JP5940630B2 - Hydrophobic group-containing copolymer and method for producing the same - Google Patents

Description

The present invention relates to a hydrophobic group-containing copolymer and a method for producing the same.

Conventionally, detergents used for apparel and the like have been blended with detergent builders (detergent assistants) such as zeolite, carboxymethylcellulose, and polyethylene glycol for the purpose of improving the cleaning effect of the detergent. In recent years, in addition to the above various detergent builders, various acrylic copolymers are blended in detergent compositions as detergent builders.

As such a technique, for example, Patent Document 1 discloses (meth) acrylic acid monomers, (meth) hydroxyalkyl monomers, (meth) alkyl monomers and / or vinyl. It is disclosed that a (meth) acrylic acid-based copolymer using an aromatic monomer is used in a detergent builder or a detergent composition. And hydrophobic stains such as oil and fat stains can be efficiently removed, and even if washing is performed with a small amount of water, it is excellent in re-contamination prevention ability that prevents the stains from adhering to the laundry again.

Patent Document 2 discloses a single amount derived from a polyalkylene glycol monomer having a hydrophobic moiety in the chain and / or terminal and having a polymerizable double bond derived from isoprenol, allyl alcohol or methallyl alcohol. It is disclosed that a polyalkylene glycol-based polymer having a body unit and having a carboxylic acid group and / or a sulfonic acid group is used as a cleaning agent builder. It describes that it has the ability to prevent recontamination of soils (precontamination prevention ability).

Patent Document 3 includes (meth) acrylic acid monomer A, unsaturated polyalkylene glycol monomer B having a polyalkylene oxide repeating unit of 6 to 300, and monomers A and B. A copolymer obtained by copolymerizing a copolymerizable monoethylenically unsaturated monomer C, having a sulfur oxygen acid at the terminal, and S = (S amount contained in polymer) / (total S amount) × 100 It is disclosed that a polymer composition having a sulfur element introduction amount S value of 3 or more as defined in (1) is used for a detergent builder or a detergent composition. It is described that it is excellent in compatibility and dispersibility, and has a good hue.

In Patent Document 4, in addition to a structural unit derived from a (meth) acrylic acid monomer and a structural unit derived from an unsaturated polyalkylene glycol monomer, an alkyl (meth) acrylate monomer or vinyl is further added. It is disclosed that a copolymer in which a structural unit having a relatively hydrophobic property derived from an aromatic monomer is introduced in a specific ratio is used for a builder or a detergent composition for detergents. However, it can efficiently remove stains on clothes, especially hydrophobic stains such as collars and oil stains, and at the same time, even if washing is performed with a small amount of water, the stains do not adhere to the laundry again and are excellently recontaminated. It is described that it exhibits the ability to prevent.

Patent Document 5 discloses a (meth) acrylic acid-based copolymer containing a structural unit derived from a (meth) acrylic acid monomer and a structural unit derived from a (meth) allyl ether monomer having a sulfonic acid group. It is described that the coalescence is used as a detergent builder or the like.

By the way, as performance required for detergent builders, not only performance to improve the cleaning power of the detergent, but also performance to suppress / prevent the precipitation of surfactants that lead to a decrease in cleaning power (hereinafter simply referred to as “deposition control ability”). Is also required. Precipitation of surfactant is caused by binding of linear alkylbenzene sulfonic acid (salt) (LAS) such as dodecylbenzene sulfonic acid (salt), which is an anionic surfactant, to calcium ions and magnesium ions present in water. Therefore, precipitation of this surfactant becomes a problem particularly when cleaning is performed using water having relatively high hardness (see Non-Patent Document 1). Regarding such a technique for improving the precipitation suppressing ability, Patent Document 6 discloses that a polyoxyalkylene compound is graft-polymerized with a monomer component containing a hydrophilic monomer having an anionic group or a hydroxyl group. It has been shown that the hydrocarbon group-containing graft polymer can exhibit excellent performance as a detergent builder.

JP 2007-231262 A International Publication No. 2007/037469 Pamphlet JP 2004-75977 A JP 2007-231260 A Japanese Patent Laid-Open No. 2002-3535 JP 2007-254679 A

Louis Ho Tan Tai, “Formulating Detergents and Personal Care Products”, AOCS Press, pp. 53-54 (2000)

As described above, despite the fact that various polymers have been reported in the past, the fact is that there is no polymer that can exhibit sufficient ability to suppress precipitation when used in detergent applications. In addition, as consumers become more aware of environmental issues in recent years, new washing styles are being established, such as consumers trying to save water by using the remaining hot water from the bath for washing. Along with this, the required performance for detergent builders is also changing. That is, the use of the remaining hot water has caused a problem that washing must be performed under high hardness conditions due to the concentration of the calcium component. Therefore, there is a demand for an agent with higher so-called gel resistance that can exhibit the effect of suppressing precipitation even under washing conditions with high hardness. Furthermore, from the demand for a compact detergent composition, there is a growing need for a single component to have a plurality of required performances.
The present invention has been made in view of the above situation, and can sufficiently suppress the precipitation of a surfactant, and is particularly useful for a polymer (and a polymer composition) particularly useful for detergent use, and the polymer efficiently. It aims at providing the manufacturing method which can be manufactured.

The present inventors have made various studies on polymers / copolymers that can exhibit precipitation-inhibiting ability. As a result, structural units derived from relatively hydrophobic ether bond-containing monomers and carboxyl group-containing monomers are derived. It has been found that a copolymer having a structural unit (hydrophobic group-containing copolymer) is particularly excellent in the performance of suppressing / preventing the precipitation of a surfactant, that is, the ability to suppress the precipitation. It was found that even under harsh conditions such as washing with water, it was possible to exhibit an excellent ability to suppress precipitation and exhibit a good cleaning effect. Further, when the copolymer further includes a structural unit derived from a polyalkylene glycol monomer and / or a structural unit derived from a sulfonic acid group-containing monomer, it is excellent in gel resistance in addition to the ability to suppress precipitation. As a result, the inventors have found that the ability to suppress precipitation can be further improved, and have come up with the idea that the above problems can be solved brilliantly. The inventors have found that these copolymers and polymer compositions containing the copolymers are particularly excellent for detergent use, and have reached the present invention.
In the present specification, the monomer means a compound having an unsaturated double bond (referred to as a carbon-carbon double bond).

That is, the present invention provides the following general formula (1) and / or (2):

(In the formula, R ⁰ represents a hydrogen atom or a CH ₃ group. ^Ra represents ^a CH ₂ group, a CH ₂ CH ₂ group or a single bond. X ¹ represents (O—CH ₂ —CH ₂ ). This represents the average number of repeating units, and is a number from 0 to 5. However, when R ^a represents ^a single bond, X ¹ is a number from ¹ to 5. R ¹ is a number from 1 to 5 carbon atoms. The structural unit (a) derived from the ether bond-containing monomer (A) represented by (20) and the structural unit (b) derived from the carboxyl group-containing monomer (B), It is a hydrophobic group-containing copolymer having a structural unit (a) of 1 to 50% by mass and a structural unit (b) of 50 to 99% by mass with respect to 100% by mass of structural units derived from all monomers.

The present invention is also a method for producing a hydrophobic group-containing copolymer, which comprises an ether bond represented by the general formula (1) and / or (2) in the presence of a polymerization initiator. Including a step of polymerizing a monomer component including the monomer (A) and the carboxyl group-containing monomer (B), and an ether bond-containing monomer (A ) Is 1 to 50% by mass, and the carboxyl group-containing monomer (B) is also a method for producing a hydrophobic group-containing copolymer having a content of 50 to 99% by mass.
The present invention is described in detail below.

[Hydrophobic group-containing copolymer]
The hydrophobic group-containing copolymer of the present invention (hereinafter also referred to as “hydrophobic group-containing copolymer (i)”) is an ether bond-containing monomer represented by the above general formula (1) and / or (2). It is a copolymer containing the structural unit (a) derived from the monomer (A) and the structural unit (b) derived from the carboxyl group-containing monomer (B). The structural unit (a) derived from the ether bond-containing monomer (A) has a hydrophobic group (that is, a portion represented by R ¹ in the general formulas (1) and (2)). Since the hydrophobic group-containing copolymer of the present invention having the structural unit (a) is improved in interaction with the surfactant, the surfactant is precipitated. It becomes possible to suppress. The monomer (A) is relatively easy to copolymerize with the monomer (B) and the like even in a hydrophilic solvent such as water, so that it can be uniformly polymerized, and the resulting hydrophobic group-containing copolymer It becomes possible to enhance the ability to suppress the precipitation of coalescence. Moreover, since the water solubility of the hydrophobic group-containing copolymer of the present invention is improved by having the structural unit (b) derived from the carboxyl group-containing monomer (B), the structural units (a) and (b) ), The effect of suppressing the precipitation of the surfactant is more fully exhibited. Therefore, the hydrophobic group-containing copolymer of the present invention is capable of exhibiting excellent precipitation suppressing ability even under severe conditions such as washing with high hardness water or a small amount of water, and can exhibit good detergency. Is particularly suitable for detergent use as a detergent builder or the like.

In the hydrophobic group-containing copolymer (i), the structural unit (a) is 1 to 50% by mass and the structural unit (b) is 50 to 99% by mass with respect to 100% by mass of the structural units derived from all monomers. % Is suitable. If it exists in this range, it will become possible to fully exhibit the effect of this invention by the synergistic effect by the said structural unit (a) and (b).

The amount of the structural unit (a) (ratio with respect to 100% by mass of structural units derived from all monomers) is preferably more than 1% by mass, more preferably 2% by mass or more, and further preferably 2%. The amount is more than 3% by weight, particularly preferably 3% by weight or more, and most preferably more than 3% by weight. Further, it is preferably less than 50% by mass, more preferably 49% by mass or less, further preferably less than 49% by mass, further preferably 45% by mass or less, further preferably less than 45% by mass, still more preferably 40% by mass or less, and further Preferably it is less than 40% by mass, more preferably 35% by mass or less, still more preferably less than 35% by mass, particularly preferably 30% by mass or less, and most preferably less than 30% by mass.

The amount of the structural unit (b) (ratio to 100% by mass of all monomer-derived structural units) is preferably an amount exceeding 50% by mass, more preferably 55% by mass or more, and still more preferably It is an amount exceeding 55% by mass, more preferably 60% by mass or more, further preferably an amount exceeding 60% by mass, further preferably 65% by mass or more, and still more preferably exceeding 65% by mass. The amount is particularly preferably 70% by mass or more, and most preferably more than 70% by mass. Further, it is preferably less than 99% by mass, more preferably 98% by mass or less, still more preferably less than 98% by mass, particularly preferably 97% by mass or less, and most preferably less than 97% by mass.

In the present invention, when calculating the proportion of the structural unit (b) derived from the carboxyl group-containing monomer (B), it is calculated as the corresponding acid conversion. For example, when the structural unit (b) is a structural unit —CH ₂ —CH (COONa) — derived from sodium acrylate, the corresponding structural unit derived from acrylic acid —CH ₂ —CH (COOH) — Calculate the mass ratio (mass%).
In addition, similarly, when calculating the mass ratio (mass%) of a carboxyl group-containing monomer (B), it shall calculate as a corresponding acid conversion. For example, if it is sodium acrylate, a mass ratio (mass%) is calculated as acrylic acid which is a corresponding acid.

Moreover, when calculating the ratio of the structural unit derived from an acid group-containing monomer other than the carboxyl group-containing monomer (B), it is calculated as a corresponding acid conversion. Similarly, when calculating the ratio (mass%) of an acid group-containing monomer other than the carboxyl group-containing monomer (B), it is calculated as a corresponding acid conversion.
Regarding the structural unit derived from the amino group-containing monomer and the amino group-containing monomer, the mass is calculated as the corresponding structural unit derived from the unneutralized amine and the unneutralized amine, respectively. For example, in the case of vinylamine hydrochloride, the mass ratio (% by mass) is calculated as vinylamine which is the corresponding unneutralized amine.

As described above, the hydrophobic group-containing copolymer (i) can exhibit the effects of the present invention by including the structural unit (a) and the structural unit (b). In addition to the structural units (a) and (b), the structural unit (c) derived from the polyalkylene glycol monomer (C) and / or a sulfonic acid group-containing monomer The structural unit (d) derived from the body (D) may be included. By including the structural unit (c) and / or (d), the hydrophobic group-containing copolymer has a polyalkylene glycol group or a sulfonic acid group, and thus has excellent dispersibility in addition to the ability to suppress precipitation. And exhibiting gel resistance. For this reason, it is possible to more fully exhibit good precipitation inhibiting ability and dispersibility even under high hardness, and it is possible to sufficiently exert good precipitation inhibiting ability even under severe washing conditions such as washing with remaining hot water. Become. As described above, the hydrophobic group-containing copolymer (i) further includes a structural unit (c) derived from the polyalkylene glycol monomer (C) (hereinafter, such a form is particularly referred to as “hydrophobic”. Group-containing copolymer (ii) ") and the hydrophobic group-containing copolymer (i) further include a structural unit (d) derived from the sulfonic acid group-containing monomer (D). (Hereinafter, such a form is also referred to as “hydrophobic group-containing copolymer (iii)” in particular) is a particularly preferred form of the present invention.

Needless to say, the hydrophobic group-containing copolymer (ii) and the hydrophobic group-containing copolymer (iii) are included in the hydrophobic group-containing copolymer (i). The hydrophobic group-containing copolymer (i) is a binary copolymer composed of the structural units (a) and (b), that is, the total amount of the structural units (a) and (b). It is clear from the examples described later that the operational effects of the present invention can be exhibited even in a form in which is 100 mass%.

Each structural unit in the hydrophobic group-containing copolymer (i) may exist in a block form or a random form. The “structural unit” is also referred to as “structural unit”.
Hereinafter, the ether bond-containing monomer (A) represented by the general formula (1) and / or (2) is referred to as “monomer (A)”, and the carboxyl group-containing monomer (B) is referred to as “single”. The monomer (B) ”, the polyalkylene glycol monomer (C) is“ monomer (C) ”, the sulfonic acid group-containing monomer (D) is“ monomer (D) ”, A monomer (that is, a monomer other than these monomers (A) to (D)) (E) may be referred to as “monomer (E)”. Each of these monomers will be described later.

In the hydrophobic group-containing copolymer (i), in the form further including the structural unit (c) derived from the polyalkylene glycol monomer (C), that is, in the hydrophobic group-containing copolymer (ii), all The structural unit (a) is 1 to 49% by mass, the structural unit (b) is 50 to 98% by mass, and the structural unit (c) is 1 to 49% by mass with respect to 100% by mass of the structural unit derived from the monomer. Preferably it is. If it exists in this range, it will become possible to further improve the precipitation inhibitory ability of the said hydrophobic group containing copolymer. As described above, the hydrophobic group-containing copolymer further includes a structural unit (c) derived from the polyalkylene glycol monomer (C), and the structural unit is composed of 100% by mass of structural units derived from all monomers. A form in which the unit (a) is 1 to 49% by mass, the structural unit (b) is 50 to 98% by mass, and the structural unit (c) is 1 to 49% by mass is also a preferred form of the present invention. is there. Preferable ranges of the contents of the structural units (a) and (b) are the ranges described above. The content of the structural unit (c) is more preferably more than 1% by mass, still more preferably 2% by mass or more, still more preferably more than 2% by mass, particularly preferably 3%. The amount is not less than mass%, and most preferably more than 3 mass%. Further, it is more preferably less than 49% by mass, particularly preferably 47% by mass or less, and most preferably less than 47% by mass.

In the hydrophobic group-containing copolymer (i), the form further including the structural unit (d) derived from the sulfonic acid group-containing monomer (D), that is, the hydrophobic group-containing copolymer (iii), The structural unit (a) is 1 to 50% by mass, the structural unit (b) is 50 to 98% by mass, and the structural unit (d) is 1 to 49% by mass with respect to 100% by mass of the structural unit derived from the monomer. Preferably it is. If it exists in this range, it will become possible to further improve the precipitation inhibitory ability of the said hydrophobic group containing copolymer. As described above, the hydrophobic group-containing copolymer further includes a structural unit (d) derived from the sulfonic acid group-containing monomer (D), and the structural unit is 100% by mass of all the structural units derived from the monomer. A form in which the unit (a) is 1 to 50% by mass, the structural unit (b) is 50 to 98% by mass, and the structural unit (d) is 1 to 49% by mass is also a preferred embodiment of the present invention. is there.
Preferable ranges of the contents of the structural units (a) and (b) are the ranges described above. The content of the structural unit (d) is more preferably more than 1% by mass, still more preferably 2% by mass or more, still more preferably more than 2% by mass, particularly preferably 3%. The amount is not less than mass%, and most preferably more than 3 mass%. Further, it is more preferably less than 49% by mass, further preferably 45% by mass or less, further preferably less than 45% by mass, particularly preferably 40% by mass or less, and most preferably less than 40% by mass.

Here, when the hydrophobic group-containing copolymer (i) further includes the structural units (c) and (d), that is, the hydrophobic group-containing copolymer (ii) and the hydrophobic group-containing copolymer. The form which is a polymer (iii) is also one of the forms of this invention. In this case, the content of each structural unit is appropriately set in consideration of the content of the structural units (a), (b), (c), and (d) being within the above-mentioned preferable ranges. It is preferable to do.

The hydrophobic group-containing copolymer (i) may further contain a structural unit (e) derived from another monomer (E) as necessary. The content of the structural unit (e) is preferably 0 to 10% by mass with respect to 100% by mass of the structural units derived from all monomers.

The hydrophobic group-containing copolymer (i) can be obtained by copolymerizing the monomers constituting the structural unit described above, and each monomer is used alone or in combination of two or more. be able to. Therefore, each structural unit may exist individually by 1 type, and may exist in 2 or more types of mixed forms. Hereinafter, first, these monomers will be specifically described.

<Ether bond-containing monomer (A)>
The ether bond-containing monomer (A) is at least one selected from the group consisting of the monomer represented by the general formula (1) and the monomer represented by the general formula (2). The structural unit (a) derived from the ether bond-containing monomer (A) in the above general formula (1) or (2) is an unsaturated double bond moiety (CH ₂ = C (R ⁰ )-) means a single bond structure. Since such a structural unit (a) is relatively hydrophobic, the hydrophobic group-containing copolymer of the present invention having the structural unit (a) has an improved interaction with a surfactant, and has an interface. It is possible to suppress the precipitation of the activator. In addition, the monomer (A) can be uniformly polymerized in a hydrophilic solvent such as water because it is relatively easy to copolymerize with the monomer (B) and the like. It becomes possible to increase the ability of the copolymer to suppress precipitation.

In the above general formulas (1) and (2), R ^a represents a CH ₂ group, a CH ₂ CH ₂ group, or a single bond, but since the effect of improving the precipitation suppression ability of the resulting copolymer is higher, R ^a is preferably ^a CH ₂ CH ₂ group. From the same viewpoint, R ^a in the general formula (2) is also preferably ^a CH ₂ CH ₂ group.

In the general formulas (1) and (2), R ¹ is a hydrophobic group (also referred to as a hydrophobic group) and represents an organic group having 1 to 20 carbon atoms. Among these, an organic group having 4 to 18 carbon atoms is preferable, and an organic group having 6 to 16 carbon atoms is more preferable.
The organic group is also preferably a hydrocarbon group, and among the hydrocarbon groups, it is an alkyl group, an aryl group, or an alkenyl group because the effect of improving the precipitation suppression ability of the resulting copolymer is higher. Is more preferred. Specifically, for example, an alkyl group of n-butyl group, isobutyl group, octyl group, lauryl group, stearyl group, cyclohexyl group, 2-ethylhexyl group; alkenyl group such as butylene group, octylene group, nonylene group; phenyl group , Aryl groups such as phenethyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, and the like are particularly suitable.

The organic group may be substituted with halogen or may contain a hetero atom. Further, it may contain a functional group such as an amino group, an amide group, a hydroxyl group, an alkoxide group, a sulfonic acid group, a carbonyl group, or a carboxyl group, and an ether bond, sulfide bond, ester bond, or amide bond. May be included. However, as will be described later, in order that the hydrophobic group-containing copolymer of the present invention can stably exhibit precipitation-inhibiting ability even under alkaline conditions, it is preferable not to contain an ester group or an amide group. is there.

In the above general formulas (1) and (2), X ¹ represents the average number of repeating units represented by (O—CH ₂ —CH ₂ ) (that is, ethylene oxide units) and is a number of 0 to 5. . In the monomer (A), when R ^a in the above formula represents ^a single bond, X ¹ is a number of ¹ to 5. By this way the average repeating number X ¹ ethylene oxide units is 5 or less, it is possible to have the hydrophobic is not too strong of monomer (A), appropriate hydrophilicity, hydrophilic such as water Even if it uses an organic solvent, it has the characteristic that it is easy to copolymerize. In addition, when X ¹ is a number exceeding 5, the hydrophilicity of the monomer (A) becomes too strong, and the effect of the group represented by R ¹ which is a hydrophobic group may be reduced.

As the monomer represented by the general formula (1), for example, compounds represented by the following general formulas (1-1) to (1-5) are preferable. Such a compound is, for example, an alcohol having an unsaturated double bond such as allyl alcohol or isoprenol, a corresponding compound (that is, a halogenated alkyl in the case of a compound represented by the general formula (1-1); If it is a compound represented by formula (1-2), it is an epoxy compound; if it is a compound represented by general formula (1-3), it is a glycidyl compound; if it is a compound represented by general formula (1-4) It is preferable to produce by reacting an ester compound; an isocyanate compound if it is a compound represented by the general formula (1-5).

In the general formulas (1-1) to (1-5), R ⁰ , R ^a and X ¹ are the same as the symbols in the general formula (1). R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms.

As the monomer represented by the general formula (2), for example, compounds represented by the following general formulas (2-1) to (2-2) are preferable. Such compounds include, for example, an epoxy compound having an unsaturated double bond such as allyl glycidyl ether, a corresponding compound (that is, an alcohol or an alkylene of an alcohol if the compound is represented by the general formula (2-1)) Oxide adduct: It is preferable to produce it by reacting an amine or an alkylene oxide adduct of an amine if it is a compound represented by the general formula (2-2).

In the general formulas (2-1) to (2-2), R ⁰ , R ^a and X ¹ are the same as the symbols in the general formula (2). R ¹¹ and R ¹² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms.

The ether bond-containing monomer (A) is also preferably in a form that does not contain an ester group or an amide group from the viewpoint of stably exhibiting the ability to suppress precipitation even under alkaline conditions. is there.

<Carboxyl group-containing monomer (B)>
The carboxyl group-containing monomer (B) is a monomer containing an unsaturated double bond (carbon-carbon double bond) and a carboxyl group and / or a carboxylate salt (however, an ether group-containing monomer) Monomers corresponding to the body (A), the polyalkylene glycol monomer (C) and the sulfonic acid group-containing monomer (D) described later are excluded from the carboxyl group-containing monomer (B). .) The structural unit (b) derived from the carboxyl group-containing monomer (B) is an unsaturated double bond portion (CH ₂ = C (R ⁰ )-) of the monomer (B), which is a single bond. It means the structure that became. By having such a structural unit (b), the hydrophobic group-containing copolymer of the present invention has good water solubility, so that the precipitation of the surfactant due to having the structural unit (a) is suppressed. The effect to do will be more fully demonstrated. Therefore, the hydrophobic group-containing copolymer of the present invention can be particularly useful as a detergent builder or the like.

Here, including a carboxyl group and / or a carboxylate salt means that a group represented by —COOZ (Z represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group) is 1 per molecule. It means having more than one. Examples of metal atoms include alkali metals such as sodium, lithium, potassium, rubidium and cesium; alkaline earth metals such as magnesium, calcium, strontium and barium; aluminum and iron. Organic amine groups include monoethanolamine groups, diethanolamine groups, triethanolamine groups and other alkanolamine groups; monoethylamine groups, diethylamine groups, triethylamine groups and other alkylamine groups; ethylenediamine groups, triethylenediamine groups and other polyamines Groups and the like. Among these, the carboxylate is more preferably an ammonium salt, a sodium salt, or a potassium salt, and more preferably a sodium salt, since the effect of improving the ability to suppress precipitation of the copolymer obtained is high.

As the unsaturated monocarboxylic acid monomer (B), an unsaturated monocarboxylic acid monomer containing an unsaturated double bond and one carboxyl group (or carboxylate) in one molecule, An unsaturated dicarboxylic acid-based monomer containing an unsaturated double bond and two carboxyl groups (or carboxylates) in one molecule is preferable.

Specific examples of the unsaturated monocarboxylic acid monomer (B) include unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and derivatives thereof. Examples thereof include carboxylic acids and salts thereof.
Specific examples of the unsaturated dicarboxylic acid monomer include unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, and fumaric acid, salts thereof, and anhydrides thereof. Further, half esters of these unsaturated dicarboxylic acid monomers and alcohols having 1 to 22 carbon atoms, half amides of unsaturated dicarboxylic acid monomers and amines having 1 to 22 carbon atoms, unsaturated dicarboxylic acids It may be a half ester of a system monomer and a glycol having 2 to 4 carbon atoms, a half amide of maleamic acid and a glycol having 2 to 4 carbon atoms, or the like.

Among the carboxyl group-containing monomers (B), acrylic acid, acrylate, maleic acid, and maleate are preferable from the viewpoint of a higher effect of improving the ability to suppress precipitation of the copolymer. Of these, acrylic acid and acrylate are essential.

<Polyalkylene glycol monomer (C)>
The polyalkylene glycol monomer (C) is a monomer containing an unsaturated double bond (carbon-carbon double bond) and a polyalkylene glycol chain (however, an ether group-containing monomer (A The monomer corresponding to) is excluded from the polyalkylene glycol monomer (C)). Specifically as such a monomer (C), the following general formula (3) and / or (4):

(In the formula, R ⁰ represents a hydrogen atom or a CH ₃ group. R ^b represents a CH ₂ group, a CH ₂ CH ₂ group, a single bond or a C (═O) group. X ² represents (O— CH ₂ —CH ₂ ) represents the average number of repeating units represented by 6 to 200. R ² represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. It is preferable to be a mer. That is, the polyalkylene glycol monomer (C) is selected from the group consisting of the monomer represented by the general formula (3) and the monomer represented by the general formula (4). At least one monomer. The structural unit (c) derived from the polyalkylene glycol monomer (C) is an unsaturated double bond moiety (CH ₂ ═C (R ⁰ ) —) in the general formula (3) or (4). Means a single bond structure. By having such a structural unit (c), in addition to the precipitation inhibiting ability, it is possible to exhibit excellent dispersibility and gel resistance, so that the sufficient precipitation inhibiting ability and dispersibility are more sufficiently even under high hardness. And can exhibit a sufficient ability to suppress precipitation even under severe washing conditions such as washing with remaining hot water.

In the above general formulas (3) and (4), R ² represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably an organic group having 1 to 20 carbon atoms. Among these, an organic group having 4 to 18 carbon atoms is preferable, and an organic group having 6 to 16 carbon atoms is more preferable.
The organic group is also preferably a hydrocarbon group, and among the hydrocarbon groups, it is an alkyl group, an aryl group, or an alkenyl group because the effect of improving the precipitation suppression ability of the resulting copolymer is higher. Is more preferred. Specifically, for example, an alkyl group of n-butyl group, isobutyl group, octyl group, lauryl group, stearyl group, cyclohexyl group, 2-ethylhexyl group; alkenyl group such as butylene group, octylene group, nonylene group; phenyl group , Aryl groups such as phenethyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, and the like are particularly suitable.

The organic group may be substituted with halogen or may contain a hetero atom. Further, it may contain a functional group such as an amino group, an amide group, a hydroxyl group, an alkoxide group, a sulfonic acid group, a carbonyl group, or a carboxyl group, and an ether bond, sulfide bond, ester bond, or amide bond. May be included. However, as will be described later, in order that the hydrophobic group-containing copolymer of the present invention can stably exhibit precipitation-inhibiting ability even under alkaline conditions, it is preferable not to contain an ester group or an amide group. is there.

In the above general formulas (3) and (4), X ² represents the average number of repeating units represented by (O—CH ₂ —CH ₂ ) (that is, ethylene oxide units) and is a number of 6 to 200. . By thus average repeating number X ² ethylene oxide units further comprises structural units derived from 6 or more monomers, dispersibility is improved, it is possible to obtain an excellent hydrophobic group-containing copolymer gel strength it can. Moreover, there exists a possibility that the viscosity of a hydrophobic group containing copolymer may become high too much that it is a number exceeding 200. X ² is preferably 7 or more, more preferably 8 or more. Moreover, Preferably it is 150 or less, More preferably, it is 100 or less.

Specific examples of the polyalkylene glycol monomer (C) include 3- (meth) allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, 3-allyloxy-1, A compound obtained by adding 6 to 200 mol of ethylene oxide to a hydroxyl group-containing unsaturated monomer such as 2-dihydroxypropane, (meth) allyl alcohol, or isoprenol (3-allyloxy-1,2-di (poly) oxyethylene ether) Propane and the like) and polyethylene glycol esters of (meth) acrylic acid are suitable.

As the polyalkylene glycol monomer (C), since the performance of the obtained hydrophobic group-containing copolymer is high over time, an allyloxy group, a metaallyloxy group, a vinyloxy group, an isoprenoxy group (CH ₂ C ( A polyalkylene glycol monomer having (CH ₃ ) CH ₂ CH ₂ O-group) is preferred. Among these, the polyalkylene glycol-based monomer having an isoprenoxy group (CH ₂ C (CH ₃ ) CH ₂ CH ₂ O— group) is most preferable because the obtained polymer has the best performance. That is, the structural unit (c) is most preferably a structure derived from a polyalkylene glycol monomer having an isoprenoxy group (CH ₂ C (CH ₃ ) CH ₂ CH ₂ O— group).

<Sulphonic acid group-containing monomer (D)>
The sulfonic acid group-containing monomer (D) is a monomer containing an unsaturated double bond (carbon-carbon double bond), a sulfonic acid group and / or a sulfonate (provided that an ether group is contained). Monomers corresponding to the monomer (A) and the polyalkylene glycol monomer (C) are excluded from the sulfonic acid group-containing monomer (D)). The structural unit (d) derived from the sulfonic acid group-containing monomer (D) means a structure in which the unsaturated double bond portion of the sulfonic acid group-containing monomer is a single bond. By having such a structural unit (d), in addition to the precipitation inhibiting ability, it is possible to exhibit excellent dispersibility and gel resistance, so that the sufficient precipitation inhibiting ability and dispersibility are more sufficiently even under high hardness. And can exhibit a sufficient ability to suppress precipitation even under severe washing conditions such as washing with remaining hot water.

Here, including a sulfonic acid group and / or a sulfonate refers to one molecule of a group represented by —SO ₃ Z (Z represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group). It means having one or more inside. The metal atom and the organic amine group are as described above. Among these, the sulfonate is more preferably an ammonium salt, a sodium salt, or a potassium salt, and more preferably a sodium salt, because the effect of improving the ability to suppress precipitation of the obtained copolymer is high.

Specific examples of the sulfonic acid group-containing monomer (D) include, for example, vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, acrylamide-2-methylpropane sulfonic acid, and 2-hydroxy-3. -Sodium allyloxypropane sulfonate, sodium 2-hydroxy-3-methallyloxypropane sulfonate, isoprene sulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-butenesulfonic acid And the salts thereof. Among these, a sulfonic acid group-containing monomer that does not contain an ester group or an amide group is preferred because the performance of the resulting polymer is high over time. For example, styrene sulfonic acid, allyl sulfonic acid, Ryl sulfonic acid, 2-hydroxy-3-allyloxypropane sulfonic acid, 2-hydroxy-3-methallyloxypropane sulfonic acid, isoprene sulfonic acid and salts thereof are preferred. More preferably, it is 2-hydroxy-3-allyloxypropanesulfonic acid and a salt thereof because the obtained polymer has the best performance. That is, the structural unit (d) derived from the sulfonic acid group-containing monomer (D) is particularly preferably a structure derived from 2-hydroxy-3-allyloxypropanesulfonic acid or a salt thereof.

<Other monomer (E)>
The hydrophobic group-containing copolymer of the present invention may also have a structural unit (e) derived from another monomer (E). The other monomer (E) is not particularly limited as long as it is copolymerizable with part or all of the monomer components constituting the hydrophobic group-containing copolymer, and is appropriately selected depending on the desired effect. Is done. Specifically, N-vinyl simple substance such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyloxazolidone, etc. Amide monomers such as (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide; (meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, etc. ) Acrylic acid alkyl ester monomers; hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate 2 Such as hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, etc. Examples include (meth) hydroxyalkyl acrylate monomers, vinylaryl monomers such as styrene, indene and vinylaniline, isobutylene and vinyl acetate.

The weight average molecular weight of the hydrophobic group-containing copolymer of the present invention can be appropriately set and is not particularly limited, but is preferably, for example, 2000 to 200000. If it exists in this range, it exists in the tendency for precipitation suppression ability to improve. In addition, when it exceeds 200,000, a viscosity becomes high too much, dispersibility cannot fully be exhibited, and there exists a possibility that precipitation suppression ability cannot be improved further. More preferably, it is 3000 or more, More preferably, it is 4000 or more, More preferably, it is 60000 or less, More preferably, it is 30000 or less, Most preferably, it is 20000 or less.
In addition, in this specification, a weight average molecular weight is a measured value by GPC (gel permeation chromatography), and can be measured on the measurement conditions mentioned later.

[Hydrophobic group-containing copolymer composition]
A hydrophobic group-containing copolymer composition (hereinafter also simply referred to as “polymer composition”) including the above-mentioned hydrophobic group-containing copolymer is also one of the preferred embodiments of the present invention. Such a polymer composition contains the hydrophobic group-containing copolymer of the present invention as an essential component, and components other than the hydrophobic group-containing copolymer are optional, but the polymer composition contains a hydrophobic group-containing copolymer. In the case of a product obtained by the method for producing a polymer, it usually contains one or more selected from a polymerization initiator residue, a residual monomer, a by-product during polymerization, and moisture.
The polymer composition preferably includes 30 to 80% by mass of the hydrophobic group-containing copolymer and 20 to 70% by mass of water.

[Method for producing hydrophobic group-containing copolymer]
In the method for producing a hydrophobic group-containing copolymer of the present invention, in the presence of a polymerization initiator, the ether bond-containing monomer (A) represented by the above general formula (1) and / or (2) and a carboxyl group It includes a step of polymerizing a monomer component containing the containing monomer (B) (hereinafter also referred to as “polymerization step”). That is, the hydrophobic group-containing copolymer (i) of the present invention can be obtained by polymerizing (copolymerizing) the monomer components essentially comprising the monomers (A) and (B).
The monomer component may further contain other monomers as necessary. For example, when the monomer component further contains the polyalkylene glycol monomer (C), the copolymer (ii) can be obtained from the hydrophobic group-containing copolymer (i). In the case where the monomer component further contains the sulfonic acid group-containing monomer (D), the copolymer (iii) is obtained from the hydrophobic group-containing copolymer (i). be able to.

In the above polymerization step, the monomer component is copolymerized in the presence of a polymerization initiator, but the monomer component is adjusted so that the constituent units constituting the hydrophobic group-containing copolymer are within the above-described range. The type and amount of the monomer contained in are appropriately set. That is, it is preferable to appropriately set the type and amount of the monomer contained in the monomer component so that the content of the structural unit constituting the hydrophobic group-containing copolymer is in the above-described range. Accordingly, the content of the monomer (A) is set to 1 to 50% by mass and the content of the monomer (B) is set to 50 to 99% by mass with respect to 100% by mass of all monomer components. Is appropriate.

The amount of the monomer (A) (ratio to 100% by mass of all monomer components) is preferably an amount exceeding 1% by mass, more preferably 2% by mass or more, and further preferably 2% by mass. The amount exceeds 3, particularly preferably 3% by mass or more, and most preferably the amount exceeds 3% by mass. Further, it is preferably less than 50% by mass, more preferably 49% by mass or less, further preferably less than 49% by mass, further preferably 45% by mass or less, further preferably less than 45% by mass, still more preferably 40% by mass or less, and further Preferably it is less than 40% by mass, more preferably 35% by mass or less, still more preferably less than 35% by mass, particularly preferably 30% by mass or less, and most preferably less than 30% by mass.

The amount of the monomer (B) (ratio to 100% by mass of all monomer components) is preferably an amount exceeding 50% by mass, more preferably 55% by mass or more, and further preferably 55% by mass. More preferably 60% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and still more preferably 65% by mass or more, Particularly preferred is 70% by mass or more, and most preferred is an amount exceeding 70% by mass. Further, it is preferably less than 99% by mass, more preferably 98% by mass or less, still more preferably less than 98% by mass, particularly preferably 97% by mass or less, and most preferably less than 97% by mass.

When the monomer component further contains the polyalkylene glycol monomer (C), the content of the monomer (A) is 1 to 49% by mass with respect to 100% by mass of all monomer components. %, The content of the monomer (B) is 50 to 98% by mass, and the content of the monomer (C) is preferably 1 to 49% by mass. If it exists in this range, it will become possible to further improve the precipitation inhibitory ability of the said hydrophobic group containing copolymer. Thus, the monomer component further includes a polyalkylene glycol monomer (C), and the content of the ether bond-containing monomer (A) is 100% by mass of the total monomer components. In the form of 1 to 49% by mass, the content of the carboxyl group-containing monomer (B) is 50 to 98% by mass, and the content of the polyalkylene glycol monomer (C) is 1 to 49% by mass. This is one of the preferred forms of the present invention.
Preferable ranges of the content ratios of the monomers (A) and (B) are the ranges described above. Further, the content of the monomer (C) is more preferably more than 1% by mass, still more preferably 2% by mass or more, still more preferably more than 2% by mass, particularly preferably. The amount is 3% by mass or more, and most preferably more than 3% by mass. Further, it is more preferably less than 49% by mass, particularly preferably 47% by mass or less, and most preferably less than 47% by mass.

Moreover, when the said monomer component further contains the said sulfonic acid group containing monomer (D), content of a monomer (A) is 1-49 mass with respect to 100 mass% of all monomer components. %, The monomer (B) content is preferably 50 to 98% by mass, and the monomer (D) content is preferably 1 to 49% by mass. If it exists in this range, it will become possible to further improve the precipitation inhibitory ability of the said hydrophobic group containing copolymer. Thus, the monomer component further contains a sulfonic acid group-containing monomer (D), and the ether bond-containing monomer (A) content is 1 with respect to 100% by mass of all monomer components. An embodiment in which the content of the carboxyl group-containing monomer (B) is 50 to 98 mass% and the content of the sulfonic acid group-containing monomer (D) is 1 to 49 mass% is also present. This is one of the preferred forms of the invention.
Preferable ranges of the content ratios of the monomers (A) and (B) are the ranges described above. The content of the monomer (D) is more preferably more than 1% by mass, still more preferably 2% by mass or more, still more preferably more than 2% by mass, particularly preferably. The amount is 3% by mass or more, and most preferably more than 3% by mass. Further, it is more preferably less than 49% by mass, further preferably 45% by mass or less, further preferably less than 45% by mass, particularly preferably 40% by mass or less, and most preferably less than 40% by mass.

Moreover, when the said monomer component further contains another monomer (E), it is suitable to set it as 0-10 mass% with respect to 100 mass% of all the monomer components.

As a polymerization method (copolymerization method) in the polymerization step, for example, it can be carried out by a commonly used method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization and the like. A polymerization method is preferred. In this case, as a solvent that can be used, as described later, a mixed solvent containing 50% by mass or more of water in a total solvent amount of 100% by mass, or a water-only solvent is preferable. This is preferable in that the process can be omitted.
The polymerization method can be carried out either batchwise or continuously.

In the polymerization step, known polymerization initiators can be used, such as hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; 2,2′-azobis (2 -Amidinopropane) hydrochloride, 4,4'-azobis-4-cyanoparerenic acid, azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds An organic peroxide such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide and the like is preferable. Of these, hydrogen peroxide and persulfate are preferable, and persulfate is most preferable.
In addition, the said polymerization initiator may be used independently and may be used with the form of 2 or more types of mixtures.
The amount of the polymerization initiator used is not particularly limited as long as it is an amount capable of initiating copolymerization of the monomer component, but is 10 g with respect to 1 mol of the total amount of monomer components (total monomer components). The following is preferable, and more preferably 1 to 5 g.

In the above production method, it is also preferable to perform polymerization (copolymerization) in the presence of a chain transfer agent in addition to the polymerization initiator. Use of a chain transfer agent has an advantage that the hydrophobic group-containing copolymer to be produced is prevented from having a higher molecular weight than necessary, and a low molecular weight hydrophobic group-containing copolymer can be efficiently produced. . The chain transfer agent that can be used is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and a known chain transfer agent can be used. Specifically, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid Thiol-based chain transfer agents such as n-dodecyl mercaptan, octyl mercaptan, butyl thioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; secondary alcohols such as isopropanol, glycerin; Phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and salts thereof (sodium hydrogen sulfite, Potassium hydrogen sulfite, dithio Sodium oxide, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.), and the like, and may be used alone or in the form of a mixture of two or more. May be used.

Among the chain transfer agents, it is preferable to use sulfite or sulfite. That is, it is preferable to use at least sulfurous acid and / or sulfite (hereinafter referred to as “sulfurous acid (salt)”) as the chain transfer agent. Thereby, a sulfonic acid group can be quantitatively introduced into the main chain terminal of the obtained hydrophobic group-containing copolymer, and the gel resistance can be improved. In addition, the fact that the sulfonic acid group can be introduced quantitatively indicates that the sulfite is functioning very well as a chain transfer agent and the like. Thus, the increase in the production cost of the copolymer is reduced, the production efficiency is improved, and the impurities can be sufficiently reduced. Further, by adding sulfite to the polymerization reaction system, it is possible to suppress the resulting copolymer from having a higher molecular weight than necessary.

The sulfurous acid (salt) refers to sulfurous acid or hydrogen sulfite, or a salt thereof, and a form in which sulfurous acid / bisulfite is a salt is preferable. When sulfite / bisulfite is a salt, in addition to the examples described above, salts of metal atoms, ammonium or organic ammonium are preferred. Examples of the metal atom include monovalent metal atoms of alkali metals such as lithium, sodium and potassium; divalent metal atoms of alkaline earth metals such as calcium and magnesium; trivalent metal atoms such as aluminum and iron And the like are preferred. As the organic ammonium (organic amine), alkanolamines such as ethanolamine, diethanolamine, and triethanolamine, and triethylamine are preferable. Further, it may be ammonium. Therefore, examples of the sulfite preferably used in the present invention include sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite and the like, and sodium bisulfite is particularly suitable.
In addition, the said sulfurous acid (salt) may be used independently and may be used with the form of 2 or more types of mixtures.

In the above production method, the addition amount of the chain transfer agent is not limited as long as the monomer component used is polymerized satisfactorily, but preferably 1 to 20 g with respect to 1 mol of all monomer components. And more preferably 2 to 15 g. If it is less than 1 g, the molecular weight may not be sufficiently controlled, and if it exceeds 20 g, impurities may not be sufficiently suppressed, and the polymer content may not be sufficient. In particular, when sulfite is used, surplus sulfite is decomposed in the reaction system, and sulfite gas may be generated. Moreover, there is a risk that it may be economically disadvantageous.

In the above production method, it is preferable to use a reaction accelerator together, and it is preferable to use heavy metal ions as the reaction accelerator. In addition, the heavy metal ion used as a reaction accelerator means a metal having a specific gravity of 4 g / cm ³ or more. As the heavy metal ions, for example, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium and the like are preferable. More than seeds can be used. Among these, iron is preferable.
The ionic valence of the heavy metal ions is not particularly limited. For example, when iron is used as the heavy metal, the iron ions in the initiator may be Fe ²⁺ or Fe ³⁺ , and these may be combined. May be.

The heavy metal ions are not particularly limited as long as they are included in the form of ions. However, it is preferable to use a method using a solution in which a heavy metal compound is dissolved because the handleability is excellent. The heavy metal compound used in that case should just contain the heavy metal ion desired to contain in an initiator, and can be determined according to the initiator to be used.
When iron is used as the heavy metal ion, the mole salt (Fe (NH ₄ ) ₂ (SO ₄ ) ₂ · 6H ₂ O), ferrous sulfate · 7 hydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal compound or the like. Moreover, when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably. In the case of using these heavy metal compounds, since they are water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability.
The solvent of the solution obtained by dissolving the heavy metal compound is not limited to water, and does not hinder the polymerization reaction in the production of the hydrophobic group-containing copolymer of the present invention, and is a heavy metal compound. As long as it dissolves.

In the case of using the heavy metal ions, the amount of heavy metal ions is preferably included in the amount of catalyst in the polymerization step. The catalyst amount referred to here is not a catalyst that is incorporated into the final target product, but acts specifically, and is specifically 100 ppm or less. Preferably it is 10 ppm or less, More preferably, it is 5 ppm or less.

The content of the heavy metal ions is also preferably 0.1 to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction. If it is less than 0.1 ppm, the effect of heavy metal ions may not be sufficiently exhibited, and if it exceeds 10 ppm, the color tone of the resulting hydrophobic group-containing copolymer may be adversely affected. Moreover, when there is much content of heavy metal ion, when using the hydrophobic group containing copolymer which is a product as a detergent builder, there exists a possibility of causing the stain | pollution | contamination of a builder for detergents.
The term “when the polymerization reaction is completed” means a point in time when the polymerization reaction is substantially completed in the polymerization reaction solution and a desired polymer is obtained. For example, when the polymer polymerized in the polymerization reaction solution is neutralized with an alkali component, the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization. When two or more kinds of heavy metal ions are included, the total amount of heavy metal ions may be in the above range.

In the polymerization step, it is also preferable to use a solvent. The solvent is not particularly limited, and known solvents can be used. For example, in addition to water, organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc .; glycerin; polyethylene glycol; benzene, toluene, xylene, cyclohexane Aromatic or aliphatic hydrocarbons such as n-heptane; esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone and diethyl ketone; amides such as dimethylformaldehyde; ethers such as diethyl ether and dioxane It can be used suitably. These may be used alone or in combination of two or more. Among these, from the viewpoint of the solubility of the monomer component and the resulting copolymer, one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms may be used. preferable.

As the solvent, it is particularly preferable that 50% by mass or more is water in 100% by mass of the total amount of the solvent to be used. Thereby, since the amount of the organic solvent used for the polymerization can be suppressed, there is an advantage that the organic solvent can be easily distilled off after the completion of the polymerization. Moreover, you may add the organic solvent (organic solvent) mentioned above as needed from a viewpoint of the solubility improvement to the solvent of the monomer used for superposition | polymerization. Even in this case, the water content in the total mixed solvent is preferably 50% by mass or more. The content of water in the total amount of the solvent to be used is 100% by mass, particularly preferably 80% by mass or more, and most preferably 100% by mass (that is, using a water-only solvent).

As the usage-amount of the said solvent, it is preferable to set it as 40-200 mass parts with respect to 100 mass parts of total amounts (all monomer components) of a monomer component. If the amount is less than 40 parts by mass, the resulting copolymer may have a high molecular weight. If the amount exceeds 200 parts by mass, the concentration of the resulting copolymer will be low, and solvent removal may be required. More preferably, it is 45 mass parts or more, More preferably, it is 50 mass parts or more, More preferably, it is 180 mass parts or less, More preferably, it is 150 mass parts or less.
The solvent may be partly or wholly charged in the reaction vessel in the initial stage of polymerization, but a part of the solvent may be added (dropped) into the reaction system during the polymerization reaction, or the monomer. Components, initiators, and the like may be added (dropped) into the reaction system during the polymerization reaction together with these components in a form in which the components and initiator are dissolved in advance.

Thus, as a particularly preferred form of the production method of the present invention, the polymerization step is performed in the presence of a polymerization initiator, a chain transfer agent and a solvent, and the total amount of the solvent is 100% by mass. Thus, the water content is 50% by mass or more. Most preferably, the polymerization step is carried out in the presence of a polymerization initiator, a chain transfer agent, a reaction accelerator and a solvent.
In addition, when using together a polymerization initiator, a chain transfer agent, and a reaction accelerator, it is preferable that these total amounts are 2-20g with respect to 1 mol of total amounts (all monomer components) of a monomer component. . By setting it as such a range, the hydrophobic group containing copolymer of this invention can be produced efficiently, and the molecular weight distribution of a hydrophobic group containing copolymer can be made into a desired thing. More preferably, it is 4-18g, More preferably, it is 6-15g.

Here, as a preferable combination of the polymerization initiator and the chain transfer agent, it is most preferable to use one or more persulfates and sulfites. In this case, the mixing ratio of persulfate and sulfite is not particularly limited, but it is preferable to use 0.5 to 5 parts by mass of sulfite with respect to 1 part by mass of persulfate. If the amount is less than 0.5 parts by mass, the total amount of the polymerization initiator may increase when the molecular weight is lowered. Conversely, if the amount exceeds 5 parts by mass, side reactions may increase, which may increase impurities. is there. More preferably, it is 1 mass part or more, More preferably, it is 2 mass parts or more, More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less.

Moreover, as a suitable combination of the polymerization initiator and the chain transfer agent, a suitable combination of the polymerization initiator and the reaction accelerator, and a suitable combination of the polymerization initiator, the chain transfer agent and the reaction accelerator, for example, , Sodium bisulfite (SBS) / hydrogen peroxide (H ₂ O ₂ ), sodium bisulfite (SBS) / sodium persulfate (NaPS), sodium bisulfite (SBS) / Fe, sodium bisulfite (SBS) / peroxide Hydrogen (H ₂ O ₂ ) / Fe, sodium bisulfite (SBS) / sodium persulfate (NaPS) / Fe, sodium bisulfite (SBS) / sodium persulfate (NaPS) / hydrogen peroxide (H ₂ O ₂ ), Examples thereof include sodium bisulfite (SBS) / oxygen / Fe. More preferred are sodium bisulfite (SBS) / sodium persulfate (NaPS), sodium bisulfite (SBS) / sodium persulfate (NaPS) / Fe, and most preferred sodium bisulfite (SBS) / sodium persulfate ( NaPS) / Fe.

As a method for adding the polymerization initiator and the chain transfer agent to the reaction vessel, a continuous charging method such as dropping or divided charging can be applied. Further, the chain transfer agent may be introduced alone into the reaction vessel, or may be previously confused with each monomer or solvent constituting the monomer component.

In the above polymerization (copolymerization) method, as a method of adding the monomer component, the polymerization initiator, etc. to the reaction vessel, all the monomer components are charged into the reaction vessel, and the polymerization initiator is added to the reaction vessel. A method in which a part of the monomer component is charged into the reaction vessel, and the polymerization initiator and the remaining monomer component are continuously or stepwise (preferably continuously) in the reaction vessel. A method of performing copolymerization by adding; a method of adding a polymerization solvent to a reaction vessel and adding the whole amount of a monomer component and a polymerization initiator; one kind of monomer among monomer components (for example, a single amount) A part of the body (B)) is charged into a reaction vessel, the polymerization initiator and the remaining monomer components (for example, the remainder of the monomer (B), the monomer (A), and a single amount if necessary) (C), (D) and / or (E)) are added (preferably continuously) into the reaction vessel. The method for performing the copolymerization is preferred by. Among such methods, the molecular weight distribution of the obtained copolymer can be narrowed (sharpened), and the dispersibility when used as a detergent builder can be improved. It is preferable to carry out copolymerization by a method in which body components are successively dropped into a reaction vessel.

In the above polymerization step, the polymerization conditions such as temperature, pressure, and time are appropriately determined depending on the polymerization method, solvent, polymerization initiator, etc. used, but the polymerization temperature is usually preferably 0 ° C. or higher, Moreover, it is preferable that it is 150 degrees C or less. More preferably, it is 40 degreeC or more, More preferably, it is 60 degreeC or more, Most preferably, it is 80 degreeC or more. Moreover, More preferably, it is 120 degrees C or less, More preferably, it is 110 degrees C or less. In particular, when using sulfurous acid (salt), the copolymerization temperature is usually 60 ° C to 95 ° C, preferably 70 ° C to 95 ° C, more preferably 80 ° C to 95 ° C. At this time, if the temperature is lower than 60 ° C., a large amount of impurities derived from sulfurous acid (salt) may be generated. On the contrary, when it exceeds 95 ° C., toxic sulfurous acid gas may be released.
The polymerization temperature need not always be kept substantially constant in the polymerization reaction. For example, the polymerization is started from room temperature, the temperature is increased to a set temperature with an appropriate temperature increase time or rate, and then the set temperature is reached. Depending on the dropping method of the monomer component, the initiator, etc., the temperature may be changed over time (temperature increase or decrease) during the polymerization reaction.
The polymerization time is preferably 30 to 300 minutes. More preferably, it is 60-240 minutes, More preferably, it is 120-180 minutes.

The pressure in the reaction system in the polymerization step may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but in terms of the molecular weight of the resulting copolymer, The reaction system is preferably sealed and the reaction is carried out under pressure. Moreover, it is preferable to carry out under a normal pressure (atmospheric pressure) at the point of equipment, such as a pressurization apparatus, a pressure reduction apparatus, a pressure-resistant reaction container, and piping. The atmosphere in the reaction system may be an air atmosphere, but is preferably an inert atmosphere. For example, the inside of the system is preferably replaced with an inert gas such as nitrogen before the start of polymerization.

In the polymerization step, the pH during the polymerization is preferably acidic. In particular, when persulfate and bisulfite are used in combination as a polymerization initiator, it is preferably carried out under acidic conditions. By carrying out under acidic conditions, the increase in the viscosity of the aqueous solution of the polymerization reaction system can be suppressed, and the copolymer can be produced satisfactorily. In addition, since the polymerization reaction can proceed under high concentration conditions, the production efficiency can be greatly increased, and a high concentration polymerization with a final solid content concentration of 40% by mass or more can be included. A total residual monomer concentration of 15000 ppm or less can be obtained. Furthermore, the polymerizability of the ether bond-containing monomer (A) can be improved.

As said acidic condition, it is preferable that pH at 25 degreeC of the reaction solution in superposition | polymerization is 1-6. More preferably, it is 5 or less, More preferably, it is 3 or less. The polymer (copolymer) obtained by the above polymerization step can be used as it is as a main component of a detergent composition (detergent builder) as it is, but if necessary, it is further neutralized with an alkaline substance. Also good. As the alkaline substance, it is preferable to use inorganic salts such as hydroxides, chlorides and carbonates of monovalent metals and divalent metals; ammonia; organic ammonium (organic amine) and the like.

Moreover, the neutralization rate at the time of superposing | polymerizing can be suitably changed with a polymerization initiator. For example, when persulfate and bisulfite are used in combination, the neutralization rate of the carboxyl group-containing monomer (B) is 0 to 60 mol% when the monomer can form a salt. It is preferable to carry out copolymerization of monomer components as The neutralization rate of the monomer (B) is represented by the mol% of the monomer forming the salt when the total number of moles of the monomer (B) is 100 mol%. . When the neutralization rate of the monomer (B) exceeds 60 mol%, the polymerization rate in the copolymerization step does not increase, and the molecular weight of the resulting copolymer may decrease, or the production efficiency may decrease. . More preferably, it is 50 mol% or less, More preferably, it is 40 mol% or less, Especially preferably, it is 30 mol% or less, More preferably, it is 20 mol% or less, Most preferably, it is 10 mol% or less.

As a method for carrying out copolymerization with the neutralization rate of the monomer (B) being 0 to 60 mol%, for example, when the monomer (B) is an unsaturated carboxylic acid monomer, all of the acid type Or a method of subjecting the unsaturated carboxylic acid monomer to copolymerization without neutralization, or using an alkaline substance for the unsaturated carboxylic acid monomer using a salt such as a sodium salt or an ammonium salt. A method in which a neutralization rate of 0 to 60 mol% is applied to copolymerization when neutralized into a form is suitable.

[Use of hydrophobic group-containing copolymer]
As the hydrophobic group-containing copolymer (or a polymer composition containing the same) of the present invention, since it is excellent in precipitation suppressing ability and can sufficiently suppress the precipitation of the surfactant, for example, a water treatment agent, a fiber treatment agent, It is preferably used for applications such as dispersants, detergent builders (or detergent compositions), scale inhibitors (scale inhibitors), metal ion sealants, thickeners, various binders, emulsifiers, skin care agents, hair care agents, etc. it can. In addition, as a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, dwelling, hair, body, toothpaste, and automobile.
Below, the use of a water treatment agent, a fiber treatment agent, an inorganic pigment dispersant, and a detergent composition is mentioned as an example, and the case where the hydrophobic group containing copolymer of this invention is used for these uses is demonstrated.

<Water treatment agent>
The hydrophobic group-containing copolymer (or polymer composition) can be used as a water treatment agent. That is, the water treatment agent containing the hydrophobic group-containing copolymer is one of the preferred embodiments of the present invention.
For the water treatment agent, a polymerized phosphate, phosphonate, anticorrosive, slime control agent, and chelating agent may be used as other compounding agents as necessary.
The water treatment agent is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor concentration tank, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effects.

<Fiber treatment agent>
The hydrophobic group-containing copolymer (or polymer composition) can be used as a fiber treatment agent. That is, the fiber treatment agent containing the hydrophobic group-containing copolymer is one of the preferred embodiments of the present invention. In this case, it is preferable that the fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide, and a surfactant, and the hydrophobic group-containing copolymer.
The content of the hydrophobic group-containing copolymer in the fiber treatment agent is preferably 1 to 100% by weight with respect to 100% by mass of the total amount of the fiber treatment agent. More preferably, it is 5 to 100% by weight. In addition, any appropriate water-soluble polymer may be included as long as performance and effects are not affected.
Below, the compounding example of the fiber processing agent which is closer to embodiment is shown. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. Examples of dyeing agents, peroxides, and surfactants include those usually used for fiber treatment agents.

The blending ratio of the hydrophobic group-containing copolymer of the present invention and at least one selected from the group consisting of a dye, a peroxide, and a surfactant is, for example, the whiteness of the fiber, the color unevenness, and the dyeing tempering degree. In order to improve, the total amount of at least one selected from the group consisting of a dye, a peroxide and a surfactant with respect to 1 part by weight of the hydrophobic group-containing copolymer of the present invention in terms of a pure amount of the fiber treatment agent. Is preferably 0.1 to 100 parts by weight, and it is preferable to use a composition formulated in such a ratio as a fiber treatment agent.
Arbitrary appropriate fiber can be employ | adopted as a fiber which can use the said fiber processing agent. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.
When the fiber treatment agent is applied to the refining process, it is preferable to blend the hydrophobic group-containing copolymer of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the hydrophobic group-containing copolymer of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for an alkaline bleaching agent.

<Inorganic pigment dispersant>
The hydrophobic group-containing copolymer (or polymer composition) can be used as an inorganic pigment dispersant. That is, the inorganic pigment dispersant containing the hydrophobic group-containing copolymer is one of the preferred embodiments of the present invention. If necessary, the inorganic pigment dispersant may use condensed phosphoric acid and a salt thereof, phosphonic acid and a salt thereof, and polyvinyl alcohol as other compounding agents.
The content of the hydrophobic group-containing copolymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by mass with respect to 100% by mass of the total amount of the inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as the performance and effects are not affected.

The inorganic pigment dispersant can exhibit good performance as a dispersant for inorganic pigments of heavy or light calcium carbonate and clay used for paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, high concentration calcium carbonate having low viscosity and high fluidity and good aging stability of their performance. High concentration inorganic pigment slurries such as slurries can be produced.
When the inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, and an effect commensurate with the addition amount can be obtained, which can be economically advantageous.

<Detergent composition>
The hydrophobic group-containing copolymer (or polymer composition) can be used in a detergent composition (also referred to as a cleaning composition). That is, the detergent composition including the hydrophobic group-containing copolymer is one of the preferred embodiments of the present invention.
The content of the hydrophobic group-containing copolymer of the present invention in the detergent composition is not particularly limited. However, from the viewpoint that excellent builder performance can be exhibited, the content of the detergent composition is 0% with respect to 100% by mass. It is preferable to set it as 1-15 mass%. More preferably, it is 0.3-10 mass%, More preferably, it is 0.5-5 mass%.

Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge can be appropriately referred to in the detergent field.
The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 100% by mass based on the total amount of the surfactant. It is 60 mass% or more, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.

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 phosphorus An acid ester or a salt thereof is preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.

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

As the cationic surfactant, a quaternary ammonium salt or the like is suitable. As the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched from an alkyl group such as a methyl group.

The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, particularly preferably 100% by mass with respect to the total amount of the detergent composition. It is 25-40 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 economy may be lowered.

Examples of the additive include other detergent builders (for example, alkali builders, chelate builders, anti-redeposition agents for preventing re-deposition of contaminants such as carboxyl derivatives of polysaccharides), benzotriazole and ethylene-thiol. Soil suppressants such as urea, soil release agents, color transfer inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, Bactericides, bleaches, bleaching aids, enzymes, dyes, solvents, etc. are preferred. In the case of a powder detergent composition, it is preferable to blend zeolite.

As the alkali builder, silicate, carbonate, sulfate and the like are preferable.
Examples of the chelate builder include tripolyphosphate, pyrophosphate, bow nitrate, nitrilotriacetate, ethylenediaminetetraacetate, citrate, (meth) acrylic acid copolymer salt, acrylic acid-maleic acid copolymer, Fumarate, zeolite, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), citric acid and the like are suitable. Moreover, you may use other water-soluble polycarboxylic acid-type polymer other than the copolymer in this invention.
As the carboxyl derivative of the above polysaccharide, sodium carboxymethyl cellulose is preferred.
Examples of the counter salt used in the other detergent builder include alkali metals such as sodium and potassium, ammonium and amine.

As the enzyme, protease, lipase, cellulase and the like are preferable. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred. The addition amount of the enzyme is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced.

The total blending ratio of the additives is preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning composition. If the amount is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 50% by mass, the economy may be lowered. More preferably, it is 0.2-40 mass%, More preferably, it is 0.3-35 mass%, Especially preferably, it is 0.4-30 mass%, Most preferably, it is 0.5-20 mass% or less.
In addition, the concept of the above-mentioned detergent composition includes specific detergents such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components. Detergents that are only used are also included.

By including the hydrophobic group-containing copolymer of the present invention, the detergent composition is excellent in the ability to suppress precipitation, and further hardly deteriorates in performance when stored for a long period of time or precipitates impurities when held at a low temperature. It is a detergent with high quality agent performance and excellent stability.
Such a detergent composition may be a powder detergent composition or a liquid detergent composition. When it is a liquid detergent composition, it is preferable that the moisture content contained in a liquid detergent composition is 0.1-75 mass% normally with respect to 100 mass% of the whole quantity of a liquid detergent composition. More preferably, it is 0.2-70 mass%, More preferably, it is 0.5-65 mass%, More preferably, it is 0.7-60 mass%, Most preferably, it is 1-55 mass%, Most preferably, 1.5- 50% by mass.

When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg / L or less. More preferably, it is 150 mg / L or less, More preferably, it is 120 mg / L or less, Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.
The kaolin turbidity can be measured as follows.
<Measurement method of kaolin turbidity>
A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed and air bubbles were removed. Then, a NDU2000 manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.

The hydrophobic group-containing copolymer of the present invention has the above-described configuration and is excellent in performance of sufficiently suppressing / preventing the precipitation of the surfactant. Therefore, when used in applications such as a detergent composition, the surfactant Is effectively suppressed.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
In Examples and Comparative Examples, the weight average molecular weight and number average molecular weight of the copolymer, the solid content (% by mass) of the polymer composition, and the precipitation inhibiting ability were determined according to the following methods.

<Measurement conditions of weight average molecular weight and number average molecular weight>
Equipment: Hitachi L-7000 series detector: RI
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 ml / min.
Calibration curve: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)

<Measuring method of precipitation inhibitory ability (LAS-Ca salt precipitation inhibitory ability)>
(1) A pure glycine buffer solution was prepared by adding pure water to 9.3793 g of glycine, 9.6252 g of sodium chloride, and 5.1975 g of sodium hydroxide.
(2) Pure water was added to 1.50 g of 15% (w / w) sodium dodecylbenzenesulfonate (LAS) aqueous solution, 0.80 g of sodium sulfate, and 11.25 g of glycine buffer prepared in (1), and 500. 0 g.
(3) A 0.1% (w / w) sample polymer aqueous solution was prepared.
(4) A 1M calcium chloride dihydrate aqueous solution was prepared.
(5) A test solution was prepared by adding 1.80 g of the 0.1% sample polymer aqueous solution prepared in (3), 8.20 g of pure water, and 80.00 g of (2) to a 100 mL beaker.
(6) To the test solution, the 1M calcium chloride dihydrate aqueous solution prepared in (4) was dropped and stirred, and the change in turbidity was measured. For the measurement, an automatic titrator manufactured by Hiranuma Sangyo (main body: COM-550, luminous intensity unit; M-500) was used. Turbidity change was measured by transmittance change at a wavelength of 650 nm.
(7) The transmittance value at the time when the addition amount of the 1M calcium chloride dihydrate aqueous solution was 0.270 ml was defined as the precipitation inhibiting ability. In addition, it means that it is excellent in precipitation suppression ability, so that a value is high.

<Method for measuring solid content of polymer composition>
In a nitrogen atmosphere, the polymer composition (polymer composition 1.0 g + water 3.0 g) was left to dry for 1 hour in an oven heated to 130 ° C. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.

Synthesis Example 1 (Monomer 1)
In a 500 mL glass separable flask equipped with a stirrer (paddle blade), 81.2 g of New Coal 2305 (manufactured by Nippon Emulsifier Co., Ltd .; ethylene oxide 5 mol adduct of C12-13 alcohol), The reaction system was dehydrated by charging 16.8 g, heating up to 120 ° C. with nitrogen blowing and stirring, and maintaining this state for 1 hour. Next, a reflux condenser was attached, and the temperature was lowered to 60 ° C., 27.0 g of methallyl chloride (hereinafter also referred to as “MLC”) was added over 30 minutes, and then reacted for 5 hours. 200.0 g of pure water was added thereto, and the mixture was reacted for 1 hour, and then neutralized with sulfuric acid. After cooling to room temperature, this aqueous solution was transferred to a 500 ml separatory funnel and allowed to stand until the layers were separated, and the lower layer was removed. The remaining upper layer was transferred to a 300 ml eggplant flask and desolvated with a rotary evaporator. Precipitated salt was removed by filtration to obtain monomer 1.

Synthesis Example 2 (Monomer 2)
In a 500 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade), 370.0 g of n-butyl alcohol and 4.27 g of KOH were charged and heated to 90 ° C. while stirring. Next, 57.0 g of allyl glycidyl ether (hereinafter also referred to as “AGE”) was added over 30 minutes, and then reacted for 5 hours. After cooling to room temperature and neutralizing with sulfuric acid, the solution was transferred to a 1000 ml eggplant flask and desolvated with a rotary evaporator. 200.0 g of pure water was added thereto, and this aqueous solution was transferred to a 500 ml separatory funnel and allowed to stand until the layers were separated, and the lower layer was removed. The remaining upper layer was transferred to a 300 ml eggplant flask and desolvated with a rotary evaporator. The precipitated salt was removed by filtration to obtain monomer 2.

Synthesis Example 3 (Monomer 3)
Into a 500 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade), 34.8 g of an ethylene oxide 1 mol adduct of methallyl alcohol (hereinafter also referred to as “MLA1”) and KOH. 8 g was charged and heated to 90 ° C. while stirring. Next, 55.8 g of 2-ethylhexyl glycidyl ether (hereinafter also referred to as “EHGE”) was added over 30 minutes, and then reacted for 5 hours. Here, 200.0 g of pure water was added and reacted for 1 hour, and then neutralized with sulfuric acid. After cooling to room temperature, this aqueous solution was transferred to a 500 ml separatory funnel and allowed to stand until the layers were separated, and the lower layer was removed. The remaining upper layer was transferred to a 300 ml eggplant flask and desolvated with a rotary evaporator. The precipitated salt was removed by filtration to obtain monomer 3.

Synthesis Example 4 (Monomer 4)
A glass separable flask having a capacity of 500 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 46.4 g of MLA1 and 2.0 g of KOH and heated to 90 ° C. while stirring. Next, 52.0 g of n-butyl glycidyl ether (hereinafter also referred to as “BGE”) was added over 30 minutes, and then reacted for 5 hours. 200.0 g of pure water was added thereto, and the mixture was reacted for 1 hour, and then neutralized with sulfuric acid. After cooling to room temperature, this aqueous solution was transferred to a 500 ml separatory funnel and allowed to stand until the layers were separated, and the lower layer was removed. The remaining upper layer was transferred to a 300 ml eggplant flask and desolvated with a rotary evaporator. Precipitated salt was removed by filtration to obtain monomer 4.

Synthesis Example 5 (Monomer 5)
Instead of New Coal 2305 (81.2 g), New Coal 2303 (manufactured by Nippon Emulsifier Co., Ltd .; ethylene oxide 3 mol adduct of C12-13 alcohol) was used in the same manner as in Synthesis Example 1, except that 63.6 g was used. Monomer 5 was obtained.

Synthesis Example 6 (Monomer 6)
Instead of New Coal 2305 (81.2 g), New Coal 1004 (manufactured by Nippon Emulsifier Co., Ltd .; ethylene oxide 4 mol adduct of 2-ethylhexyl alcohol) 61.2 g was used in the same manner as in Synthesis Example 1. Monomer 6 was obtained.

Example 1-1
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 73.0 g of pure water and 0.0127 g of Mole salt and polymerized by heating to 90 ° C. while stirring. The reaction system was used. Next, 237.5 g of an 80% aqueous acrylic acid solution (hereinafter also referred to as “80% AA”) and an aqueous 48% sodium hydroxide solution (hereinafter referred to as “48”) in a polymerization reaction system maintained at 90 ° C. with stirring. 11.0 g, Monomer 1 10.0 g, 15% sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”) 53.2 g, and 35% sodium bisulfite aqueous solution (hereinafter referred to as “% NaOH”). , Also referred to as “35% SBS”.) 30.4 g was dropped from each separate nozzle. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 120 minutes for monomer 1, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After the completion of the dropwise addition of 80% AA, the reaction solution was kept at 90 ° C. (ripening) for 30 minutes to complete the polymerization. After completion of the polymerization, 186.9 g of 48% NaOH was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization reaction liquid.
In this way, an aqueous solution of polymer 1-1 having a solid content concentration of 44.8% and a weight average molecular weight of 8500 (polymer composition 1 of the present invention) was obtained.

Examples 1-2 to 1-8, Comparative Examples 1-1 to 1-2
In Example 1-1, except that the charged composition, the polymerization temperature, the added raw material and its dropping time, the aging time and its temperature, and the materials used for the neutralization reaction were changed as shown in Table 1. In the same manner as in Example 1-1, polymer compositions 1-2 to 1-8 and comparative polymer compositions 1-1 to 1-2 were obtained. The solid content concentration and weight average molecular weight of these polymer compositions are shown in Table 1.

Example 2-1
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 60.0 g of pure water and 0.0115 g of Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize the reaction. It was a system. Next, 20% of 80% AA, 9.3 g of 48% NaOH, and 10 mol of isoprenol ethylene oxide adduct (hereinafter also referred to as “IPN10”) in a polymerization reaction system maintained at 90 ° C. with stirring. 30.0 g, Monomer 1 10.0 g, 15% NaPS 46.0 g, and 35% SBS 39.4 g were added dropwise from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 120 minutes for IPN10 and Monomer 1, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After the completion of the dropwise addition of 80% AA, the reaction solution was kept at 90 ° C. (ripening) for 30 minutes to complete the polymerization. After completion of the polymerization, 157.4 g of 48% NaOH was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization reaction liquid.
Thus, an aqueous solution of the polymer 2-1 having a solid content concentration of 47.8% and a weight average molecular weight of 9300 (polymer composition 2-1 of the present invention) was obtained.

Examples 2-2 to 2-8, Comparative Examples 2-1 to 2-2
In Example 2-1, except that the charged composition, the polymerization temperature, the added raw material and its dropping time, the aging time and its temperature, and the materials used for the neutralization reaction were changed as shown in Table 2. In the same manner as in Example 2-1, polymer compositions 2-2 to 2-8 and comparative polymer compositions 2-1 to 2-2 were obtained. Table 2 shows the solid content concentration and the weight average molecular weight of these polymer compositions.

Example 3-1.
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 55.0 g of pure water and 0.0122 g of Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize the reaction. It was a system. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 20% of 80% AA, 9.3 g of 48% NaOH, and 40% aqueous solution of sodium 3-allyloxy-2-hydroxypropanesulfonate (hereinafter referred to as the following) Also referred to as “40% HAPS”.) 75.0 g, Monomer 1 10.0 g, 15% NaPS 47.6 g, and 35% SBS 34.0 g were each dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 120 minutes for 40% HAPS and monomer 1, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After the completion of the dropwise addition of 80% AA, the reaction solution was kept at 90 ° C. (ripening) for 30 minutes to complete the polymerization. After completion of the polymerization, while stirring and allowing the polymerization reaction liquid to cool, 148.1 g of 48% NaOH was gradually added dropwise to neutralize the polymerization reaction liquid.
In this way, an aqueous solution (polymer composition 3-1) of polymer 3-1 having a solid content concentration of 44.9% and a weight average molecular weight of 12,000 was obtained.

Examples 3-2 to 3-8, Comparative examples 3-1 to 3-2
In Example 3-1, except that the preparation composition, the polymerization temperature, the added raw material and its dropping time, the aging time and its temperature, and the materials used for the neutralization reaction were changed as shown in Table 3. In the same manner as in Example 3-1, polymer compositions 3-2 to 3-8 and comparative polymer compositions 3-1 to 3-2 were obtained. Table 3 shows solid content concentrations and weight average molecular weights of these polymer compositions.

<Evaluation test of precipitation suppression ability>
About the polymer composition obtained by the Example and the comparative example, precipitation suppression ability was evaluated. The results are shown in Tables 4-6. In Tables 4 to 6, “the number of carbon atoms of the hydrophobic group” refers to the hydrophobic group of the ether bond-containing monomer (A) (represented by R ¹ in the above general formulas (1) and (2)). Group) means the number of carbon atoms. Moreover, the ratio of the structural unit was computed as a mass ratio (mass%) of the monomer with respect to 100 mass% of all monomer components.

As is clear from Tables 4 to 6, the hydrophobic group-containing copolymer of the present invention is a comparative polymer composition containing a comparative polymer that does not have an ether bond monomer (A) as a hydrophobic monomer. Compared to products, it has significantly superior precipitation control ability.

Claims (8)

The following general formula ( 1-1), (1-2), (1-3) and / or (2):

(In the formula, R ⁰ represents a hydrogen atom or a CH ₃ group. ^Ra represents ^a CH ₂ group, a CH ₂ CH ₂ group or a single bond. X ¹ represents (O—CH ₂ —CH ₂ ). This represents the average number of repeating units, and is a number from 0 to 5. However, when R ^a represents ^a single bond, X ¹ is a number from ¹ to 5. R ¹¹ is a number from 1 to 5 carbon atoms. 20 alkyl group, an alkenyl group or an aryl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms. ^{R 1} is a hydrophobic group, an organic group having 1 to 20 carbon atoms, or one R ¹ The organic group represented by represents an ether group-containing monomer (A) represented by an alkyl group, an aryl group or an alkenyl group) and a carboxyl group-containing monomer (B). The structural unit (a) is derived from 100% by mass of the structural units derived from all monomers. 1 to 50% by mass, and the structural unit (b) is 50 to 99% by mass. The hydrophobic group-containing copolymer further includes a structural unit (d) derived from the sulfonic acid group-containing monomer (D), and the structural unit (a The hydrophobic group-containing copolymer according to claim 1, wherein the structural unit (b) is 50 to 98% by mass and the structural unit (d) is 1 to 49% by mass. . The hydrophobic group-containing copolymer according to claim 2, wherein the sulfonic acid group-containing monomer (D) is 2-hydroxy-3-allyloxypropanesulfonic acid or a salt thereof. R ¹ Represents a C4-C18 organic group, The hydrophobic group containing copolymer in any one of Claims 1-3 characterized by the above-mentioned. A method for producing a hydrophobic group-containing copolymer comprising:
The production method comprises the following general formulas (1-1), (1-2), (1-3) and / or (2) in the presence of a polymerization initiator:

(In the formula, R ⁰ represents a hydrogen atom or a CH ₃ group. ^Ra represents ^a CH ₂ group, a CH ₂ CH ₂ group or a single bond. X ¹ represents (O—CH ₂ —CH ₂ ). This represents the average number of repeating units, and is a number from 0 to 5. However, when R ^a represents ^a single bond, X ¹ is a number from ¹ to 5. R ¹¹ is a number from 1 to 5 carbon atoms. 20 alkyl group, an alkenyl group or an aryl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms. ^{R 1} is a hydrophobic group, an organic group having 1 to 20 carbon atoms, or one R ¹ The organic group represented by represents an ether bond-containing monomer (A) represented by an alkyl group, an aryl group or an alkenyl group) and a monomer component containing a carboxyl group-containing monomer (B). The content of the ether bond-containing monomer (A) is 1 with respect to 100% by mass of all monomer components. A method for producing a hydrophobic group-containing copolymer, wherein the content of the carboxyl group-containing monomer (B) is 50 to 99% by mass and 50 to 99% by mass. The monomer component further includes a sulfonic acid group-containing monomer (D), and the content of the ether bond-containing monomer (A) is 1 to 49 mass% with respect to 100 mass% of all monomer components. %, The content of the carboxyl group-containing monomer (B) is 50 to 98 mass%, and the content of the sulfonic acid group-containing monomer (D) is 1 to 49 mass%. The manufacturing method of the hydrophobic group containing copolymer as described in 1 above. The method for producing a hydrophobic group-containing copolymer according to claim 6, wherein the sulfonic acid group-containing monomer (D) is 2-hydroxy-3-allyloxypropanesulfonic acid or a salt thereof. R ¹ Represents a C4-C18 organic group, The manufacturing method of the hydrophobic group containing copolymer in any one of Claims 5-7 characterized by the above-mentioned.