Oil-Repellent Compositions>.

[0056] As emulsifiers, due to their excellent dispersion stability, the use of nonionic emulsifiers alone, in combination with nonionic emulsifiers and cationic emulsifiers, in combination with nonionic emulsifiers and amphoteric emulsifiers, and in combination with anionic emulsifiers alone are preferred, with the use of nonionic emulsifiers and cationic emulsifiers being more preferred.

[0057] (Saponification) By saponifying unit (c) of polymer (A), polymer (B) having a hydroxyl group is obtained. The saponification method is not particularly limited. Various saponification methods can be employed. For example, one method involves contacting polymer (A) with an alkaline compound in the presence of an alcohol-containing medium. When a polymerization solution containing polymer (A) is obtained by solution polymerization, saponification can be performed, for example, by adding an alcohol solution of the alkaline compound to the polymerization solution. In this case, methanol and ethanol are preferred as the alcohol.

[0058] When the medium of the polymerization solution containing polymer (A) is a mixed medium containing a fluorine-containing medium, polymer (B) obtained by saponification is easily dissolved in the mixed medium. If the polymerization solution containing polymer (A) is a mixed medium containing an azeotrope with water, it is easier to remove the water before reacting polymer (B) with compound (d).

[0059] When polymer (A) is obtained by emulsion polymerization, it is preferable to perform a treatment to break down the emulsion before saponification. The emulsion can be destroyed by treatment with tetrahydrofuran, isopropyl alcohol, ethanol, methanol, or mixtures thereof.

[0060] After performing a treatment to break down the emulsion, the polymerization solution containing the obtained polymer (A) can be saponified by replacing the medium with a mixed medium of a fluorine-containing medium and an azeotropic medium, and adding an alcohol solution of an alkaline compound. The details and preferred embodiments of the mixed media described here are the same as those described in the (polymerization) section.

[0061] Examples of alkali compounds include sodium hydroxide and potassium hydroxide. The amount of alkali compound used is, for example, 0.2 to 35 parts by mass per 100 parts by mass of polymer (A) as the amount of active ingredient. The concentration of the alkali compound relative to the alcohol in the medium is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass. The saponification time can be adjusted depending on the concentration of the alkali compound used.

[0062] The degree of saponification is preferably 45 mol% or higher, more preferably 75 mol% or higher, even more preferably 95 mol% or higher, and particularly preferably 100 mol%. The higher the degree of saponification, the higher the proportion of units (c) based on monomer (c) that can be converted to units (b). Therefore, water repellency tends to improve. The reaction temperature for saponification is preferably 5 to 80°C, and more preferably 20 to 70°C. The reaction time varies depending on the reaction temperature, but can be, for example, 5 minutes to 48 hours. The reaction time is preferably 30 minutes to 30 hours. The higher the reaction temperature and the longer the reaction time, the easier it is to improve the degree of saponification.

[0063] After the reaction is complete, the reaction solution is made nearly neutral by, for example, adding an acid or washing the alkaline compound with an aqueous medium. Examples of acids include acetic acid, formic acid, citric acid, malic acid, tartaric acid, butyric acid, lactic acid, succinic acid, and fumaric acid. Subsequently, before the reaction between polymer (B) and compound (d) described below, a concentration and dehydration treatment is performed by distillation. By distillation, the fluorine-containing medium is first removed. Next, the azeotrope of the azeotrope medium and water is removed by distillation. Azeotrope medium may be added as needed to ensure that the azeotrope of the azeotrope medium and water continues during concentration and dehydration. Dehydration can be considered complete when the distillation temperature exceeds 110°C.

[0064] (Reaction between polymer (B) and compound (d)) Polymer (B) reacts with compound (d) to obtain polymer (C) as the isocyanate group of compound (d) reacts with the hydroxyl group of polymer (B). Compound (d): A compound represented by the following formula (5). O=C=NR d (5)

[0065] R in compound (d) d R is an alkyl group having 6 to 24 carbon atoms.d The number of carbon atoms is preferably 12 to 22, and more preferably 14 to 18, from the viewpoint that articles using the water-repellent and oil-repellent composition containing the polymer (C) have superior water repellency. R d It may be linear or branched. d It is preferable that it be in a linear chain.

[0066] The amount of compound (d) reacted with polymer (B) is preferably such that the ratio [NCO / OH] of the number of isocyanate groups [NCO] in compound (d) to the number of hydroxyl groups [OH] in polymer (B) is 1 or less. The ratio [NCO / OH] is more preferably 0.8 to 1, and even more preferably 0.9 to 1.

[0067] If the ratio [NCO / OH] is above the lower limit of the above range, then sufficient R is present in the polymer (C). d This allows for the introduction of [a specific feature / feature], which further improves water repellency. If the ratio [NCO / OH] is below the upper limit of the above range, it is preferable because it further reduces the amount of isocyanate groups that convert to amines in the aqueous medium remaining in the polymer (C). Furthermore, the completion of the reaction can be easily confirmed by checking whether the peak derived from the isocyanate has disappeared using infrared spectroscopy (hereinafter sometimes referred to as "IR").

[0068] Polymer (B) and compound (d) can be reacted in a mixed medium of a fluorine-containing medium and an azeotropic medium. The details and preferred embodiments of the mixed medium are the same as those described in the (polymerization) section. The reaction temperature when reacting polymer (B) and compound (d) is preferably 40 to 120°C, and more preferably 60 to 100°C. The reaction time varies depending on the reaction temperature, but may be, for example, 0.5 to 5 hours. The reaction time is preferably 1 to 4 hours.

[0069] (Mechanism of action) In the method for producing polymer (C) described above, monomer (a), which is difficult to polymerize on its own, is polymerized by combining it with monomer (c). As a result, polymer (A) having units (a) that provide excellent water-repellent and oil-repellent properties is obtained. In addition, by saponifying the polymer (A) and further reacting it with compound (d), the unit (c) based on the monomer (c) can be converted into a unit (b) with excellent water repellency. Therefore, polymer (C) is obtained that has even better water repellency and superior oil repellency than polymer (A).

[0070] <Water-repellent and oil-repellent composition> The water- and oil-repellent composition of the present invention (hereinafter also referred to as "this composition") comprises a polymer (C) and a liquid medium. This composition may further contain other components as needed. This composition may be the solution or dispersion obtained by the method for producing polymer (C) of the present invention. Alternatively, this composition may be a liquid obtained by further diluting the solution or dispersion.

[0071] Examples of liquid media include non-aqueous media, aqueous media, and mixed media of non-aqueous media and water-soluble organic solvents. When the liquid medium is a non-aqueous medium or a mixed medium, the composition is preferably a polymer solution containing polymer (C) and the non-aqueous medium or mixed medium. In this case, the composition may further contain an emulsifier. The amount of emulsifier in the polymer solution is typically 0.3 parts by mass or less per 100 parts by mass of polymer (C). When the liquid medium is an aqueous medium, the composition is preferably a polymer dispersion containing polymer (C), an aqueous medium, and an emulsifier.

[0072] (non-aqueous medium) A non-aqueous medium is a liquid medium that does not contain an aqueous medium. Typically, a non-aqueous medium is an organic solvent other than a water-soluble organic solvent. Non-aqueous media are not particularly limited as long as they can dissolve the polymer (C). Examples include ketones that do not contain an aqueous medium; compounds having an amide bond; compounds that do not contain an aqueous medium, have an ether bond, and do not have a hydroxyl group; and fluorine-containing media.

[0073] Examples of ketones that do not contain an aqueous medium include methyl ethyl ketone and methyl isobutyl ketone. Examples of compounds having an amide bond include dimethylacetamide, 3-methoxydimethylpropanamide, 3-butoxydimethylpropanamide, and methylpyrrolidone.

[0074] Examples of compounds that do not contain an aqueous medium, have an ether linkage, and do not have a hydroxyl group include diethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Examples of fluorine-containing media include the same compounds exemplified in the section on <Methods for producing polymers>. Non-aqueous media may be used individually or in combination of two or more types.

[0075] (aqueous medium) Aqueous media include water and mixed media of water and water-soluble organic solvents. A water-soluble organic solvent is an organic solvent that can be miscible with water in any proportion. Preferably, the water-soluble organic solvent is at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents. Water-soluble organic solvents may be used individually or in combination of two or more types.

[0076] 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 aprotic polar solvents include N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (hereinafter referred to as "THF"), acetonitrile, and acetone.

[0077] When the liquid medium is an aqueous medium, ether alcohols are preferred as the water-soluble organic solvent because they improve the compatibility between the polymer (C) and the aqueous medium, making it easier to form a uniform film on the object being treated. Dipropylene glycol, tripropylene glycol, and dipropylene glycol monomethyl ether are more preferred.

[0078] When the aqueous medium contains a water-soluble organic solvent, the proportion of the water-soluble organic solvent is preferably 1 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of water.

[0079] (mixed media) The mixed medium is a mixture of a non-aqueous medium capable of dissolving polymer (C) and a water-soluble organic solvent that can be arbitrarily miscible with the non-aqueous medium. Examples of non-aqueous media include the same compounds described in the (non-aqueous media) section. Among these, fluorine-containing media and ketone compounds are preferred. Preferred fluorine-containing media in the mixed media are AK-225, AE-3000, AC-6000, and AC-2000. Methyl isobutyl ketone is preferred as the ketone compound. Examples of water-soluble organic solvents include the same compounds described in the section on (aqueous media). Among these, aprotic polar solvents are preferred, with THF, acetone, and N,N-dimethylformamide being more preferred.

[0080] Preferred mixed media include a combination of a fluorine-containing medium and an aprotic polar solvent; a combination of a fluorine-containing medium and a ketone compound; and a mixed medium of AK-225 and THF is more preferred.

[0081] The proportion of the fluorine-containing medium in the mixed medium is preferably 30 to 90% by mass, and more preferably 40 to 80% by mass, relative to the total mass of the mixed medium. A proportion of the fluorine-containing medium within this range is preferable because it facilitates the dissolution of polymer (C). This proportion is the value at room temperature (25±5℃).

[0082] (emulsifier) Emulsifiers are surfactants that have both hydrophilic and hydrophobic parts. Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers. Non-fluorinated emulsifiers that do not contain fluorine atoms are preferred.

[0083] As for the emulsifier, the use of a nonionic emulsifier alone, a nonionic emulsifier and a cationic emulsifier in combination, a nonionic emulsifier and an amphoteric emulsifier in combination, and an anionic emulsifier alone are preferred, given the excellent dispersion stability of this composition, and the use of a nonionic emulsifier and a cationic emulsifier in combination is more preferred.

[0084] The ratio of nonionic emulsifier to cationic emulsifier (nonionic emulsifier / cationic emulsifier) ​​is preferably 100 / 0 to 40 / 60 (mass ratio), and more preferably 97 / 3 to 40 / 60 (mass ratio). In certain combinations of nonionic and cationic emulsifiers, the total amount of emulsifiers per 100 parts by mass of polymer (C) can be reduced to 10 parts by mass or less. Therefore, it is easier to reduce the adverse effects on water and oil repellency caused by the emulsifiers.

[0085] Examples of nonionic emulsifiers include surfactants described in paragraphs

[0067] to

[0095] of Japanese Patent Publication No. 2009-215370. 1 ~s 6 These are some examples. Surfactants 1These are polyoxyalkylene monoalkyl ethers, polyoxyalkylene monoalkenyl ethers, polyoxyalkylene monoalkaporenyl ethers, or polyoxyalkylene monopolyfluoroalkyl ethers. 1 Polyoxyethylene alkyl ethers are preferred as such. Surfactants 2 This refers to a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in its molecule. (Surfactants) 2 As such, acetylene glycol ethylene oxide adducts are preferred. Surfactants 3 This is a compound in which a polyoxyethylene chain and a polyoxyalkylene chain consisting of two or more oxyalkylene atoms with three or more carbon atoms linked together are connected, and both ends are hydroxyl groups. 3 As such, ethylene oxide propylene oxide polymers are preferred. Nonionic emulsifiers may be used individually or in combination of two or more types.

[0086] Examples of cationic emulsifiers include surfactants described in paragraphs

[0096] to

[0100] of Japanese Patent Publication No. 2009-215370. 7 These are some examples. Surfactants 7 It is a substituted ammonium salt type cationic emulsifier. Surfactants 7 Preferably, the ammonium salt is one 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, as shown in the formula (s 71 Compounds represented by (s 71 ) is preferable. [(R 21 )4N + ]·X - (s 71 ) R 21These are a hydrogen atom, an alkyl group with 1 to 22 carbon atoms, an alkenyl group with 2 to 22 carbon atoms, a fluoroalkyl group with 1 to 9 carbon atoms, or a polyoxyalkylene chain with a hydroxyl group at the end. 21 They may be the same or they may be different. However, the four R's 21 It is not a hydrogen atom at the same time. X - X is the counterion. - Preferably, chloride ions, ethyl sulfate ions, and acetate ions are used. compound(s) 71 Examples of these include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono(stearyl)monomethyldi(polyethylene glycol)ammonium chloride, monofluorohexyltrimethylammonium chloride, di(tallow alkyl)dimethylammonium chloride, and dimethylmonococonutamine acetate. Cationic emulsifiers may be used individually or in combination of two or more types.

[0087] Examples of amphoteric emulsifiers include surfactants described in paragraphs

[0101] to

[0102] of Japanese Patent Publication No. 2009-215370. 8 These include: One type of amphoteric emulsifier may be used, or two or more types may be used in combination. Surfactants 8 These are alanine, imidazolinium betaine, amide betaine, or betaine acetate.

[0088] (Other ingredients) Other components may be added to the solution or dispersion obtained by the method for producing polymer (C) of the present invention. Alternatively, other components may be added to a solution obtained by further diluting the solution or dispersion obtained by the method for producing polymer (C) of the present invention.

[0089] Other components are not limited to the examples given below. Other components may be used individually or in combination of two or more. A different type of component that produces the same effect as the other components described later may be added to the solution, dispersion, or diluted solution obtained by the method for producing polymer (C).

[0090] Other components to be added to the dispersion obtained by the polymer (C) production method of the present invention include, for example, resins other than polymer (C), adhesives, crosslinking agents, softeners, antistatic agents, catalysts, organic fillers, inorganic fillers, flocculants, buffers, pH adjusters, disinfectants, biocides, metal ion sequestering agents, hydrophobic agents, surfactants, defoamers, and volatile organic solvents.

[0091] When this composition contains a crosslinking agent, its adhesion to the article being treated tends to improve. Preferred crosslinking agents include isocyanate-based crosslinking agents, methylol-based crosslinking agents, carbodiimide-based crosslinking agents, and oxazoline-based crosslinking agents. Examples of isocyanate-based crosslinking agents include aromatic blocked-type isocyanate crosslinking agents, aliphatic blocked-type isocyanate crosslinking agents, aromatic non-blocked-type isocyanate crosslinking agents, and aliphatic non-blocked-type isocyanate crosslinking agents. The isocyanate crosslinking agent is preferably an aqueous dispersion type emulsified with a surfactant, or a self-aqueous dispersion type having hydrophilic groups.

[0092] Examples of methylol-based crosslinking agents include condensates or pre-condensates of urea or melamine with formaldehyde, methylol-dihydroxyethylene-urea and its derivatives, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, condensates of dicyandiamide-formaldehyde, methylol-carbamate, methylol-(meth)acrylamide, and polymers thereof.

[0093] Carbodiimide crosslinking agents are polymers that have carbodiimide groups in their molecules. Carbodiimide crosslinking agents exhibit excellent reactivity with carboxyl groups, amino groups, and active hydrogen groups in the articles being treated. Oxazoline crosslinking agents are polymers that have an oxazoline group in their molecule. Oxazoline crosslinking agents exhibit excellent reactivity with carboxyl groups in the article being treated.

[0094] Other crosslinking agents include, for example, divinyl sulfone, polyamides and their cationic derivatives, polyamines and their cationic derivatives, epoxy derivatives such as diglycidylglycerol, 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-epicrohydrin resins, polyvinyl alcohol or its derivatives, polyacrylamide or its derivatives, and glyoxal resin-based anti-wrinkle agents.

[0095] If the composition contains a methylol-based crosslinking agent or a glyoxal resin-based anti-wrinkle agent, it is preferable to include 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 hydrochlorides. Examples of amino alcohol hydrochlorides include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride, and 2-amino-2-methylpropanol hydrochloride.

[0096] (solid content concentration) The solid content concentration of the composition obtained when polymer (C) is produced by the manufacturing method of the present invention is not particularly limited. The solid content concentration may be, for example, in the range of 10 to 70% by mass or 20 to 60% by mass. The solid content concentration and the polymer (C) content may vary with dilution.

[0097] <Goods> The articles of the present invention are obtained by treating an article to be treated with this composition. Since the articles of the present invention are treated with this composition, they have excellent water-repellent and oil-repellent properties.

[0098] The articles to be treated with this composition are not particularly limited. Examples include textile products made of fibers, textile fabrics, textile knitted fabrics, textile cloths (clothing such as ski wear, rainwear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, protective clothing, bags, tents, etc.), nonwoven fabrics, glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded articles, and porous resins. Porous resins can be used, for example, as filters. The type of fiber is not particularly limited. Examples include natural fibers such as cotton, wool, silk, or cellulose; chemical fibers such as polyester, polyamide, acrylic, aramid, rayon, viscose rayon, and lyocell; and blended fibers of natural and chemical fibers. The materials for the porous resin are not particularly limited. Examples include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene. Examples of nonwoven fabric materials include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, cellulose, carbon fiber, cellulose acetate, and rayon. Preferred items to be processed are fibers, textile fabrics, and textile products made from textile fabrics.

[0099] The processing method is not particularly limited, as long as it allows the composition to adhere to the article to be processed. For example, if the composition contains a liquid medium, one method is to treat the article with the dispersion using various coating methods and then dry it. Examples of coating methods include, but are not limited to, coating, impregnation, dipping, spraying, brushing, padding, sizing press, and rolling.

[0100] Other processing methods include applying or impregnating the article to be processed with the composition using various coating methods, followed by drying; and molding a dispersion of the raw materials of the article to be processed with the composition, followed by drying (internal additive processing). As an internal additive method, when the item to be processed is paper, one method is to manufacture paper using a pulp slurry containing this composition.

[0101] The amount of solids in the water- and oil-repellent composition applied to the article to be treated is not particularly limited. For example, if the article to be treated is a textile fabric, the amount of solids is preferably 0.001 to 0.05 g / g relative to the unit mass of the textile fabric.

[0102] Drying may be carried out at room temperature or by heating. Heating is preferred. If heating is used, the heating temperature is preferably 40 to 200°C. Furthermore, if the water-repellent and oil-repellent composition contains a crosslinking agent, it is preferable to heat and cure it to a temperature above the crosslinking temperature of the crosslinking agent, if necessary. [Examples]

[0103] The present invention will be described below with reference to examples. However, the present invention is not limited to these examples.

[0104] <Abbreviations, raw materials> The meanings of the abbreviations and ingredients used in the following explanation are as follows: C4OLF:3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene C6OLF:3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoro-1-Octene

[0105] VAc: vinyl acetate Vst: Vinyl sterate EGMA: Ethylene glycol monoallyl ether CTFE: Chlorotrifluoroethylene

[0106] Water: Ion-exchanged water MIBK: Methyl isobutyl ketone AE-4A: AE3000 dehydrated with molecular sieve 4A DPG: Dipropylene glycol

[0107] E420: Polyoxyethylene oleyl ether (ethylene oxide adduct of approximately 12.8 moles, Emulgen 420, Kao Corporation product) P204: Ethylene oxide propylene oxide polymer (average molecular weight 3330, contains 40% by mass of ethylene oxide, Pronon 204, NOF Corporation product) SFY485: Acetylene glycol ethylene oxide adduct (30 moles of ethylene oxide added, Surfinol 485, manufactured by Nisshin Chemical Industry Co., Ltd.) LQ1863: 63% by mass solution of stearyltrimethylammonium chloride in water and isopropyl alcohol (Lipocard 18-63, Lion Specialty Chemicals product)

[0108] PPV: Perbutyl PV, a 50% xylene solution product of Nippon Oil & Fats Co., Ltd. VA-061A: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] (VA-061, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) acetate (VA-061:acetic acid = 1:0.8 (mass ratio))

[0109] AE3000: 1,1,2,2-Tetrafluoroethyl-1-(2,2,2-trifluoroethoxy)ethane (AGC product) AK-225: Dichloropentafluoropropane (Asahi Clean AK-225, AGC Corporation product) THF: Tetrahydrofuran

[0110] <Measurement method> The methods for measuring solid content concentration and molecular weight in polymerization examples, manufacturing examples, case studies, and comparative examples are as follows.

[0111] (solid content concentration) The sample was heated in an intake oven (convection dryer) heated to 120°C for 4 hours. The solid content concentration (mass %) was determined by dividing the mass of the solid obtained after heating (solid content mass) by the mass of the sample before heating.

[0112] (molecular weight) For each polymer obtained in Polymerization Example 1, Polymerization Example 2, Production Example 1, and Production Example 2 described below, measurement samples were prepared using the procedure in step 1. For each polymer obtained in Polymerization Examples 3 to 6 described below, measurement samples were prepared using the procedure in step 2. For each polymer obtained in Example 1 and Example 2 described below, measurement samples were prepared using the procedure in step 3. Using each of the obtained measurement samples, GPC measurements were performed under the following measurement conditions, and Mn and Mw were calculated in terms of polymethyl methacrylate.

[0113] Step 1 The polymerization solution was diluted with a mixed solvent of AK-225 and THF (AK-225 / THF = 6 / 4 (volume ratio)) to a solid content concentration of 0.5% by mass, and then passed through a 0.2 μm pore size filter to obtain the measurement sample.

[0114] Step 2 6 g of the polymer dispersion was added dropwise to a mixture of 6 g of hexane and 54 g of 2-butanol, and the mixture was stirred to precipitate a solid. The mixture was then centrifuged at 3000 rpm for 5 minutes, and the resulting solid was separated. 30 g of isopropyl alcohol-modified alcohol (manufactured by Imadzu, product name: 95% IPA-modified alcohol) and 30 g of deionized water were added to the separated solid and thoroughly mixed. After centrifuging at 3000 rpm for 5 minutes, the resulting solid was separated from the supernatant and vacuum-dried overnight at 35°C to obtain the polymer. This polymer was dissolved in a mixed solvent of AK-225 / THF = 6 / 4 (volume ratio) to a solid content concentration of 0.5%, and the mixture was passed through a 0.2 μm pore size filter to obtain the measurement sample.

[0115] Step 3 The polymerization solution was diluted with THF to a solid content concentration of 0.5% by mass, and then passed through a 0.2 μm pore size filter to obtain the measurement sample.

[0116] • Measurement conditions Equipment: Tosoh Corporation product, HLC-8320GPC Column: Agilent PLGEL 5μm MIXED-C, 300mm length, 7.5mm inner diameter. Mobile phase (Steps 1 and 2): Mixture of AK-225 / THF = 6 / 4 (volume ratio) Mobile phase (Step 3): THF Flow rate: 1.0mL / min Oven temperature: 37℃ Sample concentration: 1.0% by mass Injection volume: 50μL Detector: RI Molecular weight standards: Polymethyl methacrylate (Mp = 2,136,000, 955,000, 569,000, 332,800, 121,600, 67,400, 31,110, 13,300, 7,360, 1,950, 1,010, and 550)

[0117] <Example of polymerization> (Polymerization Example 1) In a 1-liter stainless steel reactor equipped with a stirring device, 250.7 g of C4OLF, 131.6 g of VAc, 100.0 g of MIBK, and 282.2 g of AE-4A were charged and stirred until homogenized. 35.5 g of PPV was then added as a polymerization initiator, and the top plate was closed. The autoclave was then purged with nitrogen, the temperature was raised to 60°C, and polymerization was carried out for 72 hours. The solid content concentration of the resulting polymerization solution was 43.0% by mass. The Mw of polymer (A1) contained in the polymerization solution was 23,400, and the Mn was 10,500.

[0118] (Polymerization example 2) In a 1-liter stainless steel reactor equipped with a stirring device, 281.0 g of C6OLF, 104.8 g of VAc, 100.0 g of MIBK, and 285.9 g of AE-4A were charged and stirred until homogenized. 28.3 g of PPV was then added as a polymerization initiator, and the top plate was closed. The autoclave was then purged with nitrogen, the temperature was raised to 60°C, and polymerization was carried out for 72 hours. The solid content concentration of the resulting polymerization solution was 44.5% by mass. The Mw of the polymer (A2) contained in the polymerization solution was 41,800, and the Mn was 13,900.

[0119] (Polymerization examples 3-6) Monomers (excluding VAc and CTFE), surfactants, and a medium shown in Tables 1 and 2 were placed in a glass container. After heating at 55°C for 30 minutes, the mixture was obtained by mixing using a homomixer (Biomixer, manufactured by Nippon Seiki Seisakusho Co., Ltd.). The obtained mixture was pre-emulsified at 10 MPa using a high-pressure emulsifier (Minilab, manufactured by APV Lannier) while maintaining the temperature at 55°C, and then processed at 40 MPa to obtain an emulsion. The obtained emulsion was placed in a stainless steel reactor and cooled to below 30°C. Polymerization initiators shown in Tables 1 and 2 were added, and the gas phase was purged with nitrogen. Then, the amounts of VAc and CTFE shown in Tables 1 and 2 were introduced. Polymerization was carried out at 55°C for 24 hours with stirring to obtain dispersions containing polymers (A3) to (A6). The solid content concentration of each obtained dispersion and the Mw and Mn of the polymers contained in each dispersion are shown in Tables 1 and 2.

[0120] [Table 1]

[0121] [Table 2]

[0122] <Saponification> (Manufacturing Example 1) A stirrer, reflux condenser, and thermometer were attached to a 300 ml four-necked flask and placed in a water bath. 80 g of the polymerization solution obtained in polymerization example 1 and 16 g of methanol solution containing 5% sodium hydroxide were added, and a stopper was attached. Stirring was started, the flask was heated to 50°C, and saponified for 60 minutes. After the flask cooled to room temperature, 150 g of 1% acetic acid aqueous solution was added to the flask and stirred for 5 minutes to neutralize. Stirring was stopped, and the mixture was allowed to stand to separate into layers. The resulting upper layer was carefully removed with a dropper. 100 g of water was then added to the remaining lower layer and stirred for 5 minutes, after which the lower layer was washed with water. Stirring was stopped, and the mixture was allowed to stand to separate into layers. The upper layer was carefully removed. The washing and removal of the upper layer were repeated two more times in the same manner.

[0123] Next, the reflux tubing attached to the flask was removed, a T-joint and a Liebig condenser were attached, and the remaining lower layer of liquid was concentrated and dehydrated. First, AE3000 was removed by distillation. Subsequently, the azeotrope of MIBK / water was removed by distillation. MIBK was added to the flask as needed to ensure that the azeotrope of MIBK / water continued during concentration and dehydration. When the distillation temperature exceeded 110°C, it was determined that dehydration was complete. The concentrated liquid obtained by cooling the flask was collected as the concentrated liquid of Production Example 1.

[0124] The concentrated solution in Production Example 1 was an MIBK solution with a solid content concentration of 63% by mass. The hydroxyl value of polymer (B1) contained in the concentrate of Production Example 1 was 228 mgKOH / g. This hydroxyl value was approximately equivalent to the saponification value of polymer (A1), which was 224 mgKOH / g, calculated from the raw material composition. This means that almost the entire amount of polymer (A1) based on its VAc was saponified. The Mw of polymer (B1) was 10,700, and the Mn was 7,100.

[0125] (Manufacturing example 2) The polymerization solution obtained in Polymerization Example 1 was replaced with the polymerization solution obtained in Polymerization Example 2, and saponification, neutralization, washing, dehydration, and concentration were performed using the same procedure as in Production Example 1. The resulting concentrate was recovered as the concentrate for Production Example 2.

[0126] The concentrated solution in Production Example 2 was an MIBK solution with a solid content concentration of 63% by mass. The hydroxyl value of polymer (B2) contained in the concentrate of Production Example 2 was 182 mgKOH / g. This hydroxyl value was approximately equivalent to the saponification value of polymer (A2), which was 177 mgKOH / g, calculated from the raw material composition. This means that almost the entire amount of polymer (A2) based on its VAc was saponified. The Mw of polymer (B2) was 23,400, and the Mn was 10,300.

[0127] (Manufacturing Example 3) 70 g of the dispersion obtained in polymerization example 3 was concentrated under reduced pressure to approximately 30 g. 50 g of THF was added to this and concentrated again under reduced pressure to approximately 30 g. Another 50 g of THF was added and concentrated under reduced pressure to obtain a solution of approximately 30 g. MIBK was added to this and concentrated under reduced pressure to replace the THF with MIBK. After further concentration, MIBK and AE-4A were added to obtain a diluted solution so that the solid content was 40% by mass and the mass ratio of MIBK to AE-4A was MIBK / AE-4A = 1 / 3.

[0128] 61.6 g of the diluent and 16 g of methanol solution containing 5% sodium hydroxide were placed in a 300 ml four-necked flask and set in a water bath. A stirrer, reflux condenser, thermometer, and stopper were attached to the four-necked flask, and stirring was started while the temperature was raised. The polymer (A3) contained in the dispersion was saponified at 50°C for 1 hour. After the flask was cooled to room temperature, 150 g of 1% acetic acid aqueous solution was added to the flask and stirred for 5 minutes to neutralize it.

[0129] The stirring was stopped, and the mixture was allowed to stand to separate into layers. The upper layer was then carefully removed. 100 g of water was added to the remaining lower layer in the flask and stirred for 5 minutes, then the lower layer was washed with water. The stirring was stopped, and the mixture was allowed to stand to separate into layers. The upper layer was then carefully removed. The washing and removal of the upper layer was repeated two more times in the same manner. The obtained lower layer was transferred to a round-bottom flask, dried under reduced pressure, and then vacuum-dried to obtain saponified polymer (B3). The hydroxyl value of polymer (B3) was 277 mg KOH / g.

[0130] <Examples 1-11> Examples 1-3 below are examples of actual cases. Examples 4-11 are comparative examples.

[0131] (Example 1) 18.7 g of the concentrate from Production Example 1 and 60.6 g of MIBK were placed in a 100 ml four-necked flask, which was then set in an oil bath. A stirrer, a nitrogen inlet tube with an injection port, a thermometer, and a Dean-Stark reflux tube were attached. Stirring was started, and while introducing nitrogen, the temperature inside the flask was raised to 110°C and reflux was performed. At this time, a total of 11.3 g of MIBK and a small amount of water were removed from the system via the Dean-Stark reflux tube to obtain concentrate (1).

[0132] Next, the flask temperature was set to 50°C, the Dean-Stark reflux tube was removed, and 15.8 mg of a mixed solution of AE-4A and MIBK (MIBK / AE-4A = 1 / 1 (mass ratio)) containing 18.8 g of AE-4A and 1 wt% dibutyltin dilaurate was added to the concentrated solution (1) in the flask, and the Dean-Stark reflux tube was reattached. While raising the temperature of the flask to 80°C over 30 minutes, 13.1 g of stearyl isocyanate was added to the flask using a syringe pump. The reaction was then allowed to proceed at 80°C for 2.5 hours, and the resulting reaction solution was sampled and analyzed by IR. After confirming the disappearance of the isocyanate-derived peak by IR analysis, the flask temperature was cooled to 40°C to obtain 62.2 g of reaction solution (1).

[0133] The resulting reaction solution (1) contained polymer (C1) obtained by the reaction of polymer (B1) with stearyl isocyanate. The solid content concentration of reaction solution (1) was 35.8% by mass. Polymer (C1) had a Mw of 18,300 and a Mn of 11,700. This reaction solution (1) was diluted with MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution of Example 1.

[0134] (Example 2) Instead of the concentrate from Production Example 1, 20.9 g of the concentrate from Production Example 2 was used, and the amount of MIBK added initially was 59.8 g. Otherwise, reflux was performed in the same manner as in Example 1, and 13.2 g of MIBK containing trace amounts of water was removed from the system to obtain concentrate (2). Next, the concentrated solution (2) was used to react stearyl isocyanate with polymer (B2) in the same manner as in Example 1. The resulting reaction solution (2) was 62.4 g.

[0135] The resulting reaction solution (2) contained polymer (C2), which was obtained by the reaction of polymer (B2) with stearyl isocyanate. The solid content concentration of this reaction solution (2) was 36.9% by mass. The Mw of polymer (C2) was 17,500, and the Mn was 11,800. This reaction solution (2) was diluted with MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution of Example 2.

[0136] (Example 3) First, 10.7 g of polymer (B3) obtained in Production Example 3 and 67.5 g of MIBK were added to dissolve polymer (B3) and obtain a MIBK solution of polymer (B3). Except for using this MIBK solution of polymer (B3) instead of the concentrate from Production Example 1, reflux was performed in the same manner as in Example 1, and 13.2 g of MIBK containing trace amounts of water was removed from the system to obtain concentrate (3). Next, the concentrated solution (3) was used to react stearyl isocyanate with polymer (B3) in the same manner as in Example 1. The resulting reaction solution (3) was 93.4 g.

[0137] The resulting reaction solution (3) contained polymer (C3) obtained by the reaction of polymer (B3) with stearyl isocyanate. The solid content concentration of reaction solution (3) was 26.2% by mass. The resulting polymer (C3) had a Mw of 23,000 and a Mn of 14,000. This reaction solution (3) was diluted with MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution of Example 3.

[0138] (Example 4) The polymerization solution obtained in Polymerization Example 1 was diluted with MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution of Example 4.

[0139] (Example 5) The polymerization solution obtained in polymerization example 2 was diluted with MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution of example 5.

[0140] (Example 6) The dispersion obtained in polymerization example 3 was diluted with MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution of example 6.

[0141] (Example 7) The concentrated solution from Production Example 1 was diluted with MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution from Example 7.

[0142] (Example 8) The concentrated solution from Production Example 2 was diluted with MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution from Example 8.

[0143] (Example 9) 6 g of the dispersion obtained in polymerization example 4 was added dropwise to 60 g of a mixture of 6 g of hexane and 54 g of 2-butanol, and the mixture was stirred to precipitate a solid. The mixture was then centrifuged at 3000 rpm for 5 minutes, and the resulting solid was separated. 30 g of isopropyl alcohol-modified alcohol (manufactured by Imadzu, product name: 95% IPA-modified alcohol) and 30 g of deionized water were added to the separated solid and stirred well. After centrifuging at 3000 rpm for 5 minutes, the supernatant was removed, and the resulting solid was vacuum-dried overnight at 35°C to obtain polymer (A4). The obtained polymer (A4) was dissolved in MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution of Example 9.

[0144] (Example 10) Polymer (A5) was obtained in the same manner as in Example 9, except that the dispersion obtained in Polymerization Example 5 was used instead of the dispersion obtained in Polymerization Example 4. The obtained polymer (A5) was dissolved in MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution of Example 10.

[0145] (Example 11) Polymer (A6) was obtained in the same manner as in Example 9, except that the dispersion obtained in Polymerization Example 6 was used instead of the dispersion obtained in Polymerization Example 4. The obtained polymer (A6) was dissolved in MIBK to a solid content concentration of 1% by mass to obtain the MIBK solution of Example 12.

[0146] Table 3 shows the polymer composition contained in each MIBK solution. In Table 3, VA is a unit derived from the saponification of the unit based on VAc. St-NCO is a unit chemically converted by the reaction of VA with stearyl isocyanate. Other units are based on the respective starting monomers. For example, C4OLF is a unit based on C4OLF.

[0147] The polymer compositions for Examples 4-6 and 9-11 in Table 3 are values ​​calculated from the raw material composition during polymerization. The polymer compositions for Examples 7 and 8 in Table 3 are values ​​calculated from the raw material composition and hydroxyl value during polymerization. The polymer compositions for Examples 1-3 in Table 3 are calculated from the composition and amount of the polymer after saponification, as well as the amount of VSt used. Here, the composition of the polymer after saponification is calculated from the raw material composition and hydroxyl value during polymerization.

[0148] [Table 3]

[0149] <Rating> The washed glass slides were placed in a dipping apparatus and repeatedly dipped three times into the MIBK solution prepared for each example at a dipping speed of 0.5 mm / second. Afterward, they were dried in a forced-retention oven set to 160°C for 20 minutes, and then conditioned for 15 hours before being used as measurement samples. For each prepared sample, the static contact angle, advancing contact angle, and receding contact angle with respect to distilled water and n-hexadecane were measured using a Dataphysics surface tensile meter (DCAT11). During the measurements, the temperature of the distilled water and n-hexadecane was maintained at 20°C ± 0.2°C. The results are shown in Table 4.

[0150] [Table 4]

[0151] As shown in Table 4, the MIBK solutions in Examples 1-3 exhibited large static contact angles with respect to distilled water. Furthermore, they also showed large dynamic contact angles with respect to distilled water and n-hexadecane. Regarding dynamic contact angles, Examples 1-3 showed particularly large receding contact angles. This indicates that distilled water and n-hexadecane were less likely to remain on the slide glass, demonstrating excellent water and oil repellency. [Industrial applicability]

[0152] The present invention provides a polymer that yields articles with excellent water-repellent and oil-repellent properties, a method for producing the polymer, a water-repellent and oil-repellent composition containing the polymer, and articles with excellent water-repellent and oil-repellent properties.

[0153] This application claims priority based on Japanese Patent Application No. 2021-159679, filed on 29 September 2021, and the entire contents of the said Japanese application are incorporated herein by reference.

Claims

1. It is a polymer, The polymer has the following units (a) and (b), The proportion of unit (a) is 20 to 60 mol% of the sum of unit (a) and unit (b), The proportion of unit (b) is 40 to 80 mol% of the sum of unit (a) and unit (b), A polymer in which the sum of unit (a) and unit (b) is 50 mol% or more of the total units. Unit (a): A unit represented by the following formula (1). -(CH ２ -CHR ｆ )- (1) However, R ｆ These are perfluoroalkyl groups having 1 to 8 carbon atoms. Unit (b): The unit represented by the following formula (2). -(CH ２ -CH-(O-C(=O)NH-R ｄ ))- (2) However, R ｄ These are alkyl groups having 6 to 24 carbon atoms.

2. The polymer according to claim 1, wherein the number average molecular weight is 1,000 to 20,000.

3. A monomer component comprising the monomer (a) and monomer (c) described below, wherein the proportion of monomer (a) to the total of monomer (a) and monomer (c) is 20 to 60 mol%, the proportion of monomer (c) is 40 to 80 mol%, and the total proportion of monomer (a) and monomer (c) is 50 mol% or more of the total monomers, is polymerized in the presence of a polymerization initiator. The unit (c) of a polymer (A) having a unit (a) based on the monomer (a) and a unit (c) based on the monomer (c) is saponified. Next, a method for producing a polymer, comprising reacting the hydroxyl group of polymer (B) obtained by saponifying the unit (c) of polymer (A) with the following compound (d). Monomer (a): A compound represented by the following formula (3). CH ２ =CH-R ｆ (3) However, R ｆ is a perfluoroalkyl group having 1 to 8 carbon atoms. Monomer (c): A compound represented by the following formula (4). CH ２ =CH-OC(=O)R (4) However, R is an alkyl group having 1 to 4 carbon atoms. Compound (d): A compound represented by the following formula (5). O=C=N-R ｄ (5) However, R ｄ These are alkyl groups with 6 to 24 carbon atoms.

4. The manufacturing method according to claim 3, wherein the polymerization is solution polymerization.

5. A water-repellent and oil-repellent composition comprising the polymer according to claim 1 or 2 and a liquid medium.

6. An article treated with the water-repellent and oil-repellent composition described in claim 5.

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