WO2020111078A1 - Dye transfer inhibiting agent, additive for detergents, and detergent composition - Google Patents

Abstract

A dye transfer inhibiting agent which contains at least one compound that is selected from the group consisting of: a polymer (I) which has a structural unit derived from a monomer (A) that contains an ethylenically unsaturated group and a hydrophilic functional group and a structural unit derived from a monomer (B) that contains an ethylenically unsaturated group and a dye affinity group; a polymer (II) which has a structural unit derived from a monomer (C) that contains an ethylenically unsaturated group, a dye affinity group and a hydrophilic functional group; and a compound (III) which has a dye affinity group and a hydrophilic functional group (provided that the compound (III) is not the polymer (I) nor the polymer (II)).

Description

Dye transfer inhibitor, detergent additive and detergent composition

The present disclosure relates to a dye transfer inhibitor, a detergent additive, and a detergent composition.

Conventionally, detergents such as zeolite, carboxymethyl cellulose, polyethylene glycol, and (meth)acrylic acid-based polymers are blended with detergent builders (detergent aids) for the purpose of improving the washing effect of detergents. Is being done. Regarding a polymer used as such a detergent builder, for example, in Patent Document 1, a structural unit (a) derived from a cationic group-containing monomer (A) represented by a predetermined structure and a carboxyl group-containing monomer are described. An amphoteric polymer essentially comprising a structural unit (b) derived from a monomer (B), wherein the amphoteric polymer has a total amount of structural units derived from all monomers forming the amphoteric polymer of 100. Disclosed is an amphoteric polymer containing 1 to 99% by mass of the structural unit (a) and 1 to 99% by mass of the structural unit (b) with respect to% by mass.

Also, when washing clothes, the dye contained in the clothes may exude and stain other parts. As a technique for preventing this, various additives such as polymers have been developed. Such an additive is called a dye transfer inhibitor (color transfer inhibitor). As a dye transfer inhibitor, for example, as described in Patent Document 2, a polymer of N-vinylpyrrolidone such as polyvinylpyrrolidone is known.

Japanese Patent Publication No. 2013-538877 Tokuyohei 8-505166

However, conventional dye transfer inhibitors still had room for improvement in dye transfer prevention ability.

The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a detergent additive or a dye transfer inhibitor having excellent dye transfer prevention ability. Another object of the present disclosure is to provide a detergent composition containing the detergent additive or the dye transfer inhibitor.

The dye transfer inhibitor or detergent additive of the present disclosure includes a structural unit derived from a monomer (A) having an ethylenically unsaturated group and a hydrophilic functional group, and an ethylenically unsaturated group and a dye affinity group. A polymer (I) having a structural unit derived from the monomer (B), a polymer having a structural unit derived from the monomer (C) containing an ethylenically unsaturated group, a dye affinity group and a hydrophilic functional group. A compound (II) and at least one compound selected from the group consisting of a compound (III) having a dye-affinity group and a hydrophilic functional group (however, not the polymer (I) or the polymer (II)). Including.

The dye affinity group is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted pyrazole group, a substituted or unsubstituted cyclic amide group, a substituted or unsubstituted imidazole group, a substituted or unsubstituted Substituted azobenzene group, substituted or unsubstituted carbazole group, quaternary ammonium group, substituted or unsubstituted piperidine group, substituted or unsubstituted benzotriazole group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyridinium Group, substituted or unsubstituted amidine group, substituted or unsubstituted pyrimidine group, substituted or unsubstituted pyrazine group, substituted or unsubstituted pyridazine group, substituted or unsubstituted indole group, and substituted or unsubstituted cyclic imide It is preferably at least one selected from the group consisting of groups.

The hydrophilic functional group is at least one selected from the group consisting of a carboxyl group and a salt thereof, a sulfonic acid group and a salt thereof, a phosphoric acid group and a salt thereof, an alkylene oxide group, a polyalkylene oxide group, a hydroxyl group, and an amino group. Is preferred.

It is preferable that the monomer (B) is at least one of the compound represented by the following formula (I) and the compound represented by the following formula (II).

(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, X is a covalent bond, —C(═O)O—, —C(═O)O—R ³⁵ —(R ³⁵ is A divalent hydrocarbon group having 2 to 20 carbon atoms), —C(═O)NH—), —CH ₂ —O—CH ₂ CH(OH)CH ₂ —, —CH(OH)—CH _2- CH ₂ —O— or a divalent group having a benzene ring substituted with a hydroxyl group and having 3 to 10 carbon atoms, and Y is represented by the following formulas (I-1), (I-2), (I -3), (I-4), (I-5), (I-6), (I-7), (I-8), (I-9), (I-10), (I-11 ), (I-12), (I-13), (I-14), (I-15) or (I-16),

In formulas (I-1) to (I-8), (I-10) to (I-14), and (I-16), one or more hydrogen atoms bonded to carbon atoms contained in the ring are substituted. Optionally substituted by a group,
In (I-1), m is an integer of 0 to 5, n in the formula (I-2) is an integer of 2 to 6, and the formula (I-8), the formula (I-9), and the formula (I-9) In I-12), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrocarbon group having 1 to 10 carbon atoms or Represents a hydrogen atom, and in the formula (I-11), Z is a divalent hydrocarbon group having 1 to 10 carbon atoms, and m11 in the formula (I-13) is an integer of 0 to 5. M12 in formula (I-14) is an integer of 0 to 5, and R ⁴⁰ , R ⁴¹ , and R ⁴² in formula (I-15) are each independently a hydrocarbon group having 1 to 6 carbon atoms. Represents a hydrogen atom or a cyano group, and in the formula (I-16), R ⁴³ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z ¹¹ is a sulfonic acid group or a salt thereof.
In the formula (II), Ar is a divalent group in which two of the hydrogen atoms bonded to the ring of naphthalene or anthracene are removed, and the divalent group may be substituted, R ⁴⁷ and R ^48's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. )

The monomer (B) is N-vinylpyrrolidone, N-vinylimidazole, styrene, benzyl (meth)acrylate, N-vinylcarbazole, allyl glycidyl ether-added pyrazole, allyl glycidyl ether-added trimethylamine, 2, 2, 6, 6-Tetramethyl-4-piperidyl (meth)acrylate, 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole, and 1,2,2,6 ,6-Pentamethyl-4-piperidyl (meth)acrylate, 4-indole (meth)acrylate, 11-[4-(4-butylphenylazo)phenoxy]undecyl (meth)acrylic acid, N,N-dimethyl-amino- 1,4-phenylene(meth)acrylamide, 1-naphthylmethyl(meth)acrylate, 9-anthrylmethyl(meth)acrylate, acenaphthylene, N-cyano-N'-(meth)acryloylguanidine, and 1-(3- It is preferably at least one of the monomers selected from the group consisting of (sulfopropyl)-2-vinylpyridinium hydroxide inner salt.

The monomer (A) is a monomer selected from the group consisting of (meth)acrylic acid, polyethylene glycol (meth)acrylate, maleic acid and 2-(meth)acrylamido-2-methylpropanesulfonic acid or a salt thereof. It is preferably at least one body.

The detergent composition of the present disclosure contains the dye transfer inhibitor or detergent additive.

According to the present disclosure, it is possible to provide a dye transfer inhibitor or a detergent additive having excellent dye transfer prevention ability. Moreover, this disclosure aims at providing the detergent composition containing the said dye transfer inhibitor or the additive for detergents.

The dye transfer inhibitor or detergent additive of the present embodiment comprises a structural unit derived from a monomer (A) having an ethylenically unsaturated group and a hydrophilic functional group, an ethylenically unsaturated group and a dye affinity group. A polymer (I) having a structural unit derived from the monomer (B) containing, a structural unit derived from the monomer (C) containing an ethylenically unsaturated group, a dye affinity group and a hydrophilic functional group. At least one compound selected from the group consisting of the polymer (II) and the compound (III) having a dye-affinitive group and a hydrophilic functional group (however, not the above-mentioned polymer (I) and polymer (II)). including.

<Polymer (I)>
The polymer (I) of the present embodiment is a monomer containing a structural unit derived from a monomer (A) containing an ethylenically unsaturated group and a hydrophilic functional group, and a monomer containing an ethylenically unsaturated group and a dye affinity group. And a structural unit derived from (B). The monomer (A) does not include those contained in the monomer (B).

The hydrophilic functional group contained in the monomer (A) is a functional group that serves as a hydrogen bond donor or acceptor, and is a carboxyl group and its salt, a sulfonic acid group and its salt, a phosphoric acid group and its salt, or an alkylene oxide group. , Polyalkylene oxide groups, hydroxyl groups, and amino groups. These may be contained in the polymer (I) alone or in combination of two or more. Examples of the cation contained in the salt include alkali metal and ammonium ion. The monomer (A) may be polymerized in a salt state and incorporated into the polymer (I), or may be polymerized in an acid state and incorporated into the polymer (I), followed by neutralization to form a salt. May be In addition, the polyalkylene oxide group may have a hydroxyl group at one end, and the hydroxyl group may be ether-bonded to the hydrocarbon group. As the hydrocarbon group which is ether-bonded to the polyalkylene oxide group, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.

When the monomer (A) contains a carboxyl group, specific monomers include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid monoesters and the like. More specifically, (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, cinnamic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate, itaconic anhydride, monomethyl itaconate. , Monobutyl itaconic acid, vinyl benzoic acid, monohydroxyethyl (meth)acrylate oxalate, carboxyl group-terminated caprolactone modified acrylate (for example, "Plaxel FA" series; manufactured by Daicel Industries, Ltd.), carboxyl group-terminated caprolactone modified methacrylate (for example, "Plaxel FMA") Series; manufactured by Daicel Industries, Ltd.) and the like. Among these, (meth)acrylic acid and itaconic acid are preferable. These can be used by appropriately selecting one kind or two or more kinds.

When the monomer (A) contains a hydroxyl group, specific monomers include a hydroxyl group-containing (meth)acrylic acid ester, and more specifically, 2-hydroxyethyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate. Hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate (for example, manufactured by Daicel Chemical Industries, Ltd. Praxel F" series, etc.) and the like.

Examples of the compound having an ethylenically unsaturated group and an alkylene oxide group or a polyalkylene oxide group include compounds represented by the following formula (A).

In the above formula (A), A represents a hydrogen atom or an organic group which may have a substituent and has 1 to 20 carbon atoms, and X ¹ is —C(═O)—, —CH ₂ —, —CH ₂ CH ₂ — or a single bond, Q represents an alkylene group having 2 to 20 carbon atoms, n1 represents a repeating unit of an alkylene oxide group and represents a number of 1 to 200, and A _k represents a hydrogen atom or a substituent Represents an organic group having 1 to 20 carbon atoms which may have.

Each of A and A _k is preferably a hydrogen atom or an organic group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an organic group having 1 to 8 carbon atoms, and when it has a substituent, More preferably, the number of carbon atoms including the substituents is in the above range. More preferably, A is a hydrogen atom or a methyl group.

The above Q is preferably an alkylene group having 2 to 5 carbon atoms, and more preferably an ethylene group, an n-propylene group or an isopropylene group. Note that Q may include only one type of alkylene group, but may include two or more types of alkylene groups. When Q contains an ethylene group, 50 to 100 mol% of the total alkylene glycol units in the polyalkylene glycol group is preferably an ethylene group, more preferably 80 to 100 mol% is an ethylene group, and 90 It is preferable that about 100 mol% is an ethylene group.

N1 may be the average number of added moles of the entire compound represented by the formula (A). n1 is preferably 2 to 150, more preferably 10 to 100, and further preferably 20 to 70.

As the monomer (A), 2-(meth)acrylamido-2-methylpropanesulfonic acid or a salt thereof (sodium salt or the like), 2-hydroxy-3-allyloxypropanesulfonic acid or a salt thereof (sodium salt) Etc.), 2-(meth)acryloyloxyethanesulfonic acid or a salt thereof (sodium salt, etc.), 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxyethyl acid phosphate, and the like.

As the monomer (A), (meth)acrylic acid, the above-mentioned polyethylene glycol (meth)acrylate, maleic acid, 2-(meth)acrylamido-2-methyl-1-propanesulfonic acid sodium salt and the like are preferable.

As the dye affinity group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted pyrazole group, a substituted or unsubstituted cyclic amide group, a substituted or unsubstituted imidazole group, a substituted or unsubstituted Substituted azobenzene group, substituted or unsubstituted carbazole group, quaternary ammonium group, substituted or unsubstituted piperidine group, substituted or unsubstituted benzotriazole group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyridinium Group, substituted or unsubstituted amidine group (-C(=NH)NH ₂ ), substituted or unsubstituted pyrimidine group, substituted or unsubstituted pyrazine group, substituted or unsubstituted pyridazine group, substituted or unsubstituted indole Groups, and substituted or unsubstituted cyclic imide groups and the like. These may be contained in the polymer (I) alone or in combination of two or more. When these groups are substituted, the substituent is not particularly limited, but from the viewpoint of imparting hydrophilicity or hydrophobicity, a hydroxyl group, a sulfonic acid group, an alkyl group having 1 to 6 carbon atoms, an amino group Etc. As the alkyl group having 1 to 6 carbon atoms, a methyl group is preferable. The substituent is preferably bonded to the aromatic ring of each dye affinity group. As the amino group, a —NH ₂ group, a —NHR ³¹ group, and a —NR ³² R ³³ group (R ³¹ , R ³² , and R ³³ are each a hydrocarbon group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms). 6 alkyl group, and may be an alkyl group having 1 to 4 carbon atoms).
Examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4- Examples thereof include a phenanthryl group and a 9-phenanthryl group.
Examples of the aralkyl group include groups represented by the formula —R ⁴⁵ —Ar ¹ . In the formula, Ar ¹ is an aryl group, specifically, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group. , 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like. R ⁴⁵ is a divalent hydrocarbon group having 1 to 5 carbon atoms, and may be an alkylene group having 1 to 5 carbon atoms. Examples of the substituent which the substituted aralkyl group has include a hydroxyl group, a sulfonic acid group, an alkyl group having 1 to 6 carbon atoms (only when the aryl moiety is substituted), an amino group and the like.

Examples of the pyrazole group include a pyrazol-1-yl group, a pyrazol-2-yl group (pyrazolium group), a pyrazol-3-yl group, a pyrazol-4-yl group, a pyrazol-5-yl group, and the like. The 1-yl group is preferred. The counter anion of the pyrazolium group is not particularly limited, but includes a halide ion.
Examples of the pyridyl group include a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.
Examples of the pyridinium group include a pyridinium-1-yl group, a pyridinium-2-yl group, a pyridinium-3-yl group, and a pyridinium-4-yl group. The counter anion of the pyridinium group is not particularly limited, and examples thereof include a halide ion, a sulfate ion, a nitrate ion and the like, and the pyridinium group is an anion moiety (sulfonic acid group etc.) existing in the same molecule as the pyridinium group and an intramolecular It may form a salt.
The pyridinium group preferably has a substituted or unsubstituted hydrocarbon group bonded to the nitrogen of the pyridinium group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 4. Further, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferable and an alkyl group is preferable. When the hydrocarbon group has a substituent, examples of the substituent include a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, and the like. When the substituent is an anionic substituent, it may form an inner salt with the pyridinium group. The substituted or unsubstituted hydrocarbon group bonded to the nitrogen of the pyridinium group is directly bonded to a moiety (vinyl group, (meth)acryloyl group, (meth)acrylamide group) having an ethylenically unsaturated group in the molecule. Good.
The substituted or unsubstituted amidine group may be an unsubstituted amidine group, but one or more of hydrogen atoms bonded to the nitrogen atom of the amidine group are substituted with a cyano group (cyano group). Amidine group) is preferable, and one in which one is substituted with a cyano group (monocyanoamidine group) is more preferable. The cyanoamidine group may be one in which a hydrogen atom which is not substituted with a cyano group is substituted with a substituent (such as an alkyl group having 1 to 6 carbon atoms).

Examples of the pyrimidine group include a pyrimidin-1-yl group (pyrimidinium group), a pyrimidin-2-yl group, a pyrimidin-4-yl group, and a pyrimidin-5-yl group. Examples of the pyrazine group include a pyrazin-1-yl group (pyrazinium group), a pyrazin-2-yl group and a pyrazin-3-yl group. Examples of the pyridazine group include a pyridazin-1-yl group (pyridazinium group), a pyridazin-3-yl group and a pyridazin-4-yl group. The counter anion of the pyridinium group, the pyradium group, and the pyridazinium group is not particularly limited, but includes a halide ion.

The cyclic amide group is preferably an N-cyclic amide group, and examples thereof include an N-pyrrolidone group, an N-5-methylpyrrolidone group, an N-piperidone group and an N-ε-caprolactam group.

Examples of the imidazole group include imidazol-1-yl group, imidazol-2-yl group, imidazol-3-yl group (imidazolium group), imidazol-4-yl group, imidazol-5-yl group, and the like. The 1-yl group is preferred. The counter anion of the imidazolium group is not particularly limited, but includes a halide ion.

Examples of the carbazol group include a carbazol-1-yl group, a carbazol-2-yl group, a carbazol-3-yl group, a carbazol-4-yl group and a carbazol-9-yl group, and a carbazol-4-yl group. A carbazol-9-yl group is preferred.

Examples of the benzotriazole group include a benzotriazol-1-yl group, a benzotriazol-2-yl group, a benzotriazol-4-yl group, and a benzotriazol-5-yl group. preferable.

Examples of the azobenzene group include an azobenzene-1-yl group, an azobenzene-2-yl group, an azobenzene-3-yl group, an azobenzene-4-yl group and the like, and an azobenzene-4-yl group is preferable. The bonding position of the azobenzene group is designated by the smallest number when counted along the ring of the benzene ring, with the carbon of the benzene ring to which the azo group is bonded as the first position.

Examples of the indole group include indol-1-yl group, indol-2-yl group, indol-3-yl group, indol-4-yl group, indol-5-yl group, indol-6-yl group, indol-7 An yl group.

The cyclic imide group is preferably a group having a 5-membered cyclic imide group, and more specifically, a succinimide group (N-succinimide group), a maleic imide group (N-maleic imide group) And a phthalimide group (N-phthalimide group).

Examples of the piperidine group include a 4-piperidin group, and a 2,2,6,6-tetraalkylpiperidin-4-yl group and a 1,2,2,6,6-pentaalkylpiperidin-4-yl group preferable. The alkyl group of the 2,2,6,6-tetraalkylpiperidin-4-yl group and the 1,2,2,6,6-pentaalkylpiperidin-4-yl group has 1 to 10 carbon atoms. It is preferably an alkyl group having. The quaternary ammonium group is preferably one having three monovalent alkyl groups, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms.

More specifically, the monomer (B) is preferably a compound represented by the following formula (I) or a compound represented by the following formula (II).

(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, X is a covalent bond, —C(═O)O—, —C(═O)O—R ³⁵ —(R ³⁵ is A divalent hydrocarbon group having 2 to 20 carbon atoms, which may be an alkylene group having 2 to 20 carbon atoms, or an alkylene group having 5 to 15 carbon atoms), -C(=O) NH—), —CH ₂ —O—CH ₂ CH(OH)CH ₂ —, —CH(OH)—CH ₂ —CH ₂ —O— or a benzene ring substituted with a hydroxyl group and having 3 to 10 carbon atoms. A divalent group, Y is represented by the following formulas (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), ( I-7), (I-8), (I-9), (I-10), (I-11), (I-12), (I-13), (I-14), (I- 15) or a functional group represented by (I-16),

In formulas (I-1) to (I-8), (I-10) to (I-14), and (I-16), one or more hydrogen atoms bonded to carbon atoms contained in the ring are substituted. It may be substituted with a group, and the substituent includes a hydroxyl group, a sulfonic acid group, an alkyl group having 1 to 6 carbon atoms, an amino group and the like, and the alkyl group includes a methyl group and the like. In the formula (I-1), m is an integer of 0 to 5, preferably 0, 1 or 2, and in the formula (I-2), n is an integer of 2 to 6 and an integer of 3 to 5. It is preferable that R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R in formula (I-8), formula (I-9) and formula (I-12) are present. ¹⁹ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and in the formula (I-11), Z is a divalent hydrocarbon having 1 to 10 carbon atoms. A group, which may contain a carbon-carbon double bond or an aromatic ring, m11 in the formula (I-13) is an integer of 0 to 5, preferably 0, 1 or 2 and represented by the formula (I-14) M12 in is an integer of 0 to 5, preferably 0, 1 or 2, and R ⁴⁰ , R ⁴¹ , and R ⁴² in formula (I-15) are independently carbonized having 1 to 6 carbon atoms. It represents a hydrogen group, a hydrogen atom, or a cyano group, preferably at least one of R ⁴⁰ , R ⁴¹ , and R ⁴² is a cyano group (—CN), and R ⁴⁰ and R ⁴¹ are each independently 1 to 6 More preferably, it is a hydrocarbon group having 1 carbon atom or a hydrogen atom, and R ⁴² is a cyano group, and in the formula (I-16), R ⁴³ is a divalent hydrocarbon group having 1 to 6 carbon atoms. And is preferably an alkylene group having 1 to 6 carbon atoms, and Z ¹¹ is a sulfonic acid group or a salt thereof.
In the formula (II), Ar is a divalent group obtained by removing two of the hydrogen atoms bonded to the ring of naphthalene or anthracene, and the divalent group may be substituted. Include a hydroxyl group, a sulfonic acid group, an alkyl group having 1 to 6 carbon atoms, an amino group, and the like, and the alkyl group includes a methyl group and the like. R ⁴⁷ and R ⁴⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group may be an alkyl group, an alkyl group having 1 to 3 carbon atoms, or a methyl group. )

When Y is a group represented by formula (I-9), Y has a counter anion. Examples of the counter anion include halide ions. When Y is a group represented by the formula (I-9), R ¹¹ , R ¹² and R ¹³ are preferably each independently a hydrocarbon group having 1 to 10 carbon atoms. A hydrocarbon group having 1 to 6 carbon atoms is more preferable, and a hydrocarbon group having 1 to 4 carbon atoms is further preferable.
When Y is a group represented by formula (I-1), the phenyl group in formula (I-1) may be an unsubstituted phenyl group, but in the case of a substituted phenyl group, it is substituted with an amino group. It may have been done. The amino group may be bonded to any position of the ortho position, the meta position and the para position in the phenyl group, but is preferably bonded to the para position. As the amino group, —NH ₂ group, —NHR ³¹ group, and —NR ³² R ³³ group (R ³¹ , R ³² , and R ³³ are each a hydrocarbon group having 1 to 6 carbon atoms, and a carbon number of 1). It may be an alkyl group having 1 to 6 carbon atoms and may be an alkyl group having 1 to 4 carbon atoms).
When Y is a group represented by the formula (I-7), the phenylene group and the phenyl group of the azobenzene group may be either unsubstituted or substituted with a phenyl group. May be When the phenyl group is substituted, the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be bonded to any of the ortho, meta and para positions of the phenyl group, but is preferably bonded to the para position.
When Y is of formula (I-15), X is preferably -C(=O)NH-. In this case, the --NH-- group of X and the amidine group of Y constitute a guanidino group.
Compounds of formula (II) include substituted or unsubstituted acenaphthylene.

When Y is a group represented by the formula (I-11), specific examples thereof are represented by the following formula (I-11a), the following formula (I-11b), or the following formula (I-11c). Groups.

Examples of the hydrocarbon group for R ¹¹ to R ¹⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group (amyl group), an n-hexyl group, an n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, sec-butyl group, isobutyl group, tert-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, isoamyl group, 1,2 -Dimethylpropyl group, 1,1-dimethylpropyl group, tert-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-methylpentyl group, 1-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, sec-heptyl group, tert-heptyl group, isoheptyl group, sec-octyl group, tert-octyl group, isooctyl group, 1-ethylhexyl group, 1-propylpentyl group Group, 2-ethylhexyl group, 2-propylpentyl group, sec-nonyl group, tert-nonyl group, neononyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-butylpentyl group, 2-ethylheptyl group, 2-propylhexyl group, 2-butylpentyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, 1-ethyloctyl group, 1-propylheptyl group, 1-butylhexyl group, 2-ethyloctyl group Group, 2-propylheptyl group, 2-butylhexyl group, vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, phenyl group Naphthyl group; aralkyl group such as benzyl group, 1-phenylethyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group; styryl group (Ph-CH=C- group); cinnamyl group ( Ph-CH=CHCH ₂ -group); 1-benzocyclobutenyl group; 1,2,3,4-tetrahydronaphthyl group and the like.

In the formula (I), when Y is a group of the formulas (I-2) to (I-6) and (I-9), X is —CH ₂ —O—CH ₂ CH(OH)CH. May be _2- . Such X is obtained, for example, by an addition reaction of allyl glycidyl ether and a nitrogen compound corresponding to the groups of formulas (I-2) to (I-6) and (I-9).

As the monomer (B), N-vinylpyrrolidone, N-vinylimidazole, styrene, benzyl (meth)acrylate, N-vinylcarbazole, allyl glycidyl ether-added pyrazole, allyl glycidyl ether-added trimethylamine, 2, 2, 6, 6-Tetramethyl-4-piperidyl (meth)acrylate, and 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole, 1,2,2,6 ,6-Pentamethyl-4-piperidyl (meth)acrylate, 4-indole (meth)acrylate, 11-[4-(4-butylphenylazo)phenoxy]undecyl (meth)acrylic acid, N,N-dimethyl-amino- 1,4-phenylene(meth)acrylamide 1-naphthylmethyl(meth)acrylate, 9-anthrylmethyl(meth)acrylate, acenaphthylene, N-cyano-N'-(meth)acryloylguanidine, and 1-(3-sulfo Propyl)-2-vinylpyridinium hydroxide inner salt and the like can be mentioned, and these may be used alone or in combination of two or more.

The polymer (I) contains a structural unit derived from the monomer (A) in an amount of 30 to 95% by mass based on the total amount of the polymer (I) from the viewpoint of further enhancing the hydrophilicity of the polymer (I). Is preferable, and it is more preferable that the content is 40 to 90% by mass. Further, the polymer (I) preferably contains 5 to 70% by mass of the structural unit derived from the monomer (B) with respect to the total amount of the polymer (I), and preferably 10 to 60% by mass. Is more preferable.

Further, the polymer (I) has a total of 80% by mass or more of the structural unit derived from the monomer (A) and the structural unit derived from the monomer (B) with respect to the total amount of the polymer (I). It is preferable to contain it, and it is more preferable to contain 90 mass% or more. The upper limit of the total amount of the structural unit derived from the monomer (A) and the structural unit derived from the monomer (B) is not particularly limited, but may be 98% by mass.

Further, the polymer (I) may have a structural unit derived from a monomer other than the monomer (A) and the monomer (B). Examples of such a structural unit include a structural unit derived from the below-mentioned monomer (C), a monomer (A), a monomer (B), and a monomer (D) other than the monomer (C). ) May have a structural unit derived from.

Examples of the monomer (D) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl. (Meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate And alkyl or cycloalkyl ester monomers of (meth)acrylic acid such as methylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate.

<Method for producing polymer>
The method for producing the polymer (I) of the present embodiment is not particularly limited, but other than the monomer (A) and the monomer (B), and optionally the monomer (A) and the monomer (B). It can be produced by polymerizing a monomer mixture containing another monomer. The mixing ratio of each monomer component contained in the monomer mixture can be appropriately adjusted so that the content of the structural unit derived from each monomer in the polymer is a predetermined ratio.

As a method for producing the polymer (I), a monomer mixture containing the monomer (A), the monomer (B), and optionally another monomer is prepared, and the monomer mixture is polymerized. The step (polymerization step) is included. The method of charging each monomer into the reaction container is not particularly limited, a method of initially charging the entire amount into the reaction container at once, a method of dividing the entire amount into the reaction container or continuously charging, and a part of the reaction container into the reaction container initially. Then, the method of dividing the rest into the reaction vessel or continuously charging the same may be used. Specific examples of suitable charging methods include the following methods (1) to (4).
(1) A method of continuously charging all of the monomers into a reaction vessel.
(2) A method of initially charging all of the monomers (A) or (B) into a reaction vessel.
(3) A method in which a part of the monomer (A) or (B) is initially charged into the reaction vessel, and the rest of the monomer (A) or (B) is continuously charged into the reaction vessel.
(4) A part of the monomer (A) or (B) is initially charged into the reaction vessel, and the rest of the monomer (A) or (B) is alternately divided into several times in the reaction vessel and divided. How to throw.
Furthermore, by changing the charging rate of each monomer into the reaction vessel continuously or stepwise during the reaction, the charging mass ratio of each monomer per unit time is changed continuously or stepwise, and You may make it synthesize|combine the mixture of the polymers from which the ratio of each structural unit in a compound (I) differs in a polymerization reaction.

The method of initiating the polymerization of the monomer component in the above-mentioned polymerization step is not particularly limited, but, for example, a method of adding a polymerization initiator, a method of irradiating with UV, a method of applying heat, or in the presence of a photoinitiator. Examples include a method of irradiating with light.
In the above polymerization step, it is preferable to use a polymerization initiator.
Examples of the above-mentioned polymerization initiator include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; dimethyl-2,2′-azobis(2-methylpropionate), 2,2′. -Azobis(isobutyronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2 Azo compounds such as'-azobis(1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride; benzoyl peroxide, lauroyl peroxide, peracetic acid, di-tert-butyl peroxide, cumene hydroperoxide, etc. And organic peroxides; redox initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, and persulfates and metal salts, are suitable. Of these polymerization initiators, hydrogen peroxide, persulfates, and azo compounds are preferable, and azo compounds are more preferable, because residual monomers tend to decrease. These polymerization initiators may be used alone or in the form of a mixture of two or more kinds.

The amount of the above-mentioned polymerization initiator used is preferably 0.1 g or more and 15 g or less, more preferably 0.1 g or more and 12 g or less, based on 1 mol of the total amount of monomers, and 0 More preferably, it is 1 g or more and 10 g or less.

In the above polymerization step, a chain transfer agent may be used if necessary. Specific examples of the chain transfer agent include thiol chain transfer agents such as mercaptoethanol and mercaptopropionic acid; halides such as carbon tetrachloride and methylene chloride; secondary or tertiary alcohols such as isopropyl alcohol and glycerin; Hypophosphorous acid such as hypophosphorous acid and sodium hypophosphite and salts thereof (including hydrates thereof); Phosphorous acid such as phosphorous acid and sodium phosphite and salts thereof; sodium sulfite And bisulfites such as sodium bisulfite and salts thereof; dithionous acids such as sodium dithionite and salts thereof; pyrosulfites such as potassium pyrosulfite and salts thereof. The above chain transfer agents may be used alone or in the form of a mixture of two or more kinds.
The amount of the chain transfer agent used is preferably 0 g or more and 30 g or less, and more preferably 1 g or more and 15 g or less, based on 1 mol of the total amount of the monomers.

When a solvent is used in the above-mentioned polymerization step, the solvent includes water, methyl alcohol, ethyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, alcohols such as diethylene glycol, dimethylformamide, dimethylsulfoxide, toluene, Examples thereof include ethyl acetate, tetrahydrofuran, methyl ethyl ketone, acetone, benzene, xylene and anisole. These may use 1 type(s) or 2 or more types. Water is preferred as the solvent.
By using water as the solvent, it can be used for detergents and the like without performing the step of replacing the solvent after the polymerization reaction.
That is, the polymerization step is preferably performed in an aqueous solution.
The amount of the above solvent used is preferably 40 to 1000% by mass based on 100% by mass of the total amount of the monomer mixture.

In the above-mentioned polymerization step, the polymerization temperature is not particularly limited, but a relatively low temperature is preferable because the molecular weight of the polymer is large, and if it is in the range of 60°C to 100°C, the polymerization rate is higher. It is more preferable because it improves. The reaction time may be appropriately set depending on the reaction temperature, the type (property) of the monomer component, the polymerization initiator, the solvent and the like, the amount of combination, and the like so that the polymerization reaction is completed.
Further, the polymer (I) may be synthesized by RAFT (reversible addition-cleavage chain transfer) polymerization. In RAFT polymerization, a chain transfer agent (that is, RAFT agent) for promoting RAFT polymerization is used. The advantages of RAFT polymerization include the ability to control the polymerization reaction of most monomers that can be polymerized by radical polymerization, unprotected functional groups (eg, —OH, —NR ₂ , —COOH, —CONR) in the monomer and solvent. ₂ , -SO ₃ H) is highly tolerant, it can be polymerized even in water or a protic solvent, the applicable range of reaction conditions is wide, and it is easier and cheaper to use than competing technologies. It can be mentioned. Further, when the polymer (I) is produced by RAFT polymerization, the molecular weight distribution tends to be narrow (polydispersity is close to 1).
Examples of RAFT agents include trithiocarbonate compounds, and more specifically, 2-{[(2-carboxyethyl)sulfanylthiocarbonyl]sulfanyl}propanoic acid, 2-(dodecylthiocarbonylthioylthio)- 2-Methylpropanoic acid, 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, 4-cyano-4-(ethylsulfanylthiocarbonylsulfanyl)pentanoic acid, 4-cyano-4-(dodecylsulfanylthiocarbonylsulfanyl)pentane Acid, 4-{[(2-carboxyethyl)sulfanylthiocarbonyl]sulfanyl}-4-cyano-pentanoic acid, methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate, S-(2- Examples thereof include cyanoprop-2-yl)-S-dodecyltrithiocarbonate, S-cyanomethyl-S-dodecyltrithiocarbonate, 2-methyl-2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid and the like. The polymerization initiator and solvent used in RAFT polymerization may be the above-mentioned polymerization initiator and solvent.
When carrying out RAFT polymerization, the monomers may be charged into the reaction vessel by the above methods (1) to (4). Further, for example, after the monomer (B), the polymerization initiator and the RAFT agent are charged into a reaction vessel to start the reaction to produce an intermediate, the intermediate, the monomer (A) and additional A method in which a polymerization initiator is added to carry out further polymerization can also be used. This method is suitable for producing a block copolymer. The monomer (A) may be charged into the reaction vessel first to obtain an intermediate, and then the monomer (B) may be charged into the reaction vessel for further polymerization.

<Polymer (II)>
The polymer (II) has a structural unit derived from the monomer (C) containing an ethylenically unsaturated group, a dye affinity group and a hydrophilic functional group. Examples of the dye-affinitive group and the hydrophilic functional group include those exemplified as the dye-affinitive group of the monomer (B) and the hydrophilic functional group of the monomer (A), respectively.

Examples of the monomer (C) include compounds having a structure in which a dye affinity group is introduced at the terminal of an alkylene oxide adduct of polyoxyalkylene (meth)acrylate or isoprenol, and specifically, the following formula (C1) And a compound represented by the following formula (C2).

In the formulas (C1) and (C2), m1 and m2 may be the average number of added moles of the compound represented by the formula (C1) or the entire compound represented by the formula (C2). m1 and m2 are each preferably 2 to 150, more preferably 10 to 100, still more preferably 20 to 70. Y is a dye-affinitive group, and examples thereof include the groups of the above formulas (I-1) to (I-16).

The weight average molecular weight of the polymer (I) or (II) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and further preferably 5,000 to 50,000. The weight average molecular weight can be measured by gel filtration chromatography (GPC) under the conditions described in the examples. The polydispersity (ratio of the weight average molecular weight to the number average molecular weight) of the polymer (I) or (II) is preferably 1 to 20, preferably 1 to 12, preferably 1 to 10, and 1 to 8. Preferably, it is 1-6, preferably 1-4, more preferably 1-3, particularly preferably 1-2. The polydispersity can also be measured by gel filtration chromatography (GPC) under the conditions described in the examples. Perhaps the preferred range depends on the molecular weight range. For example, when the molecular weight is 100,000 or less, the polydispersity is preferably 1 to 10, and when the molecular weight is 100,000 or more, the polydispersity is preferably 5 to 20. The preferred range of polydispersity varies depending on the chain transfer agent used. For example, for the polymer using the RAFT agent described above, the polydispersity is preferably in the range of 1 to 3, more preferably 1 to 2, and most preferably 1 to 1.5. The number average molecular weight can be measured by gel filtration chromatography (GPC) under the conditions described in the examples, and is preferably 1000 to 40000, more preferably 1500 to 35000.

<Compound (III)>
The compound (III) has a dye affinity group and a hydrophilic functional group (however, it is not the above polymer (I) or polymer (II)).

Examples of the compound (III) include compounds represented by the following formula (E1), (E2), (E3), or (E4).

In the formulas (E1) to (E4), r1 to r4 may be the average number of added moles of all the compounds represented by the formulas (E1) to (E4). Each of r1 to r4 is preferably 2 to 150, more preferably 2 to 100, even more preferably 2 to 50, even more preferably 2 to 30, and further preferably 2 to 20. . s1 may be an average value for the entire compound represented by formula (E4), and when it is an average value, may be a rational number. s1 may be an integer. s1 may be 1 to 20 and may be 2 to 10. Y is a dye-affinitive group, and examples thereof include the groups of the above formulas (I-1) to (I-16). It may be a group (I-4). R ²⁰ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 5 to 15 carbon atoms. preferable.

The compound (III) also includes compounds represented by the following formula (E5) or (E6).

(R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 5 to 15 carbon atoms. More preferably, r6 may be the average number of added moles of the entire compound represented by the formula (E5), and r6 is preferably 2 to 150, more preferably 2 to 100, and more preferably 2 to 50 is more preferable, 2 to 30 is still more preferable, 2 to 20 is still more preferable, Y is a dye-affinitive group, which is a group of the above formulas (I-1) to (I-16). Which may be a group of the formula (I-1), the formula (I-2), the formula (I-3) or the formula (I-4). Or a group of formula (I-4).)

(Y ¹ is a functional group represented by the formula (I-1), R ²² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group has 1 to 20 carbon atoms. Is more preferable, and an alkyl group having 5 to 15 carbon atoms is more preferable, r5 may be the average number of added moles of the entire compound represented by formula (E6), and r5 is 2 It is preferably from 150 to 150, more preferably from 2 to 100, even more preferably from 2 to 50, even more preferably from 2 to 30, and further preferably from 2 to 20.)

The polymers (I), (II) and the compound (III) of this embodiment can be used as a dye transfer inhibitor. The dye transfer inhibitor may be used as an additive for detergents, but may also be used as a fabric softening agent, a dyeing treatment agent, or the like. The polymers (I), (II) and the compound (III) are scale inhibitors, various inorganic or organic dispersants, thickeners, adhesives, adhesives, surface coating agents, cross-linking agents, moisturizers. Etc. can also be used.
When the polymers (I), (II) and the compound (III) are used as a dye transfer inhibitor and the clothes to be washed include natural vegetable fibers such as cotton, the dye-affinic group is substituted or not. Substituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted pyrazole group, substituted or unsubstituted cyclic amide group, substituted or unsubstituted azobenzene group, substituted or unsubstituted benzotriazole group, substituted or unsubstituted It is preferably at least one selected from a substituted carbazole group, a quaternary ammonium group, a substituted or unsubstituted imidazole group, and a substituted or unsubstituted piperidine group. When using the polymers (I), (II) and the compound (III) as a dye transfer inhibitor, when the clothes to be washed include chemically synthetic fibers such as nylon and polyester, the dye-affinitive group is substituted. Or an unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted pyrazole group, a substituted or unsubstituted cyclic amide group, a substituted or unsubstituted azobenzene group, a substituted or unsubstituted pyridinium group, substituted or It is preferably at least one selected from unsubstituted amidine groups.

The dye that can use the dye transfer inhibitor of the present embodiment is not particularly limited as long as it is a dye that is usually used for dyeing clothes, for example, direct dyes, acid dyes, basic dyes, mordant dyes, Examples thereof include acid mordant dyes, vat dyes, disperse dyes, reactive dyes and fluorescent whitening dyes. The dye is preferably a water-soluble dye such as a direct dye or an acid dye. Since the water-soluble dye easily discolors during washing, it is possible to more effectively exhibit the dye transfer inhibiting ability of the dye transfer inhibitor of the present embodiment.

The detergent composition (detergent composition) of the present embodiment contains the polymers (I), (II) and the compound (III). The detergent composition may contain a detergent additive other than the polymers (I), (II) and the compound (III). Further, the detergent composition of the present embodiment is preferably for clothing and is preferably used for laundry detergent and the like.

The content of the polymers (I), (II) and the compound (III) in the detergent composition is preferably 0.1 to 20% by mass relative to 100% by mass of the detergent composition, It is more preferably 1 to 15% by mass, and further preferably 0.1 to 10% by mass.

The detergent additive other than the polymers (I), (II) and the compound (III) is not particularly limited as long as it is an additive used in detergents, and specific examples thereof include a surfactant. You can Further, the detergent composition may be a solid detergent composition such as powder or a liquid detergent composition. Further, it may contain an additive other than the surfactant, and examples of such an additive include chelate, alkali, pH adjuster, enzyme, zeolite and the like.

The surfactant may be any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and one kind or two or more kinds can be used.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate. , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or The salt, polyoxyalkylene alkyl ether sulfate, and the like are preferable. The alkyl group and alkenyl group in these anionic surfactants may be branched with an alkyl group such as a methyl group.

As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkylglycoxide, fatty acid glycerin monoester Ester, alkylamine oxide and the like are preferable. An alkyl group such as a methyl group may be branched to the alkyl group and the alkenyl group in these nonionic surfactants.

Quaternary ammonium salts and the like are suitable as the cationic surfactant. Further, as the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are preferable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may have a branched alkyl group such as a methyl group.

The mixing ratio of the above-mentioned surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, and particularly preferably, the total amount of the detergent composition. Is 25 to 40% by mass. If the blending ratio of the surfactant is too low, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too high, the economical efficiency may be reduced.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, "part" means "part by mass" and "%" means "% by mass" unless otherwise specified.

<Measurement conditions of weight average molecular weight, number average molecular weight and polydispersity (gel filtration chromatography (GPC))>
When the sample is a polymer, in Examples 1 to 9 the following GPC condition I, in Examples 10 to 35 the following GPC condition II, and in Example 36, the following GPC condition III, the weight average molecular weight, respectively. The number average molecular weight and polydispersity were measured.
<GPC condition I>
Device: High-speed GPC device (manufactured by Tosoh Corporation, trade name: HLC-8320GPC)
Detector: Differential Refractive Index (RI) Detector Column: Showa Denko KK, trade name: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B
Column temperature: 40°C
Flow rate: 0.5 ml/min
Sample injection volume: 10 μl
Sample concentration: 0.5% as solid content
Molecular Weight Standards: American Polymer Standards Corp. Product name: Polyacrylic Acid Standard
Eluent: 0.1N sodium acetate/acetonitrile=3/1 (mass ratio)
The molecular weight of the used molecular weight standard substance is 900, 1250, 1770, 2925, 4100, 7500, 16000, 28000, 62900, 115000, 130500, 193800, 392600, 467300, 585400, 589700, 750000, and the order of the calibration curve is It is the third order.
<GPC condition II>
Device: High-speed GPC device (manufactured by Tosoh Corporation, trade name: HLC-8320GPC)
Detector: Differential Refractive Index (RI) Detector Column: Showa Denko KK, trade name: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B
Column temperature: 40°C
Flow rate: 0.5 ml/min
Sample injection volume: 20 μl
Sample concentration: 0.5% as solid content
Molecular Weight Standards: GL Science Inc. Product name, Polyethylene Glycol
Eluent: 0.1N sodium acetate/acetonitrile=3/1 (mass ratio)
The molecular weight of the used molecular weight standard substance is 194, 410, 615, 1020, 1450, 3860, 8160, 16100, 21160, 49930, 67600, 96100, 205500, 542500, 942000, and the order of the calibration curve is the third order. ..
<GPC condition III>
Device: High-speed GPC device (manufactured by Tosoh Corporation, trade name: HLC-8320GPC)
Detector: Differential Refractive Index (RI) Detector Column: Tosoh Corporation, trade name: TSKgel SuperMultipore HZ-M x2, TSKgel guardcolumn SuperMP (HZ)-M
Column temperature: 40°C
Flow rate: 0.35 ml/min
Sample injection volume: 5 μl
Sample concentration: 0.5% as solid content
Molecular Weight Standards: Polymer Standards Service USA, Inc. Product name: Poly(styrene)
Product name: TSK Standard POLYSTYRENE, manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran/triethylamine = 1500/21 (mass ratio)
The molecular weight of the used molecular weight standard substance is 474, 578, 2550, 10200, 37900, 184000, 778000, 1090000, and the order of the calibration curve is the third order.

<Measurement of solid content>
The polymer (0.1 g of the polymer plus 1.0 g of water) was allowed to stand for 2 hours in an oven heated to 130° C. for drying treatment. The solid content (%) and the volatile component (%) were calculated from the change in mass before and after drying.

The “finished composition” in Table 1 is a composition calculated on the assumption that all the monomers consumed during the polymerization reaction are incorporated into the polymer as structural units by the polymerization reaction. Specifically, by LC (liquid chromatography), the consumption of the monomers charged in the reaction vessel for producing the polymer in the polymerization reaction is analyzed, and the ratio of the consumption of each monomer (molar ratio ) Is the composition of the polymer calculated from. The analytical conditions and analytical method of the above LC (liquid chromatography) are as follows.

<LC analysis conditions>
Device: Waters, trade name: Alliance (2695)
Detector: Differential Refractometer (RI) Detector (Waters 2414), Multiwavelength Visible Ultraviolet (PDA) Detector (Waters 2996)
Column: manufactured by Osaka Soda Co., Ltd., product name: CAPCELL PAK C1, 4.6×250 mm, 3 pieces
Column temperature: 40°C
Flow rate: 1 ml/min
Eluent: 0.01 M disodium hydrogen phosphate aqueous solution/acetonitrile=49/51 (mass ratio)
Sample injection volume: 10 μl
Sample concentration: 0.5% as solid content

<LC analysis method>
A calibration curve was prepared for each monomer, and the consumption amount was determined from the residual amount of each monomer in the polymer solution after polymerization.

<Evaluation of transfer prevention ability>
The dye transfer prevention ability was measured by the following method. In the evaluation of the dye transfer prevention ability, first, a liquid detergent formulation and a 1.0% polymer aqueous solution were prepared. The liquid detergent composition was 25% polyoxyethylene lauryl ether sodium sulfate aqueous solution (product name: Emar 20C, manufactured by Kao) 11.0 g, and polyoxyethylene lauryl ether (product name: Emulgen 108, manufactured by Kao) 2.8 g. , 16% sodium dodecylbenzene sulfonate aqueous solution (product name: Neoperex G-15, manufactured by Kao) 17.2 g, propylene glycol 3 g, sodium oleate 1.2 g, and ethanol 1 g, and added pure water to 50 It was prepared by stirring after adjusting to 0.0 g. The 1.0% polymer aqueous solution was prepared by diluting each of the polymers synthesized in Examples 1 to 9 and the polymer of Comparative Example 1 with an appropriate amount of water to a solid content concentration of 1.0% by mass. I used one.
A rounder meter (L-20Z) manufactured by Daiei Kagaku Seiki Seisakusho was used for the evaluation of the dye transfer prevention ability. An aqueous solution for evaluation was prepared by adding 250 g of 50 ppm hardness water (Ca/Mg=3/1) to a 500 ml pot of a rounder meter, adding 0.5 g of the prepared liquid detergent composition and 0.5 g of a 1.0% polymer aqueous solution. Was prepared and the temperature was adjusted to 25°C. A 5 cm×5 cm cotton cloth (manufactured by Testfabrics, product name: Style460-6) 1.0 g and 5 cm×5 cm EMPA277 (manufactured by SWISSATEST) 6.4 g and 5 cm×5 cm EMPA496 (manufactured by SWISSATEST) 3 in an aqueous solution for evaluation 0.6 g was added, and the mixture was stirred with a round meter for 30 minutes. Then, the obtained cotton cloth was rinsed with 250 g of 50 ppm hardness water for 5 minutes using a rounder meter, and then air-dried overnight to obtain a post-evaluation cloth. The WB values of the post-evaluation cloth and the pre-evaluation white cotton cloth obtained in this step are evaluated with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., spectroscopic color difference meter SE-6000) to evaluate the ability of the polymer to prevent migration. did. The results are shown in Table 1. The evaluation result shows a value obtained by calculating the transfer prevention ability for PVP, which is a conventional technique, by Equation 1, and 0% indicates the same color as the test cloth washed by adding PVP (Comparative Example 1), which is a conventional technique. Of 100% indicates that the test cloth maintains the whiteness before evaluation. That is, if the value is positive, it means that the dye transfer prevention ability is higher than that of PVP, and the higher the value is, the higher the dye transfer prevention ability is.

<Example 1> [Monomer (B): benzyl methacrylate/monomer (A): acrylic acid]
(Synthesis of Polymer 1)
A glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 117.4 g of N,N-dimethylformamide (hereinafter, also referred to as “DMF”), and stirred at 80° C. The temperature was raised up to a polymerization reaction system. Next, under stirring, 40.0 g of 100% acrylic acid (hereinafter, also referred to as “100% AA”), 17.1 g of 100% benzyl methacrylate, and 10% of 100% acrylic acid were added to the polymerization reaction system kept at 80° C. 23.9 g of 2,2′-azobis(2,4-dimethylvaleronitrile) (hereinafter, also referred to as “10% V-65”) was dropped from separate nozzles. The dropping time of each solution was 180 minutes for 100% AA, 180 minutes for 100% benzyl methacrylate, and 180 minutes for 10% V-65. Further, the dropping rate of each solution was kept constant, and the dropping of each solution was performed continuously. After completion of the dropping, the reaction solution was kept (aged) at 80° C. for another 60 minutes to complete the polymerization. In the polymer thus obtained, the reaction rate of AA was higher than 89% and the reaction rate of benzyl methacrylate was higher than 99%. The polymer was neutralized by adding a 48% sodium hydroxide aqueous solution to the DMF solution of the obtained polymer, and then the solvent was distilled off using an evaporator. The dried polymer was finely pulverized, DMF was washed with acetone, and then dried again. Then, the polymer was dissolved in water, purified using a dialysis membrane (MWCO=1 kD), and concentrated with an evaporator to recover an aqueous polymer solution. In this way, a polymer aqueous solution having a solid content concentration of 24% was obtained. The weight average molecular weight of the polymer (Polymer 1) was 16,600. The dye transfer prevention ability was 33%.

<Example 2> [Monomer (B): benzyl methacrylate/monomer (A): acrylic acid]
(Synthesis of Polymer 2)
Into a glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade), 83.8 g of DMF was charged, and the temperature was raised to 80° C. with stirring to obtain a polymerization reaction system. Next, 20.0 g of 100% AA, 20.0 g of 100% benzyl methacrylate, and 14.3 g of 10% V-65 were charged into a polymerization reaction system kept at 80° C. with stirring through separate nozzles. Dropped. The dropping time of each solution was 180 minutes for 100% AA, 180 minutes for 100% benzyl methacrylate, and 180 minutes for 10% V-65. Further, the dropping rate of each solution was kept constant, and the dropping of each solution was performed continuously. After completion of the dropping, the reaction solution was kept (aged) at 80° C. for another 60 minutes to complete the polymerization. In the polymer thus obtained, the reaction rate of AA was higher than 87% and the reaction rate of benzyl methacrylate was higher than 99%. The polymer was neutralized by adding a 48% sodium hydroxide aqueous solution to the DMF solution of the obtained polymer, and then the solvent was distilled off using an evaporator. The dried polymer was finely pulverized, DMF was washed with acetone, and then dried again. Then, the polymer was dissolved in water, purified using a dialysis membrane (MWCO=1 kD), and concentrated with an evaporator to recover an aqueous polymer solution.
Thus, a polymer aqueous solution having a solid content concentration of 28% was obtained. The weight average molecular weight of the polymer (Polymer 2) was 12,100. Further, the dye transfer prevention ability was 35%.

<Example 3> [Monomer (B): N-vinylpyrrolidone/monomer (A): acrylic acid]
(Synthesis of Polymer 3)
A glass separable flask with a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 116.0 g of DMF, and the temperature was raised to 80° C. with stirring to obtain a polymerization reaction system. Next, under stirring, 40.0 g of 100% AA, 17.1 g of 100% N-vinylpyrrolidone and 26.0 g of 10% V-65 were separately added to the polymerization reaction system kept at 80°C. It was dropped from a nozzle. The dropping time of each solution was 180 minutes for 100% AA, 180 minutes for 100% N-vinylpyrrolidone, and 180 minutes for 10% V-65. Further, the dropping rate of each solution was kept constant, and the dropping of each solution was performed continuously. After completion of the dropping, the reaction solution was kept (aged) at 80° C. for another 60 minutes to complete the polymerization. In the polymer thus obtained, the reaction rate of AA was 96% and the reaction rate of N-vinylpyrrolidone was 96%. The polymer was neutralized by adding a 48% sodium hydroxide aqueous solution to the DMF solution of the obtained polymer, and then the solvent was distilled off using an evaporator. The dried polymer was finely pulverized, DMF was washed with acetone, and then dried again. Then, the polymer was dissolved in water, purified using a dialysis membrane (MWCO=1 kD), and concentrated with an evaporator to recover an aqueous polymer solution. Thus, a polymer aqueous solution having a solid content concentration of 31% was obtained. The weight average molecular weight of the polymer (Polymer 3) was 22,000. The dye transfer prevention ability was 5%.

<Example 4> [Monomer (B): 4-methacrylamidoazobenzene/monomer (A): acrylic acid]
(Synthesis of Monomer 1)
150 g of a THF solution of KOt-Bu was added to a glass separable flask with a capacity of 300 mL equipped with a reflux condenser and stirring blades. After stirring at room temperature, 18.8 g of a 79% THF solution of 4-aminoazobenzene was added to the reaction vessel, and subsequently 8.6 g of 100% ethyl methacrylate was added little by little over 20 minutes. Then, after stirring for 3 hours, the reaction solution was taken out and reprecipitated in water. The obtained precipitate was filtered, washed with water, and dried to obtain monomer 1.
(Synthesis of Polymer 4)
A glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 31.5 g of DMF, and the temperature was raised to 80° C. with stirring to obtain a polymerization reaction system. Next, 25.4 g of 100% AA, 54.4 g of a 20% monomer 1 DMF solution and 14.4 g of 10% V-65 were added to the polymerization reaction system kept at 80° C. under stirring. Each was dropped from a separate nozzle. The dropping time of each solution was 180 minutes for 100% AA, 180 minutes for a 20% monomer 1 DMF solution, and 180 minutes for 10% V-65. Further, the dropping rate of each solution was kept constant, and the dropping of each solution was performed continuously. After completion of the dropping, the reaction solution was kept (aged) at 80° C. for another 60 minutes to complete the polymerization. In the polymer thus obtained, the reaction rate of AA was 90% and the reaction rate of monomer 1 was 97%. The polymer was neutralized by adding a 48% sodium hydroxide aqueous solution to the DMF solution of the obtained polymer, and then the solvent was distilled off using an evaporator. The dried polymer was finely pulverized, DMF was washed with acetone, and then dried again. Then, the polymer was dissolved in water, purified using a dialysis membrane (MWCO=1 kD), and concentrated with an evaporator to recover an aqueous polymer solution. In this way, a polymer aqueous solution having a solid content concentration of 16% was obtained. The weight average molecular weight of the polymer (polymer 4) was 48,700. Further, the dye transfer prevention ability was 9%.

<Example 5> [Monomer (B): 9-vinylcarbazole/monomer (A): acrylic acid]
(Synthesis of Polymer 5)
A glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 30.6 g of DMF, and the temperature was raised to 80° C. with stirring to obtain a polymerization reaction system. Next, 25.0 g of 100% AA, 53.6 g of 20% 9-vinylcarbazole DMF solution, and 14.7 g of 10% V-65 were placed in a polymerization reaction system kept at 80° C. under stirring. It dripped from a separate nozzle. The dropping time of each solution was 180 minutes for 100% AA, 180 minutes for 20% 9-vinylcarbazole DMF solution, and 180 minutes for 10% V-65. Further, the dropping rate of each solution was kept constant, and the dropping of each solution was performed continuously. After completion of the dropping, the reaction solution was kept (aged) at 80° C. for another 60 minutes to complete the polymerization. In the polymer thus obtained, the reaction rate of AA was 92% and the reaction rate of 9-vinylcarbazole was 98%. The polymer was neutralized by adding a 48% sodium hydroxide aqueous solution to the DMF solution of the obtained polymer, and then the solvent was distilled off using an evaporator. The dried polymer was finely pulverized, DMF was washed with acetone, and then dried again. Then, the polymer was dissolved in water, purified using a dialysis membrane (MWCO=1 kD), and concentrated with an evaporator to recover an aqueous polymer solution. Thus, an aqueous polymer solution having a solid content concentration of 15% was obtained. The weight average molecular weight of the polymer (polymer 5) was 16,600. The dye transfer prevention ability was 26%.

<Example 6> [Monomer (B): benzotriazole derivative/monomer (A): acrylic acid]
(Synthesis of Polymer 6)
A glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 31.6 g of DMF, and the temperature was raised to 80° C. with stirring to obtain a polymerization reaction system. Next, 20.0 g of 100% AA and 10% 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H were added to a polymerization reaction system kept at 80° C. with stirring. -85.7 g of a DMF solution of benzotriazole was added dropwise from 11.1 g of 10% V-65 through separate nozzles. The dropping time of each solution was 180 minutes for 100% AA and 180 minutes for a DMF solution of 10% 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole. For 10% V-65, the time was 180 minutes. Further, the dropping rate of each solution was kept constant, and the dropping of each solution was performed continuously. After completion of the dropping, the reaction solution was kept (aged) at 80° C. for another 60 minutes to complete the polymerization. In the polymer thus obtained, the reaction rate of AA was 81%, and the reaction rate of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole was 99%. Was bigger. The polymer was neutralized by adding a 48% sodium hydroxide aqueous solution to the DMF solution of the obtained polymer, and then the solvent was distilled off using an evaporator. The dried polymer was finely pulverized, DMF was washed with acetone, and then dried again. Then, the polymer was dissolved in water, purified using a dialysis membrane (MWCO=1 kD), and concentrated with an evaporator to recover an aqueous polymer solution. In this way, a polymer aqueous solution having a solid content concentration of 21% was obtained. The weight average molecular weight of the polymer (Polymer 6) was 14,500. The dye transfer prevention ability was 25%.

<Example 7> [Monomer (B): AGE-pyrazole derivative/monomer (A): acrylic acid]
(Synthesis of Monomer 2)
A method for synthesizing a pyrazole derivative monomer (AGE-Py) of allyl glycidyl ether (hereinafter, also referred to as “AGE”) will be described below.
A glass four-necked flask having a capacity of 200 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 16.9 g of pure water and 25.3 g of pyrazole, and the temperature was raised to 80° C. with stirring. Next, 42.4 g of AGE was added over 10 minutes, and then reacted for 2 hours. Water contained in the obtained monomer was distilled off by a rotary evaporator to obtain 100% AGE-Py.
(Synthesis of Polymer 7)
A glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 50.2 g of DMF, and the temperature was raised to 80° C. with stirring to obtain a polymerization reaction system. Then, under stirring, 20.0 g of 100% AA, 17.1 g of 50% AGE-Py DMF solution and 11.9 g of 10% V-65 were placed in a polymerization reaction system maintained at 80°C. It dripped from a separate nozzle. The dropping time of each solution was 180 minutes for 100% AA, 180 minutes for 50% AGE-Py DMF solution, and 180 minutes for 10% V-65. Further, the dropping rate of each solution was kept constant, and the dropping of each solution was performed continuously. After completion of the dropping, the reaction solution was kept (aged) at 80° C. for another 60 minutes to complete the polymerization. In the polymer thus obtained, the reaction rate of AA was 94% and the reaction rate of AGE-Py was 31%. The polymer was neutralized by adding a 48% sodium hydroxide aqueous solution to the DMF solution of the obtained polymer, and then the solvent was distilled off using an evaporator. The dried polymer was finely pulverized, DMF was washed with acetone, and then dried again. Then, the polymer was dissolved in water, purified using a dialysis membrane (MWCO=1 kD), and concentrated with an evaporator to recover an aqueous polymer solution. In this way, a polymer aqueous solution having a solid content concentration of 24% was obtained. The weight average molecular weight of the polymer (polymer 7) was 48,600. The dye transfer prevention ability was 24%.

<Example 8> [monomer (B): styrene/monomer (A): acrylic acid]
(Synthesis of Polymer 8)
Into a glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade), 49.3 g of DMF was charged, and the temperature was raised to 80° C. with stirring to obtain a polymerization reaction system. Next, under stirring, 20.0 g of 100% AA, 17.1 g of 50% styrene DMF solution and 13.2 g of 10% V-65 were separately added to the polymerization reaction system kept at 80°C. It was dropped from a nozzle. The dropping time of each solution was 180 minutes for 100% AA, 180 minutes for 50% styrene, and 180 minutes for 10% V-65. Further, the dropping rate of each solution was kept constant, and the dropping of each solution was performed continuously. After completion of the dropping, the reaction solution was kept (aged) at 80° C. for another 60 minutes to complete the polymerization. In the polymer thus obtained, the reaction rate of AA was 57% and the reaction rate of styrene was 90%. The polymer was neutralized by adding a 48% sodium hydroxide aqueous solution to the DMF solution of the obtained polymer, and then the solvent was distilled off using an evaporator. The dried polymer was finely pulverized, DMF was washed with acetone, and then dried again. Then, the polymer was dissolved in water, purified using a dialysis membrane (MWCO=1 kD), and concentrated with an evaporator to recover an aqueous polymer solution. In this way, a polymer aqueous solution having a solid content concentration of 13% was obtained. The weight average molecular weight of the polymer (polymer 8) was 28,700. Further, the dye transfer prevention ability was 28%.

<Example 9> [Monomer (B): AGE-trimethylamine derivative/monomer (A): acrylic acid]
(Synthesis of Monomer 3)
A method for synthesizing a trimethylamine derivative monomer of AGE (AGE-TMA) is described below.
A glass four-necked flask having a capacity of 1000 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with pure water (104.9 g) and trimethylamine hydrochloride (191.1 g) and heated to 50° C. with stirring. Next, 228.3 g of AGE was added over 120 minutes and then reacted for 2 hours to obtain 80% AGE-TMA.
(Synthesis of Polymer 9)
75.5 g of DMF was charged into a glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade), and the temperature was raised to 80° C. with stirring to obtain a polymerization reaction system. Next, 30.0 g of 100% AA, 25.7 g of 50% AGE-TMA DMF solution, and 17.5 g of 10% V-65 were added to the polymerization reaction system kept at 80° C. under stirring. It dripped from a separate nozzle. The dropping time of each solution was 180 minutes for 100% AA, 180 minutes for 50% AGE-TMA DMF solution, and 180 minutes for 10% V-65. Further, the dropping rate of each solution was kept constant, and the dropping of each solution was performed continuously. After completion of the dropping, the reaction solution was kept (aged) at 80° C. for another 60 minutes to complete the polymerization. In the polymer thus obtained, the reaction rate of AA was 91% and the reaction rate of AGE-TMA was greater than 99%. The polymer was neutralized by adding a 48% sodium hydroxide aqueous solution to the DMF solution of the obtained polymer, and then the solvent was distilled off using an evaporator. The dried polymer was finely pulverized, DMF was washed with acetone, and then dried again. Then, the polymer was dissolved in water, purified using a dialysis membrane (MWCO=1 kD), and concentrated with an evaporator to recover an aqueous polymer solution. Thus, an aqueous polymer solution having a solid content concentration of 19% was obtained. The weight average molecular weight of the polymer (polymer 9) was 11,600. In addition, the dye transfer prevention ability was 18%.

<Comparative Example 1>
A powder product polyvinylpyrrolidone (PVP) (manufactured by Nippon Shokubai Co., Ltd., trade name: K-30) was used to evaluate the dye transfer prevention ability.

<Evaluation of transfer prevention ability by ΔE ^* _ab (condition 1)>
Regarding the polymers of Examples 1 to 9, the PVP of Comparative Example 1, and the polymers and compounds synthesized in Examples 10 to 24 described later, the post-evaluation cloths obtained in the same manner as in the above <Evaluation of migration resistance>, The following formula ΔE ^* _ab for white cotton cloth before evaluation was measured with a color difference meter to evaluate the dye transfer prevention ability. The results are shown in Table 2. ΔE ^* _ab indicates that the smaller the value is, the smaller the color difference from the white cloth before evaluation is, the less the color dyeing is suppressed, that is, the higher the transfer prevention ability is.

<Evaluation of transfer prevention ability by ΔE ^* _ab (condition 2)>
The following method was used to measure the dye transfer prevention ability under conditions in which dye transfer is more likely to occur. In evaluating the dye transfer prevention ability, first, a liquid detergent formulation and a 5.0% polymer aqueous solution were prepared. As a liquid detergent composition, 11.0 g of 25% sodium polyoxyethylene lauryl ether sulfate aqueous solution (product name: Emar 20C, manufactured by Kao) and 2.8 g of polyoxyethylene lauryl ether (product name: Emulgen 108, manufactured by Kao) 16.2 g of a 16% sodium dodecylbenzenesulfonate aqueous solution (product name: Neoperex G-15, manufactured by Kao), 3 g of propylene glycol, 1.2 g of sodium oleate, and 1 g of ethanol were added with pure water. What was prepared by stirring after using 50.0 g was used. The 5.0% polymer aqueous solution used was prepared by diluting the polymer synthesized in the below-mentioned Example and the polymer of Comparative Example with an appropriate amount of water to a solid content concentration of 5.0% by mass.
A rounder meter (L-20Z) manufactured by Daiei Kagaku Seiki Seisakusho was used for the evaluation of the dye transfer prevention ability. An aqueous solution for evaluation by adding 250 g of 50 ppm hardness water (Ca/Mg=3/1) to a 500 ml pot of a rounder meter, adding 0.5 g of the prepared liquid detergent composition and 0.5 g of a 5.0% polymer aqueous solution. Was prepared and the temperature was adjusted to 40°C. A 5 cm×5 cm cotton cloth (manufactured by Testfabrics, product name: Style460-6) 1.0 g and 5 cm×5 cm EMPA277 (manufactured by SWISSATEST) 6.4 g and 5 cm×5 cm EMPA496 (manufactured by SWISSATEST) 3 in an aqueous solution for evaluation 0.6 g was added, and the mixture was stirred with a round meter for 30 minutes. Then, the obtained cotton cloth was rinsed with 250 g of 50 ppm hardness water for 5 minutes using a rounder meter, and then air-dried overnight to obtain a post-evaluation cloth. The ΔE ^* _ab of the post-evaluation white cotton cloth obtained in this step was evaluated with a color difference meter to evaluate the dye transfer prevention ability of the polymer.

<Example 10>
(Synthesis of Polymer 10)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 20.0 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical "M-230G") 55.7 parts, benzyl methacrylate 23.9 parts, 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (trade name "V manufactured by Wako Pure Chemical Industries, Ltd. -65") 0.461 parts were charged. The inside of the reaction vessel was replaced with nitrogen at 500 mL/min for 30 minutes with stirring, the temperature was raised to 70° C., and the temperature was maintained at 70° C. for 5 hours to complete the polymerization reaction. 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) after 2 hours 30 minutes, 3 hours, 3 hours 30 minutes, and 4 hours have passed (trade name of Wako Pure Chemical Industries, Ltd. (V-70)) 0.572 parts each were added. After the completion of the polymerization reaction, the solution was cooled to room temperature to obtain a solution of a polymer (polymer 10) having a weight average molecular weight (Mw) of 9500. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 10. Table 2 shows ΔE ^* _ab of the obtained polymer 10 measured as described above.

<Example 11>
(Synthesis of Polymer 11)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 50.0 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd. "M-230G") 34.8 parts, 4-methacryloylaminoazobenzene 14.9 parts, 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (a product manufactured by Wako Pure Chemical Industries, Ltd. 0.218 parts (name "V-65") were prepared. The inside of the reaction vessel was replaced with nitrogen at 500 mL/min for 30 minutes with stirring, the temperature was raised to 70° C., and the temperature was maintained at 70° C. for 5 hours to complete the polymerization reaction. 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) after 2 hours 30 minutes, 3 hours, and 4 hours (trade name “V-70” manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.270 parts each was added. After completion of the polymerization reaction, it was cooled to room temperature to obtain a solution of polymer 11 having a weight average molecular weight (Mw) of 26000. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of polymer 11. Table 2 shows ΔE ^* _ab measured as described above for the obtained polymer 11.

<Example 12>
(Synthesis of Polymer 12)
In a glass reaction container equipped with a thermometer, a stirrer, and a reflux condenser, 50.0 parts of 2-butanone as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical "M-230G") 44.9 parts, 9-vinylcarbazole 4.98 parts, 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (trade name, manufactured by Wako Pure Chemical Industries, Ltd. 0.164 parts of "V-65") and 0.140 parts of 3-mercaptopropionic acid as a chain transfer agent were charged. After stirring the inside of the reaction vessel with nitrogen at 500 mL/min for 30 minutes with stirring, the temperature was raised to 70° C., and the temperature was maintained at 70° C. for 6 hours to complete the polymerization reaction. During the course of 4 hours, 0.204 part of 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (trade name “V-70” manufactured by Wako Pure Chemical Industries, Ltd.) was added. . After completion of the polymerization reaction, it was cooled to room temperature to obtain a solution of polymer 12 having a weight average molecular weight (Mw) of 26000. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 12. Table 2 shows ΔE ^* _ab of the obtained polymer 12 measured as described above.

<Example 13>
(Synthesis of Polymer 13)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 50.0 parts of toluene as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name “M” manufactured by Shin Nakamura Chemical Co., Ltd. -230G") 44.9 parts, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole 4.99 parts, 2,2'-azobis(as a polymerization initiator 0.138 parts of 2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was charged. The inside of the reaction vessel was replaced with nitrogen at 500 mL/min for 30 minutes under stirring, the temperature was raised to 70° C., and the temperature was maintained at 70° C. for 4 hours to complete the polymerization reaction. 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (product name “V-70” manufactured by Wako Pure Chemical Industries, Ltd.) at a time of 2 hours 30 minutes and 3 hours on the way. 180 parts were added each. After completion of the polymerization reaction, it was cooled to room temperature to obtain a solution of polymer 13 having a weight average molecular weight (Mw) of 82800. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 13. Table 2 shows ΔE ^* _ab of the obtained polymer 13 measured as described above.

<Example 14>
(Synthesis of Polymer 14)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 20.0 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd. "M-230G") 55.5 parts, styrene 23.8 parts, and 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (trade name "V- manufactured by Wako Pure Chemical Industries, Ltd."65") and charged 0.691 parts. The inside of the reaction vessel was replaced with nitrogen at 500 mL/min for 30 minutes with stirring, the temperature was raised to 70° C., and the temperature was maintained at 70° C. for 5 hours to complete the polymerization reaction. 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) after 2 hours 30 minutes, 3 hours, 3 hours 30 minutes, and 4 hours have passed (trade name of Wako Pure Chemical Industries, Ltd. (V-70)) 0.858 parts each was added. After the completion of the polymerization reaction, the solution was cooled to room temperature to obtain a solution of polymer 14 having a weight average molecular weight (Mw) of 14,000. The solvent and unreacted styrene were removed with an evaporator, and diluted with water 10 times to obtain an aqueous solution of the polymer 14. Table 2 shows ΔE ^* _ab of the obtained polymer 14 measured as described above.

<Example 15>
(Synthesis of Polymer 15)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 50.0 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical "M-230G") 44.9 parts, 2,2,6,6-tetramethyl-4-piperidyl methacrylate 4.98 parts, 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (Product name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) 0.155 parts was charged. The inside of the reaction vessel was replaced with nitrogen at 500 mL/min for 30 minutes under stirring, the temperature was raised to 70° C., and the temperature was maintained at 70° C. for 4 hours to complete the polymerization reaction. 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (product name “V-70” manufactured by Wako Pure Chemical Industries, Ltd.) 0. 193 parts were added. After completion of the polymerization reaction, it was cooled to room temperature to obtain a solution of polymer 15 having a weight average molecular weight (Mw) of 96200. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 15. Table 2 shows ΔE ^* _ab of the obtained polymer 15 measured as described above.

<Example 16>
(Synthesis of Polymer 16)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 50.0 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical "M-230G") 44.9 parts, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate 4.98 parts, 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator ) (Trade name "V-65" manufactured by Wako Pure Chemical Industries, Ltd.). The inside of the reaction vessel was replaced with nitrogen at 500 mL/min for 30 minutes under stirring, the temperature was raised to 70° C., and the temperature was maintained at 70° C. for 4 hours to complete the polymerization reaction. 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (product name “V-70” manufactured by Wako Pure Chemical Industries, Ltd.) 0. 189 parts each were added. After completion of the polymerization reaction, the solution was cooled to room temperature to obtain a solution of polymer 16 having a weight average molecular weight (Mw) of 70300. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 16. Table 2 shows ΔE ^* _ab of the obtained polymer 16 measured as described above.

<Example 17>
(Synthesis of Polymer 17)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 89.9 parts of ion-exchanged water as a solvent, methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd.) "M-230G") 4.93 parts, 1-vinylimidazole 4.93 parts, 2,2'-azobis(2-methylpropionamidine) dihydrochloride as a polymerization initiator (a product manufactured by Wako Pure Chemical Industries, Ltd. 0.136 parts of a compound "V-50") and 0.106 parts of 3-mercaptopropionic acid as a chain transfer agent were charged. The inside of the reaction vessel was replaced with nitrogen at 500 mL/min for 30 minutes with stirring, the temperature was raised to 70° C., and the temperature was maintained at 70° C. for 5 hours to complete the polymerization reaction. After completion of the polymerization reaction, the mixture was cooled to room temperature to obtain an aqueous solution of polymer 17 having a weight average molecular weight (Mw) of 12700. Table 2 shows ΔE ^* _ab of the obtained polymer 17 measured as described above.

<Example 18>
(Synthesis of Compound 1)
A 100 mL glass four-necked flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 6.8 g of pure water and 6.8 g of imidazole, and the temperature was raised to 60° C. with stirring. Next, polyethylene glycol diglycidyl ether (manufactured by Nagase Chemtex Co., Ltd., trade name: Denacol EX-830,1,26-bis(glycidyloxy)-3,6,9,12,15,18,21,24- 26.3 g of octaoxahexacosane) was added over 60 minutes, and then the reaction was carried out for 4 hours. Thus, the compound (1) was obtained. Table 2 shows ΔE ^* _ab of the obtained compound (1) measured as described above. Compound 1 corresponds to the compound of Formula (E2) in which Y is an imidazole group (unsubstituted in Formula (I-3)) and r2 is 8.

<Example 19>
(Synthesis of Compound 2)
A 100 mL glass four-necked flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 6.8 g of pure water and 6.8 g of imidazole, and the temperature was raised to 60° C. with stirring. Next, 37.0 g of phenol polyethylene glycol glycidyl ether (manufactured by Nagase Chemtex Co., Ltd., Denacol EX-145, 1-phenoxy-14-(oxiranylmethoxy)-3,6,9,12-tetraoxatetradecane) was added. The mixture was added over 60 minutes and then reacted for 4 hours. In this way, compound 2 was obtained. Table 2 shows ΔE ^* _ab measured as described above for the obtained compound 2. Compound 2 corresponds to the compound of formula (E2) in which Y is an imidazole group (unsubstituted in formula (I-3)) and r1 is 5.

<Example 20>
(Synthesis of Compound 3)
A 100 mL glass four-necked flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 6.8 g of pure water and 6.8 g of pyrazole, and the temperature was raised to 60° C. with stirring. Next, 26.8 g of polyethylene glycol diglycidyl ether (Denacol EX-830) was added over 60 minutes, and then the mixture was reacted for 4 hours. In this way, compound 3 was obtained. Table 2 shows ΔE ^* _ab of the obtained compound 3 measured as described above. Compound 3 corresponds to the compound of formula (E2) in which Y is a pyrazole group (unsubstituted in formula (I-4)) and r2 is 8.

<Example 21>
(Synthesis of Compound 4)
374.6 g (2.9 mol) of N-(2-hydroxyethyl)pyrrolidone (hereinafter sometimes referred to as HEP) was placed in an SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction pipe, and a nitrogen introduction pipe. Then, 0.33 g of sodium hydroxide was charged as a reaction catalyst, the inside of the reaction vessel was replaced with nitrogen under stirring, and the mixture was heated to 120° C. under a nitrogen atmosphere. Then, while maintaining 120±5° C. under a safe pressure, 1281.8 g (29.0 mol) of ethylene oxide was introduced into the reactor over 3.5 hours, and the temperature was maintained for another 2 hours after the introduction. Finally, the inside of the reaction vessel was replaced with nitrogen under stirring and cooled to room temperature. Thus, a polyalkylene glycol-containing compound (a) in which an average of 10 moles of ethylene oxide was added to HEP was obtained. 600 g (1.1 mol) of the polyalkylene glycol-containing compound (a) was charged into an SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, and the inside of the reaction vessel was replaced with nitrogen while stirring. , Heated to 120° C. under a nitrogen atmosphere. Then, while maintaining 120±5° C. under a safe pressure, 195.1 g (4.4 mol) of ethylene oxide was introduced into the reactor over 2.5 hours, and the temperature was maintained for another 1.5 hours after the introduction. Finally, the inside of the reaction vessel was replaced with nitrogen under stirring and cooled to room temperature. Thus, a polyalkylene glycol-containing compound (b) having an average of 14.2 mol of alkylene oxide added to HEP was obtained. Further, 780.7 g (1.1 mol) of the polyalkylene glycol-containing compound (b) produced above was charged into an SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction pipe and a nitrogen introduction pipe, and the mixture was stirred. The inside of the reaction vessel was replaced with nitrogen and heated to 120° C. under a nitrogen atmosphere. Then, while maintaining 120±5° C. under safe pressure, 284.2 g (6.5 mol) of ethylene oxide was introduced into the reactor over 5.3 hours, and the temperature was maintained for 4.2 hours after the introduction. Finally, the inside of the reaction vessel was replaced with nitrogen under stirring and cooled to room temperature. Thus, a compound 4 in which an average of 20.4 mol of alkylene oxide was added to HEP was obtained. Table 2 shows ΔE ^* _ab of the obtained compound 4 measured as described above.

<Example 22>
(Synthesis of Compound 5)
In a glass four-necked eggplant flask equipped with a thermometer, a reflux pipe and a nitrogen introduction pipe, 2.25 g (2.2 mmol) of compound 4 and 0.13 g (3.2 mmol) of sodium hydroxide as a reaction catalyst, A stirring bar was charged, the inside of the reaction vessel was replaced with nitrogen while stirring with a magnetic stirrer, and the mixture was heated to 80° C. in a nitrogen atmosphere. 0.60 g (2.9 mmol) of 1-lauryl chloride was added all at once to the reaction vessel while maintaining 80° C. under atmospheric pressure, and then the temperature was kept for 7.5 hours under a nitrogen atmosphere. Then, the reaction solution was allowed to cool to room temperature, ion-exchanged water was added, and the mixture was stirred well. The dispersion solution was transferred to a separatory funnel, washed with n-hexane, and the lower phase was taken out to recover an aqueous phase. This washing operation was repeated 3 times. The solvent of the recovered aqueous phase was distilled off by evaporation. Acetonitrile was added to the residue and the insoluble material was separated by centrifugation. The supernatant after centrifugation was collected and acetonitrile was distilled off by evaporation. In this way, compound 5 was obtained. Table 2 shows ΔE ^* _ab of the obtained compound 5 measured as described above.

<Example 23>
(Synthesis of Compound 6)
Compound 6 was an ethylene oxide adduct of phenol (average number of moles of ethylene oxide added: 20 mol). Table 2 shows the ΔE ^* _ab measured for compound 6 as described above.

<Example 24>
(Polymer 18)
A glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser was charged with 50.1 parts of ion-exchanged water as a solvent, and the inside of the reaction vessel was replaced with nitrogen at 500 mL/min for 30 minutes under stirring. An aqueous solution 24.1 of methoxypolyethylene glycol monomethacrylate (average mol number of ethylene glycol added: 23 mol, trade name "M-230G" manufactured by Shin-Nakamura Chemical Co., Ltd.) which was heated to 85° C. and diluted to 60% with deionized water. Parts for 2 hours and 40 minutes, 14.4 parts for N-vinylpyrrolidone for 2 hours and 40 minutes, 2,2'-azobis(2-methylpropionamidine)dihydrochloride diluted to 10% with deionized water as a polymerization initiator. 11.4 parts of an aqueous solution (trade name "V-50" manufactured by Wako Pure Chemical Industries, Ltd.) was separately added simultaneously in 3 hours and 10 minutes, and the temperature was raised to 85°C for 3 hours and 10 minutes from the start of polymerization. Maintained and completed the polymerization reaction. After completion of the polymerization reaction, it was cooled to room temperature to obtain a solution of polymer 18 having a weight average molecular weight (Mw) of 17600. Table 2 shows ΔE ^* _ab of the obtained polymer 18 measured as described above.

<Example 25>
(Synthesis of Monomer 4)
A 4-necked flask containing a stirring stirrer chip was charged with 10.0 parts of 4-hydroxyindole (manufactured by Tokyo Kasei), 66.6 parts of tetrahydrofuran and 11.3 parts of triethylamine, and stirred to obtain a uniform solution. . Then, 12.1 parts of methacrylic acid chloride was added dropwise at an internal temperature of 25° C. or lower over 20 minutes while cooling the solution with an ice bath. After aging for 2 hours after completion of dropping, water was added to the reaction solution to stop the reaction. 400 parts of ethyl acetate was added to the reaction solution, extraction was performed with a separating funnel, and the organic layer was washed with 0.5 M aqueous sodium hydroxide solution and water. The obtained organic layer was dried over magnesium sulfate, filtered using a filter paper, and then the solvent was distilled off using an evaporator to obtain a monomer 4.
(Synthesis of Polymer 19)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 49.9 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd. "M-230G") 44.8 parts, Monomer 4 4.97 parts, 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (product of Wako Pure Chemical Industries, Ltd. Name "V-65") 0.198 parts were charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. Once cooled to room temperature, 0.198 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the container. Then, the temperature was again raised to 70° C. and the temperature was maintained for 4 hours. After cooling to room temperature, a solution of polymer 19 having a weight average molecular weight (Mw) of 49800 was obtained. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 19.

<Example 26>
(Synthesis of Polymer 20)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 49.9 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd. “M-230G”) 47.3 parts, 11-[4-(4-butylphenylazo)phenoxy]undecyl methacrylate (manufactured by Tokyo Kasei) 2.49 parts, and 2,2′-azobis(as a polymerization initiator) 0.125 parts of 2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. Once cooled to room temperature, 0.125 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the container. The temperature was raised again to 70° C. and the temperature was maintained for 4 hours. After cooling to room temperature, a solution of polymer 20 having a weight average molecular weight (Mw) of 53900 was obtained. After removing the solvent with an evaporator and diluting 10 times with water, the insoluble matter was filtered with a filter paper to obtain an aqueous solution of the polymer 20.

<Example 27>
(Synthesis of Monomer 5 (N,N-Dimethyl-amino-1,4-phenylene(meth)acrylamide))
A 4-necked flask containing a stirrer tip for stirring was charged with 10.2 parts of N,N-dimethyl-1,4-phenylenediamine, 66.5 parts of tetrahydrofuran and 11.3 parts of triethylamine, and stirred to obtain a uniform mixture. Made into a solution. Then, 12.1 parts of methacrylic acid chloride was added dropwise at an internal temperature of 25° C. or lower over 20 minutes while cooling the solution with an ice bath. After aging for 2 hours after completion of dropping, the reaction was stopped by adding water to the reaction solution. 320 parts of diethyl ether was added to the reaction solution, extraction was performed with a separating funnel, and the organic layer was washed with 0.5 M aqueous sodium hydroxide solution and water. Then, the crystals precipitated from the organic layer were collected and vacuum dried to obtain a monomer 5.
(Synthesis of Polymer 21)
In a glass reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, 49.9 parts of 2-propanol as a solvent, methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical "M-230G") 44.8 parts, monomer 5 4.99 parts, and 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (a product manufactured by Wako Pure Chemical Industries, Ltd. Name "V-65") 0.159 copies were prepared. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. Once cooled to room temperature, 0.159 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the container. The temperature was raised again to 70° C. and the temperature was maintained for 4 hours. It cooled to room temperature and obtained the solution of the weight average molecular weight (Mw) 38500 polymer 21. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 21.

<Evaluation of transfer prevention ability by ΔE ^* _ab (condition 3)>
The following method was used to measure the dye transfer prevention ability under conditions in which dye transfer is more likely to occur. In evaluating the dye transfer prevention ability, first, a liquid detergent formulation and a 5.0% polymer aqueous solution were prepared. As a liquid detergent composition, 11.0 g of 25% sodium polyoxyethylene lauryl ether sulfate aqueous solution (product name: Emar 20C, manufactured by Kao) and 2.8 g of polyoxyethylene lauryl ether (product name: Emulgen 108, manufactured by Kao) 16.2 g of a 16% sodium dodecylbenzenesulfonate aqueous solution (product name: Neoperex G-15, manufactured by Kao), 3 g of propylene glycol, 1.2 g of sodium oleate, and 1 g of ethanol were added with pure water. What was prepared by stirring after using 50.0 g was used. The 5.0% polymer aqueous solution used was prepared by diluting the polymer synthesized in the below-mentioned Example and the polymer of Comparative Example with an appropriate amount of water to a solid content concentration of 5.0% by mass.
A rounder meter (trade name: L-20Z) manufactured by Daiei Kagaku Seiki Seisakusho was used for the evaluation of the dye transfer prevention ability. An aqueous solution for evaluation by adding 250 g of 50 ppm hardness water (Ca/Mg=3/1) to a 500 ml pot of a rounder meter, adding 0.5 g of the prepared liquid detergent composition and 0.5 g of a 5.0% polymer aqueous solution. Was prepared and the temperature was adjusted to 40°C. A 5 cm×5 cm nylon cloth (trade name: Nylon taffeta N50, manufactured by Toray) 1.0 g and 5 cm×5 cm EMPA277 (manufactured by SWISSATEST) 6.4 g and 5 cm×5 cm EMPA496 (manufactured by SWISSATEST) in the aqueous solution for evaluation 3 0.6 g was added, and the mixture was stirred with a round meter for 30 minutes. Then, the obtained cotton cloth was rinsed with 250 g of 50 ppm hardness water for 5 minutes using a rounder meter, and then air-dried overnight to obtain a post-evaluation cloth. The ΔE ^* _ab of the post-evaluation white cotton cloth obtained in this step was evaluated with a color difference meter to evaluate the dye transfer prevention ability of the polymer.
Table 3 shows ΔE ^* _ab measured under conditions 3 for Examples 25 to 27 and Comparative Example 1.

<Example 28>
Synthesis of Monomer 6 (1-naphthylmethyl (meth)acrylate) 16.1 parts of 1-hydroxymethylnaphthalene (manufactured by Tokyo Kasei Kogyo) and 55.0 of tetrahydrofuran were placed in a three-necked flask containing a stirring stirrer chip. And 17.1 parts of triethylamine were charged and stirred to obtain a uniform solution. Then, 11.8 parts of methacrylic acid chloride was added dropwise at an internal temperature of 5 to 20° C. over 20 minutes while cooling the solution with an ice bath. After completion of dropping, the mixture was aged for 1 hour at room temperature, and then water was added to the reaction solution to stop the reaction. 250 parts of diethyl ether was added to the reaction solution, extraction was performed with a separating funnel, and the organic layer was washed with 0.5M aqueous sodium hydroxide solution, 0.5M hydrochloric acid and water. The obtained organic layer was dried over magnesium sulfate, filtered using a filter paper, and then the solvent was distilled off using an evaporator to obtain a monomer 6.
(Synthesis of Polymer 22)
In a glass reaction container equipped with a thermometer, a stirrer, and a reflux condenser, 50.0 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd. "M-230G") 44.8 parts, monomer 6 4.95 parts, and 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (a product manufactured by Wako Pure Chemical Industries, Ltd. Name "V-65") 0.150 parts were charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. Once cooled to room temperature, 0.150 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the container. Then, the temperature was again raised to 70° C. and the temperature was maintained for 4 hours. After cooling to room temperature, a solution of polymer 22 having a weight average molecular weight (Mw) of 46100 was obtained. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 22. Table 4 shows the ΔE ^* _ab of the obtained polymer 22 measured as described above.

<Example 29>
Synthesis of Monomer 7 (9-anthrylmethyl methacrylate) 13.9 parts of 9-anthracenemethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 67.2 parts of tetrahydrofuran, and triethylamine were placed in a three-necked flask containing a stirring stirrer chip. Was charged into 11.2 parts and stirred to obtain a suspension. Then, 7.73 parts of methacrylic acid chloride was added dropwise at an internal temperature of 5 to 20° C. over 20 minutes while cooling the solution in an ice bath. After completion of dropping, the mixture was aged for 1 hour at room temperature, and then water was added to the reaction solution to stop the reaction. Diethyl ether (150 parts) was added to the reaction solution, extraction was performed with a separating funnel, and the organic layer was washed with 0.5 M aqueous sodium hydroxide solution, 0.5 M hydrochloric acid and water. The obtained organic layer was dried over magnesium sulfate, filtered using a filter paper, and the solvent was distilled off using an evaporator to obtain monomer 7.
(Synthesis of Polymer 23)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 49.6 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd. "M-230G") 44.8 parts, Monomer 7 4.92 parts, 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (product of Wako Pure Chemical Industries, Ltd. Name "V-65") 0.140 parts was charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. Then, as an aging operation, once cooled to room temperature, 0.140 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was put into a container. After the addition, the temperature was raised again to 70° C. and the temperature was maintained for 4 hours. This aging operation was performed twice in total and cooled to room temperature to obtain a solution of the polymer 23 having a weight average molecular weight (Mw) of 35400. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 23. Table 4 shows ΔE ^* _ab of the obtained polymer 23 measured as described above.

<Example 30> (Synthesis of polymer 24)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 49.6 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd. “M-230G”) 44.5 parts, acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.95 parts, and 2,2′-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (Wako Pure Chemical Industries, Ltd.) 0.184 parts of the product name "V-65" manufactured by Co., Ltd. were charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. After that, as an aging operation, once cooled to room temperature, 0.184 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a container. After the addition, the temperature was raised again to 70° C. and the temperature was maintained for 4 hours. This aging operation was carried out four times in total and cooled to room temperature to obtain a solution of polymer 24 having a weight average molecular weight (Mw) of 11300. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 24. Table 4 shows ΔE ^* _ab of the obtained polymer 24 measured as described above.

<Example 31>
Monomer 8 (N-cyano-N'-methacryloylguanidine)
A three-necked flask containing a stirring stirrer chip was charged with 12.2 parts of dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd.), 28.1 parts of acetone, 35.5 parts of water, and 12.9 parts of sodium hydroxide, and iced. Cooled in bath. Then, the internal temperature was kept at 5 to 20° C., and 11.3 parts of methacrylic acid chloride was added dropwise over 20 minutes with vigorous stirring. After completion of dropping, the mixture was aged for 1 hour at room temperature, and then water was added to the reaction solution to make a uniform solution. While cooling, acetic acid was added for neutralization, and the white crystals formed were collected by filtration. This was dissolved in acetone, cooled to -20°C and recrystallized. The produced crystal was filtered to obtain Monomer 8.
(Synthesis of Polymer 25)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 74.7 parts of 2-propanol, methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd.) "M-230G") 22.3 parts, acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.48 parts, and 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (Wako Pure Chemical Industries, Ltd.) Co., Ltd. product name "V-65") 0.100 part was charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. Then, as an aging operation, once cooled to room temperature, 0.100 part of 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a container. After the addition, the temperature was raised again to 70° C. and the temperature was maintained for 4 hours. This aging operation was carried out 5 times in total and cooled to room temperature to obtain a solution of polymer 25 having a weight average molecular weight (Mw) of 8300. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 25. Table 4 shows ΔE ^* _ab of the obtained polymer 25 measured as described above.

<Example 32> (Synthesis of Polymer 26)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 49.9 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 23 moles, trade name of Shin Nakamura Chemical Co., Ltd. "M-230G") 44.9 parts, 1-(3-sulfopropyl)-2-vinylpyridinium hydroxide inner salt (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.98 parts, and 2,2 as a polymerization initiator. 0.178 parts of'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Wako Pure Chemical Industries, Ltd.) was charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. Then, as an aging operation, once cooled to room temperature, 0.178 parts of 2,2′-azobis(2-methylpropionamidine)dihydrochloride (trade name “V-50” manufactured by Wako Pure Chemical Industries, Ltd.) After the addition in the container, the temperature was raised again to 70° C. and the temperature was maintained for 4 hours. After cooling to room temperature, a solution of polymer 26 having a weight average molecular weight (Mw) of 191600 was obtained. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 26. Table 4 shows ΔE ^* _ab of the obtained polymer 26 measured as described above.

<Example 33> (Synthesis of Polymer 27)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 50.0 parts of 2-propanol as a solvent, methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 9 moles, product name of Shin Nakamura Chemical Co., Ltd. “M-90G”) 44.7 parts, benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.04 parts, and 2,2′-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (Wako Pure Chemical Industries, Ltd. 0.271 parts of trade name "V-65" manufactured by Kogyo Co., Ltd. was charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. After cooling to room temperature, a solution of polymer 27 having a weight average molecular weight (Mw) of 9300 was obtained. The polydispersity of the polymer 27 was 2.42. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of polymer 27. Table 4 shows ΔE ^* _ab of the obtained polymer 27 measured as described above.

<Example 34> (Synthesis of polymer 28)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 44.0 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 45 moles, trade name of Shin Nakamura Chemical Co., Ltd. "M-450G") 50.8 parts, benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.00 parts, and 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (Wako Pure Chemical Industries, Ltd.) 0.100 parts of trade name "V-65" manufactured by Kogyo Co., Ltd. was charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. After cooling to room temperature, a solution of polymer 28 having a weight average molecular weight (Mw) of 66300 was obtained. The solvent was removed with an evaporator, and the solution was diluted 10 times with water to obtain an aqueous solution of the polymer 28. Table 4 shows ΔE ^* _ab of the obtained polymer 28 measured as described above.

<Example 35> (Synthesis of polymer 29)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 67.9 parts of 2-propanol and 16.9 parts of water, 10.4 parts of 2-acrylamido-2-methyl-1-propanesulfonic acid were added. , Benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.47 parts, and 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator (trade name "V- manufactured by Wako Pure Chemical Industries, Ltd."65") 0.186 parts were charged. The inside of the reaction vessel was replaced with nitrogen under stirring, the temperature was raised to 70° C., and the temperature was maintained for 4 hours. Then, as an aging operation, once cooled to room temperature, 0.186 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a container. After the addition, the temperature was again raised to 70° C., the temperature was maintained for 4 hours, and the temperature was cooled to room temperature. After removing the solvent with an evaporator and diluting 10 times with water to obtain an aqueous solution of the polymer 29, by neutralizing to pH 7 with an aqueous sodium hydroxide solution, the polymer 29 having a weight average molecular weight (Mw) of 3800 was obtained. An aqueous solution was obtained. Table 4 shows ΔE ^* _ab of the obtained polymer 29 measured as described above.

<Example 36> (Synthesis of Polymer 30)
In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 57.4 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene glycol added: 9 moles, trade name "M-90G" manufactured by Shin Nakamura Chemical Co., Ltd.) As a chain transfer agent, 4-[(2-carboxyethylsulfanylthiocarbonyl)sulfanyl]-4-cyanopentanoic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 0.355 parts, 2,2′-azobis(isobutyronitrile) 4.75 parts of a 1% ethanol solution of (Fujifilm Wako Pure Chemical Industries, Ltd.) and 37.5 parts of ethanol were charged and stirred to make a uniform solution, and then nitrogen was bubbled into the solution for 5 minutes. Then, the temperature of the solution was raised to 60° C. with stirring, the temperature was maintained for 10 hours, and then the temperature was returned to room temperature to obtain a solution of intermediate 1.
In a glass reaction container equipped with a thermometer, a stirrer, and a reflux condenser, 73.7 parts of the solution of Intermediate 1 (solid content: 58%) obtained by the above method, 3.82 parts of benzyl methacrylate, 2, 2 3.52 parts of 1% ethanol solution of'-azobis(isobutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 19.0 parts of ethanol were charged and stirred to make a uniform solution, and then nitrogen was added to the solution. Was bubbled for 5 minutes. Then, the temperature of the solution was raised to 70° C. with stirring, the temperature was maintained for 14 hours and then returned to room temperature to obtain an ethanol solution of the polymer 30. Acetone and water were added to the obtained polymer, and ethanol and acetone were distilled off using an evaporator to obtain an aqueous solution of the polymer 30, and then neutralized to pH 7 with an aqueous sodium hydroxide solution to obtain a weight average. An aqueous solution of polymer 30 having a molecular weight (Mw) of 46200 was obtained. The polydispersity of the polymer 30 was 1.33. Table 4 shows ΔE ^* _ab of the obtained polymer 30 measured as described above.

Table 5 summarizes the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw/Mn) of polymers 1 to 30.

Claims (13)

1. It has a structural unit derived from a monomer (A) containing an ethylenically unsaturated group and a hydrophilic functional group, and a structural unit derived from a monomer (B) containing an ethylenically unsaturated group and a dye affinity group. Polymer (I),
   A polymer (II) having a structural unit derived from a monomer (C) containing an ethylenically unsaturated group, a dye affinity group and a hydrophilic functional group, and
   A dye transfer inhibitor comprising at least one compound selected from the group consisting of a compound (III) having a dye affinity group and a hydrophilic functional group (however, not the polymer (I) and the polymer (II)).
2. The dye affinity group is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted pyrazole group, a substituted or unsubstituted cyclic amide group, a substituted or unsubstituted imidazole group, a substituted or unsubstituted Substituted azobenzene group, substituted or unsubstituted carbazole group, quaternary ammonium group, substituted or unsubstituted piperidine group, substituted or unsubstituted benzotriazole group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyridinium Group, substituted or unsubstituted amidine group, substituted or unsubstituted pyrimidine group, substituted or unsubstituted pyrazine group, substituted or unsubstituted pyridazine group, substituted or unsubstituted indole group, and substituted or unsubstituted cyclic imide The dye transfer inhibitor according to claim 1, which is at least one selected from the group consisting of groups.
3. The hydrophilic functional group is at least one selected from the group consisting of a carboxyl group and a salt thereof, a sulfonic acid group and a salt thereof, a phosphoric acid group and a salt thereof, an alkylene oxide group, a polyalkylene oxide group, a hydroxyl group, and an amino group. The dye transfer inhibitor according to claim 1 or 2, which is
4. The dye transfer inhibitor according to any one of claims 1 to 3, which comprises the polymer (I),
   The dye transfer inhibitor, wherein the monomer (B) is at least one kind of compounds represented by the following formula (I) or compounds represented by the following formula (II).
   

   

   (In the formula (I), R ¹ represents a hydrogen atom or a methyl group, X is a covalent bond, —C(═O)O—, —C(═O)O—R ³⁵ —(R ³⁵ is A divalent hydrocarbon group having 2 to 20 carbon atoms), —C(═O)NH—), —CH ₂ —O—CH ₂ CH(OH)CH ₂ —, —CH(OH)—CH _2- CH ₂ —O— or a divalent group having a benzene ring substituted with a hydroxyl group and having 3 to 10 carbon atoms, and Y is represented by the following formulas (I-1), (I-2), (I -3), (I-4), (I-5), (I-6), (I-7), (I-8), (I-9), (I-10), (I-11 ), (I-12), (I-13), (I-14), (I-15) or (I-16),
   

   

   

   

   

   In formulas (I-1) to (I-8), (I-10) to (I-14), and (I-16), one or more hydrogen atoms bonded to carbon atoms contained in the ring are substituted. It may be substituted with a group, m in the formula (I-1) is an integer of 0 to 5, n in the formula (I-2) is an integer of 2 to 6, and the formula (I-8) In formula (I-9) and formula (I-12), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently 1 to 10 Represents a hydrocarbon group having 1 carbon atom or a hydrogen atom, and in the formula (I-11), Z is a divalent hydrocarbon group having 1 to 10 carbon atoms, and has the formula (I-13) M11 in formula (I-14) is an integer of 0 to 5, m12 in formula (I-14) is an integer of 0 to 5, and R ⁴⁰ , R ⁴¹ , and R ⁴² in formula (I-15) are independently 1 to Represents a hydrocarbon group having 6 carbon atoms, a hydrogen atom, or a cyano group, and in the formula (I-16), R ⁴³ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z ¹¹ is , Sulfonic acid groups and salts thereof.
   In the formula (II), Ar is a divalent group in which two of the hydrogen atoms bonded to the ring of naphthalene or anthracene are removed, and the divalent group may be substituted, R ⁴⁷ and R ^48's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. )
5. The monomer (B) is N-vinylpyrrolidone, N-vinylimidazole, styrene, benzyl (meth)acrylate, N-vinylcarbazole, allyl glycidyl ether-added pyrazole, allyl glycidyl ether-added trimethylamine, 2, 2, 6, 6-Tetramethyl-4-piperidyl (meth)acrylate, 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole, 1,2,2,6 6-pentamethyl-4-piperidyl (meth)acrylate, 4-indole (meth)acrylate, 11-[4-(4-butylphenylazo)phenoxy]undecyl (meth)acrylate, N,N-dimethyl-amino-1 ,4-phenylene(meth)acrylamide, 1-naphthylmethyl(meth)acrylate, 9-anthrylmethyl(meth)acrylate, acenaphthylene, N-cyano-N'-(meth)acryloylguanidine, and 1-(3-sulfo The dye transfer inhibitor according to claim 4, which is at least one of the monomers selected from the group consisting of propyl)-2-vinylpyridinium hydroxide inner salt.
6. The monomer (A) is a unit amount selected from the group consisting of (meth)acrylic acid, polyethylene glycol (meth)acrylate, maleic acid and 2-(meth)acrylamido-2-methylpropanesulfonic acid or a salt thereof. The dye transfer inhibitor according to any one of claims 1 to 5, which is at least one body.
7. It has a structural unit derived from a monomer (A) containing an ethylenically unsaturated group and a hydrophilic functional group, and a structural unit derived from a monomer (B) containing an ethylenically unsaturated group and a dye affinity group. Polymer (I),
   A polymer (II) having a structural unit derived from a monomer (C) containing an ethylenically unsaturated group, a dye affinity group and a hydrophilic functional group, and
   A detergent additive containing at least one compound selected from the group consisting of a compound (III) having a dye-affinitive group and a hydrophilic functional group (but not the polymer (I) or the polymer (II)).
8. The dye affinity group is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted pyrazole group, a substituted or unsubstituted cyclic amide group, a substituted or unsubstituted imidazole group, a substituted or unsubstituted Substituted azobenzene group, substituted or unsubstituted carbazole group, quaternary ammonium group, substituted or unsubstituted piperidine group, substituted or unsubstituted benzotriazole group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyridinium Group, substituted or unsubstituted amidine group, substituted or unsubstituted pyrimidine group, substituted or unsubstituted pyrazine group, substituted or unsubstituted pyridazine group, substituted or unsubstituted indole group, and substituted or unsubstituted cyclic imide The detergent additive according to claim 7, which is at least one selected from the group consisting of groups.
9. The hydrophilic functional group is at least one selected from the group consisting of a carboxyl group and a salt thereof, a sulfonic acid group and a salt thereof, a phosphoric acid group and a salt thereof, an alkylene oxide group, a polyalkylene oxide group, a hydroxyl group, and an amino group. The detergent additive according to claim 7 or 8, wherein the additive is a detergent.
10. The detergent additive according to any one of claims 7 to 9, which comprises the polymer (I),
    The additive for detergents, wherein the monomer (B) is at least one kind of the compounds represented by the following formula (I) or the compound represented by the following formula (II).
    

    

    (In the formula (I), R ¹ represents a hydrogen atom or a methyl group, X is a covalent bond, —C(═O)O—, —C(═O)O—R ³⁵ —(R ³⁵ is A divalent hydrocarbon group having 2 to 20 carbon atoms), —C(═O)NH—), —CH ₂ —O—CH ₂ CH(OH)CH ₂ —, —CH(OH)—CH _2- CH ₂ —O— or a divalent group having a benzene ring substituted with a hydroxyl group and having 3 to 10 carbon atoms, and Y is represented by the following formulas (I-1), (I-2), (I -3), (I-4), (I-5), (I-6), (I-7), (I-8), (I-9), (I-10), (I-11 ), (I-12), (I-13), (I-14), (I-15) or (I-16),
    

    

    

    

    

    In formulas (I-1) to (I-8), (I-10) to (I-14), and (I-16), one or more hydrogen atoms bonded to carbon atoms contained in the ring are substituted. May be substituted with a group, m in the formula (I-1) is an integer of 0 to 5, n in the formula (I-2) is an integer of 2 to 6, and the formula (I-8) And in formula (I-9), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are each independently a hydrocarbon group having 1 to 10 carbon atoms. Or a hydrogen atom, and in the formula (I-11), Z is a divalent hydrocarbon group having 1 to 10 carbon atoms, and m11 in the formula (I-13) is an integer of 0 to 5. M12 in formula (I-14) is an integer of 0 to 5, and R ⁴⁰ , R ⁴¹ , and R ⁴² in formula (I-15) are each independently a hydrocarbon having 1 to 6 carbon atoms. Represents a group, a hydrogen atom, or a cyano group, and in the formula (I-16), R ⁴³ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z ¹¹ is a sulfonic acid group or a salt thereof. .
    In the formula (II), Ar is a divalent group in which two of the hydrogen atoms bonded to the ring of naphthalene or anthracene are removed, and the divalent group may be substituted, R ⁴⁷ and R ^48's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. )
11. The monomer (B) is N-vinylpyrrolidone, N-vinylimidazole, styrene, benzyl (meth)acrylate, N-vinylcarbazole, allyl glycidyl ether-added pyrazole, allyl glycidyl ether-added trimethylamine, 2, 2, 6, 6-tetramethyl-4-piperidyl (meth)acrylate, 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole, and 1,2,2,6 ,6-Pentamethyl-4-piperidyl (meth)acrylate, 4-indole (meth)acrylate, 11-[4-(4-butylphenylazo)phenoxy]undecyl (meth)acrylic acid, N,N-dimethyl-amino- 1,4-phenylene(meth)acrylamide, 1-naphthylmethyl(meth)acrylate, 9-anthrylmethyl(meth)acrylate, acenaphthylene, N-cyano-N'-(meth)acryloylguanidine, and 1-(3- The detergent additive according to claim 10, which is at least one of monomers selected from the group consisting of sulfopropyl)-2-vinylpyridinium hydroxide inner salt.
12. The monomer (A) is a unit amount selected from the group consisting of (meth)acrylic acid, polyethylene glycol (meth)acrylate, maleic acid and 2-(meth)acrylamido-2-methylpropanesulfonic acid or a salt thereof. The detergent additive according to any one of claims 7 to 11, which is at least one of the body.
13. A detergent composition comprising the dye transfer inhibitor according to any one of claims 1 to 6 or the detergent additive according to any one of claims 7 to 12.