JP2021054983A - Copolymer for detergents - Google Patents

Abstract

To provide a copolymer for detergents having cleaning power more excellent than conventional polymers.SOLUTION: A copolymer used for detergent applications comprises: a constituent unit (a) derived from mono(meth)acrylic acid ester or mono(meth) of polyalkylene ether that may have at least one kind of hydrophilic group selected from the group consisting of a hydroxyl group as well as a carboxyl group, a sulfonic acid group, a phosphate group, an amino group and salts of these and a constituent unit (b) derived from a hydrophobic monomer (B), in which a content ratio of the constituent unit derived from the (meth)acrylic acid (salt) is 49 mass% or smaller relative to 100 mass% of a total of constituent units and a weight average molecular weight is 10000 or larger and smaller than 105000, and the hydrophobic monomer (B) has a solubility parameter of a homopolymer of 13 or smaller and an organic group having 3 or more carbons other than an ethylenically unsaturated group.SELECTED DRAWING: None

Description

The present invention relates to a copolymer for detergents. More specifically, it relates to a copolymer useful for detergent applications such as liquid detergents and powder detergents.

Conventionally, detergents used for clothing are blended with detergent builders (detergent aids) such as zeolite, carboxymethyl cellulose, and polyethylene glycol for the purpose of improving the cleaning effect of the detergent.
In addition to the various detergent builders described above, in recent years, polymers have been incorporated into detergent compositions as detergent builders. Regarding such a polymer, for example, Patent Documents 1 and 2 disclose a copolymer of an unsaturated carboxylic acid-based monomer such as (meth) acrylic acid and a (poly) alkylene glycol-based monomer. ing. In addition to such polycarboxylic acid-based copolymers, as polymers used for detergent applications, for example, Patent Document 3 describes a polymer having a predetermined structural unit (A) and a predetermined structural unit (B). A recontamination inhibitor containing is disclosed. Patent Document 4 describes a structural unit (A) derived from an unsaturated bond-containing monomer having at least one amino group selected from 1 to 3 amino groups, and a linear or branched chain having 4 to 22 carbon atoms. Alternatively, a structural unit derived from an unsaturated bond-containing monomer having at least one hydrophobic group selected from a cyclic alkyl group or alkenyl group, or an arylalkyl group or an aryl group and having no 1st to 3rd amino acid group. (B), the content of the structural unit (A) in the polymer is 50 to 99% by weight, the content of the structural unit (B) is 1 to 50% by weight, and the weight average molecular weight is 2,000 to 30%. A fiber stain release agent consisting of 000 polymers has been disclosed.

JP-A-2007-231260 JP-A-2002-003551 Japanese Unexamined Patent Publication No. 2009-249743 JP-A-2007-247126

In recent years, synthetic fibers such as polyester have been increasing as materials used for clothing and the like because they have excellent durability, dry quickly, and are less likely to wrinkle. While polyester has the above-mentioned merits, since it is a hydrophobic fiber, it has a strong adsorption force with sebum stains and has a demerit that stains are hard to be removed as compared with cotton and the like. In addition, as the number of double-income households has increased in recent years, it has become more common to wash laundry in bulk, and leaving the laundry dirty for a long time is one of the reasons why it is difficult to remove the dirt. is there. Under such circumstances, various polymers used for conventional detergent applications are not sufficient in detergency, and there is room for improvement.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a copolymer for detergents, which is superior in detergency to conventional polymers.

As a result of various studies on polymers used for detergent applications, the present inventor has found that a copolymer of a monomer having a specific hydrophilic group and a specific hydrophobic monomer is derived from the hydrophobic monomer. By setting the content ratio of the structural unit and the structural unit derived from (meth) acrylic acid (salt) to a specific range, it was found that the detergency is superior to that of the conventional polymer, and the above problem is solved brilliantly. We came up with the idea of what we can do and arrived at the present invention.

That is, the present invention is a copolymer used for detergent applications, and the above-mentioned copolymer for detergents has the following formula (1);

(In the formula, R ¹ , R ² and R ³ are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents at least one hydrophilic group, or an alkyl group having 1 to 3 carbon atoms which may have the above hydrophilic group. Z represents a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group. Represents a hydrocarbon group having 2 to 30 carbon atoms having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. A is the same or different. Represents an alkylene group which may have at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group thereof. Represents the average number of added moles of (AO) and is a number of 0, 1, or 10 to 200. X represents a number of 0 to 4. y represents 0 or 1, where x. Is 0, y is 1, and if R ¹ , R ^2, R ³ and A do not have the above hydrophilic groups, n is a number greater than or equal to 10 and less than 90). It has a structural unit (a) and a structural unit (b) derived from the hydrophobic monomer (B), and the content ratio of the structural unit derived from (meth) acrylic acid (salt) is 100% by mass of the total structural unit. On the other hand, it is 49% by mass or less, the weight average molecular weight is 10,000 or more and less than 105,000, and the hydrophobic monomer (B) has a solubility parameter of 13 or less as a homopolymer and is not ethylenically. It is a copolymer for detergent having an organic group having 3 or more carbon atoms in addition to the saturated group.

The content ratio of the structural unit (a) in the above-mentioned copolymer for detergent is preferably 10 to 99% by mass with respect to 100% by mass of all structural units.

The content ratio of the structural unit (b) in the above-mentioned copolymer for detergent is preferably 1 to 90% by mass with respect to 100% by mass of all structural units.

The present invention is also a detergent additive containing the above-mentioned detergent copolymer.

It is also a detergent composition containing the above-mentioned copolymer for detergent and an additive for detergent other than the copolymer.

The present invention is also a copolymer used for detergent applications, and the copolymer for detergents is represented by the following formula (1);

(In the formula, R ¹ , R ² and R ³ are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents at least one hydrophilic group, or an alkyl group having 1 to 3 carbon atoms which may have the hydrophilic group. Z represents a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group. Represents a hydrocarbon group having 2 to 30 carbon atoms having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. A is the same or different. Represents an alkylene group which may have at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents the average number of added moles of (AO) and is a number of 0, 1, or 10 to 200. X represents a number of 0 to 4. y represents 0 or 1, where x. Is 0, y is 1, and if R ¹ , R ^2, R ³ and A do not have the above hydrophilic groups, n is a number greater than or equal to 10 and less than 90). It has a structural unit (a) and a structural unit (b) derived from the hydrophobic monomer (B), and the content ratio of the structural unit derived from (meth) acrylic acid (salt) is 100% by mass of the total structural unit. On the other hand, it is 49% by mass or less, the weight average molecular weight is 10,000 or more and less than 105,000, and the structural unit (b) derived from the hydrophobic monomer (B) is an ethylenically unsaturated group and 2 to 2 carbon atoms. It is also a detergent copolymer characterized by having 30 alkyl groups.

Since the copolymer for detergent of the present invention has the above-mentioned structure and is superior in detergency to the conventional polymer, it can be suitably used for detergents and the like for textile products such as polyester.

Hereinafter, preferred embodiments of the present invention will be specifically described, but the present invention is not limited to the following description, and can be appropriately modified and applied without changing the gist of the present invention. A form in which two or three or more of the individual preferred forms of the present invention described below are combined also falls under the preferred form of the present invention.

The copolymer for detergent of the present invention has a structural unit (a) represented by the above formula (1) and a structural unit (b) derived from the specific hydrophobic monomer (B), and has (meth). The content ratio of the structural unit derived from acrylic acid (salt) is 49% by mass or less with respect to 100% by mass of the total structural unit, and the weight average molecular weight is 10,000 or more and less than 105,000.
The mechanism of action by which the copolymer for detergent of the present invention exerts excellent detergency is presumed as follows. By washing clothes such as polyester with a detergent containing the copolymer for detergent of the present invention, the hydrophobic group in the structural unit (b) is adsorbed on the hydrophobic fibers such as polyester, and even after washing. The state in which the detergent copolymer is adsorbed on the fibers can be maintained. Since stains adhere to such clothes from the adsorbed copolymer for detergents, the stains are sufficiently suppressed from penetrating into the fibers, and the action of the surfactant makes it suitable for detergents. It is considered that the stain is easily removed together with the copolymer. Further, it is considered that the above-mentioned copolymer for detergent has a hydrophilic group, so that the permeation rate of washing water into clothes and the like can be improved, which also makes it easier to remove stains. Further, the copolymer for detergent of the present invention can interact with the surfactant and act on the stains adhering to the cloth to bring out the stains. Since the dirt particles to which the polymer is attached have good dispersion stability, it is possible to prevent them from adhering to the cloth again. Due to these actions, the copolymer for detergent of the present invention has excellent detergency. Further, by repeating washing using the copolymer for detergent of the present invention, the copolymer for detergent is fixed on clothes and the like, so that excellent antifouling property can be exhibited and dirt can be easily removed. Demonstrates full release.

The content ratio of the structural unit (a) in the copolymer for detergent of the present invention is preferably 10 to 99% by mass with respect to 100% by mass of all structural units. As a result, the balance between the hydrophilicity and the hydrophobicity of the above-mentioned copolymer for detergent becomes a more preferable range, and the detergency becomes more excellent. It is more preferably 15 to 95% by mass, further preferably 15 to 90% by mass, particularly preferably 20 to 85% by mass, and most preferably 20 to 80% by mass.

The content ratio of the structural unit (b) in the copolymer for detergent of the present invention is preferably 1 to 90% by mass with respect to 100% by mass of all structural units. As a result, the balance between the hydrophilicity and the hydrophobicity of the above-mentioned copolymer for detergent becomes a more preferable range, and the detergency becomes more excellent. It is more preferably 1 to 80% by mass, further preferably 1 to 75% by mass, and particularly preferably 5 to 70% by mass.

The copolymer for detergent of the present invention may contain a structural unit derived from (meth) acrylic acid (salt), but the content ratio of the structural unit is 49% by mass or less with respect to 100% by mass of the total structural unit. is there. As a result, compatibility with liquid detergent and compounding stability are improved. The content ratio of the structural unit derived from (meth) acrylic acid (salt) is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and most preferably 15% by mass. It is as follows.

In the copolymer for detergent of the present invention, the copolymer may have a structural unit (e) other than the structural units (a) and (b).
The ratio of the structural unit (e) in the copolymer is preferably 0 to 30% by mass with respect to 100% by mass of all structural units.
It is more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, and most preferably 0% by mass.

The copolymer for detergent of the present invention has a weight average molecular weight of 10,000 or more and less than 105,000. As a result, the copolymer for detergents of the present invention is also excellent in compatibility with the surfactant. It is preferably 1000 to 100,000, more preferably 1000 to 90000, and even more preferably 1500 to 80,000.
The weight average molecular weight can be measured by the method described in Examples.

<Hydrophilic group-containing monomer (A)>
The monomer forming the structural unit (a) represented by the above formula (1) in the copolymer for detergent of the present invention includes the following formula (2);

(In the formula, R ¹ , R ² and R ³ are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents at least one hydrophilic group, or an alkyl group having 1 to 3 carbon atoms which may have the above hydrophilic group. Z represents a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group. Represents a hydrocarbon group having 2 to 30 carbon atoms having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. A is the same or different. Represents an alkylene group which may have at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group thereof. Represents the average number of added moles of (AO) and is a number of 0, 1, or 10 to 200. X represents a number of 0 to 4. y represents 0 or 1, where x. Is 0, y is 1, and if R ¹ , R ^2, R ³ and A do not have the above hydrophilic groups, n is a number greater than or equal to 10 and less than 90). Examples thereof include the hydrophilic group-containing monomer (A), but the structural unit (a) is not limited to that obtained from the hydrophilic group-containing monomer (A).

Examples of the salt in the hydrophilic group include monovalent metal salts such as alkali metals such as sodium and potassium; divalent metal salts such as alkaline earth metals such as magnesium and calcium; ammonium salts; and organic amine salts.
The hydrophilic group is preferably a hydroxyl group or an oxyalkylene group.
The hydrophilic group-containing monomer (A) may have a plurality of the same or different hydrophilic groups. For example, a form having two or more hydroxyl groups or a form having a hydroxyl group and an oxyalkylene group may be used. , Is one of the preferred embodiments of the present invention.

^{R 1} , R ² and R ³ in the above formulas (1) and (2) are the same or different from hydrogen atoms, or hydroxyl groups and carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups and salts thereof. It represents at least one hydrophilic group selected from the group consisting of groups, or an alkyl group having 1 to 3 carbon atoms which may have the hydrophilic group.
The alkyl group is preferably a methyl group, an ethyl group or a propyl group, which is 1 or 2, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
R ¹ , R ² and R ³ are preferably the same or different, and are preferably hydrogen atoms or methyl groups. More preferably, R ¹ and R ² are hydrogen atoms, and R ³ is a hydrogen atom or a methyl group. More preferably, R ¹ and R ² are hydrogen atoms, and R ³ is a methyl group.

Z in the above formulas (1) and (2) is at least selected from the group consisting of a hydrogen atom, a methyl group, or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents a hydrocarbon group having 2 to 30 carbon atoms having one kind of hydrophilic group.
The hydrocarbon group is not particularly limited, and examples thereof include a chain hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group, and a cyclic hydrocarbon group such as an aryl group, a cycloalkyl group, and a cycloalkenyl group. The above-mentioned hydrocarbon group may have a branch, and the number of carbon atoms of the hydrocarbon group when having a branch means the total number of carbon atoms of the main chain and the branched chain.
Examples of the alkyl group include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a stearyl group. , Icosyl group and the like.
Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group and an icosenyl group. And so on.
Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group and an icocinyl group. And so on.

Examples of the aryl group include a phenyl group, a benzyl group, a methylphenyl group, a 1-methoxy-4-methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a butylmethylphenyl group, a dimethylphenyl group and a diethyl group. Examples thereof include phenyl group, dibutylphenyl group, biphenyl group, biphenylmethyl group, biphenylethyl group, naphthyl group, naphthylmethyl group, naphthylethyl and the like.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like.
The hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.

The number of carbon atoms of the hydrocarbon group is preferably 2 to 20, more preferably 2 to 15, still more preferably 2 to 10, and particularly preferably 2 to 5.

The Z is preferably a hydrogen atom or a methyl group.

The above-mentioned A may have at least one hydrophilic group selected from the group consisting of a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof, which are the same or different. Represents a good alkylene group. This means that all n oxyalkylene groups of AO present in the polyalkylene glycol may be the same or different.
The alkylene group represented by A has preferably 2 to 18 carbon atoms, and more preferably 2 to 4 carbon atoms.

The oxyalkylene group represented by AO is, for example, a group formed by an addition reaction of an alkylene oxide and a group having a structure in which the above hydrophilic group is added thereto. Such an alkylene oxide includes ethylene oxide and propylene. Examples thereof include oxides, butylene oxides, isobutylene oxides, 1-butene oxides, 2-butene oxides, styrene oxides and alkylene oxides having 2 to 18 carbon atoms. More preferably, it is an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and butylene oxide, and even more preferably ethylene oxide and propylene oxide.
The oxyalkylene group represented by AO in the formula (1) is not limited to the group formed by the addition reaction of the alkylene oxide.

When the polyalkylene glycol is any two or more types of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, any of random addition, block addition, alternating addition and the like. It may be in the form. In order to secure a balance between hydrophilicity and hydrophobicity, it is preferable to have an oxyethylene group as an essential component as the oxyalkylene group in the polyalkylene glycol, and more preferably 50 mol% or more is an oxyethylene group. , 90 mol% or more is more preferably an oxyethylene group.

In the above formulas (1) and (2), n represents the average number of moles added of (AO), which is 0, 1, or 10 to 200. As a result, the copolymer of the present invention has excellent detergency. It is preferably 1 or 10 to 180, more preferably 12 to 150, more preferably 15 to 100, still more preferably 20 to 80, and particularly preferably 20 to 50.
When Z is a methyl group, n is preferably 10 or more.
When n is 1, the above A is preferably an alkylene group having a hydroxyl group.

In the above formulas (1) and (2), x represents a number from 0 to 4, and y represents 0 or 1.
The x is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.
The combination of (x, y) is preferably (0,1), (1,0), (2,0), more preferably (0,1) (2,0), and most preferably (2,0). 0,1).

Specifically, as the hydrophilic group-containing monomer (A), for example, polyalkylene glycol mono (meth) acrylate such as (poly) ethylene glycol mono (meth) acrylate and (poly) propylene glycol mono (meth) acrylate; Acrylate polyalkylene glycol mono (meth) acrylates such as methoxy (poly) ethylene glycol mono (meth) acrylates and methoxy (poly) propylene glycol mono (meth) acrylates, vinyl alcohols, (meth) allyl alcohols, 3-methyl- 3-Buten-1-ol (isoprenol), 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol, 2-methyl (Poly) alkylene glycol-based monomers such as compounds in which 10 to 100 mol of alkylene oxide is added to any of -3-buten-1-ol; glycerol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Diol-containing (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; (meth) acrylic acid, Unsaturated monocarboxylic acids such as crotonic acid, α-allyloxyacrylic acid and salts thereof; unsaturated monocarboxylic acids such as maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid and the like, salts thereof and anhydrides thereof. Examples thereof include dicarboxylic acids. Among these, (poly) alkylene glycol-based monomers and hydroxyl group-containing (meth) acrylates are preferable.

<Hydrophobic monomer (B)>
The hydrophobic monomer (B) has a solubility parameter of 13 or less for the homopolymer obtained by homopolymerization, and is an organic group having 3 or more carbon atoms in addition to the ethylenically unsaturated group. Has. In addition to the ethylenically unsaturated group, it has an organic group having 3 or more carbon atoms, and even if the solubility parameter is 13 or less, it is a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, or an amino group. And those having at least one hydrophilic group selected from the group consisting of the groups of these salts are classified into the hydrophilic group-containing monomer (A).
Here, the solubility parameter is a value calculated by the method described on pages 147 to 154 of "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2).
The method is outlined below. The solubility parameter (δ) (cal / cm ³ ) ^1/2 of the homopolymer is as follows, based on the evaporation energy (Δei) and molar volume (Δvi) of the constituent units forming the polymer. It is calculated by the calculation method of.
δ = (Δei / Δvi) ^1/2 (cal / cm ³ ) ^1/2

If the solubility parameter for the homopolymer obtained by polymerizing the hydrophobic monomer alone is 13 or less, the hydrophobicity of the copolymer of the present invention is sufficient, and the hydrophobicity is sufficient. Has excellent adsorption to fibers. The solubility parameter is preferably 12 or less, and more preferably 11 or less. The solubility parameter is usually 5 or more.

The hydrophobic monomer is not particularly limited as long as the solubility parameter of the homopolymer is 13 or less, but the hydrophobic monomer is a monomer having an ethylenically unsaturated group and an alkyl group having 2 to 30 carbon atoms. Is preferable.
Examples of the hydrophobic monomer include esters of unsaturated carboxylic acids such as (meth) acrylic acid and alcohols having 2 to 30 carbon atoms which may have substituents ;; aromatic vinyls such as styrene. Monomer; Olefin-based monomer having 5 to 20 carbon atoms such as penten and hexene; Ester of unsaturated alcohol such as vinyl acetate and carboxylic acid having 3 to 8 carbon atoms; 3 to 20 carbon atoms such as propyl vinyl ether Alkyl vinyl ethers having an alkyl group of the above; cyclic vinyl-based monomers such as N-vinylpyrrolidone can be mentioned.

The substituent that the alcohol may have may be a substituent other than a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof. Halogen atoms and the like can be mentioned.
The carbon number of the alcohol is preferably 2 to 22, more preferably 2 to 16, and even more preferably 4 to 8.
The alcohol having 1 to 30 carbon atoms is preferably an alkyl alcohol having 1 to 30 carbon atoms, an aryl alcohol having 6 to 30 carbon atoms, or the like.

Examples of the alkyl alcohol having 1 to 30 carbon atoms include ethanol, propanol, butanol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), and tridecyl alcohol. , Tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecil alcohol, icosyl alcohol and the like.

The aryl alcohol having 6 to 30 carbon atoms is preferably phenol, benzyl alcohol, methylphenyl alcohol (o-cresol, m-cresol, p-cresol), creosol, ethylphenyl alcohol, propylphenyl alcohol, butylphenyl alcohol, butyl. Methylphenyl alcohol, dimethylphenyl alcohol, diethylphenyl alcohol, dibutylphenyl alcohol, hydroxybiphenyl, 4-hydroxymethylbiphenyl, 3-hydroxymethylbiphenyl, 4-hydroxyethylbiphenyl, 3-hydroxyethylbiphenyl, naphthol, 1-hydroxymethyl- Examples thereof include naphthalene, 1-hydroxyethyl-naphthalene, 2-hydroxymethyl-naphthalene, 2-hydroxyethyl-naphthalene and the like.

The hydrophobic monomer (B) preferably has the following formula (3);

(In the formula, R ⁴ , R ⁵ , and R ⁶ represent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, which are the same or different. R ⁷ represents a hydrocarbon group having 2 to 30 carbon atoms.) It is a compound represented by.
That is, the copolymer for detergent of the present invention has the following formula (4);

(In the formula, R ^{4 to} R ⁷ are the same as those in the formula (3).) It is preferable to have a structural unit represented by the formula (3).
When the copolymer for detergent of the present invention has a structural unit represented by the above formula (4), the structural unit is obtained by polymerizing using a compound represented by the above formula (3). It may be obtained by other methods.

The ^{alkyl group in R 4} , R ⁵ , and R ⁶ is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
R ⁴ , R ⁵ and R ⁶ are preferably the same or different, and are preferably hydrogen atoms or methyl groups. More preferably, R ⁴ and R ⁵ are hydrogen atoms, and R ⁶ is a hydrogen atom or a methyl group.

The hydrocarbon group preferably has 1 to 22 carbon atoms. It is more preferably 2 to 16, still more preferably 2 to 12, particularly preferably 4 to 12, and most preferably 4 to 8.

The hydrocarbon group represented by R ^7, not particularly limited, an alkyl group, an alkenyl group, a chain hydrocarbon group such as an alkynyl group, an aryl group, a cycloalkyl group, and cyclic hydrocarbon groups such as a cycloalkenyl group .. The above-mentioned hydrocarbon group may have a branch, and the number of carbon atoms of the hydrocarbon group when having a branch means the total number of carbon atoms of the main chain and the branched chain.

The preferred number of carbon atoms of the alkyl group in ^{R 7} is 2 to 22, more preferably 2 to 16, particularly preferably 2 to 12, most preferably 4-8.
The preferred number of carbon atoms of the aryl group in ^{R 7} is 6-12, more preferably 6-10, particularly preferably 6-8.

The alkyl group in the above R ^7, for example, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group , Stearyl group, icosyl group and the like.
Examples of the alkenyl group include an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group, an icosenyl group and the like. Be done.
Examples of the alkynyl group include 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, dodecynyl group, octadecynyl group, icocinyl group and the like. Be done.

The aryl group represented by R ^7, for example, a phenyl group, a benzyl group, methylphenyl group, 1-methoxy-4-methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, butyl methylphenyl group, dimethylphenyl Group, diethylphenyl group, dibutylphenyl group, 2- (2-methylphenyl) ethyl group, 2- (3-methylphenyl) ethyl group, 2- (4-methylphenyl) ethyl group, 2- (4-propylphenyl) ) Ethyl group, biphenyl group, biphenylmethyl group, biphenylethyl group, naphthyl group, naphthylmethyl group, naphthylethyl group and the like.

The cycloalkyl groups represented by R ^7, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like.

As the hydrocarbon group represented by R ^7, it is preferably an alkyl group, an aryl group, more preferably an alkyl group.
The hydrophobic monomer (B) is preferably an alkyl (meth) acrylate or an aryl (meth) acrylate, and more preferably an alkyl (meth) acrylate.

Examples of the alkyl (meth) acrylate include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth). Acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, Examples include icosyl (meth) acrylate. Of these, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and sec-butyl (meth) are preferable. ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, more preferably ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth). Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

Examples of the aryl (meth) acrylate include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylphenyl (meth) acrylate, propylphenyl (meth) acrylate, butylphenyl (meth) acrylate, and pentylphenyl (meth) acrylate. ) Acrylic, hexylphenyl (meth) acrylate, butylmethylphenyl (meth) acrylate, dimethylphenyl (meth) acrylate, diethylphenyl (meth) acrylate, dibutylphenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 4- Methylphenyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 1-methoxy-4-methylphenyl (meth) acrylate, 2- (2-methylphenyl) ethyl (meth) acrylate, 2- (3-methylphenyl) ) Ethyl (meth) acrylate, 2- (4-methylphenyl) ethyl (meth) acrylate, 2- (4-propylphenyl) ethyl (meth) acrylate, biphenylmethyl (meth) acrylate, biphenylethyl (meth) acrylate, naphthyl Examples thereof include (meth) acrylate, naphthylmethyl (meth) acrylate, and naphthylethyl (meth) acrylate. Of these, phenyl (meth) acrylate and benzyl (meth) acrylate are preferable.

The copolymer for detergent of the present invention has a structural unit (e) derived from a monomer (E) other than the hydrophilic group-containing monomer (A) and the hydrophobic monomer (B). You may.
The monomer (E) does not have a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof, and the solubility parameter of the homopolymer is greater than 13 or It is not particularly limited as long as it does not have a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof, and the number of carbon atoms of the organic group other than the ethylenically unsaturated group is 2 or less. Examples thereof include an olefin-based monomer having 2 to 4 carbon atoms such as ethylene and propylene, vinyl halide such as vinyl chloride, methyl vinyl ether, ethyl vinyl ether, and acrylonitrile.

<Method for producing copolymer>
The production of the copolymer of the present invention is not particularly limited, but it can be produced by polymerizing a monomer component, and specific examples and preferable examples of the monomer component, and a preferable ratio of each monomer. Is as described above.
The method for producing a copolymer includes a step of polymerizing a monomer component containing a hydrophilic group-containing monomer (A) and a hydrophobic monomer (B) (hereinafter, also referred to as a “polymerization step”). Is preferable.
A method for producing such a copolymer is also one of the present inventions.

The method for initiating the polymerization of the monomer component in the above polymerization step is not particularly limited, but for example, a method for adding a polymerization initiator, a method for irradiating UV, a method for applying heat, and a method in the presence of a photopolymerization initiator. There is a method of irradiating the light.
In the above polymerization step, it is preferable to use a polymerization initiator.
Examples of the polymerization initiator include hydrogen peroxide; persulfate 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-2-amidinopropane dihydrochloride), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (2- (2-) Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile) ), 2,2'-Azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 2, Azo-based compounds such as 2'-azobis (2-methylbutyronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, and cumenehydroperoxide; ascorbic acid An oxidation-reduction type initiator that generates radicals by combining an oxidizing agent and a reducing agent, such as hydrogen peroxide, persulfate and metal salt, and the like are suitable. Among these polymerization initiators, hydrogen peroxide, persulfate, and azo compounds are preferable, and persulfate is more preferable, because the residual monomer tends to decrease. These polymerization initiators may be used alone or in the form of a mixture of two or more.

The amount of the polymerization initiator used is the total amount of the monomer used (hydrophilic group-containing monomer (A), hydrophobic monomer (B) and other monomer (E)). ) With respect to 100 g, it is preferably 0.1 g or more and 10 g or less, more preferably 0.2 g or more and 8 g or less, further preferably 0.25 g or more and 7 g or less, and 0.3 g. Above, 5 g or less is most preferable.

In the above polymerization step, a chain transfer agent may be used as a molecular weight adjusting agent for the polymer, if necessary. Specifically, as the chain transfer agent, mercaptocarboxylic acids such as thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thioapple acid and salts thereof. And mercaptoethanol, thioglycerol, 2-mercaptoethanesulfonic acid, etc .; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, etc .; secondary alcohols such as isopropanol, glycerin, etc .; Hypophosphates and their hydrates, etc .; Compounds that can generate hydrogen sulfite (salt) and hydrogen sulfite (salt) (dipersulfate (salt), pyrosulfite (salt), dithioic acid (salt), sulfite (Salt) etc.); etc. Among them, a compound having a mercapto group such as mercaptocarboxylic acid is preferable, and a mercapto group-containing compound having a carboxyl group (mercaptocarboxylic acid) is more preferable.

The amount of the chain transfer agent used in the production of the copolymer of the present invention is preferably 0.5 mol% or more and 30 mol% or less with respect to 100 mol% of the amount of the monomer (all monomers) used. , More preferably 0.7 mol% or more and 25 mol% or less, further preferably 0.8 mol% or more and 20 mol% or less, and most preferably 1 mol% or more and 10 mol% or less.

In the above polymerization step, the polymerization temperature is preferably 40 ° C. or higher, and preferably 150 ° C. or lower. It is more preferably 50 ° C. or higher, and even more preferably 55 ° C. or higher. Further, it is more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.

In the above polymerization step, the method of charging the monomer component into the reaction vessel is not particularly limited, and the method of charging the entire amount into the reaction vessel at the initial stage; the method of dividing or continuously charging the entire amount into the reaction vessel; Examples thereof include a method in which the mixture is initially charged and the rest is divided or continuously charged into the reaction vessel. When a radical polymerization initiator is used, it may be charged into the reaction vessel from the beginning, may be added dropwise to the reaction vessel, or these may be combined depending on the purpose.
The copolymer obtained as described above can be used as it is as a detergent additive such as an additive for liquid detergent, but if necessary, it may be further neutralized with an alkaline substance and used. As the alkaline substance, inorganic salts such as hydroxides and carbonates of monovalent or divalent metals; ammonia; and organic amines are suitable. Further, after the reaction is completed, the concentration can be adjusted if necessary.

The solvent used at the time of polymerization is timely selected from those capable of dissolving the monomer to be used, the initiator, and the polymer to be produced, and water; 1 to 1 carbon atoms such as ethanol, 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol. Alcohols of 8; glycols such as propylene glycol, butylene glycol, hexylene glycol; polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol; diethylene glycol monomethyl ether , Alkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol monobutyl ether; sulfoxides such as sulfone, diethylsulfone, bis (2-hydroxyethyl) sulfone (dimethylsulfoxide, etc.); cyclic ethers (tetrahydropyrane, etc.); Propionitrile, butyronitrile, acrylonitrile, methacrylnitrile, etc.); carbonates (ethylene carbonate, propion carbonate, etc.); ketones (acetone, diethyl ketone, acetophenone, methyl ethyl ketone, cyclohexanone, cyclopentanone, diacetone alcohol, etc.). One or more of the above can be used. Of these, water, ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and phenoxyethanol are preferable.

<Use of copolymer>
The copolymer of the present invention is used for detergent applications. Detergents are detergents used only for specific purposes such as household clothing, synthetic dishwashing detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components. Is also included.
That is, the present invention is also a detergent additive containing the above-mentioned detergent copolymer.
The present invention is also a method of using the above-mentioned copolymer for detergent as an additive for detergent.
The present invention is also a detergent composition containing the copolymer for detergents of the present invention and additives for detergents other than the copolymer.
Since the copolymer for detergents of the present invention has excellent compatibility with surfactants, it can be suitably used for liquid detergent applications. The detergent composition is preferably a liquid detergent composition.
The present invention further comprises a method for producing a detergent composition, wherein the production method includes a step of adding the above-mentioned copolymer for detergent to a detergent additive other than the copolymer. But also.
The detergent additive other than the copolymer for detergent of the present invention is not particularly limited as long as it is an additive used for surfactants and ordinary detergents, and conventionally known findings in the detergent field can be appropriately referred to. Any suitable additive can be used as long as the effect of the present invention is not impaired.

Additives other than surfactants include, for example, anti-adhesion agents for preventing re-deposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, and colors. Anti-transfer agents, fabric softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, Examples include dyes and solvents. One or more of these can be used. Further, in the case of a powder detergent composition, it is preferable to add zeolite.

The surfactant is preferably one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.

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, and alkane sulfonic acid. Salt, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acylamino acid type surfactant, alkyl phosphate ester or its salt, alkenyl phosphate ester Alternatively, a salt thereof or the like is suitable. Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these anionic surfactants.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide, and fatty acid glycerin. Monoesters, alkylamine oxides and the like are suitable. Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these nonionic surfactants.

As the cationic surfactant, a quaternary ammonium salt or the like is suitable. Further, as the amphoteric tenside, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are suitable. Alkyl groups such as methyl groups may be branched as the alkyl groups and alkenyl groups in these cationic surfactants and amphoteric surfactants.

The blending ratio of the surfactant is usually 10 to 80% by mass, preferably 15 to 75% by mass, more preferably 18 to 70% by mass, and particularly preferably 18 to 70% by mass, based on the total amount of the detergent composition. Is 20 to 68% by mass. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economic efficiency may be lowered.

Among the above-mentioned surfactants, anionic surfactants and nonionic surfactants are preferable, and nonionic surfactants in particular. Since the nonionic surfactant is resistant to oil stains, the liquid detergent composition containing the copolymer for detergent and the nonionic surfactant of the present invention is superior in detergency against oil stains. The liquid detergent composition containing the copolymer for detergent of the present invention and a nonionic surfactant is one of the preferred embodiments of the present invention.

The content ratio of the nonionic surfactant is preferably 1 to 60% by mass with respect to 100% by mass of the detergent composition. It is more preferably 3 to 60% by mass, and further preferably 5 to 50% by mass.
The content ratio of the nonionic surfactant is also preferably 10 to 100% by mass with respect to 100% by mass of the total amount of the surfactant. It is more preferably 15 to 90% by mass, and even more preferably 20 to 90% by mass.

The detergent composition preferably contains a hydrophilic solvent.
The hydrophilic solvent is not particularly limited, and those usually used for liquid detergents can be used. For example, water; ethanol, 1-propanol, 2-propanol, 1-butanol, phenoxyethanol and the like have 1 to 1 carbon atoms. Alcohols of 8; glycols such as propylene glycol, butylene glycol, hexylene glycol; polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol; diethylene glycol monomethyl ether , Alkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol monobutyl ether; sulfoxides such as sulfone, diethylsulfone, bis (2-hydroxyethyl) sulfone (dimethylsulfoxide, etc.); cyclic ethers (tetrahydropyrane, etc.); Propionitrile, butyronitrile, acrylonitrile, methacrylnitrile, etc.); carbonates (ethylene carbonate, propion carbonate, etc.); ketones (acetone, diethyl ketone, acetophenone, methyl ethyl ketone, cyclohexanone, cyclopentanone, diacetone alcohol, etc.). One or more of the above can be used. Of these, ethanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and phenoxyethanol are preferable.

The detergent composition preferably contains a hydrophilic solvent in a proportion of 0.1 to 30% by mass with respect to 100% by mass of the liquid detergent composition. It is more preferably 1 to 27% by mass, still more preferably 2 to 25% by mass.

The detergent composition may include other detergent builders. Other detergent builders include, for example, alkali builders such as carbonates, bicarbonates, silicates; tripolyphosphate, pyrophosphate, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, citrate, (meth). Examples thereof include a copolymer salt of acrylic acid, a chelate builder such as an acrylic acid-maleic acid copolymer, fumarate, and zeolite; and a carboxyl derivative of a polysaccharide such as carboxymethyl cellulose. Examples of the anti-salt used in the above-mentioned other detergent builders include alkali metals such as sodium and potassium, and alkaline agents such as sodium hydroxide, ammonium and amines.

When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1% by mass to 80% by mass with respect to the total amount of the liquid detergent composition. It is more preferably 2% by mass to 70% by mass, further preferably 3% by mass to 60% by mass, further preferably 5% by mass to 55% by mass, and particularly preferably 5% by mass to 50% by mass. Most preferably, it is 10% by mass to 50% by mass.

The detergent composition may contain an enzyme. Examples of such an enzyme include protease, lipase, cellulase, amylase and the like.
The blending ratio of the enzyme is usually 5% by mass or less with respect to the total amount of the detergent composition.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

<Measurement of weight average molecular weight of copolymer>
The weight average molecular weight (Mw) of the copolymer was measured by GPC (gel permeation chromatography).
The measurement conditions, equipment, etc. are as follows.
Equipment: Tosoh EcoSEC HLC-8320GPC
Detector: Differential Refractometer (RI) Detector Column: Tosoh TSKgel α-M, α-2500
Column temperature: 40 ° C
Flow velocity: 0.4 mL / min
Injection volume: 20 μL (sample concentration 0.4 wt% eluent preparation solution)
Calibration curve: Polyethylene glycol GPC software manufactured by GL Sciences: EcoSEC-WS manufactured by Tosoh Corporation
Eluent: 0.5M acetic acid + 0.2M Na nitrate / acetonitrile = 50/50 (v / v)

Example 1
90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Next, under stirring, 91 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23, trade name "M-230G" manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter also referred to as PGM23E) in a polymerization reaction system in a constant state at 70 ° C. Monomer solution 1 consisting of 30.3 g of ion-exchanged water; Monomer solution 2 consisting of 39 g of benzyl methacrylate (hereinafter also referred to as BnMA; solubility parameter: 9.8); 2,2'-azobis (2,4-dimethylvaleronitrile) An aqueous initiator solution consisting of 15.1 g of a 5% ethanol solution (manufactured by Fuji Film Wako Junyaku Co., Ltd., hereinafter also referred to as V-65) was added dropwise from separate dropping nozzles. Regarding the dropping time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes.
After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and the copolymer 1 was obtained.
The solid content of the obtained copolymer was 49.1%, and the weight average molecular weight was 28500.

Example 2
90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Next, under stirring, 69.7 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23, hereinafter also referred to as PGM23E) and methacrylic acid (hereinafter also referred to as MAA) 14 were placed in a polymerization reaction system at a constant state of 70 ° C. Monomer solution 1 consisting of 1 g and 22.4 g of ion-exchanged water; Monomer solution 2 consisting of 36 g of benzyl methacrylate (hereinafter also referred to as BnMA); 2,2'-azobis (2,4-dimethylvaleronitrile) (Fuji film sum) An aqueous initiator solution consisting of 13 g of a 5% ethanol solution manufactured by Kojun Yakuhin Co., Ltd. (hereinafter, also referred to as V-65) was added dropwise from separate dropping nozzles. Regarding the dropping time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes.
After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and the copolymer 2 was obtained.
The solid content of the obtained copolymer 2 was 47.8%, and the weight average molecular weight was 77,800.

Comparative Example 1
480 parts of water was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, and the inside of the reaction vessel was heated to 80 ° C. while stirring at 200 rpm. 401.3 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23), 78.7 parts of methacrylic acid, 120 parts of water, and 5.47 parts of 3-mercaptopropionic acid (hereinafter, also referred to as MPA) as a chain transfer agent. An aqueous solution of a monomer mixed with the above was added dropwise over 4 hours, and an aqueous solution containing 5.52 parts of ammonium persulfate (hereinafter, also referred to as APS) and 110.6 parts of water was added dropwise from the same time over 5 hours. After completion of the dropping, the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and an aqueous solution of the comparative copolymer 1 having a weight average molecular weight of 17,000 was obtained.

Comparative Example 2
Unsaturated poly with an average of 50 mol of ethylene oxide added to 80% by mass of 3-methyl-3-butene-1-ol in a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel. An alkylene glycol ether (hereinafter, also referred to as MB-50) MB-50 aqueous solution: 260.2 g and ion-exchanged water: 66.6 g were charged, and after nitrogen substitution, the temperature was raised to 58 ° C. with stirring. When the temperature reached a predetermined temperature, 0.57 g of 35% by mass hydrogen peroxide solution (H ₂ O ₂ ) was added all at once. Then, 100% by mass acrylic acid (hereinafter, also referred to as AA): 14.8 g, 1.6% by mass L-ascorbic acid (hereinafter, also referred to as LAs) aqueous solution: 16.7 g, 3.5. 17.4 g of a mass% MPA aqueous solution was added dropwise. However, AA was added dropwise over 180 minutes, and the L'As aqueous solution and the MPA aqueous solution were added dropwise over 210 minutes. After completion of dropping the L-As aqueous solution, the mixture was aged at the same temperature for 60 minutes to complete the polymerization, and after the polymerization, a 49% by mass NaOH aqueous solution: 3.69 g was added to obtain an aqueous solution of the comparative copolymer 2. .. The weight average molecular weight of the obtained water-soluble copolymer was 25,700, and the solid content was 59.7% by mass.

Detergency evaluation The detergency evaluation of the copolymers 1 and 2 produced in Examples 1 and 2, Comparative Examples 1 and 2 and the comparative copolymers 1 and 2 was performed by the following method. The results are shown in Table 1.
<Cloth pretreatment method>
A style 703 (polyester fiber) manufactured by Testfabric was cut into 5 x 5 cm and prepared. 300 g of an aqueous solution prepared by adjusting the copolymers obtained in Examples and Comparative Examples to 25 ppm was prepared, 5 g of the above cloth was added while stirring with a magnetic stirrer, and the mixture was stirred for 10 minutes. After 10 minutes, it was dehydrated to 3 times the weight of the cloth and air-dried for 1 day.
<Creation of contaminated cloth>
61.5 g of olive oil, 37 g of oleic acid, 1 g of iron (III) oxide, and 0.5 g of oil red were mixed to prepare an oil and fat contaminated solution. 50 μL of this contaminated liquid was dropped onto the polymer-treated cloth obtained in the above pretreatment method 1, left to stand for 1 hour, and then excess oil and fat was sandwiched between filter papers and wiped off to prepare a contaminated cloth.
<Detergency evaluation>
(1) -1: Preparation of hardness mother liquor 8.39 g of calcium chloride dihydrate and 2.9 g of magnesium chloride hexahydrate were weighed in a beaker, and ion-exchanged water was added to make 1000 g.
(1) -2: Preparation of hard water 1.54 g of sodium hydrogen carbonate, 10 g of 0.1N hydrogen chloride, and 200 g of the hardness mother liquor (1) -1; 200 g were placed in a beaker and diluted with ion-exchanged water to make 20000 g.
(1) -3: Preparation of aqueous surfactant solution Weigh 13.85 g of Perex G-65 (manufactured by Kao Corporation) and 3 g of Emargen 108 (manufactured by Kao Corporation) in a beaker, and add ion-exchanged water to make 200 g. The agent solution was adjusted.
(2): Detergency test 16.67 g of the surfactant aqueous solution of (1) -3 and the hard water of (1) -2 were mixed to prepare 4000 g of a cleaning solution. The turgot meter was set at 25 ° C., and 500 g of the cleaning liquid was put into a pot. Put 5 contaminated cloths whose reflectance was measured in advance with a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd .: SE-6000) and a bath ratio adjusting cloth in a 16.67 g pot, and stir at 120 rpm for 10 minutes to wash. did. After discarding the water in the pot and rinsing once, the cloth was dehydrated and air-dried for 1 day.
After air-drying, the reflectance of the white cloth was measured again with a color difference meter, and the cleaning rate was calculated by the following formula. Based on the obtained cleaning rate, the cleaning power was evaluated according to the following criteria. The results are shown in Table 1.
⊚: Cleaning rate 90% or more 〇: Cleaning rate 50% or more, less than 90% ×: Cleaning rate less than 50%

Claims (6)

A copolymer used for detergent applications
The copolymer for detergent has the following formula (1);

(In the formula, R ¹ , R ² and R ³ are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents at least one hydrophilic group, or an alkyl group having 1 to 3 carbon atoms which may have the hydrophilic group. Z represents a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group. Represents a hydrocarbon group having 2 to 30 carbon atoms having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. A is the same or different. Represents an alkylene group which may have at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group thereof. Represents the average number of added moles of (AO) and is a number of 0, 1, or 10 to 200. X represents a number of 0 to 4. y represents 0 or 1, where x. Is 0, y is 1, and if R ¹ , R ^2, R ³ and A do not have the hydrophilic group, n is a number greater than or equal to 10 and less than 90). It has a structural unit (a) and a structural unit (b) derived from the hydrophobic monomer (B).
The content ratio of the structural unit derived from (meth) acrylic acid (salt) is 49% by mass or less with respect to 100% by mass of the total structural unit.
The weight average molecular weight is 10,000 or more and less than 105,000.
The hydrophobic monomer (B) has a solubility parameter of 13 or less for the homopolymer and has an organic group having 3 or more carbon atoms in addition to the ethylenically unsaturated group. Combined. The detergent copolymer according to claim 1, wherein the content ratio of the structural unit (a) is 10 to 99% by mass with respect to 100% by mass of the total structural unit. .. The detergent copolymer according to claim 1 or 2, wherein the content ratio of the structural unit (b) is 1 to 90% by mass with respect to 100% by mass of the total structural unit. Polymer. A detergent additive comprising the copolymer for detergent according to any one of claims 1 to 3. A detergent composition comprising the copolymer for detergent according to any one of claims 1 to 3 and an additive for detergent other than the copolymer. A copolymer used for detergent applications
The copolymer for detergent has the following formula (1);

(In the formula, R ¹ , R ² and R ³ are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents at least one hydrophilic group, or an alkyl group having 1 to 3 carbon atoms which may have the hydrophilic group. Z represents a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group. Represents a hydrocarbon group having 2 to 30 carbon atoms having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. A is the same or different. Represents an alkylene group which may have at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group thereof. Represents the average number of added moles of (AO) and is a number of 0, 1, or 10 to 200. X represents a number of 0 to 4. y represents 0 or 1, where x. Is 0, y is 1, and if R ¹ , R ^2, R ³ and A do not have the above hydrophilic groups, n is a number greater than or equal to 10 and less than 90). It has a structural unit (a) and a structural unit (b) derived from the hydrophobic monomer (B).
The content ratio of the structural unit derived from (meth) acrylic acid (salt) is 49% by mass or less with respect to 100% by mass of the total structural unit.
The weight average molecular weight is 10,000 or more and less than 105,000.
The structural unit (b) derived from the hydrophobic monomer (B) is a copolymer for detergents, which has an ethylenically unsaturated group and an alkyl group having 2 to 30 carbon atoms.