Polymer, coating material, and coated product

Abstract

Provided is a polymer that can be used as a resin for a coating material that has excellent weather resistance and antifouling properties. A polymer according to the present invention includes constituent units derived from (1) a fluorine-containing monomer, (2) at least one type of silicone monomer that includes a silicone unit and a polymerizable unsaturated functional group, (3) at least one type of hydrocarbon monomer that can copolymerize with (1) and / or (2), and (4) a monomer that has a crosslinkable functional group. The polymer has a glass transition temperature of at least 20°C, and a polymer solution of the polymer prepared using butyl acetate as a solvent such that the polymer concentration is 60 mass% is transparent.

Description

Polymers, paints, and coated products 【0001】 This disclosure relates to polymers, paints, and coated articles. 【0002】 Fluorine-containing polymers exhibit excellent weather resistance due to the high bonding energy of the C-F bonds within the molecule and their low polarizability. However, in applications such as building materials, excellent stain resistance is required in addition to weather resistance. 【0003】 As a coating with excellent weather resistance and stain resistance, Patent Document 1 discloses a fluorine / silicone hybrid polymer. Patent Documents 2 to 4 disclose fluorine / silicone hybrid polymers obtained by copolymerization of fluorine olefin monomers and organic silicone monomers. Patent Document 5 discloses a polymer obtained by copolymerizing chlorotrifluoroethylene, organic silicone monomers and vinyl ester monomers. 【0004】 International Publication 2021 / 054075, JP 2000-313725, International Publication 2018 / 193926, International Publication 2021-172322, Chinese Patent Publication 103193920 【0005】 The purpose of this disclosure is to provide a polymer that can be used as a resin in paints that have excellent weather resistance and stain resistance. 【0006】 This disclosure relates to a polymer having constituent units derived from a fluorine-containing monomer (1), at least one silicone monomer (2) having silicone units and polymerizable unsaturated functional groups, at least one hydrocarbon monomer (3) copolymerizable with (1) and / or (2), and a monomer (4) having crosslinkable functional groups, having a glass transition temperature of 20°C or higher, and a polymer solution prepared by adjusting the polymer concentration to 60% by mass using butyl acetate as a solvent exhibiting transparency. 【0007】 The fluorine-containing monomer (1) is preferably partially or entirely chlorotrifluoroethylene. The fluorine-containing monomer (1) is preferably tetrafluoroethylene and chlorotrifluoroethylene. 【0008】The present disclosure relates to a polymer having constituent units derived from a fluorine-containing monomer (1), at least one silicone monomer (2) having a silicone unit and a polymerizable unsaturated functional group, at least one hydrocarbon-based monomer (3) copolymerizable with (1) and / or (2), and a monomer (4) having a crosslinkable functional group. The fluorine-containing monomer (1) is partially or entirely tetrafluoroethylene, and it is also a polymer characterized in that a polymer solution adjusted to a polymer concentration of 60% by mass with butyl acetate as a solvent exhibits transparency. 【0009】 The hydrocarbon-based monomer (3) is preferably vinyl ethers and / or vinyl esters. The hydrocarbon-based monomer (3) is preferably vinyl ethers. The silicone monomer (2) is one or more organosilicon compounds represented by the following general formula (3): (where R ４ is a hydrogen atom or a methyl group, R ６ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may contain an OH group, n represents 0 to 10, and m represents 0 to 420). The hydrocarbon-based monomer (3) is vinyl ethers, and the monomer (4) having a crosslinkable functional group preferably has at least one or more functional groups selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, a cyano group, and a silyl group. 【0010】 The present disclosure is also a paint containing the above polymer and an organic solvent. The present disclosure is also a paint containing the above polymer and water. The present disclosure is also a painted article characterized by having a film obtained by applying the above paint. 【0011】 When the polymer of the present disclosure is used in the paint field, it has excellent effects in terms of weather resistance and antifouling properties. 【0012】 Hereinafter, the present disclosure will be described in detail. The present disclosure relates to a polymer that can be used in the paint field. In addition to having a specific composition, it has the feature that a polymer solution adjusted to a polymer concentration of 60% by mass with butyl acetate as a solvent exhibits transparency. 【0013】 In a polymer, if the composition is non-uniform, the uniform performance as a polymer will be impaired. In particular, when a silicone component is introduced by graft polymerization, such problems are likely to occur. Such non-uniform polymers do not fully exhibit the effect of weather resistance. This is presumably because the fluorine-containing component and the silicone component do not exist uniformly, and thus the synergistic effect of these components is not fully manifested. 【0014】 In order to improve the problems caused by this, in the present disclosure, a polymer with high uniformity is obtained. More specifically, in synthesizing a fluorine / silicone hybrid polymer, polymerization is carried out in the coexistence of a fluorine-containing monomer and a silicone monomer, thereby reducing the non-uniformity of the entire polymer. The polymer thus obtained is a polymer with high uniformity as a whole, and for this reason, it is presumed to have a significantly excellent effect in terms of weather resistance and antifouling properties. And because of the high uniformity, when dissolved in a solvent, not only some components will not become insoluble, but it shows high solubility as a whole. 【0015】 In the present disclosure, the solubility in butyl acetate was shown as an index of the uniformity of such a polymer. That is, it became clear that a polymer solution with a polymer concentration adjusted to 60% by mass using butyl acetate as a solvent and having transparency, i.e., having uniformity, can achieve the object of the present disclosure. 【0016】 Such a polymer with high uniformity becomes transparent particularly because there is no homopolymer of a monomer having a silicone polymer in the side chain, or even if it exists, its content is extremely small. For this reason, the interaction between the fluorine component and the organic silicone can be obtained without problems, and excellent weather resistance and antifouling performance can be obtained. 【0017】In this disclosure, "a polymer solution prepared by adjusting the polymer concentration to 60% by mass using butyl acetate as a solvent exhibits transparency" means that first, the polymer and butyl acetate are mixed to a polymer concentration of 60 ± 1% by mass. This mixture may be prepared by dissolving a solid or liquid polymer by stirring while applying heat as needed, or by concentrating a low-concentration polymer solution by volatilizing the butyl acetate. The transparency of the solution thus dissolved is measured using a turbidimeter. A Mitsubishi Chemical PT-200 turbidimeter is used, and measurements are taken in the absorbance range of 0 to 1000 ppm. The turbidity measurement is taken with the value when only butyl acetate is measured set to 0, and transparency means 10 or less. The measurement temperature is 25°C. 【0018】 The polymers of this disclosure consist of the following constituent units (1) to (4) as essential components. The polymers of this disclosure may be copolymers of a uniform composition, but are not necessarily required to be copolymers of a uniform composition; they may be mixtures of polymers of different compositions. However, even in such cases, it is necessary that the polymer is not mixed with components of low affinity. These monomers are described in detail below. 【0019】 (Fluorine-containing monomer (1)) The fluorine-containing monomers used as constituent units of the polymers of this disclosure are not particularly limited, and examples include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, fluorovinyl ether, hexafluoropropylene, trifluoroethylene, etc., and one or more of these can be used. 【0020】 Among these, tetrafluoroethylene and chlorotrifluoroethylene are preferred. Alternatively, a combination of these may be used. When used in combination, the amount of tetrafluoroethylene is preferably 10 to 90 mol% of the total amount of tetrafluoroethylene and chlorotrifluoroethylene. 【0021】(at least one silicone monomer (2) having a silicone unit and a polymerizable unsaturated functional group) Component (2) is a monomer having an unsaturated functional group having a silicone unit as a side chain. Such monomers are not particularly limited, but particularly preferred monomers include one or more organosilicon compounds selected from the following general formulas (1), (2), (3), (4), (5) and (6). Such monomers can be polymerized in combination with the fluorine-containing monomer (1), and the polymer is excellent in long-term water and oil repellency, repeated stain removability, chemical resistance, and weather resistance, and is useful for various applications. 【0022】 (where R １ 、R ２ 、and R ３ each represent a hydrogen atom, a methyl group, an ethyl group, a butyl group, a phenyl group, -CF ３ 、-C ２ H ４ CF ３ 、-C(CH ３ ) ３ or -OSi(CH ３ ) ３ . R １ 、R ２ 、and R ３ may be the same or different from each other. ) 【0023】 【0024】 (where R ４ is a hydrogen atom or a methyl group, R ５ is an ether group (i.e., -O-), R ６ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms that may contain an OH group, n represents 0 to 10, and m represents 0 to 420, particularly 0 to 160. ) 【0025】 (where R ７ is a hydrogen atom or a methyl group, R ８ 、R ９ 、and R １０Each of these may contain a hydrogen atom, a methyl group, an ethyl group, a butyl group (e.g., n-butyl group, isobutyl group, t-butyl group, sec-butyl group, etc.), or -OSi(CH ３ ) ３ This indicates R ８ , R ９ , and R １０ These may be the same or different. (p represents a value between 0 and 10.) 【0026】 (Here, R １１ This is an alkyl group having 1 to 6 carbon atoms or -(CH ２ ) ｒ - OOC (CH ３ ) C=CH ２ or - (CH ２ ) ｒ -OOC-HC=CH ２ Alternatively, -CH = CH ２ R １２ ha- (CH ２ ) ｒ - OOC (CH ３ ) C=CH ２ or - (CH ２ ) ｒ -OOC-HC=CH ２ Alternatively, -CH = CH ２ (This indicates that q ranges from 1 to 420, and r ranges from 1 to 6.) 【0027】 (Here, R １２(As defined above.) Specific examples of organosilicon compounds represented by general formulas (1), (2), (3), (4), (5), and (6) include vinylpentamethyldisiloxane, vinylphenyldimethylsilane, vinylmethylbis(trimethylsiloxy)silane, vinyltriethylsilane, vinyl(trifluoromethyl)dimethylsilane, vinyl(3,3,3-trifluoropropyl)dimethylsilane, vinyltrimethylsilane, vinyltris(trimethylsiloxy)silane, vinyl-t-butyldimethylsilane, vinyldiethylmethylsilane, and (3-acryloxypropyl)methylbis(trimethylsiloxy) Suitable candidates include silanes, 3-methacryloxypropylbis(trimethylsiloxy)methylsilane, (3-acryloxypropyl)tris(trimethylsiloxy)silane, methacryloxypropyltris(trimethylsiloxy)silane, methacryloxymethyltrimethylsilane, reactive silicone oils with one end modified with methacrylic, reactive silicone oils with one end modified with acrylic, reactive silicone oils with both ends modified with methacrylic, reactive silicone oils with both ends modified with acrylic, and organosilicon compounds represented by general formulas (7), (8), (9), and (10). These organosilicon compounds may be used individually or in combination of two or more. The molecular weight of these organosilicon compounds is preferably 100 to 30,000. 【0028】 (Here, R １３ (where represents an alkyl group having 1 to 6 carbon atoms, which may contain an OH group, and a represents 1 to 250.) 【0029】 (Here, R １３ (where represents an alkyl group having 1 to 6 carbon atoms, which may contain an OH group, and a represents 1 to 250.) 【0030】 (Here, R １４ ha-OOC(CH ３ ) C=CH ２ (This indicates that b represents a value between 1 and 250.) 【0031】 【0032】(Hydrogen-based monomer (3)) The polymer has constituent units derived from at least one hydrocarbon-based monomer (3) copolymerizable with (1) and / or (2). Hydrocarbon-based monomers mean monomers that do not contain fluorine atoms and crosslinking functional groups in their chemical structure, and may contain elements other than C and H, such as oxygen atoms and nitrogen atoms. In addition to hydrocarbons having unsaturated groups, vinyl ethers, vinyl esters, allyl ethers, etc. can be mentioned. Furthermore, 2,3-dihydrofurans and norbornenes, which can directly introduce a cyclic structure into the polymer main chain, are useful because they can raise the Tg. Among these, vinyl ethers and vinyl esters are particularly preferred. Two or more of these monomers may be used in combination. Furthermore, ethylene and isobutylene are also included in the hydrocarbon-based monomer (3). 【0033】 The vinyl ether described above readily copolymerizes with fluorine-containing monomer (1), and the resulting polymer can be given good weather resistance. Specifically, the monomer shown in the following formula Examples include cyclohexyl vinyl ether. 【0034】 More specifically, examples include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, octadecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, and the like. Among these, at least one selected from the group consisting of ethyl vinyl ether and cyclohexyl vinyl ether is preferred. 【0035】The vinyl esters mentioned above are preferably vinyl carboxylates, more preferably at least one selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl cyclohexylcarboxylate, even more preferably at least one selected from the group consisting of vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl cyclohexylcarboxylate, and particularly preferably at least one selected from the group consisting of vinyl acetate and vinyl versatate. Furthermore, as the vinyl esters mentioned above, vinyl carboxylates with 6 or more carbon atoms in the carboxylic acid are preferred because they offer superior adhesion and abrasion resistance, and vinyl carboxylates with 9 or more carbon atoms in the carboxylic acid are more preferred. The upper limit of the carbon atoms in the carboxylic acid in vinyl carboxylates is preferably 20, and more preferably 15. Due to their excellent adhesion to the sealing material layer, vinyl versatate such as vinyl neononanoate (VV9) and vinyl neodecanoate is most preferred. 【0036】 Furthermore, it is preferable that the vinyl ester does not contain either a hydroxyl group or an aromatic ring. It is also preferable that the vinyl ester does not contain a halogen atom. 【0037】 (Monomers having crosslinkable functional groups (4)) The polymers of the present disclosure have structural units based on monomers (4) having crosslinkable functional groups. Such crosslinkable functional groups mean functional groups that undergo a crosslinking reaction by themselves or that cause a crosslinking reaction with a crosslinking agent component. 【0038】 The crosslinkable functional groups are not particularly limited and include hydroxyl groups, amino groups, carboxyl groups, epoxy groups, cyano groups, silyl groups, and the like. A monomer may have two or more of these functional groups. Among these, monomers having hydroxyl groups are most preferred. 【0039】As the hydroxyl group-containing monomer, at least one selected from the group consisting of hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycarboxylate vinyl ester, hydroxycarboxylate allyl ester, and hydroxyalkyl (meth)acrylate is preferred, at least one selected from the group consisting of hydroxyalkyl vinyl ether and hydroxyalkyl allyl ether is more preferred, and hydroxyalkyl vinyl ether is even more preferred. 【0040】 Examples of the above-mentioned hydroxyalkyl vinyl ethers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, and 4-hydroxymethylcyclohexylmethyl vinyl ether (CHMVE). Examples of the above-mentioned hydroxyalkyl allyl ethers include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether. 【0041】 Examples of the vinyl hydroxycarboxylate esters mentioned above include vinyl hydroxyacetate, vinyl hydroxypropanoate, vinyl hydroxybutanoate, vinyl hydroxyhexanoate, and vinyl 4-hydroxycyclohexylacetate. Examples of the allyl hydroxycarboxylate esters mentioned above include allyl hydroxyacetate, allyl hydroxypropanoate, allyl hydroxybutanoate, allyl hydroxyhexanoate, and allyl 4-hydroxycyclohexylacetate. 【0042】 Examples of the above hydroxyalkyl (meth)acrylate include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. Among the above hydroxyl group-containing monomers, formula (A): CH ２ = CH - (CH ２ ) ｌ -O-(CH ２ ) ｍA more preferable example is one represented by -OH (wherein l is 0 or 1 and m is an integer from 2 to 20), and at least one monomer selected from the group consisting of 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, and 4-hydroxybutyl allyl ether is particularly preferred. 【0043】 Examples of monomers containing a carboxyl group include (meth)acrylic acid, crotonic acid, and undecylenic acid. Examples of monomers containing an epoxy group include glycidyl vinyl ether and glycidyl (meth)acrylate. 【0044】 (Content of each monomer) The preferred content of each constituent unit (1) to (4) is shown below. This polymer is determined by the "fluorine content" obtained by elemental analysis and the "silicone index" shown later. As stated above, in this disclosure, the copolymer does not necessarily have to have a uniform composition. Therefore, in the case of a mixture of polymers with different compositions, the content of each monomer is shown below when the content ratio of the polymer as a whole is calculated. 【0045】 The above fluorine-containing monomer (1) unit is preferably in an amount that falls within the range of 15 to 50% fluorine content. The lower limit is preferably 20%, more preferably 25%, and most preferably 28%. The upper limit is preferably 46%, and most preferably 42%. The fluorine content is the value measured by the combustion method. 【0046】 The content of the above-mentioned silicone monomer (2) units is preferably such that the silicone index shown below is within the range of 0.5 to 50. The content of the silicone structure greatly affects the water repellency of the polymer of this disclosure. On the other hand, as described above, the silicone structure can be made by introducing either low molecular weight silicone units or high molecular weight silicone units into the structure. For this reason, it is preferable to determine the content based on the silicone index shown below. The silicone index is an index that represents the ratio of the silicone portion to the hydrocarbon portion other than the fluorine portion. 【0047】Silicone index = (CH derived from silicone monomers) ３ (Amount of H inside) / (Total CH, CH of non-fluorinated polymer) ２ ,CH ３ (Amount of H in the substance) The above silicone index was measured by H-NMR, and the CH derived from silicone monomer appears around 0.1 to 0.3 ppm. ３ The amount of H inside and the total CH, CH of the non-fluorine polymer ２ ,CH ３ The ratio of the total amount of hydrogen in the solution is taken. In reality, hydrogen from water and hydrogen from the NMR solvent are included, so the calculation is performed using a value that excludes these. This value is preferably 0.5 to 50, and more preferably 1.0 to 45. 【0048】 The content of the above hydrocarbon monomer (3) units is preferably 20 to 60 mol% relative to the monomer units other than the fluorine-containing monomer units of the polymer. The lower limit is most preferably 30 mol%, and the upper limit is most preferably 50 mol%. 【0049】 The content of the above-mentioned crosslinkable functional group-containing monomer (4) units is preferably 20 to 60 mol% relative to the monomer units other than the fluorine-containing monomer units of the polymer. The lower limit is most preferably 30 mol%, and the upper limit is most preferably 50 mol%. 【0050】 The polymers of this disclosure may have monomer units other than the above monomers (1) to (4) (referred to as monomer (5)) to the extent that they do not impair the effects of this disclosure. In this case, the content of monomer (5) units is preferably 40 mol% or less relative to the monomer units other than fluorine-containing monomer units. The upper limit is more preferably 30 mol%, and most preferably 20 mol%. Monomer (5) may be omitted. 【0051】This disclosure discloses two inventions: (Invention 1) a glass transition temperature of 20°C or higher, and (Invention 2) a fluorine-containing monomer (1) that is tetrafluoroethylene (1-1). These are essentially the same and have overlapping parts as inventions, but they are treated as separate inventions because they differ in their means of solving the problem. Cases that fall under both (Invention 1) and (Invention 2) are naturally included in this disclosure. 【0052】 (Invention 1) In Invention 1, the glass transition temperature is 20°C or higher. In Invention 1, it is preferable that the glass transition temperature is within the above range in that the hardness of the coating film is increased. The glass transition temperature is more preferably 25°C or higher, and most preferably 28°C or higher. The upper limit of the glass transition temperature is not particularly limited, but for example it can be 70°C or lower. The glass transition temperature is the value measured by differential scanning calorimeter (DSC; second run). 【0053】 (Invention 2) In Invention 2, the "at least one type of fluorine-containing monomer (1)" described above is tetrafluoroethylene. That is, when the "at least one type of fluorine-containing monomer (1)" is tetrafluoroethylene, sufficient hardness can be obtained regardless of the glass transition temperature, and the above objective can be achieved. In Invention 2, when the "at least one type of fluorine-containing monomer (1)" is tetrafluoroethylene, it is also acceptable to use it in combination with other fluorine-containing monomers. In Invention 2, the amount of tetrafluoroethylene is preferably 10 mol% or more of the fluorine-containing monomer (1), more preferably 60 mol% or more, and even more preferably 90 mol% or more. The upper limit is not particularly limited, but for example, it is 100 mol%. 【0054】In the polymer of the present disclosure, if the monomer (4) having a crosslinkable functional group is a monomer having a hydroxyl group, the hydroxyl value is preferably 30 to 200 mgKOH / g. The lower limit of the above hydroxyl value is more preferably 50 mgKOH / g, and even more preferably 60 mgKOH / g. The upper limit of the above hydroxyl value is more preferably 150 mgKOH / g, and even more preferably 130 mgKOH / g. 【0055】 The above-mentioned fluorine-containing polymer preferably has a number-average molecular weight of 3,000 to 100,000. More preferably, the number-average molecular weight is 5,000 or more, even more preferably 8,000 or more, even more preferably 50,000 or less, and even more preferably 35,000 or less. If the number-average molecular weight is too low, it may result in poor weather resistance, solvent resistance, and stain resistance, and may not be able to form a coating film with high hardness. If the number-average molecular weight is too high, the viscosity of the paint may become high, making it difficult to handle. The above-mentioned number-average molecular weight can be measured by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent. 【0056】 The above-mentioned fluorine-containing polymer preferably has a weight-average molecular weight of 3,000 to 1,000,000. More preferably, the weight-average molecular weight is 10,000 or more, even more preferably 14,000 or more, even more preferably 500,000 or less, and even more preferably 200,000 or less. When the weight-average molecular weight is within the above range, good weather resistance, solvent resistance, and stain resistance can be obtained. In addition, the viscosity when used as a paint is appropriate and easy to handle. The above weight-average molecular weight can be measured by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent. 【0057】 The polymers of this disclosure are not particularly limited in their manufacturing method and can be produced by known methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Among these, it is preferable to obtain them by solution polymerization. 【0058】As described above, the polymer of this disclosure exhibits transparency when a polymer solution is prepared by adjusting the polymer concentration to 60% by mass using butyl acetate as a solvent. For this reason, polymerization is preferably carried out in a state in which the silicone monomer and fluorine monomer coexist, so as to minimize the formation of insoluble components. 【0059】 More specifically, it is preferable to obtain the above-mentioned monomers by reacting them in an organic solvent in the presence of a radical polymerization initiator. The reaction temperature is particularly preferably 20°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. It is also preferably 130°C or lower, more preferably 100°C or lower, and even more preferably 80°C or lower. 【0060】 Examples of the above organic solvents include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, tert-butanol, iso-propanol, and ethylene glycol monoalkyl ethers; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; dimethyl sulfoxide, or mixtures thereof. 【0061】Examples of radical polymerization initiators include: persulfates such as ammonium persulfate and potassium persulfate (reducing agents such as sodium bisulfite, sodium pyrosulfite, cobalt naphthenate, and dimethylaniline may also be used as needed); redox initiators consisting of an oxidizing agent (e.g., ammonium peroxide, potassium peroxide), a reducing agent (e.g., sodium sulfite), and a transition metal salt (e.g., iron sulfate); diacyl peroxides such as acetyl peroxide and benzoyl peroxide [BPO]; dialkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide; and ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide. Hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; alkyl peroxyesters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate; and azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobisisobutyrate dimethyl, 2,2'-azobis[2-(hydroxymethyl)propionitrile], and 4,4'-azobis(4-cyanopentenoic acid) can be used. 【0062】 The amount of the radical polymerization initiator used is preferably 0.01 to 0.5 parts by mass relative to the total amount of monomer. More preferably, it is 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or less, and even more preferably 0.2 parts by mass or less. 【0063】The above reaction is further preferably carried out in the presence of a chain transfer agent. Examples of the chain transfer agent include mercaptan group-containing compounds such as dodecyl mercaptan, lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used may be in the range of 0.1 to 50 parts by mass, for example, 2 to 20 parts by mass, per 100 parts by mass of the total amount of monomer. 【0064】 The above reaction is preferably carried out by stirring a mixture containing a monomer composition, an organic solvent, and a radical polymerization initiator. The above reaction is preferably carried out by polymerizing a monomer composition containing all of monomers (1) to (4). Even when monomers are added during the polymerization reaction, it is preferable that the added monomer composition also contains all of monomers (1) to (4). 【0065】 This disclosure also relates to a paint containing the above polymer and an organic solvent (sometimes referred to as an organic solvent). As described above, the polymer of this disclosure can be uniformly dissolved in an organic solvent, and is therefore suitable for use as a resin in solvent-based paints. 【0066】 The paints disclosed herein are not particularly limited in the organic solvents they contain, and any solvents exemplified as those that can be used in the polymerization of the polymer may be suitably used. The resin solution obtained by the solution polymerization described above may be used as a paint composition by adding the necessary components to it. 【0067】 The paints of this disclosure may contain the above polymer and water. When used as a paint containing water, the polymer may be obtained by emulsion polymerization or suspension polymerization, or a polymer obtained by solution polymerization may be made aqueous. In this case, the polymer preferably has carboxyl groups. Furthermore, it is preferable that the polymer is made aqueous by neutralizing these carboxyl groups with a basic compound such as ammonia or an amine. 【0068】The above paint preferably further contains a curing agent. Since the above polymer has structural units derived from monomers (4) having crosslinkable functional groups, it can be made into a curing type paint that can be crosslinked by a reaction between the structural units and the curing agent. 【0069】 As the curing agent mentioned above, any material that can crosslink with the crosslinkable functional group can be used. For example, isocyanates, amino resins, acid anhydrides, polyepoxy compounds, and isocyanate-containing silane compounds are commonly used. Among these, isocyanates are preferred. 【0070】 Specific examples of the above-mentioned isocyanates include, but are not limited to, 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, their trimers, their adducts, biurets, and isocyanurates, polymers thereof having two or more isocyanate groups, and blocked isocyanates. Among these, isocyanurates are preferred. 【0071】 Specific examples of the above amino resins include, for example, urea resin, melamine resin, benzoguanamine resin, and glycoluryl resin, as well as methylolated melamine resin, which is melamine that has been methylolated, and alkyl etherated melamine resin, which is methylolated melamine that has been etherified with alcohols such as methanol, ethanol, and butanol, but are not limited to these. 【0072】 Specific examples of the above-mentioned acid anhydrides include, but are not limited to, phthalic anhydride, pyromellitic anhydride, and mellic anhydride. As for polyepoxy compounds and isocyanate group-containing silane compounds, those described in, for example, Japanese Patent Publication No. 2-232250 and Japanese Patent Publication No. 2-232251 can be used. 【0073】 The content of the curing agent is not particularly limited, but it is preferable that the upper limit is 50 parts by weight or less, more preferably 45 parts by weight or less, the lower limit is 12 parts by weight or more, and more preferably 18 parts by weight or more, per 100 parts by weight of polymer in the polymer solution. 【0074】 The above composition may further contain additives. Examples of additives include curing accelerators, pigments, dispersants, flow improvers, leveling agents, defoamers, gelling inhibitors, UV absorbers, antioxidants, hydrophilic agents, matting agents, adhesion improvers, and flame retardants. 【0075】 Examples of the above-mentioned pigments include titanium dioxide. The titanium dioxide is not particularly limited and may be either rutile or anatase type, but the rutile type is preferred in terms of weather resistance. 【0076】 Examples of commercially available titanium dioxide products include D-918 (manufactured by Sakai Chemical Industry Co., Ltd.), R-960, R-706, R-931 (manufactured by DuPont), and PFC-105 (manufactured by Ishihara Sangyo Co., Ltd.). 【0077】 Carbon black is another example of the above-mentioned pigment. The carbon black is not particularly limited and generally known examples are available. In terms of ultraviolet shielding effect, the carbon black is preferably 10 to 150 nm in average particle size, and more preferably 20 to 100 nm. The above-mentioned average particle size is a value obtained by observation with an electron microscope. 【0078】 Examples of commercially available carbon black products include MA-100 (manufactured by Mitsubishi Chemical Corporation) and Raven-420 (manufactured by Columbia Carbon). 【0079】 If the above composition contains the above pigment, it is preferable that it further contains a dispersant or a flow improver as described later. 【0080】Commercially available products may be used as the above-mentioned dispersants. For example, Disparon 2150, Disparon DA-325, DA-375, DA-1200 (trade names, manufactured by Kusumoto Chemical Co., Ltd.), Floren G-700, G-900 (trade names, manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE 26000, 32000, 36000, 36600, 41000, 55000 (trade names, manufactured by Nippon Lubrizol Co., Ltd.), DISPERBY K-102, 106, 110, 111, 140, 142, 145, 170, 171, 174, 180 (trade names, manufactured by Bic Chemie Japan Co., Ltd.), etc. Among these, Disparon DA-375, Floren G-700, and SOLSPERSE 36000 are preferred in terms of their good long-term storage stability, with Disparon DA-375 being more preferred. 【0081】 Examples of the above-mentioned fluidity improvers include associated acrylic polymers having acidic groups and bases. These associated acrylic polymers are those in which polar groups contained in the acrylic polymer chain form a structure through hydrogen bonding or partial adsorption due to electrical interactions within or between polymer chains, thereby increasing the viscosity of the liquid. Examples of these acrylic polymers include copolymers composed of (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, and cyclohexyl (meth)acrylate, with the main monomer component being methyl (meth)acrylate. Note that "(meth)acrylate" includes both acrylate and methacrylate. 【0082】 Commercially available products may be used as the above-mentioned fluidity improving agent. For example, SOLTHIX250 (trade name, manufactured by Lubrizol Japan Co., Ltd.) can be used. 【0083】The above-mentioned flame retardant is preferably one that generates a non-combustible gas in the initial stages of combustion and exhibits flame retardancy by diluting the combustible gas and / or blocking oxygen. The above-mentioned flame retardant is preferably at least one selected from the group consisting of compounds containing Group 5B of the periodic table and compounds containing halogen compounds of Group 7B of the periodic table. 【0084】 The content of the above-mentioned flame retardant is preferably 1 to 45 parts by mass per 100 parts by mass of the above-mentioned polymer. When the content of the above-mentioned flame retardant is within the above range, good dispersibility in the above-mentioned composition and improved flame retardancy of the coating film obtained from the above-mentioned composition can be expected. If the content of the above-mentioned flame retardant is less than 1 part by mass, improvement in flame retardancy may not be expected, and if it exceeds 45 parts by mass, it may become difficult to maintain the physical properties of the composition and coating film. The content of the above-mentioned flame retardant is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less, per 100 parts by mass of the above-mentioned polymer. Furthermore, it is more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more. 【0085】 This disclosure also relates to a laminate (e.g., a painted product) having a film obtained by applying the above-mentioned paint. The above-mentioned paint film can be provided on various substrates. A primer layer may be provided between the substrate and the above-mentioned paint film, but because the above-mentioned paint film has excellent adhesion, it is possible to directly bond the substrate and the above-mentioned paint film with sufficient adhesive strength. A laminate (e.g., a painted product) comprising the above-mentioned paint film and the above-mentioned substrate is also one of the preferred embodiments of this disclosure. The method of applying the above-mentioned paint to the substrate is not particularly limited, and conventionally known coating methods may be used as appropriate. Examples of coating methods include air spray coating, airless spray coating, rotary atomization coating, curtain coating, dipping, casting, roll coating, bar coating, spin coating, die coating, gravure coating, etc. If the paint contains a curing agent, conventionally known curing methods such as room temperature drying, heat drying, baking drying, and UV curing may be used as appropriate. 【0086】Examples of materials for the above-mentioned base material include metals, ceramics, resins, and glass. Examples of metals include iron; stainless steel such as SUS304, SUS316L, and SUS403; aluminum; and plated steel sheets with zinc plating, aluminum plating, etc. Examples of ceramics include pottery, porcelain, alumina, zirconia, and silica oxide. Examples of resins include polyethylene terephthalate resin, polycarbonate resin, silicone resin, fluorosilicone resin, polyamide resin, polyamide-imide resin, polyimide resin, polyester resin, epoxy resin, polyphenylene sulfide resin, phenolic resin, acrylic resin, and polyethylene sulfone resin. 【0087】 The above-mentioned laminate (e.g., painted product) can be used in building materials, interior materials, automobiles, aircraft, ships (decks, bottoms, etc.), trains, tanks, bridges, etc. The laminate (e.g., painted product) of this disclosure has excellent weather resistance and water and oil repellency, making it extremely useful as a building material, for example. The laminate (e.g., painted product) of this disclosure also has excellent weather resistance and water and oil repellency, as well as excellent durability of weather resistance and water and oil repellency, making it extremely useful for anti-freezing and anti-frosting applications that take advantage of its water repellency. For anti-freezing and anti-frosting applications, it can be suitably used, for example, for wind turbine blades, anti-fouling applications for EPDM in railway vehicle coupling sections, anti-fouling and anti-freezing applications for road bridge guide signs, anti-freezing applications for power transmission lines, and anti-frosting applications for air conditioning heat exchangers. The above-mentioned laminate (e.g., painted product) can also be suitably used as a backsheet for solar cell modules. 【0088】 While embodiments of this disclosure have been described above, it will be understood that a variety of modifications to the form and details are possible without departing from the spirit and scope of the claims. 【0089】 The present disclosure will be described below in detail based on the following examples. In the following examples, unless otherwise specified, "parts" and "%" refer to "parts by mass" and "% by mass," respectively. The present disclosure is not limited to the following examples. 【0090】Example 1 352 g of butyl acetate, 5.7 g of isopropanol, 11.1 g of hydroxybutyl vinyl ether (hereinafter referred to as "HBVE"), and 15.6 g of cyclohexyl vinyl ether (hereinafter referred to as "CHVE") were placed in a 1 L pressure vessel equipped with a stirrer. The following formula 【0091】 0.5 g of the organosilicon compound (n=64) was purged with nitrogen, then 44.6 g of tetrafluoroethylene was added and the temperature was raised to 60°C while stirring, and the pressure inside the tank was adjusted to 0.8 MPa. Then, 0.84 g of tert-butyl pivalate was added to start the reaction. After the reaction started, 155.6 g of the liquid monomer mixture shown in Table 1 was continuously added at a constant rate using a charging pump over 11 hours. In order to maintain the pressure inside the tank at 0.785 MPa, 160 g of TFE was continuously added over 11 hours, then the addition was stopped and the polymerization reaction proceeded for 1 hour, after which the temperature inside the tank was raised to 75°C and maintained for 3 hours to complete the reaction. After the reaction was complete, the temperature of the polymerization tank was lowered and unreacted TFE was recovered, the contents were removed, and a colorless, transparent polymerization sample was obtained. 【0092】 Note that the organosilicone compounds in the liquid monomer mixtures shown in Table 1 are the same as those used in the initial monomer preparation. 【0093】 GC analysis confirmed that the residual liquid monomer in the polymerization sample was less than 1%. Furthermore, the solid content of the polymerization sample was measured to be 47.3% by heating. The obtained polymerization sample was mixed with a deoxidizing agent, stirred for 3-4 hours, filtered, and concentrated to 62% ± 2% solid content to obtain a concentrated sample. 【0094】 The fluorine content of the polymer was measured to be 40.3% by combustion. The OH value was measured to be 98.0 mgKOH / g by NMR. The number-average molecular weight (Mn) of the polymer was determined to be 7762 by GPC. The results for the physical properties of the coating film obtained using the concentrated sample prepared by the following method are shown in Table 1. 【0095】[Preparation of coating film] To a concentrated polymer solution (100g), 12g of Sumika Bayer Urethane Co., Ltd.'s curing agent Desmodur N3390 and 40g of butyl acetate were added so that the ratio of polymer OH value to NCO group was 1 / 1.1. The mixture was stirred at room temperature for 30 minutes, then applied to a tin-plated iron plate and dried at 80°C for 3 hours. An evaluation coating plate with a thickness of 25 μm was prepared after drying, and each evaluation was performed. 【0096】 Examples 2-4 Polymerization was carried out using the monomer amounts shown in Table 1 in the same manner as in Example 1, and concentrated samples were obtained by similar concentration procedures. The polymer properties and polymer composition are as shown in Table 1. 【0097】 Example 5 The same method as in Example 4 was used, except that VV9 and VBz were added in the amounts shown in Table 1 instead of CHVE. The results are shown in Table 1. In the table, VBz refers to vinyl benzoate and VV9 refers to vinyl neonanone ester. 【0098】 Example 6 352 g of butyl acetate, 5.7 g of isopropanol, 10.9 g of HBVE, and 15.1 g of CHVE were placed in a 1 L pressure vessel equipped with a stirrer. The following formula is used: CH2 = C(CH3)-COO-(CH2)3-Si(CH3)2-〔O-Si(CH3)2〕 60 5.5 g of the organosilicon compound represented by -OSi(CH3)2-(CH2)3-CH3 was purged with nitrogen, and the temperature was raised to 60°C. 28 g of CTFE was added to adjust the pressure in the chamber to 0.4 MPa while stirring. Then, 0.8 g of tert-butyl pivalate was added to start the reaction. After reacting at 60°C for 4 hours, the temperature was raised to 75°C and maintained for 1 hour. After the reaction was complete, the temperature of the polymerization chamber was lowered to recover the unreacted CTFE, and the contents were removed to obtain a colorless, transparent polymerization sample. After post-processing in the same manner as in Example 1, the solid content was concentrated to 62% ± 2%, and 60 g of concentrated sample was obtained. 0.18 g of stabilizer (BASF Irganox 1010) was added to this to prevent gelation of the sample. 【0099】Example 7 was carried out using the same method as in Example 6, but with the only difference being that a portion of the CTFE was replaced with TFE, and the amount used was as shown in Table 1. The results are shown in Table 1. 【0100】 Example 8: 352 g of butyl acetate, 11.1 g of HBVE, and 15.4 g of CHVE were placed in a 1 L pressure vessel equipped with a stirrer. The following formula was used: CH2 = C(CH3)-COO-(CH2)3-Si(CH3)2-〔O-Si(CH3)2〕 60 0.6 g of the organosilicon compound -OSi(CH3)2-(CH2)3-CH3 was purged with nitrogen, the temperature was raised to 60°C, and 433 g of hexafluoropropylene (HFP) was added while stirring to adjust the pressure inside the tank to 1.0 MPa. Then, 0.83 g of tert-butyl pivalate was added to start the reaction. After the reaction started, 122.4 g of the liquid monomer mixture shown in Table 1 was continuously added at a constant rate using a charging pump over 4 hours. Polymerization was then continued for another 12 hours. After that, the temperature of the polymerization tank was raised to 75°C and aged for another 3 hours, after which the polymerization tank was cooled to stop the polymerization. Unreacted HFP was recovered and the contents were removed to obtain a colorless and transparent polymerization sample. GC analysis confirmed that the residual rate of liquid monomer in the polymerization sample was less than 1%. Furthermore, the solid content of the polymerization sample was measured to be 24.5% by the heating method. After post-processing in the same manner as in Example 1, the solid content was concentrated to 62% ± 2% to obtain a concentrated sample. 【0101】 Example 9 Polymerization was carried out in the same manner as in Example 4, except that the amount of CHVE used was reduced by half and replaced with 4.3 g of equimolar 2,3-dihydrofuran (abbreviated as DHF). 【0102】[Preparation of coating film] To the concentrated polymer solution (100g) obtained in Example 9, Cytec amino resin CYMEL303 (17.2g), King catalyst Nacure 1419 (0.5g), n-butanol (23g), BASF antioxidant Irganox1010 (0.3g), BASF UV absorber Tinuvin 123 (1.5g), and WR Grase silica SYLOID ED 30 (5.4g) were added and stirred at room temperature for 30 minutes. The mixture was then applied to a tin-plated iron plate and dried at 210°C for 10 minutes to create an evaluation coating plate with a thickness of 10 μm after drying. Each evaluation was then performed. The results are shown in the table. 【0103】 In Example 10, polymerization was carried out in the same manner as in Example 4, except that HBVE was replaced with equimolar CHMVE, and the coating film was evaluated in the same manner as in Example 9. The results are shown in the table. 【0104】 Example 11 Polymerization and coating film evaluation were carried out in the same manner as in Example 10, except that the amount of the organic silicone compound was halved to 2.7 g. The results are shown in the table. 【0105】 Comparative Example 1: A fluorine / silicone hybrid polymer was prepared in the same manner as in Reference Synthesis Example 1 and Example 4 described in Patent Publication WO2021-054075. The polymer solution was cloudy, and the coating film was also cloudy. 【0106】 Comparative Example 2 Polymerization and concentration were carried out in the same manner as in Example 1, except that an organosilicon compound was not included. The results are shown in Table 1. 【0107】 Example 12 Polymerization was carried out in the same manner as in Example 11 of Patent CN116444714A, except that 3.0 g of the following silicone compound was initially added, and a colorless, transparent polymerized sample was obtained. GC analysis showed that the residual monomer in the polymerized sample was less than 1%. CH2 = C(CH3)-COO-(CH2)3-Si(CH3)2-〔O-Si(CH3)2〕 60-OSi(CH3)2-(CH2)3-CH3 The solid content of the polymerization sample was measured to be 48.5% by the heating method. Subsequently, concentration was performed in the same manner as in Example 1 of this application to obtain a transparent concentrated sample with a solid content of approximately 60%. 60g of the concentrated sample was taken and neutralized in the same manner as in Example 11 of Chinese Patent Publication 116444714, followed by water inversion, and the solvent was removed by distillation to obtain an aqueous dispersion sample. The residual solvent in the sample was analyzed by GC to be less than 1%. The solid content of the aqueous paint was measured to be 40.2% by the heating method, and the average particle size was measured to be 160nm by a particle analyzer. 【0108】 (Evaluation items and measurement methods) (Content of each monomer unit constituting the polymer) The fluorine content (mass%) measured from elemental analysis and the content (mol%) of each monomer unit were calculated from compositional analysis using 1H NMR spectroscopy. 【0109】 (Hydroxyl Value) The content of hydroxyl group-containing monomers in the polymer was calculated using fluorine content, H-NMR, and solid content concentration. 【0110】 (Appearance of polymer solution) The transparency of a butyl acetate solution of polymer (polymer concentration 60% by mass) was measured using a turbidimeter. A Mitsubishi Chemical PT-200 turbidimeter was used, with an absorbance range of 0 to 1000 ppm, and measurements were taken at 25°C. 【0111】 (Tg of polymer) The solvent of the polymer was removed, and the glass transition temperature of the resulting solid was measured. The above glass transition temperature was measured by differential scanning calorimeter (DSC; second run). 【0112】 (Number-average molecular weight Mn) The above number-average molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent. For the measurement, four columns were used in series: two Shodex KF-806M, one KF-802, and one KF-801 from Resonaq Corporation. 【0113】 (Weight-average molecular weight Mw) The above weight-average molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent. 【0114】 (Appearance of Varnish Coating) The appearance of the coating formed by the above method was evaluated according to the following criteria. Visual inspection determined whether the coating was transparent, slightly cloudy, or cloudy. 【0115】 (Gloss) Gloss was measured at 60°C using AG 4442 manufactured by BYK. 【0116】 (Water Contact Angle) The contact angle was measured using a G1 type contact angle measuring meter manufactured by Kyowa Co., Ltd. 【0117】 (Water Drop Angle) A plate coated with SZ-CAMC33 manufactured by Shanghai Sunzern Instrument Co., Ltd. was placed on a measuring stand, and water was dropped onto the surface of the plate using a microsyringe (water volume: approximately 20 microliters). The measuring stand, which has a controllable incline, was slowly tilted, and the incline angle of the measuring stand at the moment the water droplet began to move was defined as the water drop angle. 【0118】 (Ease of wiping off oil-based pen marks) A mark from a black oil-based marker manufactured by ZEBRA was wiped dry, and the remaining state of the mark was visually evaluated. 【0119】 (QUVB) Using an aging acceleration testing facility manufactured by QLAB Corporation, irradiation intensity of 0.71 W / cm² ２ The accelerated weathering test was conducted by repeatedly irradiating the sample for 4 hours (60°C) followed by 4 hours without irradiation. After 1000 hours of testing, the gloss retention rate, water contact angle, water drop angle, and wipeability to oil-based pens were tested. 【0120】 (Gloss retention rate) The gloss was measured for the initial sample and the samples after each of the above QUVB tests, and the gloss retention rate was calculated as (gloss after accelerated weathering test) / (gloss of initial sample). 【0121】 Color difference: Color difference was measured using a Konica DP 400 and CR 400 color difference meter. 【0122】 【0123】 The results in Table 1 clearly show that the polymers of this disclosure have excellent weather resistance and stain resistance. 【0124】The polymers of this disclosure can be suitably used in the field of coatings.

Claims

1. A polymer having constituent units derived from a fluorine-containing monomer (1), at least one silicone monomer (2) having silicone units and polymerizable unsaturated functional groups, at least one hydrocarbon monomer (3) copolymerizable with (1) and / or (2), and a monomer (4) having crosslinkable functional groups, having a glass transition temperature of 20°C or higher, and exhibiting transparency when a polymer solution is prepared using butyl acetate as a solvent and the polymer concentration is adjusted to 60% by mass.

2. The polymer according to claim 1, wherein the fluorine-containing monomer (1) is partially or entirely chlorotrifluoroethylene.

3. The polymer according to claim 1 or 2, wherein the fluorine-containing monomer (1) is tetrafluoroethylene and chlorotrifluoroethylene.

4. A polymer having constituent units derived from a fluorine-containing monomer (1), at least one silicone monomer (2) having silicone units and polymerizable unsaturated functional groups, at least one hydrocarbon monomer (3) copolymerizable with (1) and / or (2), and a monomer (4) having crosslinkable functional groups, wherein the fluorine-containing monomer (1) is partially or entirely tetrafluoroethylene, and the polymer solution obtained by adjusting the polymer concentration to 60% by mass using butyl acetate as a solvent exhibits transparency.

5. The polymer according to any one of claims 1 to 4, wherein the hydrocarbon monomer (3) is vinyl ethers and / or vinyl esters.

6. The polymer according to claim 5, wherein the hydrocarbon monomer (3) is a vinyl ether.

7. Silicone monomer (2) is one or more organosilicon compounds represented by the following general formula (3): (Here, R ４ R is a hydrogen atom or a methyl group. ６ (wherein is an alkyl group having 1 to 6 carbon atoms which may contain a hydrogen atom or an OH group, n is 0 to 10, and m is 0 to 420.) The hydrocarbon monomer (3) is a vinyl ether, and the monomer (4) having a crosslinkable functional group has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, a cyano group, and a silyl group. The polymer according to any one of claims 1 to 6.

8. A paint containing the polymer and organic solvent according to any one of claims 1 to 7.

9. A paint containing the polymer and water according to any one of claims 1 to 7.

10. A painted article characterized by having a film obtained by applying the paint described in claim 8.

11. A painted article characterized by having a film obtained by applying the paint described in claim 9.

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