Copolymers, methods for producing the same and their uses, as well as composite particles containing copolymers and their dispersions.

Abstract

The present invention provides a copolymer that exhibits good solubility in water and good performance in reducing the interfacial tension of water. [Solution] A copolymer containing a constituent unit (A) derived from monomer (a) and a constituent unit (B) derived from monomer (b) having a hydroxyl group or a phosphate group, wherein the mass-average molecular weight is 1,000 to 30,000, and the monomer (a) is a monomer represented by the following formula (1). TIFF2026144989000016.tif41128 [In the formula, R 1 R represents H or a linear / branched alkyl group having 1 to 20 carbon atoms. 2 R represents a single bond or a linear / branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents. 3 This represents a linear / branched alkyl group having 1 to 20 carbon atoms.

Description

[Technical Field]

[0001] This disclosure relates to copolymers, methods for producing the same and their uses, as well as composite particles containing copolymers and dispersions thereof. [Background technology]

[0002] Various proposals have been made to use copolymers as dispersants.

[0003] For example, Patent Document 1 describes a dispersion solution in which polytetrafluoroethylene (PTFE) particles coated with a copolymer obtained by copolymerizing a monomer containing hydrophilic groups excluding catechol groups with a monomer containing at least catechol groups are dispersed.

[0004] Patent Document 2 describes that an N-vinylamide copolymer can be used as a dispersant, which is a copolymer of 10 to 79 mol% of a vinyl ester compound of a specific structure and 21 to 90 mol% of N-vinylamide, wherein the interfacial tension of a 1% by mass aqueous solution of the copolymer is 65 dyn / cm or less. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2022-023797 [Patent Document 2] Japanese Patent Application Publication No. 2002-308946 [Overview of the project] [Problems that the invention aims to solve]

[0006] The invention described in Patent Document 1 has problems in that it is insoluble in water and is inferior in its ability to reduce the surface tension of water.

[0007] The invention described in Patent Document 2 has the problem of being inferior in its ability to reduce the surface tension of water. Furthermore, because the vinyl monomer used in the invention described in Patent Document 2 has low reactivity, the resulting copolymer contains a large amount of unreacted monomer.

[0008] This disclosure has been made in view of the above, and aims to provide a copolymer that has good solubility in water and good performance in reducing the interfacial tension of water. [Means for solving the problem]

[0009] The inventors, through diligent research to achieve the above objectives, discovered that the above problems could be solved by using a copolymer obtained by polymerizing a monomer of a specific structure with a monomer having a hydroxyl group or a phosphate group. This disclosure is the result of further research by the inventors.

[0010] This disclosure includes, for example, the following subjects: Item 1. Containing a constituent unit (A) derived from monomer (a) and a constituent unit (B) derived from monomer (b) having a hydroxyl group or a phosphate group, The mass-average molecular weight is between 1,000 and 30,000. A copolymer in which the monomer (a) is a monomer represented by the following formula (1). [ka] [In the formula, R 1 This represents a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20). R 2 This represents a single bond or a linear or branched oxyalkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), which may have substituents. m represents a number between 1 and 10, with an average value. R 3is a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20), -R a -Si(R b )3(R a represents a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), and R b represents a trialkylsiloxy group having 1 to 4 carbon atoms (1, 2, 3 or 4)), or represents a group represented by the following formula (1A).

Chemical Formula

Effects of the Invention

[0011] According to the present disclosure, a copolymer having good solubility in water and good performance of reducing the interfacial tension of water can be provided. Since the copolymer of the present disclosure has such excellent properties, it can be suitably used in various applications such as dispersants, coating agents, paints, lubricating coatings, and batteries.

Mode for Carrying Out the Invention

[0012] Hereinafter, preferred embodiments of the present disclosure will be described in detail. The description of the constituent requirements described below may be made based on representative embodiments and specific examples, but the present disclosure is not limited to such embodiments.

[0013] In this disclosure, the expressions “contains” and “includes” include the concepts of “contains,” “includes,” “substantially consists of,” and “consistes of only.”

[0014] In the numerical ranges described in stages in this disclosure, the upper or lower limit of one stage of the numerical range can be arbitrarily combined with the upper or lower limit of another stage of the numerical range. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced with values ​​shown in the examples or values ​​that can be uniquely derived from the examples.

[0015] In this disclosure, “A and / or B” means “either A or B” or “both A and B,” and more specifically, “A,” “B,” or “A and B.”

[0016] In this disclosure, "n-" means "normal," "sec-" means "secondary," and "tert-" means "tertiary."

[0017] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0018] In this disclosure, room temperature means a temperature within the range of 20°C to 25°C.

[0019] In this disclosure, “monomer backbone” means a carbon chain containing polymerizable double bonds (carbon-carbon double bonds). In this disclosure, “monomer side chain” means a chain attached to the monomer backbone that is shorter in length than the backbone.

[0020] In this disclosure, the content of constituent unit (A) derived from monomer (a) in all constituent units of the copolymer can be considered to be equal to the amount of monomer (a) used relative to the total amount of monomer used in the production of the copolymer.

[0021] In this disclosure, the content of a component unit (B) derived from a monomer (b) having a hydroxyl group or a phosphate group in all component units of the copolymer can be considered to be equal to the amount of monomer (b) having a hydroxyl group or a phosphate group used relative to the total amount of monomer used in the production of the copolymer.

[0022] In this disclosure, the content of a component unit (C) derived from a monomer (c) having a phenyl group in all component units of the copolymer can be considered to be equal to the amount of monomer (c) having a phenyl group used relative to the total amount of monomer used in the production of the copolymer.

[0023] In this disclosure, examples of linear or branched alkyl groups having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, and the like.

[0024] In this disclosure, examples of linear or branched alkylene groups having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, neopentylene group, cyclopentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decylene group, and the like.

[0025] In this disclosure, a linear or branched oxyalkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) is a group represented by -AO-, where A is a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0026] In this disclosure, the oxyalkylene group having 1 to 3 carbon atoms (1, 2, or 3) is -CH2-O-, -CH2-CH2-O-, -CH2-CH2-CH2-O-, or -CH2-CH(CH3)-O-.

[0027] In this disclosure, the trialkylsiloxy group having 1 to 4 carbon atoms (1, 2, 3, or 4) includes trimethylsiloxy group [(CH3)3SiO-)], triethylsiloxy group, tri-n-propylsiloxy group, triisopropylsiloxy group, tri-n-butylsiloxy group, triisobutylsiloxy group, tri-sec-butylsiloxy group, tri-tert-butylsiloxy group, and the like.

[0028] 1.Copolymer The copolymers of this disclosure have the following configurations (I), (II), (III), and (IV). (I) Contains constituent unit (A) derived from monomer (a). (II) Contains a constituent unit (B) derived from a monomer (b) having a hydroxyl group or a phosphate group. (III) The mass-average molecular weight is between 1,000 and 30,000. (IV) The monomer (a) is the monomer represented by the following formula (1). [ka] [In the formula, R 1 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. R 2 This represents a single bond or a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents. m represents a number between 1 and 10, with an average value. R 3 -R a -Si(R b )3(R a R represents a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), b (represents a trialkylsiloxy group having 1 to 4 carbon atoms (1, 2, 3, or 4), or a group represented by the following formula (1A). [ka] (In the formula, R c R represents a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), d R represents a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), p represents a number between 5 and 150 on average, and R represents a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms. e This represents a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0029] The copolymer of this disclosure, having the above-described configurations (I), (II), (III), and (IV), exhibits good solubility in water and good performance in reducing the interfacial tension of water.

[0030] In this disclosure, “monomer (a) represented by formula (1)” will also be referred to as “monomer (a)”. In this disclosure, “monomer (b) having a hydroxyl group or a phosphate group” will also be referred to as “monomer (b)”.

[0031] The monomer (a) of this disclosure typically does not have a hydroxyl group, a phosphate group, or a phenyl group.

[0032] It is preferable that monomer (a) of this disclosure does not have a hydroxyl group, a phosphate group, or a phenyl group at the terminal end of its side chain. In this case, "terminal end of side chain" of monomer (a) means the hydroxyl group, phosphate group, or phenyl group located furthest from the main chain of monomer (a).

[0033] In monomer (b) of this disclosure, the hydroxyl group does not typically include the hydroxyl group that is present in a carboxyl group (-COOH).

[0034] In monomer (b) of the present disclosure, the number of hydroxyl groups is preferably one or two, and the number of phosphate groups is preferably one.

[0035] The monomer (b) of this disclosure typically does not have a phenyl group.

[0036] The monomer (b) of this disclosure preferably has a hydroxyl group or a phosphate group at the end of its side chain. In this case, "end of the side chain" of monomer (b) means the hydroxyl group or phosphate group located furthest from the main chain of monomer (b).

[0037] In the copolymer of this disclosure, monomer (b) is Preferably, the side chain has one or two hydroxyl groups or one phosphate group at its terminal end. More preferably, the side chain has one hydroxyl group or one phosphate group at its terminus. More preferably, the side chain has one hydroxyl group at its terminal end.

[0038] The copolymers of this disclosure have a mass-average molecular weight of 1,000 to 30,000. In this disclosure, if the mass-average molecular weight of the copolymer is less than 1,000, it may be a homopolymer of monomer (a) or a homopolymer of monomer (b). A "homopolymer of monomer (a)" means a polymer in which the content of constituent units (A) derived from monomer (a) is 100% by mass. A "homopolymer of monomer (b)" means a polymer in which the content of constituent units (B) derived from monomer (b) is 100% by mass. In this disclosure, if the mass-average molecular weight of the copolymer exceeds 30,000, its solubility in water decreases significantly, and its ability to reduce the interfacial tension of water decreases significantly.

[0039] In the copolymer of this disclosure, the mass-average molecular weight is preferably 2000 to 25000, more preferably 3000 to 20000.

[0040] In the copolymer of this disclosure, the lower limit of the mass-average molecular weight can be 1500, 2000, 2500, 3000, 3500, and 4000, and the upper limit of the mass-average molecular weight can be 27500, 25000, 22500, 21000, 20000, and 19500, and these upper and lower limits can be arbitrarily combined.

[0041] The number-average molecular weight of the copolymers of this disclosure is preferably 1000 or more and 17500 or less, with the upper limit of the number-average molecular weight being 15000, 14000, 13000, 12000 and 11500, and the lower limit of the number-average molecular weight being 1500, 2000, 2500, 3000, 3500 and 4000, and these upper and lower limits can be arbitrarily combined.

[0042] The specific methods for measuring mass-average molecular weight and number-average molecular weight will be explained in the examples described later.

[0043] The copolymers of this disclosure are preferably water-soluble. In this disclosure, a water-soluble copolymer means a copolymer that receives a "○" rating (transparent and completely dissolved) in either <Soluble Evaluation Method 1> or <Soluble Evaluation Method 2> described in the examples below.

[0044] In formula (1) of this disclosure, R 1 It is preferable that this is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0045] In formula (1) of this disclosure, R 1 It is more preferable that this is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6).

[0046] In formula (1) of this disclosure, R 1 It is more preferable that the group is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0047] In formula (1) of this disclosure, R 1 It is particularly preferable that this is a hydrogen atom or a methyl group.

[0048] In formula (1) of this disclosure, R 1 It is most preferable that it be a hydrogen atom.

[0049] In formula (1) of this disclosure, R 2 It is preferable that the oxyalkylene group is a single bond or a linear or branched oxyalkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), which may have substituents.

[0050] In formula (1) of this disclosure, R 2 It is more preferable that this is a single bond or an oxyalkylene group having 1 to 3 carbon atoms (1, 2, or 3), which may have substituents.

[0051] In formula (1) of this disclosure, R 2It is more preferable that the bond is a single bond, -CH2-O-, -CH2-CH2-O-, -CH2-CH2-CH2-O-, or -CH2-CH(CH3)-O-.

[0052] In formula (1) of this disclosure, R 2 It is particularly preferable that the bond is a single bond or -CH2-CH2-O-.

[0053] In formula (1) of this disclosure, R 2 It is most preferable that the bond is a single bond.

[0054] R in formula (1) of this disclosure 2 In this disclosure, the substituent is not particularly limited as long as it is not a hydrogen atom, and examples include fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, amino group, ester group, carboxyl group, epoxy group, isocyanate group, etc., and these substituents can be used individually or in combination of two or more. 2 Except when the substituent in is a hydroxyl group, a phosphate group, or a phenyl group.

[0055] In equation (1) of this disclosure, m is the number of repetitions, and represents a number between 1 and 10 on average. The value of m can be measured by nuclear magnetic resonance (NMR) analysis. Specifically, the value of m can be calculated by measuring the integral value of 3 ppm to 4 ppm.

[0056] In formula (1) of this disclosure, the upper limit of m can take values ​​of 10, 9, 8, 7, 6, 5, 4, and 3.

[0057] In formula (1) of this disclosure, m is preferably a number between 1 and 6 on average, more preferably a number between 1 and 4 on average, and even more preferably a number between 1 and 3 on average.

[0058] In formula (1) of this disclosure, R 2 A single bond is R 2 (i.e., R 2The oxygen atom adjacent to it and R 3 This means that (and are directly joined together).

[0059] In formula (1) of this disclosure, R 3 It is preferable that the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18).

[0060] In formula (1) of this disclosure, R 3 It is more preferable that the alkyl group is a linear or branched alkyl group having 1 to 15 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15).

[0061] In formula (1) of this disclosure, R 3 It is even more preferable that the alkyl group is a linear or branched alkyl group having 1 to 11 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11).

[0062] In formula (1) of this disclosure, R 3 It is particularly preferable that the alkyl group is a linear or branched alkyl group having 1 to 9 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, or 9).

[0063] As one embodiment of the present disclosure, in formula (1), R 2 However, it is a single bond, and R 3 However, -R a -Si(R b )3(R a R is a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), b It is preferable that the group is a trialkylsiloxy group having 1 to 4 carbon atoms (1, 2, 3, or 4).

[0064] As one embodiment of the present disclosure, in formula (1), R 2 However, it is a single bond, and R 3 However, -R a -Si(R b)3(R a R is a linear or branched alkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), b It is more preferable that the group is a trialkylsiloxy group having 1 to 4 carbon atoms (1, 2, 3, or 4).

[0065] As one embodiment of the present disclosure, in formula (1), R 2 However, it is a single bond, and R 3 However, -R a -Si(R b )3(R a R is a linear alkylene group having 1 to 3 carbon atoms (1, 2, or 3), b It is even more preferable that the group is a trialkylsiloxy group having 1 to 3 carbon atoms (1, 2, or 3).

[0066] As one embodiment of the present disclosure, in formula (1), R 2 However, it is a single bond, and R 3 However, -R a -Si(R b )3(R a is an n-propylene group, R b It is particularly preferable that the group is a trimethylsiloxy group.

[0067] Another embodiment of the present disclosure, in formula (1), R 1 However, it is a hydrogen atom or a methyl group, R 2 However, it is a single bond, R 3 However, -R a -Si(R b )3(R a R is a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), b (is a trialkylsiloxy group having 1 to 4 carbon atoms (1, 2, 3, or 4), or R 3 However, it is a group represented by formula (1A), and in formula (1A), R cHowever, R is a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), d However, it is a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), and p is a number between 5 and 150 on average, and R e However, it is a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10). It is preferable.

[0068] Another embodiment of the present disclosure, in formula (1), R 1 However, it is a hydrogen atom or a methyl group, R 2 However, it is a single bond, R 3 However, -R a -Si(R b )3(R a R is a linear or branched alkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), b (is a trialkylsiloxy group having 1 to 4 carbon atoms (1, 2, 3, or 4), or R 3 However, it is a group represented by formula (1A), and in formula (1A), R c However, R is a linear or branched alkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), d However, it is a linear or branched alkyl group or phenyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), and p is a number between 5 and 150 on average, and R e However, it is a linear or branched alkyl group or phenyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6). It is preferable to do so.

[0069] Another embodiment of the present disclosure, in formula (1), R 1 However, it is a hydrogen atom or a methyl group, R 2 However, it is a single bond, R3 is -R a -Si(R b )3(R a is a linear alkylene group having 1 to 3 (1, 2 or 3) carbon atoms, and R b is a trialkylsiloxy group having 1 to 3 (1, 2 or 3) carbon atoms), or R 3 is a group represented by formula (1A), and in said formula (1A), R c is a linear alkylene group having 1 to 3 (1, 2 or 3) carbon atoms, R d is a linear alkyl group having 1 to 3 (1, 2 or 3) carbon atoms or a phenyl group, p is a number having an average value of 5 or more and 150 or less, and R e is a linear or branched alkyl group having 1 to 4 (1, 2, 3 or 4) carbon atoms or a phenyl group), it is even more preferable.

[0070] As another embodiment of the present disclosure, in formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is a single bond, R 3 is -R a -Si(R b )3(R a is an n-propylene group, and R b is a trimethylsiloxy group), or R 3 is a group represented by formula (1A), and in said formula (1A), R c is an n-propylene group, R d is a methyl group, p is a number having an average value of 5 or more and 150 or less, and R e is an n-butyl group), it is particularly preferable.

[0071] As an embodiment of the present disclosure, the monomer (a) represented by formula (1) is Preferably, at least one selected from the group consisting of tert-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, isohexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, 2-octyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, 2-hexyldecyl (meth)acrylate, isostearyl (meth)acrylate, and 2-ethylhexyl EO-modified (meth)acrylate. More preferably, at least one selected from the group consisting of tert-butyl acrylate, isobutyl acrylate, hexyl acrylate, isohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, 2-octyl acrylate, isononyl acrylate, isodecyl acrylate, lauryl acrylate, 2-hexyldecyaacrylate, isostearyl acrylate, and 2-ethylhexyl EO-modified acrylate. Particularly preferred is at least one selected from the group consisting of tert-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and 2-ethylhexyl EO-modified acrylate. That is the case.

[0072] In another embodiment of the present disclosure, monomer (a) represented by formula (1) is: Preferably, at least one selected from the group consisting of trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, methacryloxypropyl-terminated polydimethylsiloxane, and acryloxypropyl-terminated polydimethylsiloxane. More preferably, at least one selected from the group consisting of trimethylsilyl acrylate, 2-(trimethylsilyloxy)ethyl acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl acrylate, 3-(triethoxysilyl)propyl acrylate, and methacryloxypropyl-terminated polydimethylsiloxane. More preferably, 3-(tris(trimethylsilyloxy)silyl)propyl acrylate and / or methacryloxypropyl-terminated polydimethylsiloxane, Particularly preferred is 3-(tris(trimethylsilyloxy)silyl)propyl acrylate.

[0073] The copolymer of the present disclosure preferably has, in addition to the above configurations (I), (II), (III), and (IV), the following configuration (V). (V) Contains a constituent unit (C) derived from a monomer (c) having a phenyl group.

[0074] The copolymers of this disclosure, comprising components (I), (II), (III), (IV), and (V), exhibit excellent solubility in water and excellent performance in reducing the interfacial tension of water.

[0075] In this disclosure, "monomer (c) having a phenyl group" will also be referred to as "monomer (c)".

[0076] The monomer (c) of this disclosure is preferably a monomer (c) having a phenyl group with one, two, three, four, or five substituents.

[0077] The monomer (c) of this disclosure is preferably a monomer (c) having a phenyl group having one, two, three, four or five hydroxyl groups, more preferably a monomer (c) having a phenyl group having one, two, three or four hydroxyl groups, even more preferably a monomer (c) having a phenyl group having one, two or three hydroxyl groups, and still more preferably a monomer (c) having a phenyl group having two or three hydroxyl groups.

[0078] In one embodiment of the present disclosure, the monomer (c) having a phenyl group is preferably a monomer (c) having a catechol group or a galloyl group, more preferably a monomer (c) having a catechol group.

[0079] From the viewpoint of having better solubility in water and better performance in reducing the interfacial tension of water, the copolymer of the present disclosure has a content of constituent units (A) derived from monomer (a) that is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, even more preferably 15 to 50 mol%, and still more preferably 20 to 45 mol%, based on 100 mol% of the total of constituent units (A) and constituent units (B) derived from monomer (b).

[0080] The copolymer of the present disclosure has excellent dispersibility and superior solubility in water, and from the viewpoint of having superior performance in reducing the interfacial tension of water, the content of constituent unit (A) derived from monomer (a) is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, even more preferably 15 to 50 mol%, and still more preferably 20 to 45 mol%, based on 100 mol% of the total of constituent unit (A), constituent unit (B) derived from monomer (b), and constituent unit (C) derived from monomer (c).

[0081] The copolymer of this disclosure has excellent dispersibility and superior solubility in water, and from the viewpoint of having superior performance in reducing the interfacial tension of water, the content of constituent units (C) derived from monomer (c) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, even more preferably 3 to 12 mol%, and still more preferably 4 to 10 mol%, based on 100 mol% of the total of constituent units (A) derived from monomer (a), constituent units (B) derived from monomer (b), and constituent units (C).

[0082] In this disclosure, from the viewpoint of having better solubility in water, the monomer (b) having a hydroxyl group or a phosphate group is preferably a monomer represented by the following formula (2). [ka] (In the formula, R 4 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. R 5 This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, or a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents. n represents a number between 1 and 20 on average. R 5 However, in the case of a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, R 6 This represents a hydroxyl group or a phosphate group. R 5 However, in the case of a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents, R 6 (This represents a hydrogen atom or a phosphate group.)

[0083] In formula (2) of this disclosure, R 4 It is preferable that this is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0084] In formula (2) of this disclosure, R 4 It is more preferable that this is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6).

[0085] In formula (2) of this disclosure, R 4 It is more preferable that the group is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0086] In formula (2) of this disclosure, R 4 It is particularly preferable that this is a hydrogen atom or a methyl group.

[0087] In formula (2) of this disclosure, R 4It is most preferable that it be a hydrogen atom.

[0088] In formula (2) of this disclosure, R 5 Preferably, this is a linear or branched alkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6) which may have substituents, or a linear or branched oxyalkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6) which may have substituents.

[0089] In formula (2) of this disclosure, R 5 It is more preferable that this is an alkylene group having 1 to 3 carbon atoms (1, 2, or 3) which may have substituents, or an oxyalkylene group having 1 to 3 carbon atoms (1, 2, or 3) which may have substituents.

[0090] In formula (2) of this disclosure, R 5 It is more preferable that the group is an alkylene group having 1 to 3 carbon atoms (1, 2, or 3), or an oxyalkylene group having 1 to 3 carbon atoms (1, 2, or 3).

[0091] In formula (2) of this disclosure, R 5 It is particularly preferable that the compound is -CH2-CH2-O-.

[0092] In equation (2) of this disclosure, n is the number of repetitions, and represents a number between 1 and 20 on average. The value of n can be measured by nuclear magnetic resonance (NMR) analysis. Specifically, the value of n can be calculated by measuring the integral value at 3 ppm to 4 ppm.

[0093] In formula (2) of this disclosure, the upper limit of n can take values ​​of 19, 18, 17, 16, 15, 14, 13, 12, 11, and 10, and the lower limit of n can take values ​​of 1.5, 2, 2.5, 3, 3.5, 4, and 4.5, and these upper and lower limits can be combined in any way.

[0094] In formula (2) of this disclosure, n is preferably a number between 2 and 18 on average, more preferably a number between 2.5 and 16 on average, even more preferably a number between 3 and 14 on average, even more preferably a number between 3.5 and 12 on average, and particularly preferably a number between 4 and 11 on average.

[0095] R in formula (2) of this disclosure 5 In this disclosure, the substituent is not particularly limited as long as it is not a hydrogen atom, and examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an amino group, an ester group, a carboxyl group, an epoxy group, a phosphoric acid group, an isocyanate group, etc., and these substituents can be used individually or in combination of two or more. In this disclosure, R of formula (2) 5 Except when the substituent in is a phenyl group.

[0096] R in formula (2) of this disclosure 5 In this, the number of substituents is usually one to four, preferably one or two, and more preferably one.

[0097] R in formula (2) of this disclosure 5 In this, the substituent is preferably one to four hydroxyl groups, more preferably one or two hydroxyl groups, and even more preferably one hydroxyl group.

[0098] The monomer (b) represented by formula (2) in this disclosure is Preferably, at least one selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-methchloroyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, glycerin monomethacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, and polypropylene glycol monomethacrylate. More preferably, at least one selected from the group consisting of 2-methachloroyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, and polypropylene glycol monomethacrylate. More preferably, at least one selected from the group consisting of 2-methachloroyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, polyethylene glycol monoacrylate, and polyethylene glycol monomethacrylate. Particularly preferred is 2-acryloyloxyethyl acid phosphate and / or polyethylene glycol monoacrylate. Most preferably polyethylene glycol monoacrylate, That is the case.

[0099] Examples of commercially available monomers (b) represented by formula (2) of this disclosure include "Bremmer AE-200", "Bremmer AE-400", "Bremmer GLM", "Bremmer GLM-EX", "Bremmer GLM-R", "Bremmer E", "Bremmer PE-90", "Bremmer PE-200", "Bremmer PE-350", "Bremmer AP-200", "Bremmer AP-400", "Bremmer AP-550", "Bremmer AP-800", "Bremmer AP-400D", "Bremmer AP-1000D", "Bremmer P", "Bremmer PP-1000", "Bremmer PP-500", and "Bremmer PP-800" manufactured by NOF Corporation; and "Light Acrylate P-1A(N)" and "Light Ester P-1M" manufactured by Kyoeisha Chemical Co., Ltd. These commercially available products can be used individually or in combination of two or more.

[0100] In this disclosure, from the viewpoint of having excellent dispersibility and better solubility in water, the monomer (c) having a phenyl group is preferably a monomer represented by the following formula (3). [ka] (In the formula, R 7 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. X represents -C(=O)NH- or -C(=O)O-. R 8 This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have single bonds or substituents. R 9 -O-, -CH(OH)-, -OC(=O)-, or -OC(=O)O- represent a single bond, -O-, -CH(OH)-, -OC(=O)O-, or -OC(=O)O-. R 10 , R 11 , R 12 , R 13 and R 14 Each of these independently represents either a hydrogen atom or a hydroxyl group. However, R 10 , R 11 , R 12 , R 13 and R 14 (Except when all atoms are hydrogen atoms.)

[0101] In formula (3) of this disclosure, R 7 It is preferable that this is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0102] In formula (3) of this disclosure, R 7 It is more preferable that this is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6).

[0103] In formula (3) of this disclosure, R 7 It is more preferable that the group is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0104] In formula (3) of this disclosure, R 7 It is particularly preferable that this is a hydrogen atom or a methyl group.

[0105] In formula (3) of this disclosure, R 7 It is most preferable that it is a methyl group.

[0106] In formula (3) of this disclosure, R 8 A single bond is R 8 (i.e., R 8 X and R adjacent to each other 9 This means that (and are directly joined together).

[0107] In formula (3) of this disclosure, R 8 This is preferably a linear or branched alkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), which may have substituents.

[0108] In formula (3) of this disclosure, R 8 This is more preferably an alkylene group having 1 to 3 carbon atoms (1, 2, or 3), which may have substituents.

[0109] R in formula (3) of this disclosure 8 Examples of substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, hydroxyl groups, amino groups, ester groups, carboxyl groups, epoxy groups, phosphate groups, isocyanate groups, and phenyl groups. These can be used individually or in combination of two or more.

[0110] R in formula (3) of this disclosure 8 In this, the number of substituents is usually one to four, preferably one or two, and more preferably one.

[0111] R in formula (3) of this disclosure 8 In this, the substituent is preferably one to four hydroxyl groups, more preferably one or two hydroxyl groups, and even more preferably one hydroxyl group.

[0112] In formula (3) of this disclosure, R 9 A single bond or -OC(=O)- is preferred.

[0113] In formula (3) of this disclosure, R 9 A single bond is R 9 (i.e., R 9 Adjacent to R 8 This means that the phenyl group with a substituent is directly bonded to it.

[0114] A preferred embodiment of the present disclosure is, in formula (3) above, R 10 and R 14 Both are hydrogen atoms, R 11 , R 12 and R 13 Both are hydroxyl groups; or R 10 and R 14 Both are hydrogen atoms, R 12 is a hydroxyl group, R 11 and R 13 One of them is a hydroxyl group, and the other is a hydrogen atom.

[0115] In a more preferred embodiment of this disclosure, in formula (3) above, R 7 However, X is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), and X is -C(=O)NH- or -C(=O)O-. If X is -C(=O)NH-, then R 8 However, R is a linear or branched alkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), which may have substituents. 9 It is a single bond, R 10 and R 14 Both are hydrogen atoms, R 12 is a hydroxyl group, R 11 and R 13 Either one of them is a hydroxyl group and the other is a hydrogen atom; or If X is -C(=O)O-, then R 8 However, R is a linear or branched alkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), which may have substituents (preferably hydroxyl groups),9 is -OC(=O)-, and R 10 and R 14 Both are hydrogen atoms, R 12 is a hydroxyl group, R 11 and R 13 One of them is a hydroxyl group, and the other is a hydrogen atom.

[0116] The monomer (c) represented by formula (3) in this disclosure is preferably such that X is -C(=O)NH- N-[2-(3,4-dihydroxyphenyl)methyl](meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)ethyl](meth)acrylamide [also known as dopamine methacrylamide (DMA)], N-[2-(3,4-dihydroxyphenyl)propyl](meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)butyl](meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)pentyl](meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)hexyl](meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)heptyl](meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)octyl](meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)nonyl](meth)acrylamide and N-[2-(3,4-dihydroxyphenyl)decyl](meth)acrylamide It is at least one selected from the group consisting of the following:

[0117] The monomer (c) represented by formula (3) of this disclosure is preferably such that X is -C(=O)O- when X is -C(=O)O- N-[2-(3,4-dihydroxyphenyl)methyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)ethyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)propyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)butyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)pentyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)hexyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)heptyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)octyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)nonyl](meth)acrylate N-[2-(3,4-dihydroxyphenyl)decyl](meth)acrylate and 3,4,5-Trihydroxybenzoic acid [2-hydroxy-3-(methacrylroyloxy)propyl]ester It is at least one selected from the group consisting of the following:

[0118] In this disclosure, the sequences of constituent units (A) derived from monomer (a), constituent units (B) derived from monomer (b), and constituent units (C) derived from monomer (c) may each be random, block, graft, or gradient.

[0119] In one embodiment of the present disclosure, the copolymer may include, for example, a structural unit derived from a chain transfer agent, a structural unit derived from a polymerization initiator, and other structural units other than the structural unit (A) derived from monomer (a) and the structural unit (B) derived from monomer (b).

[0120] In another embodiment of the present disclosure, the copolymer may include, for example, a chain transfer agent-derived component, a polymerization initiator-derived component, and other components other than the component (A) derived from monomer (a), component (B) derived from monomer (b), and component (C) derived from monomer (c).

[0121] In one embodiment of the present disclosure, the total content ratio of constituent units (A) derived from monomer (a) and constituent units (B) derived from monomer (b) relative to the total (100% by mass) of all constituent units in the copolymer is preferably in the order of more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, 92.5% by mass or more, and 95% by mass or more.

[0122] In another embodiment of the present disclosure, the total content of constituent units (A) derived from monomer (a), constituent units (B) derived from monomer (b), and constituent units (C) derived from monomer (c) relative to the total (100% by mass) of all constituent units in the copolymer is preferably in the order of more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, 92.5% by mass or more, 95% by mass or more, and 96% by mass or more.

[0123] 2. Method for producing copolymers As one embodiment of the present disclosure, the copolymer manufacturing method A of the present disclosure (hereinafter also referred to as "manufacturing method A of the present disclosure") comprises the step of copolymerizing monomer (a) and monomer (b) having a hydroxyl group or a phosphate group in the presence of a chain transfer agent. By employing such a configuration, manufacturing method A of the present disclosure can easily produce copolymers that have good solubility in water and good performance in reducing the interfacial tension of water.

[0124] As another embodiment of the present disclosure, the copolymer manufacturing method B of the present disclosure (hereinafter also referred to as "manufacturing method B of the present disclosure") comprises the step of copolymerizing monomer (a), monomer (b) having a hydroxyl group or a phosphate group, and monomer (c) in the presence of a chain transfer agent. By employing such a configuration, manufacturing method B of the present disclosure can produce copolymers that have superior solubility in water and superior performance in reducing the interfacial tension of water in a simple manner.

[0125] The manufacturing methods A and B of this disclosure will be described in detail below. Hereinafter, monomer (b) having a hydroxyl group or a phosphate group will also be referred to as "monomer (b)". Similarly, monomer (c) having a phenyl group will also be referred to as "monomer (c)".

[0126] In the manufacturing method A of this disclosure, the step of copolymerizing monomer (a) and monomer (b) in the presence of a chain transfer agent is also referred to as "copolymerization step A".

[0127] In the manufacturing method B of this disclosure, the step of copolymerizing monomer (a), monomer (b), and monomer (c) in the presence of a chain transfer agent is also referred to as "copolymerization step B".

[0128] Details of the copolymers produced by manufacturing methods A and B of this disclosure are as described in "1. Copolymers" above, unless otherwise specified. Details of "monomer(a)", "monomer(b)", and "monomer(c)" used in manufacturing methods A and B of this disclosure are as described in "1. Copolymers" above, unless otherwise specified.

[0129] In copolymerization step A, methods for copolymerizing monomer (a) and monomer (b) include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization, and among these, solution polymerization is preferred.

[0130] In copolymerization step A, one method for copolymerizing monomer (a) and monomer (b) is to prepare a monomer mixture by adding an organic solvent to a mixture containing monomer (a) and monomer (b), and then to prepare the monomer mixture by adding a polymerization initiator and a chain transfer agent to copolymerize monomer (a) and monomer (b).

[0131] In copolymerization step B, methods for copolymerizing monomer (a), monomer (b), and monomer (c) include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization, among which solution polymerization is preferred.

[0132] In copolymerization step B, one method for copolymerizing monomer (a), monomer (b), and monomer (c) is to prepare a monomer mixture by adding an organic solvent to a mixture containing monomer (a), monomer (b), and monomer (c), and then to prepare the monomer mixture by adding a polymerization initiator and a chain transfer agent to copolymerize monomer (a), monomer (b), and monomer (c).

[0133] In copolymerization steps A and B, examples of chain transfer agents include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol, 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, octyl mercaptan, dodecyl mercaptan, 3-mercaptopropionic acid, and among these, 3-mercapto-1,2-propanediol is preferred.

[0134] In copolymerization step A, the amount of chain transfer agent used is preferably 0.01 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total of monomer (a) and monomer (b), from the viewpoint of efficiently carrying out the polymerization reaction.

[0135] In copolymerization step B, the amount of chain transfer agent used is preferably 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total of monomer (a), monomer (b), and monomer (c), from the viewpoint of efficiently carrying out the polymerization reaction.

[0136] In copolymerization steps A and B, a wide range of known azo compounds or known organic peroxides commonly used in this field can be used as polymerization initiators.

[0137] Examples of the above azo compounds include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane1-carbonitride), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and dimethyl1,1'-azobis(1 Examples include cyclohexane carbonate, dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane], among which 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile) are preferred.

[0138] Examples of the above-mentioned organic peroxides include benzoyl peroxide, t-butyl peroxy 2-ethyl hexaate, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

[0139] In copolymerization step A, the amount of polymerization initiator used is preferably 0.1 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the total of monomer (a) and monomer (b), from the viewpoint of efficiently carrying out the polymerization reaction.

[0140] In copolymerization step B, the amount of polymerization initiator used is preferably 0.1 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the total of monomer (a), monomer (b), and monomer (c), from the viewpoint of efficiently carrying out the polymerization reaction.

[0141] In copolymerization steps A and B, examples of organic solvents include ether compounds, alcohol compounds, amide compounds, ester compounds, ketone compounds, sulfoxide compounds, and hydrocarbon compounds. These organic solvents can be used individually or in combination of two or more.

[0142] Examples of the ether compounds mentioned above include linear ethers such as diethyl ether; cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; and these can be used individually or in combination of two or more.

[0143] Examples of the above-mentioned alcohol compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, etc. These can be used individually or in combination of two or more.

[0144] Examples of the above-mentioned amide compounds include N,N-dimethylacetamide and N,N-dimethylformamide (DMF), which can be used individually or in combination of two or more.

[0145] Examples of the ester compounds mentioned above include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl carbonate, and ethyl lactate. These can be used individually or in combination of two or more.

[0146] Examples of the ketone compounds mentioned above include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone, etc. These can be used individually or in combination of two or more.

[0147] Examples of the above-mentioned sulfoxide compounds include dimethyl sulfoxide.

[0148] Examples of the hydrocarbon compounds mentioned above include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane; and alicyclic hydrocarbons such as cyclohexane. These can be used individually or in combination of two or more.

[0149] In copolymerization step A, the amount of organic solvent used is preferably 100 parts by mass or more and 1000 parts by mass or less, relative to 100 parts by mass of the total of monomer (a) and monomer (b), from the viewpoint of efficiently carrying out the polymerization reaction.

[0150] In copolymerization step B, the amount of organic solvent used is preferably 100 parts by mass or more and 1000 parts by mass or less, relative to 100 parts by mass of the total of monomer (a), monomer (b), and monomer (c), from the viewpoint of efficiently carrying out the polymerization reaction.

[0151] In copolymerization steps A and B, the polymerization reaction is usually carried out at a temperature range of 30°C to 100°C, preferably 40°C to 80°C. The temperature during the polymerization reaction may be constant or may be changed during the polymerization reaction.

[0152] In copolymerization steps A and B, the polymerization reaction time is typically 0.5 hours to 48 hours, preferably 1 hour to 30 hours, from the start to the end of polymerization.

[0153] 3. Applications of copolymers The copolymers of this disclosure exhibit excellent solubility in water and superior ability to reduce the interfacial tension of water, making them suitable for a wide range of applications such as dispersants, coatings, paints, lubricating films, batteries, electrode materials, coating materials, plating, and catalysts. Unless otherwise specified, the details of the copolymers of this disclosure are as described in "1. Copolymers" above.

[0154] Specific applications of the dispersant containing the copolymer of this disclosure include, for example, dispersants for inorganic pigments, dispersants for organic pigments, dispersants for inorganic particles, dispersants for organic particles, and dispersants for cells.

[0155] Examples of inorganic pigments applicable to the above-mentioned dispersant for inorganic pigments include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate; black pigments such as carbon black, titanium black, titanium carbon, iron oxide, and graphite; and iron oxide, barium yellow, cadmium red, and chromium yellow.

[0156] Examples of organic pigments applicable to the above-mentioned dispersant for organic pigments include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; azo pigments such as azo red, azo yellow, and azo orange; quinacridone pigments such as quinacridone red, syncasha red, and syncasha magenta; perylene pigments such as perylene red and perylene maroon; diazo pigments; isoindolinone pigments; dioxazine pigments; perylene pigments; thioindigo pigments; anthraquinone pigments; and quinophthalone pigments.

[0157] Examples of inorganic particles applicable to the above-mentioned dispersant for inorganic particles include zinc oxide particles, silicon oxide (silica) particles, titanium oxide (titania) particles, zirconium oxide (zirconia) particles, magnesium oxide (magnesia) particles, aluminum oxide (alumina) particles, and cerium oxide (ceria) particles.

[0158] Examples of organic particles applicable to the above-mentioned dispersant for organic particles include polytetrafluoroethylene (PTFE) particles, hydrocarbon particles, polyethylene particles, polystyrene particles, polyvinylidene fluoride particles, polyvinyl alcohol particles, polyvinyl chloride particles, polyvinylidene chloride particles, polyethylene terephthalate particles, nylon particles, and carbon nanotube granules.

[0159] Cells to which the above-mentioned cell dispersant can be applied include, for example, mesenchymal stem cells; CHO cells derived from Chinese hamster ovaries; mouse connective tissue L929 cells; HEK293 cells derived from human fetal kidneys; HeLa cells derived from human cervical cancer; epithelial or endothelial cells that make up various tissues or organs in the body; contractile skeletal muscle cells, smooth muscle cells, or cardiomyocytes; neuronal cells, glial cells, or fibroblasts that make up the nervous system; hepatocytes, non-parenchymal cells, or adipocytes that are involved in the metabolism of the body; cells with differentiation potential (e.g., stem cells); cells differentiated from cells with differentiation potential; cells contained in blood, lymph, cerebrospinal fluid, sputum, urine, or feces; and microorganisms, viruses, or protozoa present in the body or environment.

[0160] The dispersant comprising the copolymer of the present disclosure can be suitably used as a dispersant for organic particles. The dispersant comprising the copolymer of the present disclosure can be particularly suitably used as a dispersant for PTFE particles.

[0161] In this disclosure, the content of the copolymer in the dispersant is usually more than 50% by mass, preferably 75% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, still more preferably 99% by mass or more, even more preferably 99.5% by mass or more, and particularly preferably 99.9% by mass or more. The dispersant most preferably consists only of the copolymer.

[0162] Specific applications of the coating agent containing the copolymer of this disclosure include, for example, coating agents for displays, coating agents for vehicles, coating agents for building materials, coating agents for printing, and coating agents for batteries.

[0163] Specific applications of coatings containing the copolymer of this disclosure include, for example, coatings for building materials, automotive coatings, semiconductor coatings, industrial coatings, and structural coatings.

[0164] A lubricating film containing the copolymer of the present disclosure typically comprises the copolymer of the present disclosure and has a surface free energy of 70 mJ / m². 2 It is a coating composed of particles smaller than a certain size and a surfactant.

[0165] The lubricating coating comprising the copolymer of the present disclosure is preferably a coating formed from the copolymer of the present disclosure, particles having a surface free energy of 70 mJ / m 2 or less, and a surfactant, and said particles having a surface free energy of 70 mJ / m 2 or less are at least one selected from the group consisting of PTFE particles, hydrocarbon particles, polyethylene particles, polystyrene particles, polyvinylidene fluoride particles, polyvinyl alcohol particles, polyvinyl chloride particles, polyvinylidene chloride particles, polyethylene terephthalate particles, nylon particles, zinc oxide particles and carbon nanotube granules.

[0166] The lubricating coating comprising the copolymer of the present disclosure is particularly preferably a coating formed from the copolymer of the present disclosure, PTFE particles, and a surfactant.

[0167] Specific applications of a battery comprising the copolymer of the present disclosure include, for example, nickel-metal hydride batteries, lithium ion secondary batteries, sodium ion secondary batteries, potassium ion secondary batteries, fuel cells and the like.

[0168] As one embodiment of the present disclosure, a battery comprising the copolymer of the present disclosure preferably comprises a positive electrode, a negative electrode, and an electrode film formed using a composite particle dispersion containing the copolymer of the present disclosure.

[0169] As another embodiment of the present disclosure, a battery comprising the copolymer of the present disclosure preferably comprises a positive electrode, a negative electrode, and a gas diffusion layer formed using a composite particle dispersion containing the copolymer of the present disclosure.

[0170] 4. Composite particles The composite particles of the present disclosure comprise the copolymer of the present disclosure and particles having a surface free energy of 70 mJ / m 2 or less, wherein the copolymer coats the particles having a surface free energy of 70 mJ / m 2The particles are attached to the surface of particles smaller than a certain size. The composite particles of this disclosure, having such a configuration, can be well dispersed in an aqueous solvent.

[0171] Details of the copolymers of this disclosure are as described in "1. Copolymers" above, unless otherwise specified.

[0172] In this disclosure, the surface free energy is 70 mJ / m 2 One method for measuring the surface free energy of particles less than mJ / m is the OWRK (Owens-Wendt-Rabel-Kaelble) method. Specifically, based on the OWRK (Owens-Wendt-Rabel-Kaelble) method, water and diiodomethane, whose surface free energies are known, are used. Water is dropped onto the surface of the compacted particle and the contact angle of the water is measured. Then, diiodomethane is dropped onto the surface of the compacted particle and the contact angle of the diiodomethane is measured. This allows the surface free energy of the particle (mJ / m) to be determined. 2 Calculate ).

[0173] In the composite particles of the present disclosure, if the copolymer of the present disclosure contains a constituent unit (C) derived from a monomer (c) having a phenyl group, the phenyl group contained in monomer (c) has a surface free energy of 70 mJ / m 2 It is presumed that the hydroxyl groups or phosphate groups contained in monomer (b) adhere to the surface of particles smaller than 1,000 mm and have a high affinity for aqueous solvents. Due to the presence of hydroxyl groups or phosphate groups on the surface of the composite particles of the present disclosure, the composite particles of the present disclosure have a high affinity for aqueous solvents, and therefore it is presumed that the composite particles of the present disclosure can be dispersed in aqueous solvents. Therefore, the copolymer of the present disclosure can be suitably used as a dispersant in place of conventionally used fluorinated surfactants.

[0174] The composite particles of this disclosure are a copolymer of this disclosure and a copolymer with a surface free energy of 70 mJ / m 2These are particles formed by compounding particles with a surface free energy of less than 70 mJ / m². In this disclosure, when the copolymer of this disclosure contains a constituent unit (C) derived from a monomer (c) having a phenyl group, compounding is typically defined as having a surface free energy of 70 mJ / m². 2 This refers to a state where phenyl groups contained in monomer (c) are attached to the surface of particles smaller than a certain size.

[0175] In this disclosure, the surface free energy is 70 mJ / m 2 The mass ratio of particles less than 70 mJ / m² to the copolymer of the present disclosure (surface free energy of 70 mJ / m²) 2 The mass of particles less than 100:30 to 100:0.5, more preferably 100:20 to 100:1, is preferred.

[0176] In this disclosure, the surface free energy in the composite particle is 70 mJ / m 2 The proportion of particles smaller than 70% by mass is preferably 70% by mass or more and 99% by mass or less.

[0177] In this disclosure, the content of the copolymer of this disclosure in the composite particles is preferably 1% by mass or more and 30% by mass or less.

[0178] Surface free energy is 70 mJ / m 2 Adhesion of the copolymer of this disclosure to the surface of particles less than 70 mJ / m² is achieved, for example, by mixing the copolymer in an aqueous solvent and applying it thereto. 2 This can be done by adding particles smaller than a certain size and stirring.

[0179] As the aqueous solvent mentioned above, water, water-soluble organic solvents, and mixed solvents thereof can be used. Examples of water include natural water, purified water, distilled water, ion-exchanged water, and pure water.

[0180] Examples of the water-soluble organic solvents mentioned above include alcohol compounds, ketone compounds, ether compounds, amide compounds, sulfoxide compounds, ester compounds, glycol compounds, etc. These can be used individually or in combination of two or more.

[0181] Examples of the above alcohol compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, etc. These may be used each alone or in combination of two or more kinds.

[0182] Examples of the above ketone compounds include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone, etc. These may be used each alone or in combination of two or more kinds.

[0183] Examples of the above ether compounds include diethyl ether, tetrahydrofuran (THF), dioxane, etc. These may be used each alone or in combination of two or more kinds.

[0184] Examples of the above amide compounds include N,N-dimethylformamide (DMF), N,N-dimethylacetamide, etc. These may be used each alone or in combination of two or more kinds.

[0185] Examples of the above sulfoxide compound include dimethyl sulfoxide (DMSO) and the like.

[0186] Examples of the above ester compounds include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl carbonate, ethyl lactate, etc. These may be used each alone or in combination of two or more kinds.

[0187] Examples of the glycol compounds mentioned above include ethylene glycol, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, and propylene glycol methyl ether acetate. These can be used individually or in combination of two or more.

[0188] In one embodiment of the present disclosure, the composite particles of the present disclosure preferably have a surface free energy of 70 mJ / m², in that they have even better dispersibility. 2 At least a portion of the surface of particles smaller than 10 is coated with the copolymer of the Disclosure, more preferably having a surface free energy of 70 mJ / m². 2 The entire surface of particles smaller than a certain size is coated with the copolymer of the present disclosure.

[0189] The composite particles of this disclosure further comprise a surfactant having a surface free energy of 70 mJ / m 2 Preferably, the particles are attached to the surface of particles smaller than a certain size. Having such a configuration, the composite particles of this disclosure can be well dispersed in an aqueous solvent.

[0190] When the composite particles of this disclosure contain a surfactant, the surfactant content in the composite particles is preferably 1% by mass or more and 20% by mass or less, in order to ensure good dispersion in an aqueous solvent.

[0191] As the surfactant mentioned above, a wide range of known surfactants commonly used in this field (excluding fluorinated surfactants) can be used. Examples of surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, which can be used individually or in combination of two or more. Among these surfactants, nonionic surfactants are preferred because the composite particles of this disclosure can be well dispersed in an aqueous solvent.

[0192] Examples of the above-mentioned anionic surfactants include sulfate ester salts of alkali metal salts of higher fatty acids; sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate esters. These anionic surfactants can be used individually or in combination of two or more.

[0193] Examples of the cationic surfactants mentioned above include quaternary ammonium salts such as alkyltrimethylammonium salts.

[0194] Examples of the above-mentioned amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates; and betaine-type amphoteric surfactants such as higher alkyldimethyl betaine and higher alkyldihydroxyethyl betaine. These can be used individually or in combination of two or more.

[0195] Examples of the above-mentioned nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene phenyl ethers, polyoxyethylene alkyl esters, propylene glycol-propylene oxide copolymers, perfluoroalkyl ethylene oxide adducts, and 2-ethylhexanol ethylene oxide adducts. These can be used individually or in combination of two or more.

[0196] As the surfactant mentioned above, a wide range of commercially available products can be used. Examples of commercially available products include "Neugen TDS-80" and "Neugen XL-80" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0197] In the composite particles of this disclosure, the surface free energy is 70 mJ / m 2 For particles with a surface free energy of less than 50 mJ / m², the surface free energy is preferably 50 mJ / m². 2 More preferably, 45 mJ / m 2 More preferably, 40 mJ / m 2 More preferably, 36 J / m 2 The following applies:

[0198] In the composite particles of this disclosure, the surface free energy is 70 mJ / m 2 Particles smaller than the following are preferably PTFE particles (surface free energy = 18 mJ / m 2 ), Hydrocarbon particles (surface free energy = 22 mJ / m) 2 ), Polyethylene particles (surface free energy = 31 mJ / m) 2 ), Polystyrene particles (surface free energy = 33 mJ / m 2 ), Polyvinylidene fluoride particles (surface free energy = 33 mJ / m) 2 ), Polyvinyl alcohol particles (surface free energy = 37 mJ / m 2 ), Polyvinyl chloride particles (surface free energy = 39 mJ / m 2 ), Polyvinyldenium chloride particles (surface free energy = 40 mJ / m) 2 ), Polyethylene terephthalate particles (surface free energy = 43 mJ / m) 2 ), Nylon particles (surface free energy = 46 mJ / m 2 ), Zinc oxide particles (surface free energy = 30.6~35.8 mJ / m 2 ) and Carbon nanotube granules (surface free energy = 40 mJ / m 2 More than 70mJ / m 2 It is at least one particle selected from the group consisting of (less than)

[0199] In the composite particles of this disclosure, the surface free energy is 70 mJ / m 2 For particles smaller than 1000, PTFE particles or carbon nanotube granules are preferred, and PTFE particles are particularly preferred, as they can be well dispersed in an aqueous solvent.

[0200] In the composite particles of this disclosure, the surface free energy is 70 mJ / m 2 The primary particle diameter of particles smaller than 10 nm is preferably between 10 nm and 1000 nm. This primary particle diameter can be measured, for example, by a particle size analyzer (such as the "Zetasizer Nano ZS" manufactured by Malvern Panalytical).

[0201] In the composite particles of this disclosure, the surface free energy is 70 mJ / m 2 For particles smaller than a certain size, a wide range of commercially available products can be used. Examples of commercially available products include "Dinion TF9202Z" manufactured by 3M Japan Limited and "Lubron L-5" manufactured by Daikin Industries, Ltd.

[0202] 5. Composite particle dispersion The composite particle dispersion of the present disclosure comprises the composite particles of the present disclosure and an aqueous solvent, wherein the composite particles are dispersed in the aqueous solvent.

[0203] Details of the copolymers of this disclosure are as described in "1. Copolymers" above unless otherwise specified. Details of the composite particles of this disclosure are as described in "4. Composite Particles" above unless otherwise specified.

[0204] The dispersion of the composite particles of this disclosure in an aqueous solvent can be carried out by adding the composite particles of this disclosure to the aqueous solvent and stirring.

[0205] As the aqueous solvent mentioned above, water, water-soluble organic solvents, and mixed solvents thereof can be used. Examples of water include natural water, purified water, distilled water, ion-exchanged water, and pure water.

[0206] Examples of the water-soluble organic solvents mentioned above include alcohol compounds, ketone compounds, ether compounds, amide compounds, sulfoxide compounds, ester compounds, glycol compounds, etc. These can be used individually or in combination of two or more.

[0207] Examples of the above-mentioned alcohol compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, and tert-butyl alcohol, which can be used individually or in combination of two or more.

[0208] Examples of the ketone compounds mentioned above include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone, etc. These can be used individually or in combination of two or more.

[0209] Examples of the ether compounds mentioned above include diethyl ether, tetrahydrofuran (THF), and dioxane, which can be used individually or in combination of two or more.

[0210] Examples of the above-mentioned amide compounds include N,N-dimethylformamide (DMF) and N,N-dimethylacetamide, which can be used individually or in combination of two or more.

[0211] Examples of the above-mentioned sulfoxide compounds include dimethyl sulfoxide (DMSO).

[0212] Examples of the ester compounds mentioned above include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl carbonate, and ethyl lactate. These can be used individually or in combination of two or more.

[0213] Examples of the glycol compounds mentioned above include ethylene glycol, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, and other glycol compounds. These can be used individually or in combination of two or more.

[0214] In this disclosure, the content of the composite particles of this disclosure in the composite particle dispersion is preferably 1% by mass or more and 70% by mass or less.

[0215] This disclosure provides subject matter in the following aspects: Section 1. It contains a constituent unit (A) derived from monomer (a) and a constituent unit (B) derived from monomer (b) having a hydroxyl group or a phosphate group, The mass-average molecular weight is between 1,000 and 30,000. A copolymer in which the monomer (a) is a monomer represented by the following formula (1). [ka] [In the formula, R 1 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. R 2 This represents a single bond or a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents. m represents a number between 1 and 10, with an average value. R 3 -R a -Si(R b )3(R a R represents a linear or branched alkylene group having 1 to 10 carbon atoms. b (wherein represents a trialkylsiloxy group having 1 to 4 carbon atoms), or a group represented by the following formula (1A). [ka] (In the formula, Rc R represents a linear or branched alkylene group having 1 to 10 carbon atoms. d R represents a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms, p represents a number between 5 and 150 on average, and R e This represents a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms. Section 2. In the above equation (1), R 3 The copolymer according to item 1, wherein the alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms. Section 3. In the above equation (1), R 2 However, it is a single bond, R 3 However, -R a -Si(R b )3(R a R is a linear or branched alkylene group having 1 to 10 carbon atoms. b (wherein R is a trialkylsiloxy group having 1 to 4 carbon atoms), or a group represented by the above formula (1A)). c R is a linear or branched alkylene group having 1 to 10 carbon atoms. d R is a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms, p is a number between 5 and 150 on average, and R e The copolymer according to item 1, wherein ( is a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms). Section 4. The copolymer according to any one of claims 1 to 3, further containing a constituent unit (C) derived from a monomer (c) having a phenyl group. Section 5. The copolymer according to any one of claims 1 to 4, wherein the content of the constituent unit (A) is 5 to 70 mol% relative to the total of the constituent units (A) and (B) (100 mol%). Section 6. The copolymer according to claim 4 or 5, wherein the content of the constituent unit (C) is 1 to 20 mol% relative to the total of the constituent units (A), (B), and (C) (100 mol%). Section 7. The copolymer according to any one of claims 1 to 6, wherein the monomer (b) having a hydroxyl group or a phosphate group is a monomer represented by the following formula (2). [ka] (In the formula, R 4 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. R 5 This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, or a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents. n represents a number between 1 and 20 on average. R 5 However, in the case of a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, R 6 This represents a hydroxyl group or a phosphate group. R 5 However, in the case of a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents, R 6 (This represents a hydrogen atom or a phosphate group.) Section 8. The copolymer according to any one of claims 4 to 7, wherein the monomer (c) having a phenyl group is a monomer represented by the following formula (3). [ka] (In the formula, R 7 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. X represents -C(=O)NH- or -C(=O)O-. R 8 This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have single bonds or substituents. R 9 -O-, -CH(OH)-, -OC(=O)-, or -OC(=O)O- represent a single bond, -O-, -CH(OH)-, -OC(=O)O-, or -OC(=O)O-. R 10 , R 11 , R 12 , R 13and R 14 Each of these independently represents either a hydrogen atom or a hydroxyl group. However, R 10 , R 11 , R 12 , R 13 and R 14 (Except when all atoms are hydrogen atoms.) Section 9. A copolymer according to any one of items 1 to 8, Surface free energy is 70 mJ / m 2 Particles smaller than and Includes, A composite particle in which the copolymer is attached to the surface of the particle. Section 10. The composite particles further contain a surfactant, The composite particle according to item 9, wherein the surfactant is attached to the surface of the particles. Section 11. The composite particles described in item 9, Aqueous solvent and Includes, A composite particle dispersion in which the composite particles are dispersed in the aqueous solvent. Section 12. The composite particles described in item 10, Aqueous solvent and Includes, A composite particle dispersion in which the composite particles are dispersed in the aqueous solvent. Section 13. A method for producing a copolymer according to any one of items 1, 2, 3, 5, and 7, A method for producing monomers, comprising the step of copolymerizing monomer (a) and monomer (b) having a hydroxyl group or a phosphate group in the presence of a chain transfer agent. Section 14. A method for producing a copolymer according to any one of items 4, 6, and 8, A method for producing monomers, comprising the step of copolymerizing monomer (a), monomer (b) having a hydroxyl group or a phosphate group, and monomer having a phenyl group in the presence of a chain transfer agent. Section 15. A dispersant comprising a copolymer as described in any one of items 1 to 8. Section 16. A coating agent comprising a copolymer as described in any one of items 1 to 8. Section 17. A paint comprising a copolymer as described in any one of items 1 to 8. Section 18. A lubricating film comprising a copolymer as described in any one of items 1 to 8. Section 19. A battery comprising a copolymer as described in any one of items 1 to 8. [Examples]

[0216] The present disclosure will be described in more detail below based on the examples, but the present disclosure is not limited to the embodiments of these examples. In the following examples and comparative examples, "room temperature" means a temperature within the range of 20°C to 25°C.

[0217] <Measurement Method and Evaluation Method> The measurement and evaluation methods for the examples and comparative examples are as follows. In the measurement and evaluation methods, the copolymers obtained in each example and comparative example will simply be referred to as "polymers".

[0218] <Method for measuring mass-average molecular weight and number-average molecular weight> The mass-average molecular weight and number-average molecular weight of the copolymer refer to the mass-average molecular weight and number-average molecular weight in terms of polystyrene (PS), measured using gel permeation chromatography (GPC). Specifically, the mass-average molecular weight and number-average molecular weight were measured as follows. The results are shown in Table 1. The GPC measurement conditions for the copolymer were as follows. (Sample preparation) As a pretreatment, approximately 10 mg of copolymer was weighed into a 2 mL volumetric flask and diluted to a final volume with 2 mL of THF. After confirming that the copolymer was dissolved, the solution was filtered through a non-aqueous 0.45 μm syringe filter manufactured by Shimadzu GLC Corporation and measured. (GPC measurement conditions) • Equipment: Shimadzu Corporation "Prominence 20A" high-performance liquid chromatograph (GPC optional software) • Guard column = Shimadzu Corporation "Shim-pack GPC-800P" (4.6mm I.D. x 10mm) x 1 • Columns = Shimadzu Corporation's "Shim-pack GPC-801" (8mm I.D. x 300mm) x 2, "Shim-pack GPC-803" (8mm I.D. x 300mm) x 1, "Shim-pack GPC-804" (8mm I.D. x 300mm) x 1 Column temperature = 40°C Mobile phase = tetrahydrofuran (THF) ·Mobile phase flow rate = 1.0mL / min • Detector = RI ·Injection volume=100μL • Measurement time = 45 minutes • Sampling pitch = 500 msec The standard polystyrene samples used for the calibration curve were Showa Denko Corporation's product names "STANDARD SM-105" and "STANDARD SH-75," with mass-average molecular weights of 5,620,000, 3,120,000, 1,250,000, 442,000, 151,000, 53,500, 17,000, 7,660, 2,900, and 1,320. A[(I) 5,620,000, (II) 1,250,000, (III) 151,000, (IV) 17,000, (V) 2,900] and The compounds were grouped into categories B[(VI)3,120,000, (VII)442,000, (VIII)53,500, (IX)7,660, (X)1,320]. Then, A was weighed [(I)2mg, (II)3mg, (III)4mg, (IV)4mg, (V)4mg] and dissolved in 30mL of THF to prepare a solution for A. Next, B was weighed ((VI)3mg, (VII)4mg, (VIII)4mg, (IX)4mg, (X)4mg) and dissolved in 30mL of THF to prepare a solution for B. A standard polystyrene calibration curve was obtained by injecting 100μL each of the prepared solutions for A and B, measuring the results, and then creating a calibration curve (cubic equation) from the retention times obtained. The mass-average molecular weight and number-average molecular weight were calculated using the obtained calibration curve.

[0219] <Method 1 for evaluating solubility> First, 5 g of deionized water and 0.05 g of copolymer were added to a glass container, and then the mixture was stirred at room temperature for 120 seconds using a vortex mixer ("Mixer N-61" manufactured by Nisshin Rika Co., Ltd.) to prepare an aqueous solution. The state of the aqueous solution immediately after preparation was visually inspected, and the solubility was evaluated according to the following evaluation criteria. The results are shown in Table 1. (Evaluation Criteria) ○: Transparent and completely dissolved △: Cloudy and partially dissolved ×: Does not dissolve

[0220] <Method for evaluating interfacial tension> The interfacial tension was measured using the DropMaster 300 solid-liquid interface analyzer (manufactured by Kyowa Interface Science Co., Ltd.) by the suspension drop method. First, a 22G gauge needle was used to create a suspension drop of the aqueous solution prepared using the solubility evaluation method described above. Next, the suspension drop was inflated to just before dropping, and the interfacial tension (mN / m) was determined using the ds / de method. Five tests were performed, and the average value was taken as the interfacial tension (mN / m) of the copolymer. This measurement was conducted in a constant temperature and humidity chamber at 20±2℃ and 65±10% humidity. A copolymer with an interfacial tension of 60 mN / m or less was evaluated as having excellent performance in reducing the interfacial tension of water.

[0221] (Example 1) In a glass container, 0.384 g of tert-butyl acrylate (trade name "TBA", manufactured by Osaka Organic Chemical Industry Co., Ltd., 128.2 g / mol) as monomer (a), 0.154 g of dopamine methacrylamide (DMA) (manufactured by Tokyo Chemical Industry Co., Ltd., 221.26 g / mol) as monomer (c), and 4.619 g of polyethylene glycol monoacrylate (n≒10) (trade name "Bremmer AE-400", manufactured by NOF Corporation, 513 g / mol) as monomer (b) are mixed together. 0.103 g of 3-mercapto-1,2-propanediol (trade name "1-thioglycerol", Asahi Chemical Industries, Ltd.) as a transfer agent, 0.052 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, 7.85 g of tetrahydrofuran (THF) as an organic solvent, and 7.85 g of isopropanol (IPA) as an organic solvent were mixed and dissolved at room temperature using a vortex mixer. Next, the container was purged with nitrogen and polymerization was carried out in a glove box at 55°C for 24 hours. After polymerization, the copolymer was purified by reprecipitation in hexane, and the purified copolymer was dried in a vacuum oven (ESPEC Corporation's "Vacuum Oven LHV-112") at 70°C under vacuum conditions for 16 hours. The above measurements and evaluations were performed on the copolymer after drying.

[0222] (Example 2) A copolymer was prepared using the same formulation and method as in Example 1, except that 0.650 g of TBA was used as monomer (a), 3.551 g of Bremmer AE-400 was used as monomer (b), 0.087 g of 1-thioglycerol was used as a chain transfer agent, and 0.044 g of V-65 was used as a polymerization initiator. The prepared copolymer was subjected to the above measurements and evaluations.

[0223] (Example 3) A copolymer was prepared using the same formulation and method as in Example 1, except that 0.384 g of isobutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 128.2 g / mol) was used as monomer (a). The prepared copolymer was subjected to the above measurements and evaluations.

[0224] (Example 4) A copolymer was prepared using the same formulation and method as in Example 1, except that 0.650 g of isobutyl acrylate, 3.551 g of Bremmer AE-400, 0.087 g of 1-thioglycerol, and 0.044 g of V-65 were used as monomer (a). The prepared copolymer was subjected to the above measurements and evaluations.

[0225] (Example 5) A copolymer was prepared using the same formulation and method as in Example 1, except that 0.468 g of hexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 156.2 g / mol) was used as monomer (a), 0.155 g of DMA as monomer (c), 2.45 g of polyethylene glycol monoacrylate ("Bremmer AE-200" manufactured by NOF Corporation, n ≈ 4.5, 272 g / mol) as monomer (b), 0.026 g of 1-thioglycerol as a chain transfer agent, 0.026 g of V-65 as a polymerization initiator, and 16.1 g of IPA alone as the organic solvent. The prepared copolymer was subjected to the above measurements and evaluations. In Example 5, unlike Example 1, THF was not used as the organic solvent.

[0226] (Example 6) A copolymer was prepared using the same formulation and method as in Example 1, except that 0.553 g of 2-ethylhexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 184.28 g / mol) was used as monomer (a), 0.155 g of DMA was used as monomer (c), 2.45 g of Bremmer AE-200 was used as monomer (b), 0.026 g of 1-thioglycerol was used as a chain transfer agent, 0.026 g of V-65 was used as a polymerization initiator, and 16.5 g of IPA alone was used as the organic solvent. The prepared copolymer was subjected to the above measurements and evaluations. In Example 6, unlike Example 1, THF was not used as the organic solvent.

[0227] (Example 7) Copolymers were prepared using the same formulation and method as in Example 1, except that 0.594 g of isononyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., 198.3 g / mol) was used as monomer (a), 0.155 g of DMA was used as monomer (c), 2.45 g of Bremmer AE-200 was used as monomer (b), 0.026 g of 1-thioglycerol was used as a chain transfer agent, 0.026 g of V-65 was used as a polymerization initiator, and 16.8 g of IPA alone was used as the organic solvent. The prepared copolymers were subjected to the above measurements and evaluations. In Example 7, unlike Example 1, THF was not used as the organic solvent.

[0228] (Example 8) A copolymer was prepared using the same formulation and method as in Example 1, except that 0.815 g of 2-ethylhexyl EO-modified acrylate (manufactured by Toagosei Co., Ltd., 272 g / mol) was used as monomer (a), 0.155 g of DMA was used as monomer (c), 4.617 g of Bremmer AE-400 was used as monomer (b), 0.048 g of 1-thioglycerol was used as a chain transfer agent, 0.048 g of V-65 was used as a polymerization initiator, and 17.9 g of IPA alone was used as the organic solvent. The prepared copolymer was subjected to the above measurements and evaluations. In Example 8, unlike Example 1, THF was not used as the organic solvent.

[0229] (Example 9) Copolymers were prepared using the same formulation and method as in Example 1, except that 0.385 g of TBA was used as monomer (a), 0.207 g of DMA as monomer (c), 4.617 g of Bremmer AE-400 as monomer (b), 0.026 g of 1-thioglycerol as a chain transfer agent, and 30.0 g of ethanol alone as the organic solvent. The prepared copolymers were subjected to the above measurements and evaluations. In Example 9, unlike Example 1, THF was not used as the organic solvent.

[0230] (Example 10) Copolymers were prepared using the same formulation and method as in Example 1, except that 0.385 g of TBA was used as monomer (a), 0.207 g of DMA as monomer (c), 4.617 g of Bremmer AE-400 as monomer (b), 0.208 g of 1-thioglycerol as a chain transfer agent, and 30.0 g of ethanol alone as the organic solvent. The prepared copolymers were subjected to the above measurements and evaluations. In Example 10, unlike Example 1, THF was not used as the organic solvent.

[0231] (Example 11) Copolymers were prepared using the same formulation and method as in Example 1, except that 0.384 g of TBA was used as monomer (a), 0.236 g of 3,4,5-trihydroxybenzoic acid [2-hydroxy-3-(methacrylloyloxy)propyl] ester was used as monomer (c), 4.619 g of Bremmer AE-400 was used as monomer (b), 0.105 g of 1-thioglycerol was used as a chain transfer agent, and 30.0 g of IPA alone was used as the organic solvent. The prepared copolymers were subjected to the above measurements and evaluations. In Example 11, unlike Example 1, THF was not used as the organic solvent.

[0232] (Example 12) Copolymers were prepared using the same formulation and method as in Example 1, except that 0.384 g of isobutyl acrylate was used as monomer (a), 0.236 g of 3,4,5-trihydroxybenzoic acid [2-hydroxy-3-(methacrylloyloxy)propyl] ester was used as monomer (c), 4.619 g of Bremmer AE-400 was used as monomer (b), 0.105 g of 1-thioglycerol was used as a chain transfer agent, and 30.0 g of IPA alone was used as the organic solvent. The prepared copolymers were subjected to the above measurements and evaluations. In Example 12, unlike Example 1, THF was not used as the organic solvent.

[0233] (Example 13) Copolymers were prepared using the same formulation and method as in Example 1, except that 1.226 g of (3-acryloxypropyl)tris(trimethylsiloxy)silane (manufactured by NOF Corporation, "Bremmer SI-A") was used as monomer (a), 4.619 g of Bremmer AE-400 was used as monomer (b), 0.103 g of 1-thioglycerol was used as a chain transfer agent, 7.85 g of THF was used as an organic solvent, and 7.9 g of IPA was used as an organic solvent. The prepared copolymers were subjected to the above measurements and evaluations.

[0234] (Comparative Example 1) In a glass container, 0.200 g of DMA (manufactured by Tokyo Chemical Industry Co., Ltd., 221.26 g / mol) as monomer (c), 1.43 g of 2-(2-ethoxyethoxy)ethyl acrylate (EEA) (manufactured by Tokyo Chemical Industry Co., Ltd., 188.2 g / mol) as a hydrophilic monomer, 0.015 g of 2,2′-azobis(isobutyronitrile) (trade name "AIBN", manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization initiator, and 40 mL of 1,4-dioxane (dehydrated) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an organic solvent were mixed and dissolved at room temperature using a vortex mixer. Next, the container was purged with nitrogen, and polymerization was carried out in a glove box at 55°C for 24 hours. After polymerization, the copolymer was purified by reprecipitation in hexane, and the purified copolymer was dried in a vacuum oven (ESPEC Corporation's "Vacuum Oven LHV-112") at 70°C for 16 hours. In Comparative Example 1, unlike Example 1, monomer (a) and chain transfer agent were not used.

[0235] (Comparative Example 2) In a glass container, 0.385 g of TBA as monomer (a), 0.207 g of DMA as monomer (c), 4.617 g of Bremmer AE-400 as monomer (b), 0.052 g of V-65 as a polymerization initiator, and 30.0 g of ethanol as an organic solvent were mixed and dissolved at room temperature using a vortex mixer. Next, the container was purged with nitrogen, and polymerization was carried out in a glove box at 55°C for 24 hours. After polymerization, the copolymer was purified by reprecipitation in hexane, and the purified copolymer was dried in a vacuum oven (ESPEC Corporation's "Vacuum Oven LHV-112") at 70°C under vacuum conditions for 16 hours. The above measurements and evaluations were performed on the copolymer after drying. In Comparative Example 2, no chain transfer agent was used.

[0236] To evaluate the dispersibility of composite particles composed of copolymers and polytetrafluoroethylene (PTFE) particles obtained in Examples 1-4, the following Test Examples 1-1 to 1-4 were performed. In Test Examples 1-1 to 1-4, if the average particle diameter of the measured composite particle dispersion was within the range of 200 nm to 300 nm, it was evaluated that the composite particles were dispersed at their primary particle size. On the other hand, if the average particle diameter of the measured composite particle dispersion was greater than 300 nm, it was evaluated that the composite particles were aggregated.

[0237] (Test Example 1-1) First, 27 g of deionized water, 1.8 g of surfactant (polyoxyethylene tridecyl ether, "Neugen TDS-80" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 0.30 g of the copolymer obtained in Example 1 were added to a glass container. The mixture was then stirred at 6000 rpm for 2 minutes at room temperature using a homogenizer to dissolve the copolymer. Next, 15 g of polytetrafluoroethylene (PTFE) particles (primary particle size: 200 nm to 300 nm) ("Lebron L-5" manufactured by Daikin Industries, Ltd.) were added, and the mixture was stirred at 6000 rpm for 4 minutes at room temperature using a homogenizer ("Polytron PT10-35 GT" manufactured by KINEMATICA). Finally, ultrasonic treatment was performed at room temperature for 3 minutes using an ultrasonic homogenizer ("SONIFIER 450" manufactured by Branson) to obtain a composite particle dispersion (solid content concentration of PTFE particles = 40% by mass). The average particle size of the obtained composite particle dispersion was measured using a particle size analyzer ("Zetasizer Nano ZS" manufactured by Malvern Panalytical Corporation) under the following measurement conditions. (Measurement conditions for the average particle size of a composite particle dispersion) Cell: DTS0012 ·Temperature: 25℃ • Measurement time: 60 seconds Using the data analysis software installed in the above-mentioned particle size measuring device, the average particle size of the composite particle dispersion was measured, and it was found that the average particle size of the composite particle dispersion was 264 nm, confirming that the composite particles were dispersed at their primary particle size.

[0238] (Test Example 1-2) A composite particle dispersion (solid content of PTFE particles = 40% by mass) was obtained using the same formulation and method as in Test Example 1-1, except that 0.30 g of the copolymer obtained in Example 2 was used. When the average particle size of the obtained composite particle dispersion was measured using the same method as in Test Example 1, the average particle size of the composite particle dispersion was 270 nm, confirming that the composite particles were dispersed at the primary particle size.

[0239] (Test Examples 1-3) A composite particle dispersion (solid content of PTFE particles = 40% by mass) was obtained using the same formulation and method as in Test Example 1-1, except that 0.30 g of the copolymer obtained in Example 3 was used. When the average particle size of the obtained composite particle dispersion was measured using the same method as in Test Example 1, the average particle size of the composite particle dispersion was found to be 256 nm, confirming that the composite particles were dispersed at the primary particle size.

[0240] (Test Examples 1-4) A composite particle dispersion (solid content of PTFE particles = 40% by mass) was obtained using the same formulation and method as in Test Example 1-1, except that 0.30 g of the copolymer obtained in Example 4 was used. When the average particle size of the obtained composite particle dispersion was measured using the same method as in Test Example 1, the average particle size of the composite particle dispersion was 230 nm, confirming that the composite particles were dispersed at the primary particle size.

[0241] To evaluate the dispersion stability of composite particles in a composite particle dispersion, the following test examples 2-1 to 2-4 were performed. In test examples 2-1 to 2-4, if the measured sedimentation layer thickness was 5 mm or less, the composite particles in the composite particle dispersion were evaluated as having excellent dispersion stability.

[0242] (Test Example 2-1) The composite particle dispersion prepared in Test Example 1-1 was stored at room temperature and 20-40% humidity for 5 days after preparation, and the thickness of the settling layer was measured. Since the thickness of the settling layer was 3 mm, it was confirmed that the composite particles in the composite particle dispersion had excellent dispersion stability.

[0243] (Test Example 2-2) The composite particle dispersions prepared in Test Example 1-2 were stored at room temperature and 20-40% humidity for 5 days after preparation, and the thickness of the settling layer was measured. Since the thickness of the settling layer was 3 mm, it was confirmed that the composite particles in the composite particle dispersion exhibited excellent dispersion stability.

[0244] (Test Example 2-3) The composite particle dispersions prepared in Test Examples 1-3 were stored at room temperature and 20-40% humidity for 5 days after preparation, and the thickness of the settled layer was measured. Since the settled layer thickness was 2.5 mm, it was confirmed that the composite particles in the dispersion exhibited excellent dispersion stability.

[0245] (Test Example 2-4) The composite particle dispersions prepared in Test Example 1-4 were stored at room temperature and 20-40% humidity for 5 days after preparation, and the thickness of the settling layer was measured. Since the thickness of the settling layer was 2 mm, it was confirmed that the composite particles in the composite particle dispersion exhibited excellent dispersion stability.

[0246] The solubility of the copolymers obtained in Examples 5-8 was evaluated using Solubility Evaluation Method 2 described below. The solubility of the copolymers obtained in Examples 1-4 and 9-13, as well as Comparative Examples 1-2, was evaluated using Solubility Evaluation Method 1 described above.

[0247] <Method 2 for evaluating solubility> First, 1 g of deionized water and 0.25 g of copolymer were added to a glass container, and then the mixture was stirred at room temperature for 120 seconds using a vortex mixer ("Mixer N-61" manufactured by Nisshin Rika Co., Ltd.) to prepare an aqueous solution. The state of the aqueous solution immediately after preparation was visually inspected, and the solubility was evaluated according to the following evaluation criteria. (Evaluation Criteria) ○: Transparent and completely dissolved △: Cloudy and partially dissolved ×: Does not dissolve

[0248] The copolymers obtained in Examples 5-8 all showed solubility of "○".

[0249] Table 1 shows the formulation composition and results for each example and comparative example.

[0250] [Table 1]

[0251] [Discussion of the results in Table 1] The copolymers obtained in Examples 1 to 13 all had an interfacial tension of 60 mN / m or less, confirming their excellent ability to reduce the interfacial tension of water. Furthermore, the copolymers obtained in Examples 1 to 4 and 9 to 13 all received a "○" rating according to the solubility evaluation method 1, and the copolymers obtained in Examples 5 to 8 all received a "○" rating according to the solubility evaluation method 2, confirming that the copolymers obtained in Examples 1 to 13 all exhibited excellent solubility in water. The copolymers obtained in Comparative Examples 1 and 2 were insoluble in water. In addition, because the copolymers obtained in Comparative Examples 1 and 2 were insoluble in water, it was not possible to measure their interfacial tension.

Claims

1. It contains a constituent unit (A) derived from monomer (a) and a constituent unit (B) derived from monomer (b) having a hydroxyl group or a phosphate group, The mass-average molecular weight is between 1,000 and 30,000. A copolymer in which the monomer (a) is a monomer represented by the following formula (1). 【Chemistry 1】 [In the formula, R １ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. R ２ This represents a single bond or a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents. m represents a number between 1 and 10, with an average value. R ３ -R ａ -Si(R ｂ ) ３ (R ａ R represents a linear or branched alkylene group having 1 to 10 carbon atoms. ｂ (wherein it represents a trialkylsiloxy group having 1 to 4 carbon atoms), or a group represented by the following formula (1A). 【Chemistry 2】 (wherein R ｃ represents a linear or branched alkylene group having 1 to 10 carbon atoms, R ｄ represents a linear or branched alkyl group having 1 to 10 carbon atoms or a phenyl group, p represents a number with an average value of 5 or more and 150 or less, R ｅ represents a linear or branched alkyl group having 1 to 10 carbon atoms or a phenyl group.)]

2. In the above formula (1), R ３ The copolymer according to claim 1, wherein the alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms.

3. In the above formula (1), R ２ However, it is a single bond, R ３ However, -R ａ -Si(R ｂ ) ３ (R ａ R is a linear or branched alkylene group having 1 to 10 carbon atoms. ｂ (wherein R is a trialkylsiloxy group having 1 to 4 carbon atoms), or a group represented by the above formula (1A)). ｃ R is a linear or branched alkylene group having 1 to 10 carbon atoms. ｄ R is a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms, p is a number between 5 and 150 on average, and ｅ The copolymer according to claim 1, wherein ( is a linear or branched alkyl group or phenyl group having 1 to 10 carbon atoms).

4. The copolymer according to claim 2 or 3, further containing a constituent unit (C) derived from a monomer (c) having a phenyl group.

5. The copolymer according to claim 2 or 3, wherein the content of the constituent unit (A) is 5 to 70 mol% with respect to a total of 100 mol% of the constituent unit (A) and the constituent unit (B).

6. The copolymer according to claim 4, wherein the content of the constituent unit (C) is 1 to 20 mol% with respect to the total of 100 mol% of the constituent units (A), (B), and (C).

7. The copolymer according to claim 2 or 3, wherein the monomer (b) having a hydroxyl group or a phosphate group is a monomer represented by the following formula (2). 【Transformation 3】 (In the formula, R ４ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. R ５ This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, or a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents. n represents a number between 1 and 20 on average. R ５ However, in the case of a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, R ６ This indicates a hydroxyl group or a phosphate group. R ５ However, in the case of a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents, R ６ (This represents a hydrogen atom or a phosphate group.)

8. The copolymer according to claim 4, wherein the monomer (c) having a phenyl group is a monomer represented by the following formula (3). 【Chemistry 4】 (In the formula, R ７ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. X represents -C(=O)NH- or -C(=O)O-. R ８ This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have single bonds or substituents. R ９ This indicates a single bond, -O-, -CH(OH)-, -OC(=O)-, or -OC(=O)O-. R １０ , R １１ , R １２ , R １３ and R １４ Each of these independently represents either a hydrogen atom or a hydroxyl group. However, R １０ , R １１ , R １２ , R １３ and R １４ (Except when all atoms are hydrogen atoms.)

9. The copolymer according to claim 1 or 2, Surface free energy is 70 mJ / m ２ Particles smaller than and Includes, A composite particle in which the copolymer is attached to the surface of the particle.

10. The composite particles further contain a surfactant, The composite particle according to claim 9, wherein the surfactant is attached to the surface of the particles.

11. The composite particles according to claim 9, Aqueous solvent and Includes, A composite particle dispersion in which the composite particles are dispersed in the aqueous solvent.

12. The composite particles according to claim 10, Aqueous solvent and Includes, A composite particle dispersion in which the composite particles are dispersed in the aqueous solvent.

13. A method for producing the copolymer according to claim 1 or 2, A method for producing monomers, comprising the step of copolymerizing monomer (a) and monomer (b) having a hydroxyl group or a phosphate group in the presence of a chain transfer agent.

14. A method for producing the copolymer according to claim 4, A method for producing monomers, comprising the step of copolymerizing monomer (a), monomer (b) having a hydroxyl group or a phosphate group, and monomer (c) having a phenyl group in the presence of a chain transfer agent.

15. A dispersant comprising the copolymer according to claim 1 or 2.

16. A coating agent comprising the copolymer according to claim 1 or 2.

17. A paint comprising the copolymer according to claim 1 or 2.

18. A lubricating film comprising the copolymer described in claim 1 or 2.

19. A battery comprising the copolymer according to claim 1 or 2.

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