Polymer and water-repellent oil-resistant composition

Abstract

Provided is a polymer having a structure represented by the general formula: R1-R2-(CH2) p-O-R3 (in the formula, R1 is-CH3,-CH2F,-CHF2,-CH2I, or-CHFI, and R2 is-CH3,-CH2F,-CHF2,-CH2I, or-CHFI; r2 is an alkylene group having 1 to 49 carbon atoms and comprising only a unit represented by-CFH-, or an alkylene group having 2 to 49 carbon atoms and comprising only a unit represented by-CFH-and a unit represented by-CH2-, or an alkylene group having 3 to 49 carbon atoms and comprising only a unit represented by-CFH-, a unit represented by-CH2-and a unit represented by-CHI-, p is an integer of 0 to 2, and n is an integer of 0 to 2. And R3 represents an organic residue having an ethylenically unsaturated polymerizable group).

Description

Technical Field

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

[0002] Patent Document 1 describes a water- and oil-repellent composition having as an essential component a copolymer substantially composed of polymerization units of the following monomer (a) and polymerization units of the following monomer (b).

[0003] Monomer (a): a monomer having a polyfluoroalkyl group, wherein a homopolymer of the monomer has no melting point or a melting point of 50° C. or less in crystallites produced by the polyfluoroalkyl group.

[0004] Monomer (b): a monomer having an organic group other than a polyfluoroalkyl group, wherein a homopolymer of the monomer has a melting point of crystallites derived from the organic group other than a polyfluoroalkyl group of 30° C. or higher.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2002 / 083809 Summary of the invention

[0008] Problems to be solved by the invention

[0009] The present disclosure aims to provide a polymer exhibiting water repellency or oil resistance, and a water- and oil-resistant agent composition capable of imparting water repellency or oil resistance to an article.

[0010] Means for solving problems

[0011] According to the present disclosure, a polymer is provided, which has the general formula: R 1 -R 2 -(CH2) p -OR 3 (Where R 1 is -CH3, -CH2F, -CHF2, -CH2I or -CHFI, R 2 is an alkylene group having 1 to 49 carbon atoms consisting only of a unit represented by -CFH-, an alkylene group having 2 to 49 carbon atoms consisting only of a unit represented by -CFH- and a unit represented by -CH2-, or an alkylene group having 3 to 49 carbon atoms consisting only of 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 R 3 The repeating unit derived from the monomer (a) is an organic residue having an ethylenically unsaturated polymerizable group.

[0012] Effects of the Invention

[0013] According to the present disclosure, a polymer exhibiting good water repellency or oil resistance, and a water and oil repellent composition capable of imparting good water repellency or oil resistance to an article can be provided. DETAILED DESCRIPTION

[0014] Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0015] Conventionally, fluorinated water- and oil-repellents containing fluorine compounds are known. When a substrate such as a fiber product is treated with such a water- and oil-repellent, a substrate exhibiting water- and oil-repellency can be obtained.

[0016] Patent Document 1 describes, as a technique for imparting both water and oil repellency to a surface, the use of a polymer containing a polymerizable monomer containing a polyfluoroalkyl group in the molecule or a copolymer thereof with other monomers to form an organic solvent solution or an aqueous dispersion to treat an article. Furthermore, Patent Document 1 describes that by combining a monomer containing a polyfluoroalkyl group with a crystalline hydrocarbon monomer, the crystallinity of the crystalline hydrocarbon monomer can be enhanced, and by strengthening the synergistic effect of surface orientation, there are no crystallites from the polyfluoroalkyl group in the polymer, or even if the crystallites have a low melting point, they exhibit water and oil repellency; as the polyfluoroalkyl group, F(CF2) is preferred. k -(k is an integer of 1 to 20). However, a polymer showing water repellency even without having a perfluoroalkyl group is desired.

[0017] The polymers disclosed herein have the general formula: R 1 -R 2 -(CH2) p -OR 3 (Where R 1 is -CH3, -CH2F, -CHF2, -CH2I or -CHFI, R 2 is an alkylene group consisting only of a unit represented by -CFH-, or an alkylene group consisting only of a unit represented by -CFH- and a unit represented by -CH2-, or an alkylene group having 3 to 49 carbon atoms consisting only of a unit represented by -CFH-, a unit represented by -CH2-, and a unit represented by -CHI-, p is an integer of 0 to 2, and R 3 The repeating unit derived from the monomer (a) is an organic residue having an ethylenically unsaturated polymerizable group.

[0018] Since the polymer disclosed in the present invention has a repeating unit derived from monomer (a), it exhibits water repellency or oil resistance, preferably water repellency and oil resistance, even if it does not have a perfluoroalkyl group or a perfluoroalkylene group. Therefore, by using the polymer disclosed in the present invention, a water-repellent and oil-resistant composition that can impart good water repellency or oil resistance, preferably good water repellency and oil resistance to an article can be obtained.

[0019] (a) Monomer

[0020] In the general formula representing the monomer (a), R 1 is -CH3, -CH2F, -CHF2, -CH2I or -CHFI, preferably -CH2F, -CHF2 or -CHFI. One of the characteristics of the polymer disclosed in the present invention is that the organic residue (R 3 ) does not have a CF3-(trifluoromethyl) group.

[0021] R 2 is an alkylene group consisting of only units represented by -CFH-, or an alkylene group consisting of only units represented by -CFH- and -CH2-, or an alkylene group consisting of only units represented by -CFH-, -CH2-, and -CHI-. One of the characteristics of the polymer disclosed in the present invention is that the organic residue (R 3 ) does not contain a unit represented by -CF2-.

[0022] 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 further preferably 10 or less.

[0023] R 2 In the case of an alkylene group consisting only of units represented by -CFH-, R 2 For example, -(CFH) n1 -(wherein n1 is an integer greater than 1), preferably -(CFH) n1 -(wherein n1 is an integer from 3 to 49), more preferably -CHF-(CHF-CHF) n -(n is an integer of 1 to 24). n1 is preferably an integer of 2 to 10. n is preferably an integer of 1 to 5.

[0024] R 2 In the case of an alkylene group consisting only of a unit represented by -CFH- and a unit represented by -CH2-, R 2 , for example -CHF-(CHF-CHF) n -(CH2) m-(n is an integer greater than or equal to 0, m is an integer greater than or equal to 1), etc.

[0025] R 2 In the case of an alkylene group consisting only of a unit represented by -CFH- and a unit represented by -CH2-, R 2 , preferably -CHF-(CHF-CHF) n -(CH2) m -(n is an integer of 1 to 24, and m is an integer of 1 or more), more preferably -CHF-(CHF-CHF) n -CH2- (n is an integer of 1 to 24), or -CHF- (CHF-CHF) n -CH2CH2- (n is an integer of 1 to 24). n is preferably an integer of 1 to 5. m is preferably 1 or 2.

[0026] R 2 In the case of an alkylene group consisting only of a unit represented by -CFH-, a unit represented by -CH2-, and a unit represented by -CHI-, R 2 , preferably -CHF-(CHF-CHF) n -CH2-CHI-(CH2) q -(n is an integer of 0 or more, q is an integer of 1 or more). 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.

[0027] p is an integer of 0 to 2, and preferably 1 or 2.

[0028] R 3 It is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has double bonds between carbon atoms. Specifically, organic residues having an ethylenically unsaturated polymerizable group such as CH2=C(-X)-C(=O)-, CH2=C(-X)-, and CH2=C(-X)-CH2- can be cited, and X can be a hydrogen atom, a methyl group, or a halogen atom. In addition, R 3 In addition to the ethylenically unsaturated polymerizable group, it may have various organic groups. Examples of such organic groups include chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, polysiloxane groups, and the like. These organic groups may be substituted with various substituents.

[0029] As R 3 , preferably a group represented by the general formula: CH2=C(-X)-C(=O)-YZ- (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).

[0030] 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 by 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.

[0031] Z may be a direct bond or a divalent organic group. In the case of a divalent organic group, examples include

[0032] Aliphatic groups with 1 to 10 carbon atoms,

[0033] An aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,

[0034] -(CH2) m -N(R 1 )SO2-(CH2) n - group (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 is an alkyl group having 1 to 18 carbon atoms),

[0035] -CH2CH(OZ 1 )CH2-yl(Z 1 is a hydrogen atom or R 1 C(=O)-,R 1 is an alkyl group having 1 to 18 carbon atoms),

[0036] -CH2CH(OZ 1 )CH2-(Ph-O)-yl(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),

[0037] -(CH2) n -Ph-O- group (wherein Ph is a phenylene group and n is an integer from 0 to 10),

[0038] -(CH2) m -SO2-(CH2) n -base (m is an integer from 1 to 10, n is an integer from 0 to 10),

[0039] -(CH2) m -OC(=O)N(R 1 )-(CH2) n - group (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 is an alkyl group having 1 to 18 carbon atoms),

[0040] -(CH2) m -N(R 1)C(=O)O-(CH2) n - group (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 is an alkyl group having 1 to 18 carbon atoms),

[0041] -(CH2) m -C(=O)N(R 1 )-(CH2) n - group (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 is an alkyl group having 1 to 18 carbon atoms),

[0042] -(CH2) m -(R 1 )NC(=O)-(CH2) n - group (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 is an alkyl group having 1 to 18 carbon atoms),

[0043] -(CH2) m -(R 1 )NC(=O)N(R 1 )-(CH2) n - group (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 is an alkyl group having 1 to 18 carbon atoms) or

[0044] -(CH2) m -S-(CH2) n -base (m is an integer from 1 to 10, n is an integer from 0 to 10), etc.

[0045] The monomer (a) can be prepared, for example, by using the general formula: R 1 -R 2 -(CH2) p -OH (where R 1 , R 2 and p) are as described above) and is produced by reacting a compound having an ethylenically unsaturated polymerizable group and having a carboxyl group, a carboxylic acid halide group, an amide group or an isocyanate group.

[0046] More specifically, monomer (a) can be prepared by making the general formula: R 1 -R 2 -(CH2) p -OH (where R 1 , R 2 and p as described above) and the alcohol represented by the general formula: CH2=C(-X)-C(=O)-YZL 11 (where X, Y and Z are as described above, L 11It is produced by reacting a compound represented by -OH, a halogen atom, -NH2 or -NCO).

[0047] General formula: R 1 -R 2 -(CH2) p The alcohol represented by -OH can be prepared by adding CHF=CHF to methanol. The general formula is: CH2F-CHF-(CHF-CHF) n -CH2OH (wherein n is an integer greater than 0) is produced by a method for producing an alcohol represented by -CH2OH (wherein n is an integer greater than 0).

[0048] n in alcohol represents the polymerization degree of CHF=CHF, and is an integer greater than or equal to 0. n is, for example, an integer of 0 to 23, and preferably an integer of 0 to 4.

[0049] The reaction of methanol and CHF=CHF can be carried out in the presence of a free radical initiator. When the reaction is carried out in the presence of a free radical initiator, the free radical initiator decomposes to generate free radicals, and the generated free radicals extract the hydrogen atom on the carbon to which the hydroxyl group of methanol is bonded, thereby generating methanol free radicals, and a reaction of adding CHF=CHF to the methanol free radical is carried out (so-called telomerization reaction).

[0050] As the free radical initiator, an organic peroxide is preferred, and examples thereof include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0051] The amount of CHF=CHF used is preferably 0.01 mol to 100 mol relative to 1 mol of methanol.

[0052] The amount of the radical initiator used is preferably 0.01 mol to 2 mol per 1 mol of methanol.

[0053] The reaction temperature of methanol and CHF=CHF can be appropriately selected, and is preferably -78°C to 200°C. The reaction temperature of methanol and CHF=CHF is preferably not less than the decomposition temperature of the radical polymerization initiator and preferably less than the decomposition temperature of the substrate and the product.

[0054] The pressure of the reaction of methanol and CHF=CHF can be appropriately selected, and is preferably 0 to 5.0 MPaG. The time of the reaction of methanol and CHF=CHF can be appropriately selected, and is preferably 0.1 to 96 hours.

[0055] In addition, the general formula: R 1 -R 2 -(CH2) pThe alcohol represented by -OH can be produced by a production method comprising the following steps:

[0056] Step (5), by reacting CHF=CHF with the general formula: X 1 I(X 1 H or F) to produce an iodinated compound represented by the general formula: R 1 -CHF-I (where R 1 A first fluorinated alkyl iodide represented by -CH2F or -CHF2) is prepared by adding CHF=CHF to the first fluorinated alkyl iodide to produce a compound of the general formula: R 1 -CHF-(CHF-CHF) n -I(where R 1 As described above, n is an integer greater than 1) represented by a second fluorinated alkyl iodide;

[0057] Step (6), adding ethylene to the first fluorinated alkyl iodide or the second fluorinated alkyl iodide to produce a compound of the general formula: 1 -CHF-(CHF-CHF) n -CH2CH2-I (where R 1 As described above, n is an integer greater than 0); and

[0058] Step (7), reacting the third fluorinated alkyl iodide with fuming sulfuric acid to hydrolyze the fluorinated alkyl iodide to produce a compound of the general formula: 1 -CHF-(CHF-CHF) n -CH2CH2-OH (where R 1 As described above, n is an integer greater than or equal to 0).

[0059] In step (5), CHF=CHF is reacted with a compound of the general formula: X 1 I(X 1 H or F) to produce an iodinated compound of the general formula: R 1 -CHF-I (where R 1 A first fluorinated alkyl iodide represented by -CH2F or -CHF2) is prepared by adding CHF=CHF to the first fluorinated alkyl iodide to produce a compound of the general formula: R 1 -CHF-(CHF-CHF) n -I(where R 1 As described above, the second fluorine-containing alkyl iodide represented by (n is an integer greater than 1).

[0060] The amount of the iodinated compound used is preferably 0.5 mol to 4 mol relative to 1 mol of CHF=CHF.

[0061] The reaction of CHF=CHF with the iodinated compound can be carried out without a solvent or in a solvent.

[0062] The reaction temperature of CHF=CHF and the iodide compound can be appropriately selected, preferably -78°C to 200°C. The reaction pressure of CHF=CHF and the iodide compound can be appropriately selected, preferably 0 to 5.0 MPaG. The reaction time of CHF=CHF and the iodide compound can be appropriately selected, preferably 0.1 hour to 96 hours.

[0063] Through the reaction of CHF=CHF with iodinated compounds, the general formula: R 1 -CHF-I (where R 1 In the step (5), CHF=CHF is then added to the first fluorine-containing alkyl iodide.

[0064] The reaction of the first fluorinated alkyl iodide and CHF=CHF is a telogenation reaction of a product having CHF=CHF as a main chain using the first fluorinated alkyl iodide as a telogen, and the second fluorinated alkyl iodide is produced by this reaction.

[0065] In the second fluorine-containing alkyl iodide, n represents the degree of polymerization of CHF=CHF, and is an integer greater than or equal to 1. n is preferably an integer of 1-24, and more preferably an integer of 1-5.

[0066] The reaction of the first fluorine-containing alkyl iodide and CHF=CHF may be carried out in the presence of a radical initiator. Examples of the radical initiator include organic peroxides and azo compounds.

[0067] Examples of the organic peroxide include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0068] Examples of the azo compound include azobisisobutyronitrile and the like.

[0069] The amount of CHF=CHF used is preferably 0.01 mol to 100 mol relative to 1 mol of the fluorine-containing alkyl iodide.

[0070] The amount of the radical initiator used is preferably 0.01 mol to 2 mol per 1 mol of the fluorine-containing alkyl iodide.

[0071] The reaction temperature of the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, and is preferably -78°C to 200°C. The reaction temperature of the first fluorinated alkyl iodide and CHF=CHF is preferably not less than the decomposition temperature of the radical polymerization initiator and preferably less than the decomposition temperature of the substrate and the product.

[0072] The pressure of the reaction of the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, and is preferably 0 to 5.0 MPaG. The time of the reaction of the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, and is preferably 0.1 to 96 hours.

[0073] In step (6), a compound of the general formula: R is prepared by step (5). 1 -CHF-(CHF-CHF) n -I(where R 1 As described above, after preparing the first fluorinated alkyl iodide or the second fluorinated alkyl iodide represented by (n is an integer greater than 0), ethylene is added to the first fluorinated alkyl iodide or the second fluorinated alkyl iodide to produce a compound of the general formula: 1 -CHF-(CHF-CHF) n -CH2CH2-I (where R 1 As described above, the third fluorine-containing alkyl iodide represented by (n is an integer greater than or equal to 0).

[0074] R of the third fluorinated alkyl iodide 1 and R of the first fluorinated alkyl iodide or the second fluorinated alkyl iodide 1 The same is -CH2F or -CHF2.

[0075] n of the third fluorine-containing alkyl iodide is an integer greater than or equal to 0. The preferred range of n of the third fluorine-containing alkyl iodide is preferably an integer of 0-24, and more preferably an integer of 0-5.

[0076] The reaction of the first fluorine-containing alkyl iodide or the second fluorine-containing alkyl iodide with ethylene can be carried out in the presence of a metal catalyst. Examples of the metal catalyst include copper and the like.

[0077] The reaction of the first fluorine-containing alkyl iodide or the second fluorine-containing alkyl iodide with ethylene may be carried out in the presence of a compound that generates free radicals. Examples of such a compound include organic peroxides and azo compounds.

[0078] Examples of the organic peroxide include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0079] Examples of the azo compound include azobisisobutyronitrile and the like.

[0080] The amount of ethylene used is preferably 0.01 mol to 100 mol per 1 mol of the first fluorine-containing alkyl iodide or the second fluorine-containing alkyl iodide.

[0081] The amount of the radical-generating compound used is preferably 0.001 mol to 1 mol per 1 mol of the first fluorine-containing alkyl iodide or the second fluorine-containing alkyl iodide.

[0082] The temperature of the reaction of the first fluorinated alkyl iodide or the second fluorinated alkyl iodide with ethylene can be appropriately selected, and is preferably 50° C. to 200° C. The pressure of the reaction of the first fluorinated alkyl iodide or the second fluorinated alkyl iodide with ethylene can be appropriately selected, and is preferably 0.1 MPaG to 5 MPaG. The time of the reaction of the first fluorinated alkyl iodide or the second fluorinated alkyl iodide with ethylene can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0083] In step (7), a compound of the general formula: R is prepared by step (6). 1 -CHF-(CHF-CHF) n -CH2CH2-I (where R 1 As described above, a third fluorinated alkyl iodide represented by (n is an integer greater than 0) is prepared, and the third fluorinated alkyl iodide is reacted with fuming sulfuric acid to hydrolyze the fluorinated alkyl iodide to produce a general formula: R 1 -CHF-(CHF-CHF) n -CH2CH2-OH (where R 1 As described above, n is an integer greater than or equal to 0).

[0084] R 1 With the third fluorinated alkyl iodide R 1 The same is -CH2F or -CHF2.

[0085] n of the alcohol is the same value as n of the third fluorine-containing alkyl iodide, and is an integer greater 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.

[0086] The content of sulfur trioxide in fuming sulfuric acid is not particularly limited, but is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and still more preferably 50 to 70% by mass.

[0087] The amount of oleum used is preferably 1 mol to 50 mol per mol of the third fluorine-containing alkyl iodide in terms of the amount equivalent to sulfur trioxide in the oleum.

[0088] The temperature of the reaction of the third fluorinated alkyl iodide with oleum can be appropriately selected, and is preferably 0 to 90° C. The pressure of the reaction of the third fluorinated alkyl iodide with oleum can be appropriately selected, and is preferably 0 to 10.0 MPaG. The time of the reaction of the third fluorinated alkyl iodide with oleum can be appropriately selected, and is preferably 0.1 to 96 hours.

[0089] In step (7), the third fluorinated alkyl iodide is reacted with fuming sulfuric acid to generate a compound of the general formula: 1 -CHF-(CHF-CHF) n -CH2CH2-OSO3H (where R 1 As described above, n is an integer greater than or equal to 0), and therefore, the fluorinated alkyl hydrosulfate is then hydrolyzed to produce a compound of the general formula: R 1 -CHF-(CHF-CHF) n -CH2CH2-OH (where R 1 As described above, n is an integer greater than or equal to 0).

[0090] The hydrolysis of the fluorinated alkyl hydrosulfate can be carried out using water or an aqueous sodium sulfite solution. The hydrolysis of the fluorinated alkyl hydrosulfate can be carried out by, for example, dropping an aqueous sodium sulfite solution into a solution (a solution containing the fluorinated alkyl hydrosulfate) obtained by the reaction of the third fluorinated alkyl iodide and fuming sulfuric acid.

[0091] The amount of water or sodium sulfite aqueous solution used is not particularly limited as long as it is an amount required to neutralize the solution obtained by the reaction of the third fluorinated alkyl iodide and fuming sulfuric acid and further hydrolyze the fluorinated alkyl hydrosulfate.

[0092] The temperature of the hydrolysis can be appropriately selected, and is preferably 15° C. to 100° C. The time of the hydrolysis can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0093] In addition, the general formula: R 1 -R 2 -(CH2) p The alcohol represented by -OH can be produced by a production method comprising the following steps:

[0094] Step (8), preparing a compound of the general formula: R by reacting CHF=CHF with I2 and IF5 1 -CHF-I (where R 1 A fourth fluorinated alkyl iodide represented by -CHF2 or -CHFI) is added with CHF=CHF to the fourth fluorinated alkyl iodide, thereby preparing a compound of the general formula: R 1 -CHF-(CHF-CHF) n -I(where R1 As described above, n is an integer greater than 1) represented by a fifth fluorinated alkyl iodide;

[0095] Step (9), comprising reacting the fourth fluorinated alkyl iodide or the fifth fluorinated alkyl iodide with a compound of the general formula: CH2=CH-(CH2) q -OH (wherein q is an integer greater than 1) to produce an unsaturated compound represented by the general formula: R 1 -CHF-(CHF-CHF) n -CH2-CHI-(CH2) q -OH (where R 1 As described above, n is an integer greater than or equal to 0, and q is an integer greater than or equal to 1).

[0096] In step (8), CHF=CHF is reacted with I2 and IF5 to produce a compound of the general formula: R 1 -CHF-I (where R 1 A fourth fluorinated alkyl iodide represented by -CHF2 or -CHFI) is added with CHF=CHF to the fourth fluorinated alkyl iodide, thereby preparing a compound of the general formula: R 1 -CHF-(CHF-CHF) n -I(where R 1 As described above, the fifth fluorine-containing alkyl iodide represented by (n is an integer greater than 1).

[0097] The usage-amount of I2 and IF5 is preferably 0.5 mol to 2 mol with respect to 1 mol of CHF=CHF.

[0098] The reaction of CHF=CHF with I2 and IF5 can be carried out in a solvent.

[0099] The temperature of the reaction of CHF=CHF with I2 and IF5 can be appropriately selected, preferably -78°C to 200°C. The pressure of the reaction of CHF=CHF with I2 and IF5 can be appropriately selected, preferably 0 to 5.0 MPaG. The time of the reaction of CHF=CHF with I2 and IF5 can be appropriately selected, preferably 0.1 hour to 96 hours.

[0100] The reaction of the fourth fluorinated alkyl iodide and CHF=CHF is a telomerization reaction using the fourth fluorinated alkyl iodide as a telogen and CHF=CHF as a main chain product, and the fifth fluorinated alkyl iodide is produced by this reaction.

[0101] In the fifth fluorine-containing alkyl iodide, n represents the polymerization degree of CHF=CHF and is an integer greater than 1. n is preferably an integer of 1-22, more preferably an integer of 1-7, further preferably an integer of 1-5, and particularly preferably an integer of 1-3.

[0102] The reaction of the fourth fluorine-containing alkyl iodide with CHF=CHF can be carried out in the presence of a radical initiator. Examples of the radical initiator include organic peroxides and azo compounds.

[0103] Examples of the organic peroxide include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0104] Examples of the azo compound include azobisisobutyronitrile and the like.

[0105] The amount of CHF=CHF used is preferably 0.01 mol to 100 mol relative to 1 mol of the fluorine-containing alkyl iodide.

[0106] The amount of the radical initiator used is preferably 0.01 mol to 2 mol per 1 mol of the fluorine-containing alkyl iodide.

[0107] The reaction temperature of the fourth fluorinated alkyl iodide and CHF=CHF can be appropriately selected, and is preferably -78°C to 200°C. The reaction temperature of the fourth fluorinated alkyl iodide and CHF=CHF is preferably not less than the decomposition temperature of the radical polymerization initiator and preferably less than the decomposition temperature of the substrate and the product.

[0108] The pressure of the reaction of the fourth fluorinated alkyl iodide with CHF=CHF can be appropriately selected, and is preferably 0 to 5.0 MPaG. The time of the reaction of the fourth fluorinated alkyl iodide with CHF=CHF can be appropriately selected, and is preferably 0.1 to 96 hours.

[0109] In step (9), the fourth fluorinated alkyl iodide or the fifth fluorinated alkyl iodide is reacted with an unsaturated compound represented by the general formula: CH2=CH-CH2-OH, thereby producing a compound represented by the general formula: R 1 -CHF-(CHF-CHF) n -CH2-CHI-(CH2) q -OH (where R 1 As described above, n is an integer greater than or equal to 0, and q is an integer greater than or equal to 1).

[0110] R 1 and the fourth fluorinated alkyl iodide or the fifth fluorinated alkyl iodide R 1 The same is -CHF2 or -CHFI.

[0111] n of the alcohol is an integer greater than or equal to 0. The preferred range of 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.

[0112] q of the alcohol is an integer of 1 or more. The preferred range of q of the alcohol is an integer of 1-24, preferably an integer of 1-18, and more preferably an integer of 1-12.

[0113] The reaction of the fourth fluorine-containing alkyl iodide or the fifth fluorine-containing alkyl iodide with the unsaturated compound may be carried out in the presence of a compound that generates free radicals. Examples of such a compound include organic peroxides and azo compounds.

[0114] Examples of the organic peroxide include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0115] Examples of the azo compound include azobisisobutyronitrile and the like.

[0116] The amount of the unsaturated compound used is preferably 0.01 mol to 100 mol per 1 mol of the fourth fluorine-containing alkyl iodide or the fifth fluorine-containing alkyl iodide.

[0117] The amount of the radical-generating compound used is preferably 0.001 mol to 1 mol per 1 mol of the fourth fluorine-containing alkyl iodide or the fifth fluorine-containing alkyl iodide.

[0118] The temperature of the reaction of the fourth fluorinated alkyl iodide or the fifth fluorinated alkyl iodide with the unsaturated compound can be appropriately selected, and is preferably 50° C. to 200° C. The pressure of the reaction of the fourth fluorinated alkyl iodide or the fifth fluorinated alkyl iodide with the unsaturated compound can be appropriately selected, and is preferably 0.1 MPaG to 5 MPaG. The time of the reaction of the fourth fluorinated alkyl iodide or the fifth fluorinated alkyl iodide with the unsaturated compound can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0119] The resulting alcohol can be reduced to produce a compound of the general formula: R 1 -CHF-(CHF-CHF) n -CH2-CH2-(CH2) q -OH (where R 1 The reduction can be carried out, for example, by using a metal catalyst and hydrogen, or by using zinc as a reducing agent.

[0120] (b) Non-fluorinated non-crosslinking monomer

[0121] The polymer disclosed herein may also have repeating units derived from a non-fluorine non-crosslinkable monomer (b). The non-fluorine non-crosslinkable monomer (b) is a monomer that does not contain fluorine atoms and cannot be crosslinked (or does not have a crosslinkable functional group). The non-fluorine non-crosslinkable monomer (b) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (b) is preferably a fluorine-free vinyl monomer. The non-fluorine non-crosslinkable monomer (b) is generally a compound having one carbon-carbon double bond.

[0122] The preferred non-fluorine-free non-crosslinking monomer (b) is represented by the general formula: CH2=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 chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 20 carbon atoms having an ester bond, an amide bond, a carbamate bond, or a urea bond).

[0123] Examples of the chain or cyclic hydrocarbon group having 1 to 30 carbon atoms include a straight chain or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, a cyclic aliphatic 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 a long chain hydrocarbon group having 12 to 30 carbon atoms and a saturated cyclic hydrocarbon group.

[0124] Examples of chain or cyclic organic groups having 1 to 30 carbon atoms and having an ester bond are -C(=O)-OQ and -OC(=O)-Q (here, Q is a straight-chain or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic 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).

[0125] Examples of chain or cyclic organic groups having 1 to 20 carbon atoms and having an amide bond, a urethane bond or a urea bond are -C(=O)-NH-Q, -NH-C(=O)-Q, -NH-C(=O)-OQ, -OC(=O)-NH-Q and -NH-CO-NH-Q (where Q is a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic 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).

[0126] Preferred examples of the non-fluorine-free non-crosslinking monomer (b) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, and vinyl alkyl ether. The non-fluorine-free non-crosslinking monomer (b) is not limited to these examples.

[0127] The non-fluorine-free non-crosslinking monomer (b) may be a (meth)acrylate 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 non-fluorine-free non-crosslinking monomer (b) may be of the general formula: CH2=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 (such as a chlorine atom, a bromine atom, and an iodine atom), 2 C n H 2n+1 Acrylic acid esters represented by an alkyl group represented by (n=1 to 30).

[0128] The non-fluorine-free non-crosslinking 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, bridged ring groups, and the like. The cyclic hydrocarbon group is preferably a saturated cyclic hydrocarbon group. The number of carbon atoms in the cyclic hydrocarbon group is preferably 4 to 20. Examples of the cyclic hydrocarbon group include cyclic aliphatic groups having 4 to 20 carbon atoms, especially 5 to 12 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and aromatic aliphatic groups having 7 to 20 carbon atoms. The number of carbon atoms in the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 10 or less. The carbon atoms on the ring of the cyclic hydrocarbon group are preferably 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 are cyclohexyl, tert-butylcyclohexyl, isobornyl, dicyclopentyl, and dicyclopentenyl. The (meth)acrylate group is an acrylate group or a methacrylate group, preferably a methacrylate group. Specific examples of monomers having a cyclic hydrocarbon group include cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentyl methacrylate, dicyclopentyl acrylate, and dicyclopentenyl acrylate.

[0129] The polymer disclosed herein may have a repeating unit derived from a non-fluorine-containing monomer having a long-chain hydrocarbon group as a repeating unit derived from the non-fluorine-free non-crosslinking monomer (b).

[0130] The non-fluorine monomer containing a long-chain hydrocarbon group does not have a fluoroalkyl group. The non-fluorine monomer containing a long-chain hydrocarbon group does not contain a fluorine atom.

[0131] The long-chain hydrocarbon group is a saturated or unsaturated group. The long-chain hydrocarbon group is preferably a saturated hydrocarbon group, and particularly preferably an alkyl group.

[0132] The long-chain hydrocarbon group is preferably a straight-chain or branched hydrocarbon group having 7 to 40 carbon atoms. The straight-chain or branched hydrocarbon group may have 10 to 40 carbon atoms, 12 to 40 carbon atoms, or 18 to 40 carbon atoms. The straight-chain or branched hydrocarbon group is preferably 12 to 40, more preferably 12 to 30, particularly preferably 18 to 28, particularly preferably 18 to 22 (or 18 to 24), and is usually preferably a saturated aliphatic hydrocarbon group, particularly an alkyl group. The long-chain hydrocarbon group is particularly preferably a stearyl group, an eicosyl group, or a behenyl group.

[0133] As the non-fluorinated monomer containing a long-chain hydrocarbon group, the preferred general formula is: CH2=C(-X 11 )-C(=O)-Y 11 -R 11 n (Where 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-, R 11 is a hydrocarbon group having 7 to 40 carbon atoms, and n is an integer of 1 to 3).

[0134] X 11 X may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 11 Examples of X are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, and cyano group. 11 Preferred are a hydrogen atom, a methyl group and a chlorine atom.

[0135] Y 11 Y is a single bond or a divalent to tetravalent group. 11 Preferably it is a single bond or a divalent group. 11 Preferably, it is a divalent group containing at least one group selected from -O-, -NH-, or -O- and -NH-, and at least one group selected from a hydrocarbon group having 1 carbon atom, -C6H6-, -C(=O)-, and -S(C=O)2-. Examples of the hydrocarbon group having 1 carbon atom include -CH2-, -CH=, or -C≡.

[0136] Y as a divalent group 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'-(where Y' is -O- or -NH-, R' is -(CH2) m-(m is an integer from 1 to 5) or -C6H6-(phenylene)).

[0137] Y as a divalent group 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-C6H6-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H6-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H6-, -NH-(CH2) m -NH-C6H6- (in each formula, m is an integer of 1 to 5, particularly 2 or 4).

[0138] Y as a divalent group 11 More preferably, -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m-OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH- (in each formula, m is an integer of 1 to 5, particularly 2 or 4) 11 Particularly preferred is -O-(CH2) m -NH-C(=O)-.

[0139] Y as a divalent group 11 Particularly preferred are -O-, -NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH- (in each formula, m is an integer of 1 to 5, particularly 2 or 4).

[0140] R 11 It is preferably a straight-chain or branched hydrocarbon group. The hydrocarbon group may be a straight-chain hydrocarbon group in particular. The hydrocarbon group is preferably an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group, in particular an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, in particular 18 to 22.

[0141] n is an integer of 1 to 3, and is preferably 1.

[0142] In Y 11 In the case of a tetravalent hydrocarbon group having 1 carbon atom, n=3 is preferred. 11 In the case of a trivalent hydrocarbon group having 1 carbon atom, n=2 is preferred. 11 When there is no trivalent or tetravalent hydrocarbon group having 1 carbon atom, n=1.

[0143] Examples of non-fluorinated monomers containing long chain hydrocarbon groups are *

[0144] (b1) an acrylic monomer comprising 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

[0145] (b2) An acrylic monomer comprising 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.

[0146] The acrylic monomer (b2) is a compound different from the acrylic monomer (b1).

[0147] The acrylic monomer (b2) may be a (meth)acrylate or (meth)acrylamide having an amide group (not directly bonded to C(=O)-O- or C(=O)-NH- but directly bonded to a hydrocarbon group having 7 to 40 carbon atoms), a urethane group or a urea group. The acrylic monomer (b2) is preferably an acrylate containing, in addition to the divalent group represented by -C(=O)-O- or -C(=O)-NH-, an amide group not directly bonded to the divalent group (i.e., an amide group bonded to the divalent group via another group) and an amide group directly bonded to a hydrocarbon group having 7 to 40 carbon atoms.

[0148] (b1) Acrylic monomer

[0149] The acrylic monomer (b1) is preferably of the general formula: CH2=C(-X 111 )-C(=O)-Y 111 -R 111 (Where X 111 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 111 is -O- or -NH-, R 111 is a hydrocarbon group having 7 to 40 carbon atoms).

[0150] The acrylic monomer (b1) is Y 111 A long-chain acrylic ester monomer of -O-, or Y 111 It is a long-chain acrylamide monomer with -NH-.

[0151] X 111 X may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 111 Examples of X are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, and cyano group. 111 Preferred are a hydrogen atom, a methyl group and a chlorine atom.

[0152] Y 111 It is -O- or -NH-.

[0153] R 111 Preferably, it is a straight-chain or branched hydrocarbon group. The hydrocarbon group may be a straight-chain hydrocarbon group in particular. The hydrocarbon group is preferably an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group, in particular an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, in particular 18 to 22 (or 18 to 24).

[0154] Specific examples of the long-chain acrylic acid ester monomers include lauryl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate, and behenyl α-chloroacrylate.

[0155] Specific examples of the long-chain acrylamide monomer include lauryl (meth)acrylamide, stearyl (meth)acrylamide, eicosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0156] (b2) Acrylic monomer

[0157] The acrylic monomer (b2) may be a (meth)acrylate or (meth)acrylamide having a divalent to tetravalent connecting group between C(=O)-O- or C(=O)-NH- and a hydrocarbon group having 7 to 40 carbon atoms, wherein the divalent to tetravalent connecting group has at least one group selected from -O- and -NH-.

[0158] The acrylic monomer (b2) is preferably of the general formula: CH2=C(-X 112 )-C(=O)-Y 112 -Z 111 (-Z 112 -R 112 ) p (Where X 112 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 112 is -O- or -NH-, Z 111 is a directly bonded, divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, Z 112 Each independently represents a direct bond, a divalent to tetravalent linking group having at least one group selected from -O- and -NH-, R 112 Each independently represents a hydrocarbon group having 7 to 40 carbon atoms, and p is 1 or 2).

[0159] The acrylic monomer (b2) is Y 112 A long-chain acrylic ester monomer of -O-, or Y 112 It is a long-chain acrylamide monomer with -NH-.

[0160] X 112 X 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 hydrogen, methyl, chlorine, bromine, iodine, and cyano. The less rigid the main chain of the resulting polymer is, the less it hinders the crystallinity of the side chain. 112 Preferred are a hydrogen atom, a methyl group and a chlorine atom, more preferred are a hydrogen atom and a methyl group, and particularly preferred are a hydrogen atom.

[0161] Y 112 It is -O- or -NH-.

[0162] Z 111 It is a direct bond, a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms (particularly an alkyl group), and may have a branched structure. 111 The number of carbon atoms in Z is preferably 2 to 4, particularly preferably 2. 111 Specific examples include a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, and -CH2CH2CH2CH2CH2- as divalent groups, and -CH2CH=, -CH2(CH-)CH2-, -CH2CH2CH=, -CH2CH2CH2CH2CH=, -CH2CH2(CH-)CH2-, and -CH2CH2CH2CH= (as trivalent groups) having a branched structure. 111 Preferably, it is not a direct bond.

[0163] Z 112 Specific examples are direct bonds, -O-, -NH-, -(O) k -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -(O)kC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -(O)k-C6H6-, -(O)k-(CH2) m -O-, -NH-(CH2) m -NH-, -(O)k-(CH2) m -NH-, -NH-(CH2) m -O-, -(O)k-(CH2) m -OC(=O)-, -(O)k-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -(O)k-(CH2) m -OC(=O)-NH-, -(O)k-(CH2) m -NH-C(=O)-O-, -(O)k-(CH2) m -C(=O)-NH-, -(O)k-(CH2) m -NH-C(=O)-, -(O)k-(CH2) m -NH-C(=O)-NH-, -(O)k-(CH2) m-O-C6H6-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H6-, -NH-(CH2) m -NH-C6H6- (in each formula, k is 0 or 1, and m is an integer of 1 to 5, particularly 2 or 4), etc.

[0164] Z 112 Particularly preferred is -(O) k -、-NH-、-(O) k -(CH2) m -OC(=O)-, -(O)k-(CH2) m -NH-C(=O)-, -(O)k-(CH2) m -OC(=O)-NH-, -(O)k-(CH2) m -NH-C(=O)-O-, -(O) k -(CH2) m -NH-C(=O)-NH- (in each formula, k is 0 or 1, and m is an integer of 1 to 5, particularly 2 or 4).

[0165] Z 111 and Z 112 Not directly bonded at the same time.

[0166] R 112 Preferably, it is a straight-chain or branched hydrocarbon group. The hydrocarbon group may be a straight-chain hydrocarbon group in particular. The hydrocarbon group is preferably an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group, in particular an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, in particular 18 to 22 (or 18 to 24).

[0167] The acrylic monomer (b2) is preferably CH2=C(-X 112 )-C(=O)-O-(CH2) m -NH-C(=O)-R 112 、CH2=C(-X 112 )-C(=O)-OR 112 or a combination thereof (here, X 112 , m and R 112The acrylic monomer (b2) is particularly preferably CH2=C(-X 112 )-C(=O)-O-(CH2) m -NH-C(=O)-R 112 .

[0168] 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 the long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate.

[0169] Alternatively, the acrylic monomer (b2) can also be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl isocyanate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of the long-chain alkylamine include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0170] Specific examples of the acrylic monomer (b2) are as follows: The compound of the following chemical formula is an acrylic acid ester having a hydrogen atom at the α-position, and specific examples thereof include methacrylic acid ester having a methyl group at the α-position and acrylic acid ester having a chlorine atom at the α-position.

[0171] [Chemistry 1]

[0172] yes:

[0173]

[0174] (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.

[0175] Representative specific examples of the acrylic monomer (b2) include palmitamide ethyl (meth)acrylate, stearamide ethyl (meth)acrylate, behenamide ethyl (meth)acrylate, and myristamide ethyl (meth)acrylate.

[0176] The acrylic monomer (b2) is particularly preferably a monomer of the general formula: R 22 -C(=O)-NH-R 23 -OR 21 (Where R 21 is an organic residue having an ethylenically unsaturated polymerizable group, R 22 is a hydrocarbon group having 7 to 40 carbon atoms, R 23 An amide group-containing monomer represented by (a) is a hydrocarbon group having 1 to 5 carbon atoms.

[0177] R 21 It is an organic residue having an ethylenically unsaturated polymerizable group and is not particularly limited as long as it has a double bond between carbon atoms. Specific examples thereof include -C(=O)CR 24 =CH2, -CHR 24 =CH2, -CH2CHR 24 = an organic residue having an ethylenically unsaturated polymerizable group such as CH2, R 24 Examples thereof include a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. 21 In addition to the ethylenically unsaturated polymerizable group, it may also have various organic groups, for example, organic groups such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, polysiloxane groups, etc., and these organic groups may be substituted with various substituents. 21 Preferably -C(=O)CR 24 =CH2.

[0178] R 22 It is a hydrocarbon group having 7 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbons and cyclic hydrocarbons. Among them, chain hydrocarbons are preferred, and straight-chain saturated hydrocarbon groups are particularly preferred. 22 The carbon number of the moiety is 7-40, preferably 11-27, and particularly preferably 15-23.

[0179] 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 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 An alkylene group is preferred.

[0180] The monomer containing an amide group may be R 21 For a single monomer (e.g., only R 21 is a compound with 17 carbon atoms), or R 21 A monomer that is a combination of multiple monomers (for example, R 21 The compound with 17 carbon atoms and R 21 A mixture of compounds having 15 carbon atoms).

[0181] An example of the amide group-containing monomer is carboxamide alkyl (meth)acrylate.

[0182] Specific examples of the amide group-containing monomer include palmitamide ethyl (meth)acrylate, stearamide ethyl (meth)acrylate, behenamide ethyl (meth)acrylate, myristamide ethyl (meth)acrylate, lauramide ethyl (meth)acrylate, isostearic acid ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tert-butylcyclohexylhexanamide ethyl (meth)acrylate, adamantanecarboxylic acid ethyl amide (meth)acrylate, naphthylcarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitamide propyl (meth)acrylate, stearamide propyl (meth)acrylate, palmitamide ethyl vinyl ether, stearamide ethyl vinyl ether, palmitamide ethyl allyl ether, stearamide ethyl allyl ether, or a mixture thereof.

[0183] 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% by weight, preferably 60% to 85% by weight, and more preferably 65% ​​to 80% by weight, relative to the weight of the entire amide group-containing monomer, and the remaining monomer may be, for example, palmitamideethyl (meth) acrylate.

[0184] (c) Non-fluorinated crosslinking monomer

[0185] The polymer disclosed herein may have a repeating unit derived from a non-fluorine crosslinking monomer (c). The non-fluorine crosslinking monomer (c) is a monomer that does not contain fluorine atoms and can be crosslinked. The non-fluorine crosslinking monomer (c) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and does not contain fluorine. The non-fluorine crosslinking 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 reactive groups are hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, carboxyl, etc. The non-fluorine crosslinking monomer (c) may be a mono(meth)acrylate, (meth)diacrylate or mono(meth)acrylamide having a reactive group. Alternatively, the non-fluorine crosslinking monomer (c) may be a di(meth)acrylate.

[0186] Examples of the non-fluorine-containing crosslinking 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.

[0187] (d) Halogenated olefin monomers

[0188] The polymer disclosed in the present invention may have a repeating unit derived from a halogenated olefin monomer (d) (except 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, and particularly preferably 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.

[0189] The polymer disclosed herein may be formed from a monomer raw material, the monomer raw material comprising a monomer (a), and optionally at least one selected from the group consisting of (b), (c) and (d). With respect to the polymer, the monomer (a) and, if present, (b), (c) and (d) (more specifically, repeating units derived from these monomers, the same below) may each be one kind, or may be a mixture of two or more kinds.

[0190] As an example of the mass ratio of each monomer in the polymer, the total of monomers (a) to (d) is 100 mass %.

[0191] The proportion of the monomer (a) may be 0.1% to 99.9% by mass, for example, 20% to 90% by mass, particularly 50% to 80% by mass.

[0192] The proportion of the monomer (b) may be 0 to 99.8% by mass, for example, 0.5 to 50% by mass, particularly 1 to 30% by mass.

[0193] The proportion of the monomer (c) may be 0 to 99.8% by mass, for example, 0.1 to 10% by mass, particularly 0.1 to 5% by mass.

[0194] The proportion of the monomer (d) may be 0 to 99.8% by mass, for example, 0.5 to 50% by mass, particularly 1 to 30% by mass.

[0195] In addition, these mass ratios are considered to be equal to each mass ratio in the total of the monomers used as the raw material of the polymer (first monomer raw material).

[0196] In the present disclosure, the molecular weight of the polymer is not particularly limited, but the mass average molecular weight determined by gel permeation chromatography in terms of polystyrene is, for example, 3,000 or more, and preferably in the range of 5,000 to 1,500,000.

[0197] The polymer disclosed in the present invention can be produced by any common polymerization method, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0198] In solution polymerization, the following method is adopted: in the presence of a polymerization initiator, a monomer is dissolved in an organic solvent, nitrogen substitution is performed, and then heating and stirring are performed at a range of 30° C. to 120° C. for 1 to 10 hours. As the polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, etc. can be cited. The polymerization initiator is used in a range of 0.01 to 20 parts by mass, for example, 0.01 to 10 parts by mass, relative to 100 parts by mass of the monomer.

[0199] The organic solvent is a substance that is inactive to the monomer but can dissolve it, and may be, for example, an ester (e.g., an ester having 2 to 30 carbon atoms, specifically, ethyl acetate and butyl acetate), a ketone (e.g., a ketone having 2 to 30 carbon atoms, specifically, methyl ethyl ketone and 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, trichlorotrifluoroethane, and the like. The organic solvent is used in an amount of 10 to 2000 parts by mass, for example, 50 to 100 parts by mass, based on 100 parts by mass of the total monomers.

[0200] In the emulsion polymerization, a method is adopted 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° C. to 80° C. for 1 to 10 hours. As the polymerization initiator, a water-soluble polymerization initiator such as benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutyramidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[2-(2-imidazol-2-yl)propane]dihydrochloride or an oil-soluble polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, 2,2'-azobis[2-(2-imidazol-2-yl)propane] is used. The polymerization initiator is used in an amount within a range of 0.01 to 10 parts by mass based on 100 parts by mass of the monomer.

[0201] In order to obtain an aqueous polymer dispersion having excellent shelf stability, it is preferred to use an emulsifying device such as a high-pressure homogenizer or an ultrasonic homogenizer that can impart strong crushing energy to micronize the monomer in water and polymerize it. In addition, as an emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and are used in the range of 0.5 to 20 parts by mass relative to 100 parts by mass of the monomer. Anionic and / or nonionic and / or cationic emulsifiers are preferably used. In the case where the monomers are not completely compatible, it is preferred to add a compatibilizer that makes these monomers fully compatible, for example, a water-soluble organic solvent or a low molecular weight monomer is added. By adding a compatibilizer, emulsification and copolymerizability can be improved.

[0202] As the water-soluble organic solvent, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. can be mentioned, and can be used in the range of 1 to 50 parts by mass, for example, 10 to 40 parts by mass, relative to 100 parts by mass of water. In addition, as the low molecular weight monomer, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc. can be mentioned, and can be used in the range of 1 to 50 parts by mass, for example, 10 to 40 parts by mass, relative to 100 parts by mass of the total amount of the monomer.

[0203] In the polymerization, a chain transfer agent may also be used. The molecular weight of the polymer can be changed by the amount of the chain transfer agent used. Examples of chain transfer agents include mercapto-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly (e.g., alkyl mercaptan having 1 to 30 carbon atoms), sodium hypophosphite, sodium bisulfite and other inorganic salts. The amount of the 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, relative to 100 parts by mass of the total amount of the monomer.

[0204] The water- and oil-repellent composition disclosed herein contains the above-mentioned polymer and a medium. The water- and oil-repellent composition disclosed herein imparts excellent water repellency or oil resistance to a substrate, preferably imparts excellent water repellency and oil resistance to a substrate.

[0205] The water-repellent and oil-resistant composition disclosed herein can be in the form of a solution, an emulsion (especially a water-dispersible composition) or an aerosol, preferably a solution or a water-dispersible composition, and more preferably a water-dispersible composition. The water-repellent and oil-resistant composition comprises a polymer (an active ingredient of the water-repellent and oil-resistant composition) and a medium (especially a liquid medium, such as an organic solvent and / or water). The amount of the medium can be, for example, 5% to 99.9% by weight, especially 10% to 80% by weight, relative to the water-repellent and oil-resistant composition. In the water-repellent and oil-resistant composition, the concentration of the polymer can be 0.01% to 95% by weight, for example, 5% to 50% by weight.

[0206] 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.

[0207] When the water-repellent and oil-resistant composition of the present invention is an external treatment agent, it can be applied to the treated object by existing known methods. Usually, the water-repellent and oil-resistant composition is dispersed in an organic solvent or water for dilution, and is attached to the surface of the treated object and dried by known methods such as dip coating, spray coating, foam coating, etc. In addition, if necessary, it can also be used together with a suitable cross-linking agent (such as blocked isocyanate) and cured. Furthermore, in the water-repellent and oil-resistant composition of the present invention, insect repellents, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixatives, wrinkle-proofing agents, etc. can also be added and used simultaneously. The concentration of the polymer in the treatment liquid in contact with the treated object can be 0.01% by weight to 10% by weight (especially in the case of dip coating), for example, 0.05% by weight to 10% by weight.

[0208] As the treated object treated with the treatment agent composition (water-repellent and oil-resistant composition) of the present disclosure, fiber products, stone materials, filters (e.g., electrostatic filters), dust covers, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, coatings and plaster, etc. can be cited. Various examples can be cited as fiber products. For example, natural fibers of animals and plants such as cotton, hemp, wool, silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers, carbon fibers, asbestos fibers, or mixed fibers thereof can be cited.

[0209] The fiber product may be in any form such as fiber or cloth.

[0210] The water- and oil-repellent composition disclosed herein can also be used as an antifouling agent, a stripping agent, or a release agent (e.g., an internal release agent or an external release agent). For example, the surface of a substrate can be easily stripped from another surface (another surface of the substrate, or a surface of another substrate).

[0211] The polymer can be applied to a fibrous substrate (e.g., a fiber product) by any known method for treating a fiber product with a liquid. When the fiber product is a cloth, the cloth can be immersed in the solution, or the solution can be attached or sprayed on the cloth. The treated fiber product is dried to exert water repellency or oil resistance, preferably heated at 100° C. to 200° C., for example.

[0212] Alternatively, the polymer may be applied to the fiber article by a washing process, for example, by washing or in a dry washing process or the like.

[0213] Typical fiber products to be processed are cloth, including woven fabrics, knitted fabrics and non-woven fabrics, cloth in the form of clothing and carpets, and may also be fibers or yarns or intermediate fiber products (such as fiber strips or rovings, etc.). The fiber product material may be natural fibers (such as cotton or wool, etc.), chemical fibers (such as viscose or lyocell, etc.), or synthetic fibers (such as polyester, polyamide or acrylic fibers, etc.), or a mixture of fibers (such as a mixture of natural fibers and synthetic fibers, etc.). The fiber product is preferably a carpet.

[0214] Alternatively, the fibrous substrate may be leather. In order to render the leather hydrophobic and oleophobic, the manufacturing polymer may be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, for example during wet processing of the leather, or during final treatment of the leather.

[0215] Alternatively, the fibrous substrate may be paper.The manufacturing polymer may be applied to a preformed paper or it may be applied at various stages of papermaking, for example during drying of the paper.

[0216] "Treatment" means applying a treatment agent to the object to be treated by dipping, spraying, coating, etc. Through the treatment, the polymer as an 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.

[0217] When the water- and oil-repellent 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-repellent composition can be used when manufacturing a molded body of a resin.

[0218] The polymer is obtained by removing the liquid medium from the liquid (solution or dispersion) containing the polymer. For example, the polymer dispersion (aqueous dispersion or organic solvent dispersion) is reprecipitated with water or an organic solvent and then dried to obtain the polymer.

[0219] For example, the molded article can be produced by a production method including a step of mixing a resin and a polymer to obtain a resin composition and a step of molding the resin composition. The molded article is preferably produced by melt kneading using an extruder or the like.

[0220] Usually, thermoplastic resins and polymers are compatible in a molten state. Mixing can be carried out by existing known methods such as single-screw extruders, twin-screw extruders, rollers, etc. The resin composition thus obtained is molded by extrusion molding, injection molding, compression molding, blow molding, pressurization, etc. The resin composition can be molded into molded bodies of various shapes. The obtained molded body can be further heat-treated using an oven, a drying furnace, etc. after the molding process. The molded product can be a single layer, or it can be a multilayer of 2 to 10 layers, for example, 3 to 5 layers.

[0221] The molded body can be used in the use of thermoplastic resin, especially preferably with excellent wiping ease and excellent scratch resistance for dirt. The use of the molded body includes automobiles (exterior parts and interior parts) (such as bumpers, dashboards, door trims), household electrical products (such as washing machines and refrigerators) (such as housings, doors in refrigerators, trays, vegetable compartment containers), various boxes, buildings (interiors and parts) (such as handrails, wallpapers, tables, chairs, toilets and toilet covers, bathtubs), electronic devices (such as housings of smart phones), drains, pipes, tableware, floor materials, gasoline tanks, fuel pipes, OA equipment, etc. Among them, the interior parts of automobiles, the interior parts of household electrical products, and buildings are further preferred.

[0222] Although the embodiments have been described above, it should be understood that various modifications may be made to the embodiments and details without departing from the spirit and scope of the claims.

[0223] The main embodiments of the present disclosure are as follows.

[0224] <1> According to a first aspect of the present disclosure, there is provided a polymer having a general formula: R 1 -R 2 -(CH2) p -OR 3 The repeating unit is derived from the monomer (a) shown.

[0225] (Where,

[0226] R 1 is -CH3, -CH2F, -CHF2, -CH2I or -CHFI,

[0227] R 2 is an alkylene group having 1 to 49 carbon atoms consisting only of a unit represented by -CFH-, or an alkylene group having 2 to 49 carbon atoms consisting only of a unit represented by -CFH- and a unit represented by -CH2-, or an alkylene group having 3 to 49 carbon atoms consisting only of a unit represented by -CFH-, a unit represented by -CH2-, and a unit represented by -CHI-,

[0228] p is an integer from 0 to 2,

[0229] R 3 is an organic residue having an ethylenically unsaturated polymerizable group)

[0230] <2> According to a second aspect of the present disclosure, there is provided a polymer according to the first aspect, wherein R 2 It is an alkylene group having 2 to 10 carbon atoms.

[0231] <3> According to a third aspect of the present disclosure, there is provided a polymer according to the first aspect or the second aspect, wherein R 2 The general formula is: -(CFH) n1 - the alkylene group shown.

[0232] (where n1 is an integer from 2 to 10)

[0233] <4> According to a fourth aspect of the present disclosure, there is provided a polymer according to any one of the first aspect to the third aspect, wherein R 3 It is a group represented by the general formula: CH2=C(-X)-C(=O)-YZ-.

[0234] (Where,

[0235] X is a hydrogen atom, a methyl group or a halogen atom,

[0236] Y is -O- or -NH-,

[0237] Z is a direct bond or a divalent organic group)

[0238] <5> According to a fifth aspect of the present disclosure, there is provided a polymer based on the fourth aspect, wherein 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, -(CH2) m -N(R 1 )SO2-(CH2) n -yl, -CH2CH(OZ 1 )CH2-, -CH2CH(OZ 1 )CH2-(Ph-O)-, -(CH2) n -Ph-O- group, -(CH2) m -SO2-(CH2) n -yl, -(CH2) m -OC(=O)N(R 1 )-(CH2) n -yl, -(CH2) m -N(R 1 )C(=O)O-(CH2) n -yl, -(CH2) m -C(=O)N(R 1 )-(CH2) n -yl, -(CH2) m -(R 1 )NC(=O)-(CH2) n -yl, -(CH2) m -(R 1 )NC(=O)N(R 1 )-(CH2) n -yl, or -(CH2) m -S-(CH2) 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).

[0239] <6> According to a sixth aspect of the present disclosure, there is provided a polymer according to any one of the first to fifth aspects, wherein the polymer further contains at least one repeating unit derived from the group consisting of (b) a non-fluorine-free non-crosslinkable monomer, (c) a non-fluorine-free crosslinkable monomer, and (d) a halogenated olefin monomer.

[0240] <7> According to a seventh aspect of the present disclosure, there is provided a polymer according to any one of the first aspect to the sixth aspect, wherein the polymer further comprises a 11 )-C(=O)-Y 11 -R 11 n Repeating units derived from the monomers shown.

[0241] (Where,

[0242] X 11 is a hydrogen atom, a methyl group or a halogen atom,

[0243] Y 11 is a divalent to tetravalent linking group having at least one group selected from -O- and -NH-,

[0244] R 11 is a hydrocarbon group having 7 to 40 carbon atoms,

[0245] n is an integer from 1 to 3)

[0246] <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.

[0247] <9> According to a ninth aspect of the present disclosure, there is provided the 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.

[0248] <10> According to a tenth aspect of the present disclosure, there is provided the water and oil repellent composition according to the eighth aspect or the ninth aspect, which is a water-dispersible composition.

[0249] <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.

[0250] <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 aspect to the eleventh aspect.

[0251] <13> According to a 13th aspect of the present disclosure, there is provided a fiber product treated with the water- and oil-repellent composition according to any one of the 8th to 11th aspects.

[0252] Example

[0253] Next, the embodiments of the present disclosure will be described with reference to experimental examples, but the present disclosure is not limited to the experimental examples.

[0254] Experimental Example 1 Synthesis of 1,1,2-trifluoro-2-iodoethane

[0255] 37.1 g of iodine and 16.1 g of IF5 were added to a 300 mL pressure-resistant container, and the container was sealed. After the container was cooled to -78°C, 10 g of (E)-1,2-difluoroethylene was introduced into the container, and the container was heated at 80°C for 20 hours. After the container was cooled with ice water, the contents of the pressure-resistant container were washed with water, and then further washed with a 5% Na2S2O4 aqueous solution to obtain 5.8 g of the title compound.

[0256] 19 F NMR (282MHz, CDCl3): δ-169.1~-169.4(m,1F), -124.0~-124.3(m,1F).

[0257] 1 H NMR (400MHz, CDCl3): δ6.79 (d with fine coupling, J=48.0Hz, 1H), 7.26 (tdwith fine coupling, J=54.8, 3.6Hz, 1H).

[0258] LRMS (EI 70eV) m / z (%): 210 (M+, 100), 190 (8), 171 (3), 83 (62), 64 (37), 51 (14).

[0259] Experimental Example 2 Synthesis of 4,5,5-trifluoro-2-iodopentanol

[0260] 1.84 g of 1,1,2-trifluoro-2-iodoethane, 509 mg of allyl alcohol, and 288 mg of azobisisobutyronitrile were added to a 10 mL pressure vessel. The vessel was then heated at 80° C. for 22 hours. The vessel was cooled with ice water, and the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The result showed that the title compound was generated at an area ratio of 75.9% relative to the area ratio of 24.1% of the raw material 1,1,2-trifluoro-2-iodoethane.

[0261] LRMS (EI 70eV) m / z (%): 268 (M+, 1), 251 (1), 185 (2), 141 (95), 73 (100), 51 (38).

[0262] Experimental Example 3 Synthesis of 7,8,8-trifluoro-5-iodooctan-1-ol

[0263] 1.00 g of 1,1,2-trifluoro-2-iodoethane, 477 mg of 5-hexene-1-ol, and 235 mg of azobisisobutyronitrile were added to a 10 mL pressure vessel. The vessel was then heated at 80° C. for 22 hours. The vessel was cooled with ice water, and the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The result showed that the title compound was generated with an area ratio of 66.8% (total of two isomers) relative to the area ratio of 37.2% of the raw material 1,1,2-trifluoro-2-iodoethane.

[0264] LRMS (EI 70eV) m / z (%): 293 ([M-OH]+, 100), 259 (5), 207 (25), 207 (25), 155 (34).

[0265] Experimental Example 4 Synthesis of 4,5,5-trifluoro-2-iodopentane methacrylate

[0266] 200 mg of 4,5,5-trifluoro-2-iodopentanol was added to a 10 mL glass container. After nitrogen substitution, 1.1 mL of dichloromethane and 0.15 mL of pyridine were added to the container. After cooling the container to 0°C, 0.18 mL of methacryloyl chloride was added and stirred for 1 hour. The contents were analyzed by gas chromatography-mass spectrometry. The result showed that the title compound was generated with an area ratio of 77.7% (total of 2 isomers) relative to the area ratio of 22.3 of the raw material 4,5,5-trifluoro-2-iodopentanol.

[0267] LRMS (EI 70eV) m / z (%): 250 ([M-CH2=C(Me)COO]+, 100), 209 (95), 69 (90).

[0268] Experimental Example 5 Synthesis of 7,8,8-trifluorooctane-1-ol

[0269] In a 10 mL glass container, 67.5 mg of zinc was added to a mixed solution of 200 mg of 7,8,8-trifluoro-5-iodooctane-1-ol and 0.4 mL of methanol. 0.33 mL of 2M aqueous hydrochloric acid solution was added. After stirring for 6 hours, the contents were analyzed by gas chromatography-mass spectrometry. The result showed that the title compound was generated with an area ratio of 75.6% relative to the area ratio of 24.4% of the raw material 7,8,8-trifluoro-5-iodooctane-1-ol.

[0270] LRMS (EI 70eV) m / z (%): 167 ([M-OH]+, 100), 127 (54), 51 (4).

[0271] Experimental Example 6 Synthesis of 7,8,8-trifluorooctane methacrylate

[0272] 119 mg of 7,8,8-trifluorooctane-1-ol was added to a 10 mL glass container. After nitrogen substitution, 0.6 mL of dichloromethane and 51.3 μL of pyridine were added to the container. The container was cooled to 0°C, 62.4 μL of methacryloyl chloride was added, and stirred for 1 hour. The contents were analyzed by gas chromatography-mass spectrometry, and the raw materials disappeared, and the title compound was generated.

[0273] LRMS(EI 70eV)m / z(%): 252([M] + ,2),166(18),87(100),69(52).

[0274] Experimental Example 7 Oligomerization Reaction of 1,1,2-Trifluoro-2-iodoethane and (E)-1,2-Difluoroethylene

[0275] 1.00 g of 1,1,2-trifluoro-2-iodoethane and 0.35 mL of 2-ethylhexanoyl (tert-butyl) peroxide were added to a 30 mL pressure vessel, the vessel was sealed, cooled to -78°C, and then 1.5 g of (E)-1,2-difluoroethylene was introduced. The vessel was heated at 80°C for 24 hours. After that, the pressure vessel was cooled with ice water, and the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The results showed that H-CF2CHF-(CHFCHF)-I, H-CF2CHF-(CHFCHF)2-I and H-CF2CHF-(CHFCHF)3-I were generated at an area ratio of 36.1% (total of 4 isomers), 20.5% (total of 8 isomers) and 21.3% (total of multiple isomers) respectively, relative to the area ratio of 22.2% of the raw material 1,1,2-trifluoro-2-iodoethane.

[0276] H-CF2CHF-(CHFCHF)-I: LRMS (EI 70eV) m / z (%): 274 (M+, 87), 191 (11), 159 (30), 147 (76), 83 (45), 77 (100), 51 (82).

[0277] 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).

[0278] 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).

[0279] It is known from common technical knowledge that a polymer can be easily obtained by using a radical initiator when the methacrylate obtained in Experimental Examples 4 and 6 is used. These polymers can be suitably used as a water and oil repellent composition.

[0280] Furthermore, according to common technical knowledge, it can be seen from the results of Experimental Examples 2 to 6 that, by using the compound obtained in Experimental Example 7, it is possible to easily synthesize a product having H-CF2CHF-(CHFCHF) n -(CH2) p -(meth)acrylates.

Claims

1. A polymer having the general formula: R 1 -R 2 -(CH2) p -OR 3 The repeating unit derived from the monomer (a) shown, In the formula, R 1 is -CH3, -CH2F, -CHF2, -CH2I or -CHFI, R 2 is an alkylene group having 1 to 49 carbon atoms consisting only of a unit represented by -CFH-, or an alkylene group having 2 to 49 carbon atoms consisting only of a unit represented by -CFH- and a unit represented by -CH2-, or an alkylene group having 3 to 49 carbon atoms consisting only of a unit represented by -CFH-, a unit represented by -CH2-, and a unit represented by -CHI-, p is an integer from 0 to 2, R 3 It is an organic residue having an ethylenically unsaturated polymerizable group.

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

3. The polymer according to claim 1 or 2, wherein R 2 The general formula is: -(CFH) n1 - the alkylene group shown, In the formula, n1 is an integer from 2 to 10.

4. The polymer according to any one of claims 1 to 3, wherein R 3 A group represented by the general formula: CH2=C(-X)-C(=O)-YZ-, 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.

5. The polymer according to claim 4, wherein 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, -(CH2) m -N(R 1 )SO2-(CH2) n -yl, -CH2CH(OZ 1 )CH2-, -CH2CH(OZ 1 )CH2-(Ph-O)-, -(CH2) n -Ph-O- group, -(CH2) m -SO2-(CH2) n -yl, -(CH2) m -OC(=O)N(R 1 )-(CH2) n -yl, -(CH2) m -N(R 1 )C(=O)O-(CH2) n -yl, -(CH2) m -C(=O)N(R 1 )-(CH2) n -yl, -(CH2) m -(R 1 )NC(=O)-(CH2) n -yl, -(CH2) m -(R 1 )NC(=O)N(R 1 )-(CH2) n -yl, or -(CH2) m -S-(CH2) n -based, where 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 according to any one of claims 1 to 5, wherein The polymer further contains a repeating unit derived from at least one selected from the group consisting of (b) a non-fluorine-free non-crosslinkable monomer, (c) a non-fluorine-free crosslinkable monomer, and (d) a halogenated olefin monomer.

7. The polymer according to any one of claims 1 to 6, wherein The polymer also contains the general formula: CH2=C(-X 11 )-C(=O)-Y 11 -R 11 n The repeating unit derived from the monomer shown, 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 of 1 to 3.

8. A water and oil repellent composition comprising the polymer according to any one of claims 1 to 7 and a liquid medium.

9. The water- and oil-repellent 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 repellent composition according to claim 8 or 9, which is a water-dispersible composition.

11. The water and oil repellent composition according to any one of claims 8 to 10, 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 fiber product treated with the water and oil repellent composition according to any one of claims 8 to 11.

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