Polymer and water-repellent oilproof composition

Abstract

Provided is a polymer that has a repeating unit derived from a monomer (a) represented by the general formula R1-R2-(CH2)p-O-R3 (in the formula, R1 is -CH3, -CH2F, -CHF2, -CH2I, or -CHFI; R2 is a C1 to C49 alkylene group formed only from a unit represented by -CFH-, a C2 to C49 alkylene group formed only from a unit represented by -CFH- and a unit represented by -CH2-, or a C3 to C49 alkylene group formed only from a unit represented by -CFH-, a unit represented by -CH2-, and a unit represented by -CHI-; p is an integer from 0 to 2; and R3 is an organic residue having an ethylenically-unsaturated polymerizable group).

Description

Polymer and water- and oil-repellent composition

[0001] The present disclosure relates to polymers and water- and oil-repellent compositions.

[0002] Patent Document 1 describes a water / oil repellent composition essentially comprising a copolymer consisting essentially of polymerized units of the following monomer (a) and polymerized units of the following monomer (b): Monomer (a): A monomer having a polyfluoroalkyl group, wherein the melting point of microcrystals derived from the polyfluoroalkyl group of a homopolymer of the monomer is absent or is 50°C or lower; Monomer (b): A monomer having an organic group other than a polyfluoroalkyl group, wherein the melting point of microcrystals derived from the organic group of the homopolymer is 30°C or higher;

[0003] WO 2002 / 083809

[0004] An object of the present disclosure is to provide a polymer that exhibits water repellency or oil resistance, and a water- and oil-resistant agent composition that can impart water repellency or oil resistance to an article.

[0005] According to the present disclosure, a compound of the general formula: R １ -R ２ - (CH ２ ) ｐ -O-R ３ (In the formula, R １ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I or -CHFI, and R ２ represents an alkylene group having 1 to 49 carbon atoms and consisting only of units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ an alkylene group having 2 to 49 carbon atoms and consisting only of units represented by -, or a unit represented by -CFH-, -CH ２ is an alkylene group having 3 to 49 carbon atoms and consisting only of units represented by - and units represented by -CHI-, p is an integer of 0 to 2, R ３is an organic residue having an ethylenically unsaturated polymerizable group), a polymer is provided which has a repeating unit derived from a monomer (a) represented by the formula:

[0006] According to the present disclosure, it is possible to provide a polymer that exhibits good water repellency or oil resistance, and a water- and oil-resistant agent composition that can impart good water repellency or oil resistance to an article.

[0007] Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

[0008] Fluorine-containing water and oil repellents containing fluorine compounds have been known in the art. Treating substrates such as textiles with such water and oil repellents provides substrates with water and oil repellency.

[0009] Patent Document 1 describes that, as a technique for simultaneously imparting water repellency and oil repellency to a surface, an article is treated with an organic solvent solution or aqueous dispersion of a polymer containing a polymerized unit of a polymerizable monomer containing a polyfluoroalkyl group in the molecule, or a copolymer of this and other monomers.Furthermore, Patent Document 1 also describes that by combining a polyfluoroalkyl group-containing monomer with a crystalline hydrocarbon-based monomer, the crystallinity of the crystalline hydrocarbon-based monomer can be strengthened, and due to the synergistic effect of strengthening the surface orientation, water and oil repellency can be expressed even if there are no microcrystals derived from the polyfluoroalkyl group in the polymer or the melting point of the microcrystals is low, and that as the polyfluoroalkyl group, F(CF ２ ) ｋ It is described that perfluoroalkyl groups represented by - (k is an integer of 1 to 20) are preferred. However, polymers that exhibit water repellency even without perfluoroalkyl groups are desired.

[0010] The polymers of the present disclosure have the general formula: R １ -R ２ - (CH ２ ) ｐ -O-R ３ (In the formula, R １ is -CH ３ , -CH ２ F, -CHF ２, -CH ２ I or -CHFI, and R ２ represents an alkylene group consisting of only units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ an alkylene group consisting of only units represented by -, or a unit represented by -CFH-, ２ is an alkylene group having 3 to 49 carbon atoms and consisting only of units represented by - and units represented by -CHI-, p is an integer of 0 to 2, R ３ is an organic residue having an ethylenically unsaturated polymerizable group).

[0011] Since the polymer of the present disclosure has a repeating unit derived from the monomer (a), it exhibits water repellency or oil resistance, preferably water repellency and oil resistance, even though it does not have a perfluoroalkyl group or a perfluoroalkylene group. Therefore, by using the polymer of the present disclosure, it is possible to obtain a water- and oil-resistant agent composition that can impart good water repellency or oil resistance, preferably good water repellency and oil resistance, to an article.

[0012] (a) Monomer In the general formula representing the monomer (a), R １ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I or -CHFI, preferably -CH ２ F, -CHF ２ or -CHFI. The polymer of the present disclosure is an organic residue (R ３ ) is CF ３ One of the features is that it does not have a -(trifluoromethyl group).

[0013] R ２ represents an alkylene group consisting of only units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ an alkylene group consisting of only units represented by -, or a unit represented by -CFH-, ２The polymer of the present disclosure is an alkylene group consisting of only units represented by - and units represented by -CHI-. ３ ) is -CF ２ One of its characteristics is that it does not contain units indicated by -.

[0014] R ２ The number of carbon atoms is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, and is preferably 49 or less, more preferably 11 or less, and even more preferably 10 or less.

[0015] R ２ is an alkylene group consisting only of units represented by -CFH-, R ２ Examples of the group include -(CFH) ｎ１ -(wherein n1 is an integer of 1 or more), -(CFH) ｎ１ - (wherein n1 is an integer of 3 to 49) is preferred, and -CHF- (CHF-CHF) ｎ - (n is an integer of 1 to 24) is more preferred. n1 is preferably an integer of 2 to 10. n is preferably an integer of 1 to 5.

[0016] R ２ is a unit represented by -CFH- and -CH ２ When the alkylene group is composed only of units represented by -, R ２ Examples of the alkyl group include -CHF-(CHF-CHF) ｎ - (CH ２ ) ｍ - (n is an integer of 0 or more, m is an integer of 1 or more), etc.

[0017] R ２ is a unit represented by -CFH- and -CH ２ When R is an alkylene group consisting of only units represented by -, ２ Examples include -CHF- (CHF-CHF) ｎ - (CH ２ ) ｍ - (n is an integer of 1 to 24, m is an integer of 1 or more) is preferred, and -CHF- (CHF-CHF) ｎ -CH２ - (n is an integer from 1 to 24), or -CHF- (CHF-CHF) ｎ -CH ２ CH ２ - (n is an integer of 1 to 24) is more preferred. n is preferably an integer of 1 to 5. m is preferably 1 or 2.

[0018] R ２ is a unit represented by -CFH-, -CH ２ When R is an alkylene group consisting of only units represented by - and units represented by -CHI-, ２ Examples include -CHF- (CHF-CHF) ｎ -CH ２ -CHI- (CH ２ ) ｑ - (n is an integer of 0 or more, and q is an integer of 1 or more) is preferred. n is preferably 1 or 2. q is preferably an integer of 1 to 24, more preferably an integer of 1 to 18, and even more preferably an integer of 1 to 12.

[0019] p is an integer of 0 to 2, preferably 1 or 2.

[0020] R ３ is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. ２ =C(-X)-C(=O)-, CH ２ =C(-X)-, CH ２ ═C(—X)—CH ２ -, and X is a hydrogen atom, a methyl group, a halogen atom, or the like. ３ may have various organic groups in addition to the ethylenically unsaturated polymerizable group. Examples of such organic groups include chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents.

[0021] R ３ Examples of the compound include those represented by the general formula: CH ２A group represented by =C(-X)-C(=O)-Y-Z- (wherein X is a hydrogen atom, a methyl group or a halogen atom, Y is -O- or -NH-, and Z is a direct bond or a divalent organic group) is preferred.

[0022] X is a hydrogen atom, a methyl group, or a halogen atom, and therefore the α-position (of the acrylate or methacrylate) of the monomer (a) may be a hydrogen atom or may be substituted with a halogen atom, etc. Examples of X include a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0023] Z may be a direct bond or a divalent organic group, and when it is a divalent organic group, it is selected from the group consisting of an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, -(CH ２ ) ｍ -N(R １ ) SO ２ - (CH ２ ) ｎ - group (m is an integer of 1 to 10, n is an integer of 0 to 10, R １ is an alkyl group having 1 to 18 carbon atoms), —CH ２ CH (OZ １ ) CH ２ -Group (Z １ is a hydrogen atom or R １ C(=O)-, R １ is an alkyl group having 1 to 18 carbon atoms), —CH ２ CH (OZ １ ) CH ２ -(Ph-O)- group (Z １ is a hydrogen atom or R １ C(=O)-, R １ is an alkyl group having 1 to 18 carbon atoms, Ph is a phenylene group), -(CH ２ ) ｎ -Ph-O- group (wherein Ph is a phenylene group and n is an integer of 0 to 10), -(CH ２ ) ｍ -SO ２ - (CH ２ ) ｎ - group (m is an integer of 1 to 10, n is an integer of 0 to 10), -(CH ２ ) ｍ -OC(=O)N(R １)-(CH ２ ) ｎ - group (m is an integer of 1 to 10, n is an integer of 0 to 10, R １ is an alkyl group having 1 to 18 carbon atoms), -(CH ２ ) ｍ -N(R １ )C(=O)O-(CH ２ ) ｎ - group (m is an integer of 1 to 10, n is an integer of 0 to 10, R １ is an alkyl group having 1 to 18 carbon atoms), -(CH ２ ) ｍ -C(=O)N(R １ )-(CH ２ ) ｎ - group (m is an integer of 1 to 10, n is an integer of 0 to 10, R １ is an alkyl group having 1 to 18 carbon atoms), -(CH ２ ) ｍ - (R １ )NC(=O)-(CH ２ ) ｎ - group (m is an integer of 1 to 10, n is an integer of 0 to 10, R １ is an alkyl group having 1 to 18 carbon atoms), -(CH ２ ) ｍ - (R １ )NC(=O)N(R １ )-(CH ２ ) ｎ - group (m is an integer of 1 to 10, n is an integer of 0 to 10, R １ is an alkyl group having 1 to 18 carbon atoms), or -(CH ２ ) ｍ -S-(CH ２ ) ｎ - group (wherein m is an integer of 1 to 10, and n is an integer of 0 to 10), and the like.

[0024] The monomer (a) can be, for example, a monomer represented by the general formula: R １ -R ２ - (CH ２ ) ｐ -OH (in the formula, R １ , R ２and p is as defined above) with a compound having an ethylenically unsaturated polymerizable group and also having a carboxyl group, a carboxylic acid halide group, an amide group or an isocyanate group.

[0025] More specifically, the monomer (a) is represented by the general formula: R １ -R ２ - (CH ２ ) ｐ -OH (in the formula, R １ , R ２ and p is as defined above), and an alcohol represented by the general formula: CH ２ =C(-X)-C(=O)-Y-Z-L １１ (wherein X, Y and Z are as defined above, and L １１ represents -OH, a halogen atom, -NH ２ or —NCO) with

[0026] General formula: R １ -R ２ - (CH ２ ) ｐ Alcohols represented by —OH can be obtained by adding CHF═CHF to methanol to give the general formula: CH ２ F-CHF-(CHF-CHF) ｎ -CH ２ It can be produced by a production method for producing an alcohol represented by the formula OH (wherein n is an integer of 0 or more).

[0027] In the alcohol, n represents the degree of polymerization of CHF=CHF and is an integer of 0 or more. n is, for example, an integer of 0 to 23, and preferably an integer of 0 to 4.

[0028] The reaction of methanol with CHF=CHF can be carried out in the presence of a radical initiator. When the reaction is carried out in the presence of a radical initiator, the radical initiator decomposes to generate radicals, which then abstract hydrogen atoms from the carbon atom to which the hydroxyl group of methanol is bonded, generating methanol radicals, and a reaction (so-called telomerization reaction) in which CHF=CHF is added to the methanol radicals proceeds.

[0029] The radical initiator is preferably an organic peroxide, and examples thereof include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0030] The amount of CHF=CHF used is preferably 0.01 to 100 moles per mole of methanol.

[0031] The amount of the radical initiator used is preferably 0.01 to 2 moles per mole of methanol.

[0032] The temperature for the reaction of methanol with CHF=CHF can be appropriately selected, but is preferably −78 to 200° C. The temperature for the reaction of methanol with CHF=CHF is preferably equal to or higher than the decomposition temperature of the radical polymerization initiator, and is preferably lower than the decomposition temperatures of the substrate and the product.

[0033] The pressure for the reaction of methanol with CHF=CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The time for the reaction of methanol with CHF=CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0034] Also, the general formula: R １ -R ２ - (CH ２ ) ｐ The alcohol represented by —OH is CHF═CHF and the general formula: X １ I (X １is H or F), to obtain a compound represented by the general formula: １ -CHF-I (wherein R １ Ha-CH ２ F or -CHF ２ ) to produce a first fluorine-containing alkyl iodide represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -I (wherein, R １ is as described above, and n is an integer of 1 or more), and adding ethylene to the first or second fluorine-containing alkyl iodide to produce a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -I (wherein, R １ (n is an integer of 0 or more, as described above), and reacting the third fluorine-containing alkyl iodide with fuming sulfuric acid and hydrolyzing it to obtain a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -OH (in the formula, R １ As described above, n is an integer of 0 or more), and the alcohol represented by the formula (7) can be produced by a production method including the step (7) of producing an alcohol represented by the formula:

[0035] In step (5), CHF=CHF and a compound of the general formula: X １ I (X １ is H or F), to obtain a compound represented by the general formula: R １ -CHF-I (wherein R １ Ha-CH ２ F or -CHF ２ ) to produce a first fluorine-containing alkyl iodide represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -I (wherein, R １As described above, a second fluorine-containing alkyl iodide represented by the formula (where n is an integer of 1 or more) is produced.

[0036] The amount of the iodide compound used is preferably 0.5 to 4 moles per mole of CHF=CHF.

[0037] The reaction of CHF=CHF with the iodide compound can be carried out in the absence of a solvent or in a solvent.

[0038] The temperature for the reaction of CHF=CHF with the iodide compound can be appropriately selected but is preferably −78 to 200° C. The pressure for the reaction of CHF=CHF with the iodide compound can be appropriately selected but is preferably 0 to 5.0 MPaG. The time for the reaction of CHF=CHF with the iodide compound can be appropriately selected but is preferably 0.1 to 96 hours.

[0039] The reaction of CHF=CHF with an iodide compound gives a compound of the general formula: R １ -CHF-I (wherein R １ Ha-CH ２ F or -CHF ２ In step (5), CHF=CHF is then added to the first fluorine-containing alkyl iodide.

[0040] The reaction between the first fluorine-containing alkyl iodide and CHF=CHF is a telomerization reaction in which the first fluorine-containing alkyl iodide serves as a telogen and CHF=CHF serves as a taxogen, and a second fluorine-containing alkyl iodide is produced by this reaction.

[0041] In the second fluorine-containing alkyl iodide, n represents the degree of polymerization of CHF═CHF and is an integer of 1 or more. n is preferably an integer of 1 to 24, and more preferably an integer of 1 to 5.

[0042] The reaction of the first fluorine-containing alkyl iodide with CHF=CHF can be carried out in the presence of a radical initiator, such as an organic peroxide or an azo compound.

[0043] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0044] Examples of the azo compounds include azobisisobutyronitrile.

[0045] The amount of CHF=CHF used is preferably 0.01 to 100 moles per mole of the fluorine-containing alkyl iodide.

[0046] The amount of the radical initiator used is preferably 0.01 to 2 moles per mole of the fluorine-containing alkyl iodide.

[0047] The temperature for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably −78 to 200° C. The temperature for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF is preferably not less than the decomposition temperature of the radical polymerization initiator, and is preferably lower than the decomposition temperatures of the substrate and the product.

[0048] The pressure for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The time for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0049] In step (6), a compound of the general formula: R １ -CHF- (CHF-CHF) ｎ -I (wherein, R １ is as described above, and n is an integer of 0 or more), and then ethylene is added to the first or second fluorine-containing alkyl iodide to obtain a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ CH２ -I (wherein, R １ As described above, n is an integer of 0 or more), to produce a third fluorine-containing alkyl iodide represented by the formula:

[0050] R of the third fluorine-containing alkyl iodide １ is R of the first or second fluorine-containing alkyl iodide １ is the same as -CH ２ F or -CHF ２ is.

[0051] The third fluorine-containing alkyl iodide has an integer of 0 or more as its n. The preferred range of the third fluorine-containing alkyl iodide is an integer of 0 to 24, and more preferably an integer of 0 to 5.

[0052] The reaction of the first or second fluorine-containing alkyl iodide with ethylene can be carried out in the presence of a metal catalyst, such as copper.

[0053] The reaction of the first or second fluorine-containing alkyl iodide with ethylene can be carried out in the presence of a radical-generating compound, such as an organic peroxide or an azo compound.

[0054] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0055] Examples of the azo compounds include azobisisobutyronitrile.

[0056] The amount of ethylene used is preferably 0.01 to 100 moles per mole of the first or second fluorine-containing alkyl iodide.

[0057] The amount of the radical-generating compound used is preferably 0.001 to 1 mole per mole of the first or second fluorine-containing alkyl iodide.

[0058] The temperature for the reaction of the first or second fluorine-containing alkyl iodide with ethylene can be appropriately selected but is preferably 50 to 200° C. The pressure for the reaction of the first or second fluorine-containing alkyl iodide with ethylene can be appropriately selected but is preferably 0.1 to 5 MPaG. The time for the reaction of the first or second fluorine-containing alkyl iodide with ethylene can be appropriately selected but is preferably 0.1 to 96 hours.

[0059] In step (7), a compound of the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -I (wherein, R １ is as described above, n is an integer of 0 or more), and then the third fluorine-containing alkyl iodide is reacted with fuming sulfuric acid and hydrolyzed to obtain a compound represented by the general formula: １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -OH (in the formula, R １ As described above, n is an integer of 0 or more) to produce an alcohol represented by the formula:

[0060] R for alcohol １ is R of the third fluorine-containing alkyl iodide １ is the same as -CH ２ F or -CHF ２ is.

[0061] n of the alcohol has the same value as n of the third fluorine-containing alkyl iodide and is an integer of not less than 0. The preferred range of n of the alcohol is the same as the preferred range of n of the third fluorine-containing alkyl iodide.

[0062] The sulfur trioxide content of fuming sulfuric acid is not particularly limited, but is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and even more preferably 50 to 70% by mass.

[0063] The amount of fuming sulfuric acid used is preferably 1 to 50 moles per mole of the third fluorine-containing alkyl iodide, in terms of the amount equivalent to sulfur trioxide in fuming sulfuric acid.

[0064] The temperature for the reaction of the third fluorine-containing alkyl iodide with oleum can be suitably selected, but is preferably 0 to 90° C. The pressure for the reaction of the third fluorine-containing alkyl iodide with oleum can be suitably selected, but is preferably 0 to 10.0 MPaG. The time for the reaction of the third fluorine-containing alkyl iodide with oleum can be suitably selected, but is preferably 0.1 to 96 hours.

[0065] In step (7), the third fluorine-containing alkyl iodide is reacted with fuming sulfuric acid to give a compound of the general formula: １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -OSO ３ H (wherein, R １ As described above, n is an integer of 0 or more), and then the fluorine-containing alkyl hydrogen sulfate is hydrolyzed to give a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -OH (in the formula, R １ As described above, n is an integer of 0 or more) to produce a fluorine-containing alcohol represented by the formula:

[0066] The hydrolysis of the fluorine-containing alkyl hydrogen sulfate can be carried out, for example, using water or an aqueous sodium sulfite solution by adding the aqueous sodium sulfite solution dropwise to a solution (a fluorine-containing alkyl hydrogen sulfate-containing solution) obtained by reacting the third fluorine-containing alkyl iodide with fuming sulfuric acid.

[0067] The amount of water or aqueous sodium sulfite solution used is not particularly limited, as long as it is an amount that can neutralize the solution obtained by the reaction of the third fluorine-containing alkyl iodide with fuming sulfuric acid and is also an amount necessary to hydrolyze the fluorine-containing alkyl hydrogen sulfate.

[0068] The hydrolysis temperature can be selected as appropriate, but is preferably 15 to 100° C. The hydrolysis time can be selected as appropriate, but is preferably 0.1 to 96 hours.

[0069] Also, the general formula: R １ -R ２ - (CH ２ ) ｐ The alcohol represented by -OH is CHF=CHF and I ２ and IF ５ by reacting the compound of the general formula: R １ -CHF-I (wherein R １ Ha-CHF ２ or —CHFI), and CHF═CHF is added to the fourth fluorine-containing alkyl iodide to obtain a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -I (wherein, R １ is as described above, n is an integer of 1 or more), and ２ =CH-(CH ２ ) ｑ -OH (wherein q is an integer of 1 or more), to give an unsaturated compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ -CHI- (CH ２ ) ｑ -OH (in the formula, R １ As described above, n is an integer of 0 or more, and q is an integer of 1 or more) can be produced by a production method including a step (9) of producing an alcohol represented by the formula:

[0070] In step (8), CHF=CHF and I２ and IF ５ by reacting the compound of the general formula: R １ -CHF-I (wherein R １ Ha-CHF ２ or —CHFI), and CHF═CHF is added to the fourth fluorine-containing alkyl iodide to obtain a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -I (wherein, R １ As described above, a fifth fluorine-containing alkyl iodide represented by the formula (where n is an integer of 1 or more) is produced.

[0071] I ２ and IF ５ The amount of is preferably 0.5 to 2 moles per mole of CHF=CHF.

[0072] CHF = CHF and I ２ and IF ５ The reaction can be carried out in a solvent.

[0073] CHF = CHF and I ２ and IF ５ The reaction temperature can be appropriately selected, but is preferably −78 to 200° C. ２ and IF ５ The pressure of the reaction can be appropriately selected, but is preferably 0 to 5.0 MPaG. ２ and IF ５ The reaction time can be appropriately selected, but is preferably 0.1 to 96 hours.

[0074] The reaction between the fourth fluorine-containing alkyl iodide and CHF=CHF is a telomerization reaction in which the fourth fluorine-containing alkyl iodide serves as a telogen and CHF=CHF serves as a taxogen, and a fifth fluorine-containing alkyl iodide is produced by this reaction.

[0075] In the fifth fluorine-containing alkyl iodide, n represents the degree of polymerization of CHF=CHF and is an integer of not less than 1. n is preferably an integer of 1 to 22, more preferably an integer of 1 to 7, still more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.

[0076] The reaction of the fourth fluorine-containing alkyl iodide with CHF=CHF can be carried out in the presence of a radical initiator, such as an organic peroxide or an azo compound.

[0077] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0078] Examples of the azo compounds include azobisisobutyronitrile.

[0079] The amount of CHF=CHF used is preferably 0.01 to 100 moles per mole of the fluorine-containing alkyl iodide.

[0080] The amount of the radical initiator used is preferably 0.01 to 2 moles per mole of the fluorine-containing alkyl iodide.

[0081] The temperature for the reaction of the fourth fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably −78 to 200° C. The temperature for the reaction of the fourth fluorine-containing alkyl iodide with CHF═CHF is preferably not less than the decomposition temperature of the radical polymerization initiator, and is preferably lower than the decomposition temperatures of the substrate and the product.

[0082] The pressure for the reaction of the fourth fluorine-containing alkyl iodide with CHF=CHF can be appropriately selected, but is preferably 0 to 5.0 MPa G. The time for the reaction of the fourth fluorine-containing alkyl iodide with CHF=CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0083] In the step (9), a fourth or fifth fluorine-containing alkyl iodide is reacted with a compound represented by the general formula: CH ２ =CH-CH ２ By reacting with an unsaturated compound represented by —OH, a compound of the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ -CHI- (CH ２ ) ｑ -OH (in the formula, R １ As described above, n is an integer of 0 or more, and q is an integer of 1 or more) to produce an alcohol represented by the formula (1).

[0084] R for alcohol １ is R of the fourth or fifth fluorine-containing alkyl iodide １ is the same as -CHF ２ Or -CHFI.

[0085] The n of the alcohol is an integer of 0 or more. A suitable range for n of the alcohol is an integer of 0 to 22, preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and even more preferably an integer of 0 to 3.

[0086] The q of the alcohol is an integer of 1 or greater. A suitable range for q of the alcohol is an integer of 1 to 24, preferably an integer of 1 to 18, and more preferably an integer of 1 to 12.

[0087] The reaction of the fourth or fifth fluorine-containing alkyl iodide with the unsaturated compound can be carried out in the presence of a compound capable of generating radicals, such as an organic peroxide or an azo compound.

[0088] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0089] Examples of the azo compounds include azobisisobutyronitrile.

[0090] The amount of the unsaturated compound used is preferably 0.01 to 100 moles per mole of the fourth or fifth fluorine-containing alkyl iodide.

[0091] The amount of the radical-generating compound used is preferably 0.001 to 1 mole per mole of the fourth or fifth fluorine-containing alkyl iodide.

[0092] The temperature for the reaction of the fourth or fifth fluorine-containing alkyl iodide with the unsaturated compound can be appropriately selected but is preferably 50 to 200° C. The pressure for the reaction of the fourth or fifth fluorine-containing alkyl iodide with the unsaturated compound can be appropriately selected but is preferably 0.1 to 5 MPaG. The time for the reaction of the fourth or fifth fluorine-containing alkyl iodide with the unsaturated compound can be appropriately selected but is preferably 0.1 to 96 hours.

[0093] The resulting alcohol is reduced to give a compound of the general formula: １ -CHF- (CHF-CHF) ｎ -CH ２ -CH ２ - (CH ２ ) ｑ -OH (in the formula, R １ , X, q, and n are as defined above), the reduction can be carried out, for example, using a metal catalyst and hydrogen or using zinc as a reducing agent.

[0094] (b) Non-fluorine-containing non-crosslinkable monomer The polymer of the present disclosure may have a repeating unit derived from a non-fluorine-containing non-crosslinkable monomer (b). The non-fluorine-containing non-crosslinkable monomer (b) is a monomer that does not contain a fluorine atom and is not crosslinkable (or does not have a crosslinkable functional group). The non-fluorine-containing non-crosslinkable monomer (b) is preferably a non-fluorine-containing monomer having a carbon-carbon double bond. The non-fluorine-containing non-crosslinkable monomer (b) is preferably a vinyl monomer that does not contain fluorine. The non-fluorine-containing non-crosslinkable monomer (b) is generally a compound having one carbon-carbon double bond.

[0095] A preferred fluorine-free non-crosslinkable monomer (b) is a monomer represented by the general formula: CH ２ =CA-T (wherein A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom, and T is a hydrogen atom, a linear or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a linear or cyclic organic group having 1 to 20 carbon atoms and having an ester bond, an amide bond, a urethane bond, or a urea bond).

[0096] Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 4 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 20 carbon atoms. T can be selected from long-chain hydrocarbon groups and saturated cyclic hydrocarbon groups having 12 to 30 carbon atoms.

[0097] Examples of the linear or cyclic organic group having 1 to 30 carbon atoms and an ester bond include -C(=O)-O-Q and -O-C(=O)-Q (wherein Q represents a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic hydrocarbon group having 4 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic aliphatic hydrocarbon group having 7 to 20 carbon atoms).

[0098] Examples of the linear or cyclic organic group having 1 to 20 carbon atoms and having an amide bond, a urethane bond or a urea bond include -C(=O)-NH-Q, -NH-C(=O)-Q, -NH-C(=O)-O-Q, -O-C(=O)-NH-Q and -NH-CO-NH-Q (wherein Q is a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic hydrocarbon group having 4 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic aliphatic hydrocarbon group having 7 to 20 carbon atoms).

[0099] Preferred examples of the non-fluorine-containing non-crosslinkable monomer (b) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and vinyl alkyl ether. The non-fluorine-containing non-crosslinkable monomer (b) is not limited to these examples.

[0100] The fluorine-free non-crosslinkable monomer (b) may be a (meth)acrylate ester having an alkyl group. The number of carbon atoms in the alkyl group may be 1 to 30, for example, 6 to 30 (e.g., 10 to 30). For example, the fluorine-free non-crosslinkable monomer (b) may be a (meth)acrylate ester having a general formula: CH ２ = CA １ COOA ２ (In the formula, A １ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom, or an iodine atom), and A ２ is C ｎ H ２ｎ＋１ (n=1 to 30).

[0101] The fluorine-free, non-crosslinkable monomer (b) may be a (meth)acrylate monomer having a cyclic hydrocarbon group. The (meth)acrylate monomer (B) having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth)acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth)acrylate group are directly bonded. Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged ring groups. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group preferably has 4 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include cyclic aliphatic groups having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and araliphatic groups having 7 to 20 carbon atoms. The cyclic hydrocarbon group preferably has 15 or fewer carbon atoms, for example 10 or fewer carbon atoms. It is preferable that a carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth)acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group. The (meth)acrylate group may be an acrylate group or a methacrylate group, with a methacrylate group being preferred. Specific examples of monomers having a cyclic hydrocarbon group include cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, and dicyclopentenyl acrylate.

[0102] The polymer of the present disclosure may have, as the repeating unit derived from the fluorine-free non-crosslinkable monomer (b), a repeating unit derived from a fluorine-free monomer containing a long-chain hydrocarbon group.

[0103] The long-chain hydrocarbon group-containing non-fluorine-containing monomer does not have a fluoroalkyl group. The long-chain hydrocarbon group-containing non-fluorine-containing monomer does not contain a fluorine atom. The long-chain hydrocarbon group is a saturated or unsaturated group. The long-chain hydrocarbon group is preferably a saturated hydrocarbon group, particularly an alkyl group.

[0104] The long-chain hydrocarbon group is preferably a linear or branched hydrocarbon group having 7 to 40 carbon atoms. The linear or branched hydrocarbon group may have 10 to 40, 12 to 40, or 18 to 40 carbon atoms. The linear or branched hydrocarbon group preferably has 12 to 40, more preferably 12 to 30, particularly 18 to 28, and especially 18 to 22 (or 18 to 24) carbon atoms, and is generally a saturated aliphatic hydrocarbon group, particularly an alkyl group. The long-chain hydrocarbon group is particularly preferably a stearyl group, an icosyl group, or a behenyl group.

[0105] The long-chain hydrocarbon group-containing non-fluorine-containing monomer includes a monomer represented by the general formula: CH ２ = C (-X １１ )-C(=O)-Y １１ -R １１ ｎ (In the formula, X １１ is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom, and Y １１ is a divalent to tetravalent linking group having at least one group selected from —O— and —NH—, and R １１ is a hydrocarbon group having 7 to 40 carbon atoms, and n is an integer of 1 to 3).

[0106] X １１ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. １１ Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. １１ is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0107] Y １１ is a single bond or a divalent to tetravalent group. １１ is preferably a single bond or a divalent group. １１ represents at least one group selected from -O-, -NH-, or -O- and -NH-, and a hydrocarbon group having one carbon atom, -C ６ H ６ -, -C(=O)- and -S(C=O) ２and at least one group selected from the group consisting of - and -. Examples of hydrocarbon groups having one carbon atom include -CH ２ -, -CH= or -C≡.

[0108] A divalent group Y １１ Examples are -Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'- Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- (wherein, Y' is -O- or -NH-, and R' is -(CH ２ ) ｍ - (m is an integer of 1 to 5) or -C ６ H ６ -(phenylene group).

[0109] A divalent group Y １１ Specific examples include -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ６ -, -O-(CH ２ ) ｍ -O-, -NH-(CH ２ ) ｍ -NH-, -O-(CH ２ ) ｍ -NH-, -NH-(CH ２ ) ｍ -O-, -O-(CH ２ ) ｍ -O-C(=O)-, -O-(CH ２ ) ｍ -C(=O)-O-, -NH-(CH ２ ) ｍ -OC(=O)-, -NH-(CH ２ ) ｍ -C(=O)-O-, -O-(CH ２ ) ｍ -OC(=O)-NH-, -O-(CH ２ ) ｍ -NH-C(=O)-O-, -O-(CH２ ) ｍ -C(=O)-NH-, -O-(CH ２ ) ｍ -NH-C(=O)-, -O-(CH ２ ) ｍ -NH-C(=O)-NH-, -O-(CH ２ ) ｍ -O-C ６ H ６ -, -NH-(CH ２ ) ｍ -OC(=O)-NH-, -NH-(CH ２ ) ｍ -NH-C(=O)-O-, -NH-(CH ２ ) ｍ -C(=O)-NH-, -NH-(CH ２ ) ｍ -NH-C(=O)-, -NH-(CH ２ ) ｍ -NH-C(=O)-NH-, -NH-(CH ２ ) ｍ -O-C ６ H ６ -, -NH-(CH ２ ) ｍ -NH-C ６ H ６ wherein m is an integer of 1 to 5, particularly 2 or 4.

[0110] A divalent group Y １１ is -O-, -NH-, -O-(CH ２ ) ｍ -O-C(=O)-, -O-(CH ２ ) ｍ -NH-C(=O)-, -O-(CH ２ ) ｍ -OC(=O)-NH-, -O-(CH ２ ) ｍ -NH-C(=O)-O-, -O-(CH ２ ) ｍ More preferably, it is —NH—C(═O)—NH— (wherein m is an integer of 1 to 5, particularly 2 or 4). １１ is -O-(CH ２ ) ｍ It is particularly preferably —NH—C(═O)—.

[0111] A divalent group Y １１ is -O-, -NH-, -O-(CH ２ ) ｍ -NH-C(=O)-, -O-(CH ２ ) ｍ -OC(=O)-NH-, -O-(CH ２ ) ｍ -NH-C(=O)-O-, -O-(CH ２ ) ｍ Particularly preferred is --NH--C(.dbd.O)--NH-- (wherein m is an integer of 1 to 5, particularly 2 or 4).

[0112] R １１ is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example 16 to 26 carbon atoms, particularly 18 to 22 carbon atoms.

[0113] n is an integer of 1 to 3, preferably 1. １１ When Y has a tetravalent hydrocarbon group having 1 carbon atom, it is preferable that n=3. １１ When Y has a trivalent hydrocarbon group having one carbon atom, it is preferable that n=2. １１ When there is no trivalent or tetravalent hydrocarbon group having one carbon atom, n=1.

[0114] Examples of the long-chain hydrocarbon group-containing non-fluorine-containing monomer are * (b1) an acrylic monomer containing a divalent group represented by -C(=O)-O-* or -C(=O)-NH-* and a hydrocarbon group having 7 to 40 carbon atoms, wherein the bond represented by * is directly bonded to the hydrocarbon group having 7 to 40 carbon atoms, and (b2) an acrylic monomer containing a divalent group represented by -C(=O)-O-* or -C(=O)-NH-* and a hydrocarbon group having 7 to 40 carbon atoms, wherein the bond represented by * is not directly bonded to the hydrocarbon group having 7 to 40 carbon atoms.

[0115] The acrylic monomer (b2) is a compound different from the acrylic monomer (b1). The acrylic monomer (b2) may be a (meth)acrylate or (meth)acrylamide having an amide group, urethane group, or urea group (which is not directly bonded to C(=O)-O- or C(=O)-NH-, but is directly bonded to a hydrocarbon group having 7 to 40 carbon atoms). The acrylic monomer (b2) is preferably an acrylate that contains a divalent group represented by -C(=O)-O- or -C(=O)-NH-, and also contains an amide group that is not directly bonded to the divalent group (i.e., an amide group that is bonded to the divalent group via another group) and is directly bonded to a hydrocarbon group having 7 to 40 carbon atoms.

[0116] (b1) Acrylic Monomer The acrylic monomer (b1) is a monomer represented by the general formula: CH ２ = C (-X １１１ )-C(=O)-Y １１１ -R １１１ (In the formula, X １１１ is a hydrogen atom, a monovalent organic group, or a halogen atom, and Y １１１ is —O— or —NH—, and R １１１ is a hydrocarbon group having 7 to 40 carbon atoms).

[0117] The acrylic monomer (b1) is Y １１１ a long chain acrylate ester monomer in which Y is —O—; １１１ is a long chain acrylamide monomer in which is —NH—.

[0118] X １１１ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. １１１ Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. １１１ is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0119] Y １１１ is —O— or —NH—.

[0120] R １１１is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example 16 to 26 carbon atoms, particularly 18 to 22 (or 18 to 24) carbon atoms.

[0121] Specific examples of long-chain acrylate ester monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, and behenyl α-chloroacrylate.Specific examples of long-chain acrylamide monomers are lauryl (meth)acrylamide, stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0122] (b2) Acrylic Monomer The acrylic monomer (b2) may be a (meth)acrylate or (meth)acrylamide having a divalent to tetravalent linking group having at least one group selected from —O— and —NH— between C(═O)—O— or C(═O)—NH— and a hydrocarbon group having 7 to 40 carbon atoms.

[0123] The acrylic monomer (b2) is a monomer represented by the general formula: CH ２ = C (-X １１２ )-C(=O)-Y １１２ -Z １１１ (-Z １１２ -R １１２ ) ｐ (In the formula, X １１２ is a hydrogen atom, a monovalent organic group, or a halogen atom, and Y １１２ is —O— or —NH—, and Z １１１ is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; Z １１２ are each independently a divalent to tetravalent linking group having at least one group selected from a direct bond, —O—, and —NH—; R １１２ are each independently a hydrocarbon group having 7 to 40 carbon atoms, and p is 1 or 2).

[0124] The acrylic monomer (b2) is Y １１２ a long chain acrylate ester monomer in which Y is —O—; １１２ is a long chain acrylamide monomer in which is —NH—.

[0125] X １１２ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. １１２ Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. The less rigid the main chain of the resulting polymer, the less it inhibits the crystallinity of the side chains. １１２ is preferably a hydrogen atom, a methyl group, or a chlorine atom, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0126] Y １１２ is —O— or —NH—.

[0127] Z １１１ is a direct bond or a divalent or trivalent hydrocarbon group (particularly an alkyl group) having 1 to 5 carbon atoms, which may have a branched structure. １１１ The carbon number of Z is preferably 2 to 4, and particularly preferably 2. １１１ Specific examples of the divalent group include a direct bond and —CH ２ -, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ CH ２ -, -CH having a branched structure (a trivalent group) ２ CH=, -CH ２ (CH-)CH ２ -, -CH ２ CH ２ CH=, -CH ２ CH ２ CH２ CH ２ CH=, -CH ２ CH ２ (CH-)CH ２ -, -CH ２ CH ２ CH ２ CH= is. Z １１１ It is preferred that it is not a direct bond.

[0128] Z １１２ Specific examples of are direct bond, -O-, -NH-, -(O) ｋ -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -(O) ｋ -C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -(O) ｋ -C ６ H ６ -, -(O) ｋ -(CH ２ ) ｍ -O-, -NH-(CH ２ ) ｍ -NH-, -(O) ｋ -(CH ２ ) ｍ -NH-, -NH-(CH ２ ) ｍ -O-, -(O) ｋ -(CH ２ ) ｍ -O-C(=O)-, -(O) ｋ -(CH ２ ) ｍ -C(=O)-O-, -NH-(CH ２ ) ｍ -O-C(=O)-, -NH-(CH ２ ) ｍ -C(=O)-O-, -(O) ｋ -(CH ２ ) ｍ -O-C(=O)-NH-, -(O) ｋ -(CH​​​​​​​​​​​​​​​-NH-C(=O)-, -(O) ｋ - (CH ２ ) ｍ -NH-C(=O)-NH-, -(O) ｋ - (CH ２ ) ｍ -O-C ６ H ６ -, -NH-(CH ２ ) ｍ -OC(=O)-NH-, -NH-(CH ２ ) ｍ -NH-C(=O)-O-, -NH-(CH ２ ) ｍ -C(=O)-NH-, -NH-(CH ２ ) ｍ -NH-C(=O)-, -NH-(CH ２ ) ｍ -NH-C(=O)-NH-, -NH-(CH ２ ) ｍ -O-C ６ H ６ -, -NH-(CH ２ ) ｍ -NH-C ６ H ６ - (wherein k is 0 or 1, and m is an integer of 1 to 5, particularly 2 or 4), etc.

[0129] Z １１２ is -(O) ｋ -, -NH-, -(O) ｋ - (CH ２ ) ｍ -O-C(=O)-,-(O) ｋ - (CH ２ ) ｍ -NH-C(=O)-, -(O) ｋ - (CH ２ ) ｍ -OC(=O)-NH-, -(O) ｋ - (CH ２ ) ｍ -NH-C(=O)-O-,-(O) ｋ - (CH ２ ) ｍ Particularly preferred is --NH--C(.dbd.O)--NH-- (wherein k is 0 or 1, and m is an integer of 1 to 5, particularly 2 or 4).

[0130] Z １１１ and Z １１２ cannot simultaneously be a direct bond.

[0131] R １１２ is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example 16 to 26 carbon atoms, particularly 18 to 22 (or 18 to 24) carbon atoms.

[0132] The acrylic monomer (b2) is CH ２ = C (-X １１２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-R １１２ , C.H. ２ = C (-X １１２ )-C(=O)-OR １１２ or a combination thereof (wherein X １１２ , m and R １１２ has the same meaning as above). The acrylic monomer (b2) is CH ２ = C (-X １１２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-R １１２ It is particularly preferred that:

[0133] The acrylic monomer (b2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, the acrylic monomer (b2) can be produced by reacting a (meth)acrylate having an isocyanate group in its side chain, such as 2-methacryloyloxyethyl isocyanate, with a long-chain alkylamine or long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0134] Specific examples of the acrylic monomer (b2) are as follows: The compound of the following chemical formula is an acrylate having a hydrogen atom at the α-position, but specific examples may be a methacrylate having a methyl group at the α-position and an acrylate having a chlorine atom at the α-position.

[0135] (In each formula, m is an integer of 1 to 5, and n is an integer of 7 to 40), and methacrylates in which the α-position is a methyl group and acrylates in which the α-position is a chlorine atom in the above chemical formula.

[0136] Typical examples of the acrylic monomer (b2) include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, behenic acid amidoethyl (meth)acrylate, and myristate amidoethyl (meth)acrylate.

[0137] The acrylic monomer (b2) is represented by the general formula: R ２２ -C(=O)-NH-R ２３ -O-R ２１ (In the formula, R ２１represents an organic residue having an ethylenically unsaturated polymerizable group, R ２２ represents a hydrocarbon group having 7 to 40 carbon atoms, R ２３ is a hydrocarbon group having 1 to 5 carbon atoms).

[0138] R ２１ is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. ２４ =CH ２ , -CHR ２４ =CH ２ , -CH ２ CHR ２４ =CH ２ and the like. ２４ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ２１ R may have various organic groups in addition to the ethylenically unsaturated polymerizable group, such as organic groups of chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. ２１ is -C(=O)CR ２４ =CH ２ It is preferable that:

[0139] R ２２ R is a hydrocarbon group having 7 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbons and cyclic hydrocarbons. Of these, chain hydrocarbons are preferred, and linear saturated hydrocarbon groups are particularly preferred. ２２ has 7 to 40 carbon atoms, preferably 11 to 27 carbon atoms, and particularly preferably 15 to 23 carbon atoms.

[0140] R ２３ is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, and may have an unsaturated bond, but is preferably linear. ２３ The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. ２３ is preferably an alkylene group.

[0141] The amide group-containing monomer is R ２１ is alone (e.g., R ２１ is only a compound having 17 carbon atoms), or R ２１ A combination of multiple ２１ a compound having 17 carbon atoms, and R ２１ and a compound having 15 carbon atoms.

[0142] An example of the amide group-containing monomer is a carboxylic acid amide alkyl (meth)acrylate.

[0143] Specific examples of the amide group-containing monomer include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, behenic acid amidoethyl (meth)acrylate, myristate amidoethyl (meth)acrylate, laurate amidoethyl (meth)acrylate, isostearate ethyl amido(meth)acrylate, oleic acid ethyl amido(meth)acrylate, tert-butylcyclohexylcaproic acid amidoethyl (meth)acrylate, adamantanecarboxylic acid ethyl amido(meth)acrylate, naphthalenecarboxylic acid amidoethyl (meth)acrylate, anthracenecarboxylic acid amidoethyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl vinyl ether, palmitic acid amidoethyl allyl ether, stearic acid amidoethyl allyl ether, and mixtures thereof.

[0144] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 55 to 99 wt %, preferably 60 to 85 wt %, and more preferably 65 to 80 wt %, based on the total weight of the amide group-containing monomers, and the remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0145] (c) Non-Fluorine-Containing Crosslinkable Monomer The polymer of the present disclosure may have a repeating unit derived from a non-fluorine-containing crosslinkable monomer (c). The non-fluorine-containing crosslinkable monomer (c) is a crosslinkable monomer that does not contain a fluorine atom. The non-fluorine-containing crosslinkable monomer (c) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorine-containing crosslinkable monomer (c) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, etc. The non-fluorine-containing crosslinkable monomer (c) may be a mono(meth)acrylate, (meth)diacrylate, or mono(meth)acrylamide having a reactive group. Alternatively, the non-fluorine-containing crosslinkable monomer (c) may be a di(meth)acrylate.

[0146] Examples of the non-fluorine-containing crosslinkable monomer (c) include, but are not limited to, diacetone (meth)acrylamide, (meth)acrylamide, N-methylol (meth)acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0147] (d) Halogenated Olefin Monomer The polymer of the present disclosure may have a repeating unit derived from a halogenated olefin monomer (d) (excluding monomer (a)). The halogenated olefin monomer (d) is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin monomer (d) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer (d) are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

[0148] The polymer of the present disclosure can be formed from a monomeric raw material, and the monomeric raw material includes a monomer (a) and, optionally, at least one selected from the group consisting of (b), (c), and (d). With respect to the polymer, the monomers (a) and, if present, (b), (c), and (d) (more specifically, repeating units derived from these monomers, the same applies hereinafter) may each be one type or a mixture of two or more types.

[0149] Examples of the mass proportions of each monomer in the polymer, assuming that the total of monomers (a) to (d) is 100 mass%, are: the proportion of monomer (a) is 0.1 to 99.9 mass%, for example, 20 to 90 mass%, and particularly 50 to 80 mass%; the proportion of monomer (b) is 0 to 99.8 mass%, for example, 0.5 to 50 mass%, and particularly 1 to 30 mass%; the proportion of monomer (c) is 0 to 99.8 mass%, for example, 0.1 to 10 mass%, and particularly 0.1 to 5 mass%; and the proportion of monomer (d) may be 0 to 99.8 mass%, for example, 0.5 to 50 mass%, and particularly 1 to 30 mass%.

[0150] These mass proportions may be considered to be equal to the mass proportions of the total of the monomers used as the raw material for the polymer (first monomer raw material).

[0151] In the present disclosure, there are no particular limitations on the molecular weight of the polymer, but the weight average molecular weight determined by gel permeation chromatography in terms of polystyrene is, for example, 3,000 or more, preferably in the range of 5,000 to 1,500,000.

[0152] The polymer of the present disclosure can be produced by any conventional polymerization method, and the polymerization reaction conditions can be selected arbitrarily. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0153] In solution polymerization, a method is employed in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by mass, for example, 0.01 to 10 parts by mass, per 100 parts by mass of the monomer.

[0154] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 30 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 2000 parts by mass, for example, 50 to 1000 parts by mass, per 100 parts by mass of the total of the monomers.

[0155] In emulsion polymerization, a method is employed in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the mixture is polymerized by stirring at a temperature in the range of 50 to 80°C for 1 to 10 hours. Examples of the polymerization initiator that can be used include water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and 2,2'-azobis[2-(2-imidazol-2-yl)propane] dihydrochloride, and oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and 2,2'-azobis[2-(2-imidazol-2-yl)propane]. The polymerization initiator is used in an amount of 0.01 to 10 parts by mass per 100 parts by mass of the monomer.

[0156] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in a range of 0.5 to 20 parts by mass per 100 parts by mass of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0157] Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, which may be used in an amount of 1 to 50 parts by mass, for example, 10 to 40 parts by mass, per 100 parts by mass of water. Examples of the low-molecular-weight monomer include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, which may be used in an amount of 1 to 50 parts by mass, for example, 10 to 40 parts by mass, per 100 parts by mass of the total amount of the monomers.

[0158] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by mass, for example, 0.1 to 5 parts by mass, per 100 parts by mass of the total amount of monomers.

[0159] The water- and oil-resistant composition of the present disclosure contains the above-described polymer and medium, and imparts excellent water repellency or oil resistance to a substrate, preferably excellent water repellency and oil resistance to a substrate.

[0160] The water- and oil-resistant composition of the present disclosure may be in the form of a solution, emulsion (particularly, a water-dispersed composition), or aerosol, but is preferably a solution or a water-dispersed composition, and more preferably a water-dispersed composition. The water- and oil-resistant composition comprises a polymer (the active ingredient of the water- and oil-resistant composition) and a medium (particularly, a liquid medium, such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, relative to the water- and oil-resistant composition. In the water- and oil-resistant composition, the concentration of the polymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight.

[0161] The water- and oil-repellent composition of the present disclosure can be used as an external treatment agent (surface treatment agent) or an internal treatment agent.

[0162] When the water- and oil-resistant agent composition of the present disclosure is an external treatment agent, it can be applied to the object to be treated by a conventionally known method. Typically, the water- and oil-resistant agent composition is dispersed and diluted in an organic solvent or water, and then applied to the surface of the object to be treated by a known method such as dip coating, spray coating, or foam coating, followed by drying. If necessary, the composition may be applied together with an appropriate crosslinking agent (e.g., a blocked isocyanate) and cured. Furthermore, the water- and oil-resistant agent composition of the present disclosure may be used in combination with an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixative, or an anti-wrinkle agent. The polymer concentration in the treatment solution to be contacted with the object to be treated may be 0.01 to 10 wt % (particularly in the case of dip coating), for example, 0.05 to 10 wt %.

[0163] Examples of substrates that can be treated with the treatment composition (water-repellent and oil-resistant composition) of the present disclosure include textiles, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Examples of textiles include various natural fibers of animal and plant origin, such as cotton, hemp, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fiber, carbon fiber, and asbestos fiber; and mixtures of these fibers.

[0164] The textile product may be in the form of a fiber, a cloth, or the like. The water- and oil-repellent composition of the present disclosure can also be used as a stain repellent, a release agent, or a release agent (e.g., an internal or external release agent). For example, it can easily release the surface of a substrate from another surface (another surface of the substrate or a surface of another substrate).

[0165] The polymer can be applied to a fibrous substrate (e.g., a textile) by any of the methods known for treating textiles with a liquid. When the textile is a fabric, the fabric can be immersed in the solution, or the solution can be applied or sprayed onto the fabric. The treated textile is dried and preferably heated, for example, at 100°C to 200°C, to develop water or oil repellency.

[0166] Alternatively, the polymer may be applied to the textile by a cleaning process, such as in a laundry application or a dry cleaning process.

[0167] The textiles to be treated are typically fabrics, including woven, knitted and nonwoven fabrics, fabrics in the form of apparel and carpets, but may also be fibres or yarns or intermediate textile products (such as slivers or rovings). The textile material may be natural fibres (such as cotton or wool), chemical fibres (such as viscose rayon or leocell), or synthetic fibres (such as polyester, polyamide or acrylic fibres), or may be a mixture of fibres (such as a mixture of natural and synthetic fibres). Preferably the textile is a carpet.

[0168] Alternatively, the fibrous substrate may be leather. The manufacturing polymer may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during the wet processing of the leather or during the finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The manufacturing polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example, during the drying of the paper.

[0169] "Treatment" means applying a treatment agent to an object to be treated by immersion, spraying, coating, etc. Through the treatment, the polymer, which is the active ingredient of the treatment agent, penetrates into the interior of the object to be treated and / or adheres to the surface of the object to be treated.

[0170] When the water- and oil-resistant agent composition is an internal treatment agent, it can be added to a resin, such as a thermoplastic resin, to impart water repellency or oil resistance to the resin. The water- and oil-resistant agent composition can be used when producing a resin molded article. The liquid medium is removed from a liquid (solution or dispersion) containing a polymer to obtain a polymer. For example, a polymer can be obtained by reprecipitating a polymer dispersion (aqueous dispersion or organic solvent dispersion) with water or an organic solvent, followed by drying.

[0171] For example, a molded article can be produced by a manufacturing method including a step of mixing a resin and a polymer to obtain a resin composition and a step of molding the resin composition. It is preferable to produce a molded article by melt-kneading using an extruder or the like. Generally, thermoplastic resins and polymers are compatible in a molten state. Kneading can be performed by a conventional method, such as a single-screw extruder, a twin-screw extruder, or a roll. The resin composition thus obtained is molded by extrusion molding, injection molding, compression molding, blow molding, press molding, or the like. The resin composition can be molded into molded articles of various shapes. The obtained molded article may be further heat-treated in an oven, drying furnace, or the like after molding. The molded article may be a single layer or a multi-layered article having 2 to 10 layers, for example, 3 to 5 layers.

[0172] The molded article can be used in applications where thermoplastic resins are used, particularly applications where excellent wipeability and scratch resistance are preferred. Applications of the molded article include automobiles (exterior and interior parts) (e.g., bumpers, instrument panels, door trims), household electrical appliances (e.g., washing machines and refrigerators) (e.g., housings, refrigerator doors, trays, vegetable compartments), various cases, building interiors and parts (e.g., handrails, wallpaper, desks, chairs, toilet seats and toilet seat support bars, bathtubs), electronic devices (e.g., smartphone housings), drains, pipes, tableware, flooring, gasoline tanks, fuel hoses, office equipment, etc. Among these, automotive interior parts, interior parts of household electrical appliances, and buildings are more preferred.

[0173] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0174] The main embodiments of the present disclosure are as follows.

[0175] <1> According to a first aspect of the present disclosure, there is provided a compound represented by the general formula: R １ -R ２ - (CH ２ ) ｐ -O-R ３ (In the formula, R １ is -CH ３ , -CH２ F, -CHF ２ , -CH ２ I or -CHFI, R ２ represents an alkylene group having 1 to 49 carbon atoms and consisting only of units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ an alkylene group having 2 to 49 carbon atoms and consisting only of units represented by -, or a unit represented by -CFH-, -CH ２ an alkylene group having 3 to 49 carbon atoms and consisting only of units represented by - and units represented by -CHI-, p is an integer of 0 to 2, R ３ <2> According to a second aspect of the present disclosure, there is provided a polymer having a repeating unit derived from a monomer (a) represented by the formula: R ２ <3> According to a third aspect of the present disclosure, there is provided a polymer in which R ２ is represented by the general formula: -(CFH) ｎ１ - (wherein n1 is an integer of 2 to 10). <4> According to a fourth aspect of the present disclosure, there is provided a polymer comprising: ３ is represented by the general formula: CH ２ There is provided a polymer according to any one of the first to third aspects, wherein Z is a group represented by the formula: ═C(—X)—C(═O)—Y—Z— (wherein X is a hydrogen atom, a methyl group, or a halogen atom, Y is —O— or —NH—, and Z is a direct bond or a divalent organic group). <5> According to a fifth aspect of the present disclosure, there is provided a polymer wherein Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cyclic aliphatic group having 6 to 18 carbon atoms, —(CH ２ ) ｍ -N(R １ ) SO ２ - (CH ２ ) ｎ - group, -CH ２ CH (OZ １ ) CH ２ - group, -CH ２ CH (OZ１ ) CH ２ -(Ph-O)- group, -(CH ２ ) ｎ -Ph-O- group, -(CH ２ ) ｍ -SO ２ - (CH ２ ) ｎ - group, -(CH ２ ) ｍ -OC(=O)N(R １ )-(CH ２ ) ｎ - group, -(CH ２ ) ｍ -N(R １ )C(=O)O-(CH ２ ) ｎ - group, -(CH ２ ) ｍ -C(=O)N(R １ )-(CH ２ ) ｎ - group, -(CH ２ ) ｍ - (R １ )NC(=O)-(CH ２ ) ｎ - group, -(CH ２ ) ｍ - (R １ )NC(=O)N(R １ )-(CH ２ ) ｎ - group, or -(CH ２ ) ｍ -S-(CH ２ ) ｎ - group (wherein, in each formula, Z １ is a hydrogen atom or R １ C(=O)-, R １(a) is an alkyl group having 1 to 18 carbon atoms, Ph is a phenylene group, m is an integer of 1 to 10, and n is an integer of 0 to 10. <6> According to a sixth aspect of the present disclosure, there is provided a polymer according to any of the first to fifth aspects, wherein the polymer further contains a repeating unit derived from at least one selected from the group consisting of: (b) a non-fluorine-containing non-crosslinkable monomer, (c) a non-fluorine-containing crosslinkable monomer, and (d) a halogenated olefin monomer. <7> According to a seventh aspect of the present disclosure, there is provided a polymer according to any of the first to fifth aspects, wherein the polymer further contains a repeating unit derived from at least one selected from the group consisting of: (a) a non-fluorine-containing non-crosslinkable monomer, (b) a non-fluorine-containing crosslinkable monomer, and (c) a halogenated olefin monomer ２ = C (-X １１ )-C(=O)-Y １１ -R １１ ｎ (In the formula, X １１ is a hydrogen atom, a methyl group or a halogen atom, １１ is a divalent to tetravalent linking group having at least one group selected from —O— and —NH—, and R １１ is a hydrocarbon group having 7 to 40 carbon atoms, and n is an integer of 1 to 3). <8> According to an eighth aspect of the present disclosure, there is provided a water- and oil-repellent composition comprising the polymer according to any one of the first to seventh aspects and a liquid medium. <9> According to a ninth aspect of the present disclosure, there is provided a water- and oil-repellent composition according to the eighth aspect, wherein the liquid medium is water, an organic solvent, or a mixture of water and an organic solvent. <10> According to a tenth aspect of the present disclosure, there is provided a water- and oil-repellent composition according to the eighth or ninth aspect, which is an aqueous dispersion composition. <11> According to an eleventh aspect of the present disclosure, there is provided a water- and oil-repellent composition according to any one of the eighth to tenth aspects, which is an external treatment agent or an internal treatment agent. <12> According to a twelfth aspect of the present disclosure, there is provided a substrate treated with the water- and oil-repellent composition according to any one of the eighth to eleventh aspects. <13> According to a thirteenth aspect of the present disclosure, there is provided a textile product treated with the water- and oil-resistant composition according to any one of the eighth to eleventh aspects.

[0176] Next, an embodiment of the present disclosure will be described using experimental examples, but the present disclosure is not limited to such experimental examples.

[0177] Experimental Example 1 Synthesis of 1,1,2-trifluoro-2-iodoethane In a 300 mL pressure vessel, 37.1 g of iodine, IF ５ After the vessel was cooled to -78°C, 10 g of (E)-1,2-difluoroethene was added to the vessel, and the vessel was heated at 80°C for 20 hours. After the vessel was cooled with ice water, the contents of the pressure vessel were washed with water and then added with 5% Na ２ S ２ O ４ Further washing with aqueous solution gave the title compound in 5.8 g. １９ F NMR (282MHz, CDCl ３ ): δ-169.1 to -169.4 (m, 1F), -124.0 to -124.3 (m, 1F). １ H NMR (400 MHz, CDCl3): δ 6.79 (d with fine coupling, J = 48.0 Hz, 1H), 7.26 (td with fine coupling, J = 54.8, 3.6 Hz, 1H). LRMS (EI 70eV) m / z (%): 210 (M+, 100), 190 (8), 171 (3), 83 (62), 64 (37), 51 (14).

[0178] Experimental Example 2: Synthesis of 4,5,5-trifluoro-2-iodopentanol. 1.84 g of 1,1,2-trifluoro-2-iodoethane, 509 mg of allyl alcohol, and 288 mg of azobisisobutyronitrile were placed in a 10 mL pressure vessel. The vessel was then heated at 80°C for 22 hours. After cooling the vessel with ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The title compound was found to have been produced in an area ratio of 75.9% compared to 24.1% for the starting material, 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70 eV) m / z (%): 268 (M+, 1), 251 (1), 185 (2), 141 (95), 73 (100), 51 (38).

[0179] Experimental Example 3 Synthesis of 7,8,8-trifluoro-5-iodooctan-1-ol 1.00 g of 1,1,2-trifluoro-2-iodoethane, 477 mg of 5-hexen-1-ol, and 235 mg of azobisisobutyronitrile were placed in a 10 mL pressure vessel. The vessel was then heated at 80°C for 22 hours. After cooling the vessel with ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. It was found that the title compound was produced in an area ratio of 66.8% (total of two isomers) compared to an area ratio of 37.2% for the starting material 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70eV) m / z (%): 293 ([M-OH]+, 100), 259 (5), 207 (25), 207 (25), 155 (34).

[0180] Experimental Example 4: Synthesis of 4,5,5-trifluoro-2-iodopentane methacrylate. 200 mg of 4,5,5-trifluoro-2-iodopentanol was placed in a 10 mL glass vessel. After purging with nitrogen, 1.1 mL of dichloromethane and 0.15 mL of pyridine were added to the vessel. The vessel was cooled to 0°C, and 0.18 mL of methacryloyl chloride was added and stirred for 1 hour. Gas chromatography-mass spectrometry analysis of the contents revealed that the title compound was produced in an area ratio of 77.7% (total of two isomers) relative to the area ratio of the starting material 4,5,5-trifluoro-2-iodopentanol, 22.3%. LRMS (EI 70 eV) m / z (%): 250 ([M-CH2=C(Me)COO]+, 100), 209 (95), 69 (90).

[0181] Experimental Example 5: Synthesis of 7,8,8-trifluorooctan-1-ol. 67.5 mg of zinc was added to a mixed solution of 200 mg of 7,8,8-trifluoro-5-iodooctan-1-ol and 0.4 mL of methanol in a 10 mL glass vessel. 0.33 mL of 2 M aqueous hydrochloric acid was added. After stirring for 6 hours, the contents were analyzed by gas chromatography-mass spectrometry. It was found that the title compound was produced at an area ratio of 75.6% compared to 24.4% for the starting material 7,8,8-trifluoro-5-iodooctan-1-ol. LRMS (EI 70 eV) m / z (%): 167 ([M-OH]+, 100), 127 (54), 51 (4).

[0182] Experimental Example 6 Synthesis of 7,8,8-trifluorooctane methacrylate 119 mg of 7,8,8-trifluorooctan-1-ol was placed in a 10 mL glass vessel, and the vessel was purged with nitrogen. Then, 0.6 mL of dichloromethane and 51.3 μL of pyridine were added to the vessel. The vessel was cooled to 0°C, and 62.4 μL of methacryloyl chloride was added, followed by stirring for 1 hour. Analysis of the contents by gas chromatography-mass spectrometry revealed that the raw materials had disappeared and the title compound had been produced. LRMS (EI 70 eV) m / z (%): 252 ([M] ＋ , 2), 166 (18), 87 (100), 69 (52).

[0183] Experimental Example 7 Oligomerization reaction of 1,1,2-trifluoro-2-iodoethane with (E)-1,2-difluoroethene 1.00 g of 1,1,2-trifluoro-2-iodoethane and 0.35 mL of 2-ethylhexanoyl(tert-butyl)peroxide were placed in a 30 mL pressure vessel, and the vessel was sealed and cooled to −78° C., after which 1.5 g of (E)-1,2-difluoroethene was introduced. The vessel was heated at 80° C. for 24 hours. After cooling with ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. Compared to the area ratio of the starting material 1,1,2-trifluoro-2-iodoethane (22.2%), H-CF2CHF-(CHFCHF)-I, H-CF2CHF-(CHFCHF)2-I, and H-CF2CHF-(CHFCHF)3-I were produced at area ratios of 36.1% (total of four isomers), 20.5% (total of eight isomers), and 21.3% (total of multiple isomers), respectively. H-CF2CHF-(CHFCHF)-I: LRMS (EI 70 eV) m / z (%): 274 (M+, 87), 191 (11), 159 (30), 147 (76), 83 (45), 77 (100), 51 (82). H-CF2CHF-(CHFCHF)2-I: LRMS (EI 70eV) m / z (%): 338 (M+, 18), 211 (4), 191 (27), 159 (22), 147 (27), 83 (38), 77 (84), 51 (100). H-CF2CHF-(CHFCHF)3-I: LRMS (EI 70eV) m / z (%): 402 (M+, 2), 191 (23), 159 (34), 147 (18), 83 (36), 77 (89), 51 (100).

[0184] It is clear from common technical knowledge that polymers can be easily obtained by using a radical initiator from the methacrylates obtained in Experimental Examples 4 and 6. These polymers can be suitably used as water-repellent and oil-resistant compositions.

[0185] Furthermore, from the results of Experimental Examples 2 to 6, it was found that the compound obtained in Experimental Example 7 could be easily used to obtain H-CF2CHF-(CHFCHF) ｎ - (CH2) pIt is clear from common technical knowledge that (meth)acrylates having - can be synthesized.

Claims

1. General formula: R １ -R ２ -(CH ２ ) ｐ -O-R ３ (In the formula, R １ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I or -CHFI, R ２ represents an alkylene group having 1 to 49 carbon atoms composed only of units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ An alkylene group having 2 to 49 carbon atoms composed only of units represented by -, or a unit represented by -CFH-, -CH ２ an alkylene group having 3 to 49 carbon atoms and consisting only of - units and -CHI- units, p is an integer from 0 to 2, R ３ is an organic residue having an ethylenically unsaturated polymerizable group. A polymer having a repeating unit derived from a monomer (a) represented by the following formula:

2. R ２ The polymer according to claim 1, wherein is an alkylene group having 2 to 10 carbon atoms.

3. R ２ is represented by the general formula: -(CFH) ｎ１ - (wherein n1 is an integer from 2 to 10).

3. The polymer according to claim 1, wherein the alkylene group is represented by the following formula:

4. R ３ is represented by the general formula: CH ２ =C(-X)-C(=O)-Y-Z- (In the formula, X is a hydrogen atom, a methyl group or a halogen atom; Y is -O- or -NH-; Z is a direct bond or a divalent organic group.

3. The polymer according to claim 1, wherein the group is represented by the formula:

5. Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, -(CH ２ ) ｍ -N(R １ ) S.O. ２ - (CH ２ ) ｎ - group, -CH ２ CH (OZ １ ) CH ２ - group, -CH ２ CH (OZ １ ) CH ２ -(Ph-O)- group, -(CH ２ ) ｎ -Ph-O- group, -(CH ２ ) ｍ -SO ２ - (CH ２ ) ｎ - group, -(CH ２ ) ｍ -OC(=O)N(R １ )-(CH ２ ) ｎ - group, -(CH ２ ) ｍ -N(R １ )C(=O)O-(CH ２ ) ｎ - group, -(CH ２ ) ｍ -C(=O)N(R １ )-(CH ２ ) ｎ - group, -(CH ２ ) ｍ - (R １ )NC(=O)-(CH ２ ) ｎ - group, -(CH ２ ) ｍ - (R １ )NC(=O)N(R １ )-(CH ２ ) ｎ - group or -(CH ２ ) ｍ -S-(CH ２ ) ｎ - group (wherein, in each formula, Z １ is a hydrogen atom or R １ C(=O)-, R １ is an alkyl group having 1 to 18 carbon atoms, Ph is a phenylene group, m is an integer of 1 to 10, and n is an integer of 0 to 10.

6. The polymer is (b) a fluorine-free non-crosslinkable monomer, (c) a non-fluorine-containing crosslinkable monomer, and (d) Halogenated olefin monomers The polymer according to claim 1 or 2, further comprising a repeating unit derived from at least one selected from the group consisting of:

7. The polymer has the general formula: CH ２ =C(-X １１ )-C(=O)-Y １１ -R １１ ｎ (In the formula, X １１ is a hydrogen atom, a methyl group or a halogen atom, Y １１ is a divalent to tetravalent linking group having at least one group selected from —O— and —NH—, R １１ is a hydrocarbon group having 7 to 40 carbon atoms, n is an integer from 1 to 3.

3. The polymer according to claim 1, further comprising a repeating unit derived from a monomer represented by the formula:

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

9. 9. The water- and oil-resistant composition according to claim 8, wherein the liquid medium is water, an organic solvent or a mixture of water and an organic solvent.

10. The water- and oil-resistant composition according to claim 8, which is a water-dispersed composition.

11. The water- and oil-resistant composition according to claim 8, which is an external treatment agent or an internal treatment agent.

12. A substrate treated with the water- and oil-repellent composition according to claim 8.

13. A textile product treated with the water- and oil-repellent composition according to claim 8.