JP5270843B2 - (Meth) acrylic acid copolymer, process for producing the same, and detergent composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic or a methacrylic acid-based copolymer efficiently removing soil of clothes, etc., having an excellent re-deposition preventing ability and useful for a detergent composition. <P>SOLUTION: The (meth)acrylic acid copolymer comprises &ge;30 to &lt;95 mass% of a constituent unit (a) derived from an acrylic or a methacrylic acid-based monomer (A), &ge;5 to &lt;70 mass% of a constituent unit (b) derived from an unsaturated monomer (B), &gt;0 to &le;50 mass% of a constituent unit (c) derived from an alkyl acrylate or methacrylate-based monomer (C) and/or a constituent unit (d) derived from a vinyl aromatic monomer (D) as essential constituent units. The acrylic or methacrylic acid-based monomer (A) is represented by formula (1). The unsaturated monomer (B) is represented by formula (2). The alkyl acrylate or methacrylate-based monomer (C) is represented by formula (3). <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a (meth) acrylic acid copolymer, a method for producing the same, and a detergent composition using the same. In particular, the present invention relates to a (meth) acrylic acid copolymer excellent in the ability to remove dirt such as clothing, particularly hydrophobic dirt such as collar and oily dirt, and the ability to prevent re-contamination, a method for producing the same, and a method for producing the same. The present invention relates to a detergent composition to be used.

  2. Description of the Related Art Conventionally, detergents used in apparel are known in which a builder such as zeolite, carboxymethylcellulose, or polyethylene glycol is blended as a recontamination inhibitor. However, these builders are not expected to have a sufficient cleaning effect on, for example, both relatively hydrophilic cotton fibers and highly hydrophobic synthetic fibers such as polyester blended fabrics. It is not satisfactory as a detergent composition, such as insufficient re-contamination preventing ability to prevent clay from adhering during washing, and further performance improvement is desired. In addition to the above points, environmental issues have been emphasized in recent years, and efforts to reduce the amount of water used for washing are being actively carried out. However, when the amount of water during one wash is reduced, the concentration of dirt in the water is reduced. As a result, the problem of re-contamination, in which dirt in the water reappears on the laundry, becomes more prominent. Therefore, for example, unsaturated carboxylic acid (co) polymers such as acrylic acid, methacrylic acid, α-hydroxyacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and citraconic acid, and polyether compounds ( ) A hydrophilic polymer such as a graft polymer obtained by graft polymerization of an unsaturated carboxylic acid monomer such as acrylic acid is blended. However, although these polymers are effective in soiling hydrophilic particles such as clay, they are hardly effective in removing hydrophobic soils such as oils and fats, which are one of the main components of soils attached to clothing. The prevention effect is not enough.

On the other hand, it has been reported that a copolymer of a (meth) acrylic acid monomer and an unsaturated polyalkylene glycol monomer is used in a detergent builder or detergent composition (see, for example, Patent Document 1). ). In Patent Document 1, copolymerization is possible with unsaturated polyalkylene glycol monomer B and monomers A and B having a repeating unit of (meth) acrylic acid monomer A and polyalkylene oxide of 6 to 300. Is a polymer obtained by copolymerizing a monoethylenically unsaturated monomer C, having a sulfur oxygen acid at the terminal, and defined by S = (S amount contained in polymer) / (total S amount) × 100 A polymer composition having a sulfur element introduction amount S value of 3 or more is disclosed. However, although the copolymer composition described in Patent Document 1 is excellent in compatibility and dispersibility with a liquid detergent and has a good hue, it has the ability to remove hydrophobic stains such as collars and oil stains, The ability to prevent contamination was not sufficient.
JP 2004-75977 A

  As described above, despite the fact that various detergent compositions have been reported in the past, it is possible to efficiently remove stains such as clothing, especially hydrophobic stains such as collars and oil stains, and washing with a small amount of water. There is still a strong demand for a detergent that has excellent anti-recontamination ability that does not cause this soil to adhere to the laundry again. However, there is actually no detergent that sufficiently satisfies the performance of both.

  Therefore, the present invention has been made in view of the above circumstances, and can remove dirt such as clothing, especially hydrophobic dirt such as collars and oily and dirt, even if washing is performed with a small amount of water. An object of the present invention is to provide a (meth) acrylic acid-based copolymer that is useful as a detergent having excellent anti-recontamination ability that does not adhere to the laundry again.

  Another object of the present invention is to provide a method capable of efficiently producing such a (meth) acrylic acid copolymer.

  Another object of the present invention is to re-contaminate dirt such as clothing, especially hydrophobic dirt such as collars and oily and fat stains, and to prevent the dirt from adhering to the laundry again even after washing with a small amount of water. It is an object of the present invention to provide a detergent composition that is useful for a detergent having excellent preventive ability.

  As a result of intensive studies on various polymers / copolymers to achieve the above object, the present inventors have found that a structural unit derived from a (meth) acrylic acid monomer and an unsaturated polyalkylene glycol single monomer. In addition to the structural unit derived from the monomer, a copolymer further introduced with a specific proportion of a structural unit having a relatively hydrophobic property derived from an alkyl (meth) acrylate monomer or a vinyl aromatic monomer, Efficiently removes dirt from clothing, especially hydrophobic dirt such as collars and oils and fats. At the same time, even if washing is performed with a small amount of water, the dirt does not adhere to the laundry again, and it is excellent in preventing recontamination. It was learned that the performance was demonstrated. Based on the above findings, the present invention has been completed.

  That is, the above-mentioned purpose is the following formula (1) of 30% by mass or more and less than 95% by mass:

In the formula, R ¹ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group.
The structural unit (a) derived from the (meth) acrylic acid monomer (A) represented by the following formula (2) of 5% by mass or more and less than 70% by mass:

In the formula, R ² represents an alkenyl group having 2 to 5 carbon atoms; AO represents the same or different group derived from an alkylene oxide having 2 to 20 carbon atoms; R ³ represents a hydrogen atom or a carbon number Represents an alkyl group of 2 to 5; n is an integer of 1 to 200;
The structural unit (b) derived from the unsaturated monomer (B) represented by the following formula (3): more than 0% by mass and 50% by mass or less:

In the formula, R ⁴ represents a hydrogen atom or a methyl group, and Y represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a hydroxyalkyl group having 2 to 12 carbon atoms,
The structural unit (c) derived from the alkyl (meth) acrylate monomer (C) and / or the structural unit (d) derived from the vinyl aromatic monomer (D) (however, the structural unit ( a), (b), (c), and (d) is a total of 100% by mass), and is achieved by a (meth) acrylic acid copolymer.

  The (meth) acrylic acid-based copolymer of the present invention can efficiently remove dirt such as clothing, especially hydrophobic dirt such as collars and oily dirt, and can be washed again even if washing is performed with a small amount of water. Excellent anti-recontamination ability without attaching to objects.

  Hereinafter, the present invention will be described in detail.

  The first of the present invention is the following formula (1) of 30% by mass or more and less than 95% by mass:

In the formula, R ¹ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group.
The structural unit (a) derived from the (meth) acrylic acid monomer (A) represented by the following formula (2) of 5 mass% or more and less than 70 mass%

In the formula, R ² represents an alkenyl group having 2 to 5 carbon atoms; AO represents the same or different group derived from an alkylene oxide having 2 to 20 carbon atoms; R ³ represents a hydrogen atom or a carbon number Represents an alkyl group of 2 to 5; n is an integer of 1 to 200;
The structural unit (b) derived from the unsaturated monomer (B) represented by the following formula (3): more than 0% by mass and 50% by mass or less:

In the formula, R ⁴ represents a hydrogen atom or a methyl group, and Y represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a hydroxyalkyl group having 2 to 12 carbon atoms,
The structural unit (c) derived from the alkyl (meth) acrylate monomer (C) and / or the structural unit (d) derived from the vinyl aromatic monomer (D) (however, the structural unit ( a), (b), (c), and (d) total composition is 100% by mass), and a (meth) acrylic acid copolymer.

  The present invention relates to a (meth) acrylic acid-based copolymer comprising a relatively hydrophilic or hydrophilic structural unit (a) and (b), and a relatively hydrophobic or hydrophobic structural unit. It is characterized in that (c) and (d) are combined at a specific ratio. According to the present invention, the introduction of the structural units (a) and (b) exhibits an excellent detergency for fibers such as cotton fibers having a relatively high hydrophilicity, and relatively hydrophilic soils, particularly for clays. In addition to exhibiting excellent effects on dispersibility and anti-recontamination ability, it is sufficient for hydrophobic synthetic fibers by further introducing structural units (c) and / or (d) at a specific ratio. And the ability to prevent re-contamination can be significantly improved to prevent dirt, particularly hydrophobic dirt such as oil and fat dirt from adhering during washing. Therefore, the (meth) acrylic acid copolymer of the present invention can exhibit a sufficient cleaning effect and recontamination preventing ability against both hydrophilic and hydrophobic soils. The reason why the (meth) acrylic acid copolymer of the present invention can exhibit an excellent cleaning effect and anti-recontamination ability against hydrophobic soils is not clear, but is considered as follows. That is, since the polymer / copolymer composed of hydrophilic structural units such as the structural units (a) and (b) has a low interaction with hydrophobic soils as in the past, such as collars and oily soils, etc. However, when the structural unit (c) and / or (d) having a relatively hydrophobic property is introduced, the structural unit (c) and / or (d) itself is introduced. Since the interaction with hydrophobic soils can be increased and the dispersibility of these soils can be significantly increased, a sufficient cleaning effect and anti-recontamination ability can be exerted on hydrophobic soils. It is guessed that there is not.

  In the present invention, the structural unit (a) constituting the (meth) acrylic acid copolymer is represented by the following formula (1):

It is derived from the (meth) acrylic acid monomer (A) represented by In the present invention, the structural unit (a) may be present alone or in the form of a mixture of two or more. In the above formula (1), R ¹ represents a hydrogen atom or a methyl group. X represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group. In this case, as the metal atom, a monovalent metal atom of an alkali metal such as sodium, lithium, potassium, rubidium or cesium; a divalent metal atom of an alkaline earth metal such as magnesium, calcium, strontium or barium; aluminum, Preferable examples include trivalent metal atoms such as iron. Moreover, as an organic amine, residues derived from organic amines such as alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as monoethylamine, diethylamine and triethylamine; polyamines such as ethylenediamine and triethylenediamine are preferable. Can be mentioned. Of these, X is preferably a hydrogen atom, ammonium, sodium or potassium, more preferably a hydrogen atom or sodium.

  The (meth) acrylic acid monomer (A) forming such a structural unit (a) is represented by the above formula (1), and is not particularly limited. For example, acrylic acid, methacrylic acid, Crotonic acid and the like; these monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like are suitable. Among these, in the use of the detergent composition, it is preferable to use (meth) acrylic acid, its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt and the like from the viewpoint of improving the dispersion performance. In the present invention, the (meth) acrylic acid monomer (A) may be used alone or in the form of a mixture of two or more.

  It is essential that the structural unit (a) is 30% by mass or more and less than 95% by mass with respect to 100% by mass of the total composition of the structural units (a), (b), (c) and (d). . At this time, when the proportion of the structural unit (a) in the (meth) acrylic acid copolymer is less than 30% by mass, the effect obtained from the hydrophilic group of the (meth) acrylic acid monomer (A) Cannot be sufficiently exerted, and there is a problem that the cleaning ability with respect to dirt (for example, clay) which is hydrophilic or relatively hydrophilic is lowered. In addition, when the proportion of the structural unit (a) in the (meth) acrylic acid copolymer is 95% by mass or more, the other structural units (b), (c), and (d) are too few, and these There is a problem that the structural unit cannot exhibit a sufficient effect, and the cleaning ability against hydrophobic or relatively hydrophobic dirt (for example, oil dirt) is lowered. In addition to the above points, if the composition of the structural unit (a) exceeds the above range, the desired copolymer may not be produced efficiently. Considering the balance of the effects exerted by the structural units (a), (b), (c) and (d), the proportion of the structural unit (a) in the (meth) acrylic acid copolymer is preferably 35 to 90% by mass, more preferably 35 to 85% by mass, and most preferably 40 to 80% by mass with respect to 100% by mass of the total composition of the structural units (a), (b), (c) and (d). It is. In the present embodiment, the content of the repeating unit (a) is calculated as a value converted to the corresponding acid.

  In the present invention, the structural unit (b) constituting the (meth) acrylic acid copolymer is represented by the following formula (2):

It is derived from an unsaturated monomer (B) represented by In the present invention, the structural unit (b) may be present alone or in the form of a mixture of two or more. The structural unit (b) is in the (—CH ₂ —CH—) form in which the double bond of the alkenyl group having 2 to 5 carbon atoms represented by R ² is a single bond in the above formula (2).

In the above formula (2), R ² represents an alkenyl group having 2 to 5 carbon atoms. Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ² include CH ₂ ═CH—, CH ₂ ═CHCH ₂ —, CH ₂ ═CHCH ₂ CH ₂ —, and CH ₂ ═CHCH ₂ CH ₂ CH ₂ —. _{, CH (CH 3) = CH-} , CH (CH 3) = CHCH 2 -, CH (CH 3) = CHCH 2 CH 2 -, CH 2 = C (CH 3) -, CH 2 = C (CH 3) _{CH 2 -, CH 2 = C} (CH 3) CH 2 CH 2 -, CH (CH 3) = C (CH 3) -, CH (CH 3) = C (CH 3) CH 2 - and the like. Of _{these, CH 2 = C (CH 3} ) CH 2 CH 2 -, CH 2 = CHCH 2 -, CH 2 = C (CH 3) CH 2 -, CH 2 = CH- are preferred, _CH 2 = C ( CH ₃ ) CH ₂ CH ₂ —, CH ₂ ═CHCH ₂ —, and CH ₂ ═C (CH ₃ ) CH ₂ — are more preferred. In addition, when R ² is CH ₂ ═C (CH ₃ ) CH ₂ CH ₂ —, CH ₂ ═CHCH ₂ — or CH ₂ ═C (CH ₃ ) CH ₂ —, R ³ is a hydrogen atom. It is particularly preferred.

In the above formula (2), AO represents a group derived from an alkylene oxide having 2 to 20 carbon atoms, and preferably represents a group derived from an alkylene oxide having 2 to 18 carbon atoms. In this case, preferred examples of the alkylene oxide having 2 to 20 carbon atoms include styrene oxide, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, and 2-butene oxide. More preferred are ethylene oxide, propylene oxide, butylene oxide, even more preferred are ethylene oxide and propylene oxide, and most preferred is ethylene oxide. These oxyalkylene groups may be present alone or in the form of a mixture of two or more, and in the case of the form of a mixture of two or more, the bond of each oxyalkylene group There is no particular restriction on the order. N represents an average addition mole number of AO which is a group derived from the alkylene oxide having 2 to 20 carbon atoms, and is an integer of 1 to 200, preferably 2 to 150, more preferably 3 to 100. It is an integer. In this case, if n exceeds 200, no improvement in the effect commensurate with the addition of the group derived from alkylene oxide is observed, and the viscosity of the (meth) acrylic acid copolymer is remarkably increased, making it difficult to handle. There is sex. In the above formula (2), when n is 2 or more, the oxyalkylene groups (AO) present in one structural unit (b) may be the same or of different types. There may be. Further, in the above formula (2), R ³ represents a hydrogen atom or an alkyl group having 2 to 5 carbon atoms. At this time, as the alkyl group having 2 to 5 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, Examples thereof include linear, branched and cyclic alkyl groups such as neopentyl group and cyclopentyl group. Among these, R ³ is preferably a hydrogen atom, a methyl group, a group, an ethyl group, or a propyl group, and more preferably a hydrogen atom or a methyl group.

  Therefore, the unsaturated monomer (B) preferably used in the present invention includes 3-methyl-3-buten-1-ol (isoprenol), 3-methyl-2-buten-1-ol, 2-methyl 1 to 200 mol, preferably 2 to 150 mol, more preferably 2 to 1 to 200 mol of alkylene oxide with respect to 1 mol of unsaturated alcohol such as -3-buten-2-ol, allyl alcohol, and methallyl alcohol. The compound which added -120 mol, most preferably 3-100 mol can be mentioned. In this case, isoprenol and methallyl alcohol are preferable from the viewpoint of copolymerization with the monomers (A), (C), (D) and, if necessary, (E).

  It is essential that the structural unit (b) is 5% by mass or more and less than 70% by mass with respect to 100% by mass of the total composition of the structural units (a), (b), (c) and (d). . At this time, if the proportion of the structural unit (b) in the (meth) acrylic acid copolymer is less than 5% by mass, the effect obtained from the unsaturated monomer (B) cannot be sufficiently exhibited, and the hydrophilicity Or there exists a problem that the cleaning capability with respect to dirt (for example, clay) which is comparatively hydrophilic falls. Moreover, when the abundance ratio of the structural unit (b) in the (meth) acrylic acid copolymer is 70% by mass or more, the other structural units (a), (c) and (d) are too few, and these There is a problem that the structural unit cannot exhibit a sufficient effect, and the cleaning ability against hydrophobic or relatively hydrophobic dirt (for example, oil dirt) is lowered. In addition to the above points, if the composition of the structural unit (b) exceeds the above range, the desired copolymer may not be produced efficiently. Considering the balance of the effects exerted by the structural units (a), (b), (c) and (d), the proportion of the structural unit (b) in the (meth) acrylic acid copolymer is preferably 6 to 65% by mass, more preferably 8 to 60% by mass, and most preferably 10 to 55% by mass with respect to 100% by mass of the total composition of the structural units (a), (b), (c) and (d). It is.

  The (meth) acrylic acid copolymer of the present invention is characterized by having at least one of the structural units (c) and (d) in addition to the structural units (a) and (b). Thus, by introducing the relatively hydrophobic structural units (c) and (d) into the copolymer of the present invention, the (meth) acrylic acid copolymer interacts with the hydrophobic substance. In order to improve the dispersibility of such stains, it is possible to remove hydrophobic stains such as collars and oil stains efficiently and even under severe conditions such as washing with a small amount of water. It is possible to significantly improve the ability to prevent re-contamination without causing hydrophobic dirt to adhere to the laundry again.

  At this time, the structural unit (c) constituting the (meth) acrylic acid copolymer is represented by the following formula (3):

It is derived from an alkyl (meth) acrylate monomer represented by (C). In the present invention, the structural unit (c) may be present alone or in the form of a mixture of two or more. Further, the structural unit (c) is in the form (—CH ₂ —C (R ⁴ ) (COOY) —) in which the double bond of the vinyl group is a single bond in the above formula (3).

In the above formula (3), R ⁴ represents a hydrogen atom or a methyl group. Y represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a hydroxyalkyl group having 2 to 12 carbon atoms. In this case, the alkyl group having 1 to 12 carbon atoms is not particularly limited as long as it can exhibit a desired effect. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group , Sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 2-ethylhexyl group, etc. Or a branched group is mentioned. Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Further, the hydroxyalkyl group having 2 to 12 carbon atoms is not particularly limited as long as it can exert a desired effect. For example, the hydroxyalkyl group having 2 to 12 carbon atoms includes, for example, hydroxyethyl, hydroxypropyl , Hydroxyisopropyl, hydroxybutyl, hydroxyisobutyl, hydroxy sec-butyl, hydroxy t-butyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyneopentyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxyundecyl, hydroxydodecyl, etc. , A linear, branched or cyclic hydroxyalkyl group. Among these, Y is preferably an n-butyl group, a 2-ethylhexyl group, a dodecyl group, a hydroxypropyl group, a hydroxyisopropyl group, or a hydroxybutyl group, and an n-butyl group, a 2-ethylhexyl group, or a hydroxyisopropyl group. Is more preferable.

  Therefore, the alkyl (meth) acrylate monomer (C) preferably used in the present invention includes (meth) acrylic such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate and the like. Acid alkyl ester monomers; hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, alpha-hydroxymethylethyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, hydroxyhex Examples include (meth) acrylate hydroxyalkyl monomers such as (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate are preferable, and butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate are more preferable. As described above, in the present invention, the alkyl (meth) acrylate monomer (C) may be used alone or in the form of a mixture of two or more. Good.

Further, the structural unit (d) constituting the (meth) acrylic acid copolymer is derived from the vinyl aromatic monomer (D). In the present invention, the structural unit (d) may be present alone or in the form of a mixture of two or more. Further, the structural unit (d) is in a (—CH ₂ —CH ₂ —) form in which the double bond of the vinyl group is a single bond. The vinyl aromatic monomer (D) is not particularly limited, and vinyl aromatics having an aromatic hydrocarbon group such as styrene, α-methylstyrene, o-chlorostyrene, vinyltoluene, vinylnaphthalene, vinylanthracene and the like. And vinyl aromatic monomers having a heterocyclic aromatic hydrocarbon group such as vinyl pyridine and vinyl imidazole. In addition, the structural unit (d) derived from the vinyl aromatic monomer (D) is a vinyl having an aromatic hydrocarbon group in consideration of the interaction with the hydrophobic soil (and hence the dispersibility of the hydrophobic soil). It is preferably derived from an aromatic monomer, and more preferably satisfies any requirement of having a phenyl group or consisting of an aromatic group having only carbon atoms and hydrogen atoms. The vinyl aromatic monomer (D) is not particularly limited as long as it has a vinyl group and can exhibit a desired effect. For example, styrene, α-methylstyrene, vinyl toluene, vinyl Naphthalene, vinyl anthracene, etc. are mentioned. Among these, the vinyl aromatic monomer (D) is preferably styrene or vinyl toluene, and styrene is particularly preferable. As described above, in the present invention, the vinyl aromatic monomer (D) may be used alone or in the form of a mixture of two or more.

  In the present invention, the total of the structural units (c) and (d) exceeds 0% by mass with respect to 100% by mass of the total composition of the structural units (a), (b), (c) and (d). It is essential that the amount be 50% by mass or less. At this time, when the total proportion of the structural units (c) and (d) in the (meth) acrylic acid copolymer exceeds 50% by mass, the other structural units (a) and (c) are too few. These structural units cannot exhibit a sufficient effect (for example, there is a problem that the cleaning ability with respect to dirt (for example, clay) having hydrophilicity or relatively hydrophilicity is lowered. Structural units (a) and (b). , (C) and (d) in consideration of the balance of the effects exerted, the total proportion of the structural units (c) and (d) in the (meth) acrylic acid copolymer is preferably the structural unit ( It is 1-40 mass% with respect to 100 mass% of total composition of a), (b), (c), and (d), More preferably, it is 2-35 mass%, Most preferably, it is 3-30 mass%. In the present invention, the structural units (a), (b), The total proportion of c) and (d) is 100% by weight.

  Further, the (meth) acrylic acid copolymer of the present invention has a constitution derived from another monomer (E) in addition to the structural units (a), (b), (c) and (d). Unit (e) may be included. At this time, the proportion of the structural unit (e) present in the (meth) acrylic acid copolymer is not particularly limited, but the structural units (a), (b), (c) and the essential structural units are not limited. In consideration of not inhibiting the effect of (d), it exceeds 0% by mass and is 10% by mass or less with respect to 100% by mass of the total composition of the structural units (a), (b), (c) and (d). More preferably, the ratio is more than 0% by mass and 7% by mass or less, most preferably more than 0% by mass and 5% by mass or less. Within such a range, the effects of the structural units (a), (b), (c) and (d) which are essential structural units, that is, hydrophilicity or comparison by the structural units (a) and (b). Ability to clean dirt (eg clay) that is hydrophilic and hydrophilic, high removal ability of hydrophobic dirt such as oil and fat dirt by the structural units (c) and (d), and severe conditions such as washing with a small amount of water In addition to being able to maintain an excellent ability to prevent re-contamination at the same time, effects due to the structural unit (e) such as chelating ability and viscosity adjusting ability are further imparted. When the proportion of the structural unit (e) exceeds 10% by mass, gelation or cross-linking reaction occurs in the preparation of the copolymer, the water solubility of the copolymer is lowered, the color tone is deteriorated, and a bad odor is emitted. There is a fear.

  As the other monomer (E) when the (meth) acrylic acid copolymer of the present invention contains another monomer (E), copolymerization with the above monomers (A) to (D) is carried out. It is not particularly limited as long as it is possible, and is appropriately selected depending on a desired effect. Specifically, sulfonic acid monomers such as vinyl sulfonic acid and styrene sulfonic acid and salts thereof; N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methyl formamide, N -N-vinyl monomers such as vinyl-N-methylacetamide and N-vinyloxazolidone; Amide monomers such as (meth) acrylamide, N, N-dimethylacrylamide and N-isopropylacrylamide; 3- (meth) Compounds obtained by adding 1 to 200 mol of ethylene oxide to allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane (3-allyloxy-1,2) -Di (poly) oxyethylene ether propane, etc.), (meth) a Allyl ether monomers such as alcohols; Isoprene monomers such as isoprenol; α-hydroxymethylacrylic acid and its derivatives; Unsaturated dicarboxylic acids such as itaconic acid, fumaric acid and maleic acid, and salts thereof Is mentioned. In this case, the unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two carboxyl groups in the molecule, such as maleic acid, itaconic acid, citraconic acid, and fumaric acid. In addition, a monovalent metal salt, a divalent metal salt, an ammonium salt, an organic ammonium salt (organic amine salt), or the like thereof, or an anhydride thereof is preferable. Alternatively, the (meth) acrylic acid monomer (A) is a half ester of an unsaturated dicarboxylic acid monomer and an alcohol having 1 to 22 carbon atoms, an unsaturated dicarboxylic acid and an amine having 1 to 22 carbon atoms. And a half amide of an unsaturated dicarboxylic acid 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, and the like. Moreover, the said other monomer (E) may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.

  In the (meth) acrylic acid copolymer of the present invention, the structural units (a), (b), (c) and (d) and, if necessary, the structural unit (e) are specified as described above. It is sufficient that each structural unit is introduced in a block form or a random form. Further, the weight average molecular weight of the (meth) acrylic acid copolymer of the present invention can be set as appropriate, and is not particularly limited. Specifically, the weight average molecular weight of the (meth) acrylic acid copolymer is preferably 2,000 to 100,000, more preferably 3,000 to 80,000, and most preferably 4,000. ~ 60,000. If it is less than 2,000, the dispersibility with respect to dirt is lowered, and the recontamination preventing ability may be lowered. On the contrary, when it exceeds 100,000, there is a possibility that adhesion of dirt to the cloth may be promoted. In addition, in this specification, a weight average molecular weight is a measured value by GPC (gel permeation chromatography), and the specific measuring method is computed according to the method described in an Example.

  As described above, the (meth) acrylic acid-based copolymer of the present invention has a cleaning ability for hydrophilic or relatively hydrophilic dirt (for example, clay), and hydrophobic dirt such as glue or oily dirt. It is particularly suitable for detergent compositions because of its excellent removability and anti-recontamination ability under severe conditions such as washing with a small amount of water.

  Such a (meth) acrylic acid copolymer exhibits excellent recontamination prevention ability particularly when used in a detergent composition because the structural units (c) and (d) are introduced. To do. Specifically, when the (meth) acrylic acid copolymer is used in a detergent composition, the recontamination prevention rate is 65.0% or more, more preferably 65.3% or more, and still more preferably. It is 65.6% or more, and most preferably 65.9% or more. In the present specification, the “recontamination prevention rate” means a value measured according to the method described in Examples.

  The production method of the (meth) acrylic acid copolymer of the present invention is not particularly limited, and a known polymerization method can be used in the same manner or modified. For example, the method for producing the (meth) acrylic acid copolymer of the present invention includes (meth) acrylic acid monomer (A), unsaturated monomer (B), and alkyl (meth) acrylate. It can manufacture by copolymerizing the monomer component which contains a system monomer (C) and / or a vinyl aromatic monomer (D) as an essential component. Moreover, when copolymerizing a monomer component, you may further copolymerize said other monomer (E) as needed.

  In such a production method, the monomer component may be copolymerized using a polymerization initiator. In addition, the kind and usage-amount of the monomer contained in a monomer component are suitably set so that the structural unit which comprises a (meth) acrylic-acid type copolymer may become as mentioned above. That is, the composition ratio of each monomer forming the (meth) acrylic acid copolymer is such that the (meth) acrylic acid monomer (A) is 30% by mass or more and 95% by mass with respect to the total monomers. Less than mass%, unsaturated monomer (B) is 5 mass% or more and less than 70 mass%, and (meth) alkyl acrylate monomer (C) and / or vinyl aromatic monomer (D) It is more than 0 mass% and 50 mass% or less. As described above, when the total of the monomers (A) to (D) is 100% by mass, the other monomer (E) that can be copolymerized with these is 0 to 10% by mass. May be used in quantities. More preferably, the (meth) acrylic acid monomer (A) is 35 to 85% by mass, the unsaturated monomer (B) is 8 to 60% by mass, and the (meth) acrylic acid alkyl monomer ( C) and / or vinyl aromatic monomer (D) is 2 to 35% by mass, and more preferably, (meth) acrylic acid monomer (A) is 40 to 80% by mass, unsaturated monomer. The monomer (B) is 10 to 55% by mass, and the alkyl (meth) acrylate monomer (C) and / or the vinyl aromatic monomer (D) is 3 to 30% by mass. The total amount of the monomers (A), (B), (C) and (D) is 100% by mass. In addition, when the other monomer (E) is further present, the mixing amount of the other monomer (E) is as follows: (meth) acrylic acid monomer (A), unsaturated monomer (B) ), When the total of the alkyl (meth) acrylate monomer (C) and the vinyl aromatic monomer (D) is 100% by mass, preferably 10% by mass or less, more preferably 7% by mass. Hereinafter, it is most preferably 5% by mass or less.

  In the present invention, the copolymerization of the monomers (A) to (D) and, if necessary, other monomers (E) uses water in 50% by mass or more of the solvent used and / or a chain. It is preferably carried out in the presence of a transfer agent, more preferably 50% by mass or more of the solvent used and water in the presence of a chain transfer agent. At this time, by using water in 50% by mass or more of the solvent to be used, the amount of the organic solvent used for the polymerization can be suppressed, so that there is an advantage that the organic solvent can be easily distilled off after the completion of the polymerization. In addition, when a chain transfer agent is used, the (meth) acrylic acid copolymer produced is prevented from becoming too high in molecular weight, and a low molecular weight (meth) acrylic acid copolymer is efficiently produced. There is an advantage that you can. In particular, when sulfurous acid or sulfite is used as a chain transfer agent, the sulfonic acid group can be introduced quantitatively at the terminal of the resulting (meth) acrylic acid copolymer, and the gel resistance is improved. Can be improved.

  Therefore, the second of the present invention is a (meth) acrylic acid monomer (A) of the formula (1) of 10% by mass or more and less than 95% by mass of the formula (2) of 5% by mass or more and less than 90% by mass. Unsaturated monomer (B), an alkyl (meth) acrylate monomer (C) of formula (3) and / or a vinyl aromatic monomer (D) of more than 0% by mass and not more than 50% by mass ) (However, the total ratio of the monomers (A), (B), (C) and (D) is 100% by mass), water is used in 50% by mass or more of the solvent used, and chain transfer is performed. The present invention relates to a method for producing a (meth) acrylic acid copolymer, which includes a step of performing a polymerization reaction using an agent.

  The solvent used in the above embodiment is not particularly limited as long as it contains water in a proportion of 50% by mass with respect to the total amount of the solvent used. From the viewpoint of improving the solubility of the monomer used for polymerization in a solvent, an organic solvent may be added as necessary. Even in this case, the content of water in the total mixed solvent is 50% by mass or more. Examples of organic solvents that can be used include lower alcohols such as methanol, ethanol, and isopropyl alcohol; lower ketones such as acetone, methyl ethyl ketone, and diethyl ketone; ethers such as dimethyl ether and dioxane; and amides such as dimethylformaldehyde. . These solvents may be used alone or in the form of a mixture of two or more. In the present invention, the amount of water is preferably 80% by mass or more, and most preferably water alone (ie, 100% by mass) with respect to the total amount of solvent used.

  In the second method of the present invention, it is essential to carry out the copolymerization in the presence of a chain transfer agent. The chain transfer agent that can be used in this case 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, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n -Thiol chain transfer agents such as dodecyl mercaptan, octyl mercaptan, butylthioglycolate; Halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; Secondary alcohols such as isopropanol, glycerin; Acids, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and salts thereof (sodium hydrogen sulfite, hydrogen bisulfite) Potassium, sodium dithionite Um, potassium dithionite, sodium metabisulfite, metabisulfite potassium, etc.) and the like, and the like lower oxides and salts thereof. The chain transfer agent may be used alone or in the form of a mixture of two or more. Among these, in the copolymerization reaction according to the present invention, it is preferable to use sulfite or sulfite. Thereby, it becomes possible to introduce a sulfonic acid group quantitatively to the end of the main chain of the (meth) acrylic acid copolymer to be obtained, and to improve the gel resistance. 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, it is possible to reduce the increase in the production cost of the copolymer, improve the production efficiency, and sufficiently reduce the impurities. 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.

  In the above production method, as described above, sulfurous acid and / or sulfite (hereinafter simply referred to as “sulfurous acid (salt)”) is preferably included as a chain transfer agent. Moreover, in the said manufacturing method, in addition to a sulfurous acid (salt), an initiator is used. Furthermore, heavy metal ions may be used in combination as a reaction accelerator.

  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. The above sulfurous acid (salt) may be used alone or in the form of a mixture of two or more.

  In the method of the present invention, the addition amount of the chain transfer agent is such that the monomers (A), (B), (C) and (D) and, if necessary, other monomers (E) are polymerized well. The amount of the monomer component is not limited, but preferably all monomer components consisting of the monomers (A), (B), (C) and (D), and, if necessary, other monomers (E) It is 1-20g with respect to 1 mol, More preferably, it is 2-15g. If the molecular weight is less than 1 g, the molecular weight may not be controlled. On the other hand, if it exceeds 20 g, a large amount of impurities may be generated and the pure polymer content may be reduced. Especially when sulfite is used. Excess sulfite may be decomposed in the reaction system, and sulfurous acid gas may be generated. Moreover, there is a risk that it may be economically disadvantageous.

  As the initiator, known ones can be used, for example, hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; 2,2′-azobis (2-amidinopropane) Azo compounds such as hydrochloride, 4,4′-azobis-4-cyanoparerenic acid, azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide Organic peroxides such as lauroyl peroxide, peracetic acid, di-t-butyl peroxide and cumene hydroperoxide are preferred. Of these polymerization initiators, hydrogen peroxide and persulfate are preferable, and persulfate is most preferable. These polymerization initiators may be used alone or in the form of a mixture of two or more.

  The initiator is used in an amount that can initiate copolymerization of the monomers (A), (B), (C), and (D), and, if necessary, other monomers (E). Although not limited, 10 g per 1 mol of all monomer components consisting of monomers (A), (B), (C) and (D), and other monomer (E) if necessary. Hereinafter, it is more preferably 1 to 5 g.

The heavy metal ion used as a reaction accelerator in the present invention means a metal having a specific gravity of 4 g / cm ³ or more. As said metal ion, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc. are preferable, for example. These heavy metals can be used alone or in combination of two or more. Among these, iron is more 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 interfere with the polymerization reaction in the production of the (meth) acrylic acid copolymer of the present invention, and Any material that dissolves heavy metal compounds can be used.

  In the polymerization step in the present invention, the amount of heavy metal ions in the case of using the above heavy metal ions, it is preferable that a catalyst amount is included. The amount of catalyst referred to in the present specification means that the catalyst acts as a catalyst rather than being incorporated into the final target product. Specifically, it is 100 ppm or less, preferably 10 ppm or less, more preferably 5 ppm. It is as follows.

  The content of the heavy metal ions is 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 the content of heavy metal ions is less than 0.1 ppm, the effect of heavy metal ions may not be sufficiently exhibited. On the other hand, if the content of heavy metal ions exceeds 10 ppm, the color tone of the resulting polymer may be deteriorated. Moreover, when there is much content of heavy metal ion, when using the polymer which is a product as a detergent builder, there exists a possibility of causing the stain | pollution | contamination of a builder for detergents.

  The time when the polymerization reaction is completed means the 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.

  As a combination of the 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. More preferably, with respect to 1 part by mass of persulfate, the lower limit of sulfite is 1 part by mass, and most preferably 2 parts by mass. Further, the upper limit of the sulfite is more preferably 4 parts by mass, and most preferably 3 parts by mass with respect to 1 part by mass of the persulfate. Here, if the amount of sulfite is less than 0.5 parts by mass, the total amount of the initiator may increase when the molecular weight is lowered. Conversely, if the amount exceeds 5 parts by mass, side reactions increase, resulting in impurities. May increase.

The combination of the chain transfer agent, the initiator, and the reaction accelerator is not particularly limited, and can be appropriately selected from the above examples. For example, a combination of a chain transfer agent, an initiator, and a reaction accelerator includes sodium bisulfite (SBS) / hydrogen peroxide (H ₂ O ₂ ), sodium bisulfite (SBS) / sodium persulfate (NaPS), and bisulfite. Sodium (SBS) / Fe, Sodium bisulfite (SBS) / Hydrogen peroxide (H ₂ O ₂ ) / Fe, Sodium bisulfite (SBS) / Sodium persulfate (NaPS) / Fe, Sodium bisulfite (SBS) / Over Forms such as sodium sulfate (NaPS) / hydrogen peroxide (H ₂ O ₂ ) and sodium bisulfite (SBS) / oxygen / Fe are preferred. 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.

  The total amount of the chain transfer agent, initiator, and reaction accelerator used is the monomer (A), (B), (C) and (D), and other monomer (E) if necessary. It is preferable that it is 2-20g with respect to 1 mol of all the monomer components which consist of. By setting it as such a range, the (meth) acrylic acid-type copolymer of this invention can be produced efficiently, and the molecular weight distribution of a (meth) acrylic-acid-type copolymer is made into a desired thing. be able to. More preferably, it is 4-18g, More preferably, it is 6-15g.

  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. In addition, a chain transfer agent may be introduced alone into the reaction vessel, and is previously confused with each monomer (A) to (D), other monomer (E), solvent, etc. constituting the monomer component. You may keep it.

  In the above copolymerization method, monomer components, polymerization initiators, etc. can be added to the reaction vessel by charging all of the monomer components into the reaction vessel and adding the polymerization initiator into the reaction vessel. Method of performing polymerization: charging a part of the monomer component into the reaction vessel, and adding the polymerization initiator and the remaining monomer component continuously or stepwise (preferably continuously) into the reaction vessel. A method in which a polymerization solvent is charged into a reaction vessel and a total amount of monomer components and a polymerization initiator is added; one of monomers (A) to (D) (for example, a monomer) A part of (B)) is charged into the reaction vessel, the polymerization initiator and the remaining monomer components (the remainder of monomer (B) and monomers (A), (C) and (D), and necessary) If so, add all of the monomer (E) into the reaction vessel (preferably continuously). Therefore a method for performing a copolymerization is preferable. 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.

  The copolymerization method can be carried out by commonly used methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization, and is not particularly limited, but solution polymerization is preferred. As described above, the solvent that can be used in this case is preferably a mixed solvent in which 50% by mass of water or water is based on the total solvent. When only water is used, it is preferable in that the solvent removal step can be omitted.

  The copolymerization method can be carried out either batchwise or continuously. In addition, a known solvent can be used as needed during copolymerization, and water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol; glycerin; polyethylene glycol; benzene, toluene, xylene Aromatic or aliphatic hydrocarbons such as cyclohexane and n-heptane; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Amides such as dimethylformaldehyde; Ethers such as diethyl ether and dioxane It is. 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 usage-amount of the said solvent, 40-200 mass% is preferable with respect to 100 mass% of monomer components. More preferably, it is 45 mass% or more, More preferably, it is 50 mass% or more. Moreover, More preferably, it is 180 mass% or less, More preferably, it is 150 mass% or less. If the amount of the solvent used is less than 40% by mass, the resulting copolymer may have a high molecular weight. If it exceeds 200% by mass, the concentration of the obtained copolymer will be low, and solvent removal is required. There is a risk. 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.

  In the above copolymerization method, the copolymerization conditions such as the copolymerization temperature are appropriately determined depending on the copolymerization method used, the solvent, and the polymerization initiator, but the copolymerization 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 sulfurous acid (salt) is used, the copolymerization temperature is usually 60 ° C to 95 ° C, preferably 70 ° C to 95 ° C, and 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. Conversely, when it exceeds 95 ° C., toxic sulfurous acid gas may be released.

  The copolymerization 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 at 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 copolymerization 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 copolymerization method 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.

  The pH during the polymerization in the copolymerization is preferably acidic. In particular, when persulfate and bisulfite are used in combination as the 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 the final solid content concentration can be high concentration polymerization of 40% or more, and the residual contained A monomer having a total monomer concentration of 15000 ppm or less can be obtained. Furthermore, the polymerizability of the unsaturated polyalkylene glycol monomer 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 copolymer obtained by the above copolymerization method can be used as it is as a main component of a detergent composition (detergent builder) or the like, but may be further neutralized with an alkaline substance if necessary. 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.

  The neutralization rate at the time of copolymerization can be appropriately changed depending on the initiator. For example, when persulfate and bisulfite are used in combination, if the monomer is capable of forming a salt, the neutralization rate of the monomer is set to 0 to 60 mol%. It is preferable to carry out copolymerization. The neutralization rate of the monomer is represented by mol% of the monomer forming the salt when the total number of moles of the monomer is 100 mol%. If the neutralization rate of the monomer 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 40 mol% or less, particularly preferably 30 mol% or less, more particularly preferably 20 mol% or less, and most preferably 10 mol%. It is as follows.

  Examples of a method for carrying out the copolymerization with the neutralization rate of the monomer being 0 to 60 mol% include, for example, when the monomer is an unsaturated carboxylic acid monomer, all of which are unsaturated acid carboxylic acid When neutralizing monomeric unsaturated carboxylic acid monomers into salt forms such as sodium salts and ammonium salts using alkaline substances A method in which a neutralization rate of 0 to 60 mol% is added to the copolymer is suitable.

  The (meth) acrylic acid copolymer is preferably used in a detergent composition (cleaning builder), a water treatment agent, a fiber treatment agent, or a dispersant. As a detergent application, the (meth) acrylic acid copolymer can be used in various applications such as clothing, tableware, dwelling, hair, body, toothpaste, and automobile. As described above, a detergent composition (cleaning builder), a water treatment agent, or a fiber comprising the (meth) acrylic acid copolymer having the unsaturated polyalkylene glycol monomer unit as an essential component. Treatment agents and dispersants are also one of the preferred embodiments of the present invention. Accordingly, the third aspect of the present invention relates to a detergent composition containing the (meth) acrylic acid copolymer of the present invention.

  The detergent composition of the present invention may contain a builder for powder detergents or a builder for liquid detergents, in order to prevent dirt from re-adhering to the clothes being washed, etc. It exerts the action of. When the (meth) acrylic acid copolymer prevents the reattachment of dirt, it has a high affinity for hydrophobic dirt due to the presence of hydrophobic groups derived from the structural units (c) / (d). It exhibits the effect of reducing the affinity between the cloth and the dirt, and the action of dispersing the dirt is exhibited due to the presence of the hydrophilic group derived from the structural units (a) and (b). . In addition, the interaction with dirt also changes depending on ionic properties such as anionic property and cationic property.

  The detergent composition of the present invention has excellent anti-recontamination ability, and also has a very high quality agent performance and excellent stability that is less likely to cause performance degradation when stored for a long period of time and precipitation of impurities when held at low temperatures. Can be a builder. When the (meth) acrylic acid copolymer of the present invention is used as a detergent composition, the recontamination prevention rate is 65.0% or more, more preferably 65.3% or more, and further preferably 65.6% or more, Most preferably, it is 65.9% or more.

  As a content rate of the (meth) acrylic-acid type copolymer in the detergent composition of this invention, it is preferable that it is 0.1-30 mass% with respect to 100 mass% of detergent compositions, for example. More preferably, it is 1-20 mass%, and it is further more preferable that it is 0.1-10 mass%. If it is less than 0.1% by mass, the cleaning power when used as a cleaning composition may be insufficient, and if it exceeds 30% by mass, it may be uneconomical.

  As other composition components and blending ratios other than the (meth) acrylic acid copolymer in the detergent composition of the present invention, based on various components that can be used in conventionally known detergent builders and blending ratios thereof, It can use suitably in the range which does not impair the effect of invention.

  The (meth) acrylic acid copolymer is also capable of exhibiting performance such as dispersibility in various applications. For example, a water treatment agent, a dispersant, a fiber treatment agent, a scale inhibitor ( Scale inhibitor), cement additive, metal ion sealing agent, thickener, various binders, emulsifiers, skin care agents, hair care agents, and other uses can also be suitably used.

  The said water treatment agent is added to water systems, such as a cooling water system and a boiler water system, for example. In this case, the (meth) acrylic acid copolymer may be added as it is, or one containing other components other than the (meth) acrylic acid copolymer may be added. As other composition components and blending ratios other than the (meth) acrylic acid-based copolymer in the water treatment agent, various components that can be used in conventionally known water treatment agents and the blending ratios of the present invention are used. It can be used as appropriate as long as the effects are not impaired.

  The dispersant may be an aqueous dispersant, and for example, a pigment dispersant, a cement dispersant, a calcium carbonate dispersant, a kaolin dispersant, and the like are suitable. Such a dispersant can express extremely excellent dispersibility inherently possessed by the (meth) acrylic acid copolymer. In addition, it is possible to obtain a very high quality, high performance, and excellent stability agent that does not cause performance degradation or precipitation of impurities when kept at a low temperature even when stored for a long period of time. As other composition components and blending ratios other than the (meth) acrylic acid copolymer in the dispersant, various effects that can be used in conventionally known dispersants, and the effects of the present invention are based on the blending ratio. Can be used as long as the above is not impaired.

  The detergent composition of the (meth) acrylic acid copolymer of the present invention may be a powder detergent composition or a liquid detergent composition. In the cleaning composition, additives that are usually used in detergents can be used. Examples of the additives include alkali builder, chelate builder, anti-redeposition agent for preventing redeposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color Anti-transfer agent, softener, alkaline substance for pH adjustment, fragrance, solubilizer, fluorescent agent, colorant, foaming agent, foam stabilizer, glossing agent, bactericidal agent, bleaching agent, bleaching aid, enzyme, Dyes, solvents and the like are preferred. In the case of a powder detergent composition, it is preferable to blend zeolite.

  In addition, the composition according to the present invention may consist only of the (meth) acrylic acid copolymer of the present invention, or may be used by mixing with other known detergent builders. In addition, the form neutralized with the alkaline substance may be used as necessary. Examples of other detergent builders include, but are not limited to, for example, sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, pour glass, sodium carbonate, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate and potassium, zeolite, and polysaccharides. Examples thereof include water-soluble polymers such as carboxyl derivatives, (meth) acrylic acid (co) polymer salts, and fumaric acid (co) polymer salts.

  The blending ratio of the additive / known detergent builder is usually preferably 0.1 to 80% by mass with respect to 100% by mass of the cleaning composition. More preferably, they are 0.2 mass% or more and 70 mass% or less, More preferably, they are 0.3 mass% or more and 60 mass% or less, Especially preferably, they are 0.4 mass% or more, 50 mass%. And most preferably 0.5% by mass or more and 40% by mass or less. If the blending ratio of the detergent builder is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 80% by mass, the economy may be lowered.

  The blending form of the (meth) acrylic acid-based copolymer in the cleaning composition may be either liquid or solid, and is in the form at the time of sale of the detergent (for example, liquid or solid). Can be determined accordingly. You may mix | blend with the form of the aqueous solution after superposition | polymerization, you may mix | blend in the state which reduced the water | moisture content of the aqueous solution to some extent, and may mix | blend in the state solidified dry.

  The above detergent composition is used only for specific applications such as household detergent synthetic detergents, textile industry and other industrial detergents, hard surface detergents, and bleach detergents that enhance the function of one of its components. Also included is a detergent.

  The surfactant is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and these surfactants include one or more. Can be used. When using 2 or more types, the combined use amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more with respect to 100% by mass of the total surfactant. More preferably, 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 thereof, alkane sulfone. Acid salt, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate Esters or their salts are preferred.

  The alkyl group or alkenyl group in the anionic surfactant may have a branched alkyl group such as a methyl group.

  Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin. Monoesters, alkylamine oxides and the like are preferred. The alkyl group or alkenyl group in the nonionic surfactant may have a branched alkyl group such as a methyl group.

  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 the cationic surfactant and amphoteric surfactant may be branched from an alkyl group such as a methyl group.

  In general, the blending ratio of the surfactant is preferably 10 to 60% by mass with respect to 100% by mass of the cleaning composition. More preferably, they are 15 mass% or more and 50 mass% or less, More preferably, they are 20 mass% or more and 45 mass% or less, Especially preferably, they are 25 mass% or more and 40 mass% or less. If the blending ratio of the surfactant is less than 10% by mass, sufficient detergency may not be exhibited, and if it exceeds 60% by mass, the economy may be lowered.

  When the said detergent composition is a liquid detergent composition, 0.1-75 mass% is preferable normally with respect to 100 mass% of liquid detergent compositions. More preferably, it is 0.2 mass% or more and 70 mass% or less, More preferably, it is 0.5 mass% or more and 65 mass% or less, Especially preferably, it is 0.7 mass% or more, 60 mass% Or less, more preferably 1% by mass or more and 55% by mass or less, and most preferably 1.5% by mass or more and 50% by mass or less.

  The liquid 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.

  Further, the change (difference) in kaolin turbidity when the (meth) acrylic acid copolymer of the present invention is added to the liquid detergent composition as a detergent builder is preferably 500 mg / L or less. More preferably, it is 400 mg / L or less, More preferably, it is 300 mg / L or less, Especially preferably, it is 200 mg / L or less, Most preferably, it is 100 mg / L or less. The kaolin turbidity can be measured, for example, by a method for measuring kaolin turbidity described later.

<Measurement method of kaolin turbidity>
A uniformly stirred sample (liquid detergent) was placed in a 10 mm thick 50 mm square cell to remove bubbles, and then Tubidity (at 25 ° C.) using NDH2000 (trade name, turbidimeter) manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.

  Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning composition. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.

  The amount of the enzyme added 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.

  As the alkali builder, silicate, carbonate, sulfate and the like are preferable. As the chelate builder, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), citric acid and the like are preferable. Other water-soluble polycarboxylic acid-based polymers other than the copolymer in the present invention may be used.

  The above detergent composition should be a detergent with excellent dispersibility, extremely high quality agent performance and excellent stability that is less likely to cause performance degradation when stored for a long time and precipitation of impurities when held at low temperatures. Can do.

  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 mass” and “%” means “% by mass”.

  Moreover, the weight average molecular weight and recontamination preventing ability of the (meth) acrylic acid copolymer of the present invention were measured according to the following methods.

<Measurement conditions of weight average molecular weight>
Device: 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)

<Measurement method of recontamination prevention rate>
(1) A polyester cloth obtained from Test fabric was cut into 5 cm × 5 cm to prepare a white cloth. The whiteness of the white cloth was measured by reflectance using a colorimetric color difference meter SE2000 type manufactured by Nippon Denshoku Industries Co., Ltd. in advance.

  (2) Hard water was prepared by adding pure water to 4.41 g of calcium chloride dihydrate to 15 kg.

  (3) Pure water was added to 4.0 g of sodium linear alkylbenzene sulfonate, 6.0 g of sodium carbonate, and 2.0 g of sodium sulfate to make 100.0 g to prepare an aqueous surfactant solution.

  (4) A targot meter is set at 25 ° C., 1 L of hard water, 5 g of a surfactant aqueous solution, 1 g of a 2% polymer aqueous solution in terms of solid content, 0.15 g of zeolite, and 0.25 g of carbon black are put in a pot, and 100 rpm For 1 minute. Then, 10 white cloths were put and stirred at 100 rpm for 10 minutes.

  (5) The white cloth was drained by hand, 1 L of tap water adjusted to 25 ° C. was placed in the pot, and stirred at 100 rpm for 2 minutes. This was done twice.

  (6) A white cloth was applied and dried while stretching the wrinkle with an iron, and then the whiteness of the white cloth was measured again with the above colorimetric colorimeter with reflectance.

  (7) The recontamination prevention rate was calculated from the above measurement results using the following formula.

Example 1-1
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 334.0 g of pure water and 0.0107 g of Mohr's salt, and the temperature was raised to 90 ° C. while stirring. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 437.5 g of an 80% aqueous acrylic acid solution (hereinafter abbreviated as 80% AA) and an aqueous 48% sodium hydroxide solution (hereinafter referred to as 48% NaOH). 20.3 g, 100% isoprenol ethylene oxide 10 mol adduct (hereinafter abbreviated as 100% IPN10) 100.0 g, 100% styrene (hereinafter abbreviated as 100% St) 50.0 g, 15% excess 110.6 g of an aqueous sodium sulfate solution (hereinafter abbreviated as 15% NaPS) and 94.8 g of a 35% aqueous sodium hydrogensulfite solution (hereinafter abbreviated as 35% SBS) were dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 170 minutes for 100% IPN10 and 100% St, 185 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, 48% NaOH; 372.6 g was gradually added dropwise to neutralize the polymerization reaction liquid. Thus, an aqueous solution of polymer 1 having a solid content concentration of 45% and a weight average molecular weight of 14,000 was obtained. The composition of the structural units (a), (b) and (d) in the polymer 1 thus obtained was 70% by mass, 20% by mass and 10% by mass, respectively.

Example 1-2
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 337.0 g of pure water and 0.0107 g of Mohr's salt, and the temperature was raised to 90 ° C. while stirring. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 437.5 g, 48% NaOH; 20.3 g, 100% IPN10; 125.0 g, 100% St; 25.0 g, 15% NaPS; 106.8 g and 35% SBS; 91.5 g were added dropwise from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 170 minutes for 100% IPN10 and 100% St, 185 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, 48% NaOH; 372.6 g was gradually added dropwise to neutralize the polymerization reaction liquid. Thus, an aqueous solution of polymer 2 having a solid content concentration of 45% and a weight average molecular weight of 11,000 was obtained. The composition of the structural units (a), (b) and (d) in the polymer 2 thus obtained was 70% by mass, 25% by mass and 5% by mass, respectively.

Example 1-3
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 415.0 g of pure water and 0.0101 g of a Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize the reaction system. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 312.5 g, 48% NaOH; 14.5 g, 100% IPN10; 150.0 g, 100% St; 100.0 g, 15% NaPS; 94.4 g and 35% SBS; 80.9 g were dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 170 minutes for 100% IPN10 and 100% St, 185 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, 48% NaOH; 266.1 g 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 polymer 3 having a solid content concentration of 45% and a weight average molecular weight of 34,000 was obtained. The composition of the structural units (a), (b) and (d) in the polymer 3 thus obtained was 50% by mass, 30% by mass and 20% by mass, respectively.

Example 1-4
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 330.0 g of pure water and 0.0107 g of Mohr's salt, and the temperature was raised to 90 ° C. while stirring. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 437.5 g, 48% NaOH; 20.3 g, 100% IPN10; 75.0 g, 100% St; 75.0 g, 15% NaPS; 114.5 g and 35% SBS; 98.1 g were dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 170 minutes for 100% IPN10 and 100% St, 185 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, 48% NaOH; 372.6 g was gradually added dropwise to neutralize the polymerization reaction liquid. Thus, an aqueous solution of polymer 4 having a solid content concentration of 45% and a weight average molecular weight of 17,000 was obtained. The compositions of the structural units (a), (b), and (d) in the polymer 4 thus obtained were 70% by mass, 15% by mass, and 15% by mass, respectively.

Example 1-5
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 352.0 g of pure water and 0.0105 g of Mohr's salt, and the temperature was raised to 90 ° C. while stirring. It was. Next, in a polymerization reaction system maintained at 90 ° C. under stirring, 80% AA; 406.3 g, 48% NaOH; 18.8 g, 100% IPN10; 100.0 g, 100% St; 75.0 g, 15% NaPS; 108.5 g and 35% SBS; 93.0 g were dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 170 minutes for 100% IPN10 and 100% St, 185 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, 48% NaOH; 345.9 g 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 polymer 5 having a solid content concentration of 45% and a weight average molecular weight of 19,000 was obtained. The compositions of the structural units (a), (b) and (d) in the polymer 5 thus obtained were 65% by mass, 20% by mass and 15% by mass, respectively.

Example 1-6
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 432.0 g of pure water and 0.0099 g of a Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize the reaction system. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 312.5 g, 48% NaOH; 14.5 g, 100% IPN10; 225.0 g, 100% St; 25.0 g, 152.8% NaPS; 82.8 g and 35% SBS; 71.0 g were dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 160 minutes for 100% IPN10 and 100% St, 185 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, 485.8% NaOH; 245.8 g was gradually added dropwise to neutralize the polymerization reaction liquid. Thus, an aqueous solution of polymer 6 having a solid content concentration of 45% and a weight average molecular weight of 17,000 was obtained. The compositions of the structural units (a), (b) and (d) in the polymer 6 thus obtained were 50% by mass, 45% by mass and 5% by mass, respectively.

Example 1-7
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 170.0 g of pure water and 0.0250 g of Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize the reaction system. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 300.0 g, 48% NaOH; 13.9 g, 50% isoprenol ethylene oxide 10 mol adduct aqueous solution (hereinafter, 50% IPN 10 240.0 g, 100% St; 40.0 g, 15% NaPS; 100.5 g, and 35% SBS; 86.2 g were dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA, 48% NaOH and 35% SBS, 60 minutes for 50% IPN10, 120 minutes for 100% St, and 210 minutes for 15% NaPS. 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, 486.1% NaOH; 236.1 g was gradually added dropwise to neutralize the polymerization reaction liquid. Thus, an aqueous solution of polymer 7 having a solid content concentration of 45% and a weight average molecular weight of 20,000 was obtained. The compositions of the structural units (a), (b) and (d) in the polymer 7 thus obtained were 60% by mass, 30% by mass and 10% by mass, respectively.

Example 1-8
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 433.0 g of pure water and 0.0099 g of a Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize the reaction system. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 312.5 g, 48% NaOH; 14.5 g, 100% IPN10; 225.0 g, 100% butyl acrylate (hereinafter, 100% 25.0 g, 15% NaPS; 81.9 g, and 35% SBS; 70.2 g were dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 160 minutes for 100% IPN10 and 100% BA, 185 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, 485.8% NaOH; 245.8 g was gradually added dropwise to neutralize the polymerization reaction liquid. Thus, an aqueous solution of polymer 8 having a solid content concentration of 45% and a weight average molecular weight of 28,000 was obtained. The compositions of the structural units (a), (b) and (c) in the polymer 8 thus obtained were 50% by mass, 45% by mass and 5% by mass, respectively.

Example 1-9
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 316.0 g of pure water and 0.0103 g of Mohr's salt, and the temperature was raised to 90 ° C. while stirring. It was. Next, 80% AA; 468.8 g, 48% NaOH; 21.7 g, 100% IPN10; 100.0 g, 100% 2-ethylhexyl acrylate (hereinafter referred to as “80% AA”; 468.8 g, 48% NaOH; And abbreviated as 100% EHA.) 25.0 g, 15% NaPS; 110.7 g, and 35% SBS; 94.9 g were added dropwise from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 170 minutes for 100% IPN10 and 100% EHA, 185 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, 48% NaOH; 325.7 g 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 polymer 9 having a solid content concentration of 45% and a weight average molecular weight of 18,000 was obtained. The compositions of the structural units (a), (b) and (c) in the polymer 9 thus obtained were 75% by mass, 20% by mass and 5% by mass, respectively.

Example 1-10
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 365.0 g of pure water and 0.0103 g of a Mole salt, and the temperature was raised to 90 ° C. while stirring. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 437.5 g, 48% NaOH; 20.3 g, 100% IPN10; 125.0 g, 100% EHA; 25.0 g, 15% NaPS; 104.7 g and 35% SBS; 89.7 g were added dropwise from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA and 48% NaOH, 170 minutes for 100% IPN10 and 100% EHA, 185 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, 48% NaOH; 304.0 g 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 polymer 10 having a solid content concentration of 45% and a weight average molecular weight of 21,000 was obtained. The composition of the structural units (a), (b) and (c) in the polymer 10 thus obtained was 70% by mass, 25% by mass and 5% by mass, respectively.

Example 1-11
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 434.0 g of pure water and 0.0099 g of a Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize the reaction system. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 312.5 g, 48% NaOH; 14.5 g, 100% IPN10; 225.0 g, 100% EHA; 25.0 g, 15% NaPS; 80.7 g and 35% SBS; 69.2 g were dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA, 48% NaOH and 35% SBS, 170 minutes for 100% IPN10 and 100% EHA, and 210 minutes for 15% NaPS. 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, 485.8% NaOH; 245.8 g was gradually added dropwise to neutralize the polymerization reaction liquid. Thus, an aqueous solution of polymer 11 having a solid content concentration of 45% and a weight average molecular weight of 32,000 was obtained. The compositions of the structural units (a), (b) and (c) in the polymer 11 thus obtained were 50% by mass, 45% by mass and 5% by mass, respectively.

Example 1-12
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 170.0 g of pure water and 0.0250 g of Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize the reaction system. It was. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 300.0 g, 48% NaOH; 13.9 g, 50% isoprenol ethylene oxide 50 mol adduct aqueous solution (hereinafter referred to as 50% IPN50). 240.0 g, 100% St; 40.0 g, 15% NaPS; 100.5 g, and 35% SBS; 86.2 g were dropped from separate nozzles. The drop time of each solution is 180 minutes for 80% AA and 48% NaOH, 60 minutes for 50% IPN50, 120 minutes for 100% St, 210 minutes for 15% NaPS, and 180 minutes for 35% SBS. It was. 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, 486.1% NaOH; 236.1 g was gradually added dropwise to neutralize the polymerization reaction liquid. Thus, an aqueous solution of polymer 12 having a solid content concentration of 45% and a weight average molecular weight of 18,000 was obtained. The composition of the structural units (a), (b) and (d) in the polymer 12 thus obtained was 60% by mass, 30% by mass and 10% by mass, respectively.

Example 1-13
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 310.0 g of deionized water and 0.0106 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, 80% AA; 437.5 g, 48% NaOH; 20.3 g, 100% IPN10; 100.0 g, 100% St; 25.0 g, 50% N-isopropylacrylamide (hereinafter abbreviated as 50% NIPAM) which is an aqueous solution of the monomer (E); 50.0 g, 15% NaPS; 105.8 g, and 35% SBS; 90.7 g, Dropped from separate nozzles. The drop time for each solution was 180 minutes for 80% AA and 48% NaOH, 170 minutes for 100% IPN10, 100% St and 50% NIPAM, 185 minutes for 15% NaPS, and 175 minutes for 35% SBS. It was. 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, 48% NaOH; 372.6 g was gradually added dropwise to neutralize the polymerization reaction liquid. Thus, an aqueous solution of polymer 13 having a solid content concentration of 45% and a weight average molecular weight of 13,000 was obtained. The compositions of the structural units (a), (b), (c) and (e) in the polymer 13 thus obtained are 70% by mass, 20% by mass, 5% by mass and 5% by mass, respectively. Met.

Comparative Example 1
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 255.0 g of pure water and heated to 90 ° C. while stirring to prepare a polymerization reaction system. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 80% AA; 342.0 g, 48% NaOH; 15.8 g, 80% isoprenol ethylene oxide 10 mol adduct (hereinafter referred to as 80% IPN10). Abbreviated.) 131.5 g, 15% NaPS; 106.7 g, and 35% SBS; 91.4 g were dropped from separate nozzles. The dropping time of each solution was 180 minutes for 80% AA, 48% NaOH and 35% SBS, 170 minutes for 80% IPN10, and 210 minutes for 15% NaPS. 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, 482.5% NaOH; 142.5 g was gradually added dropwise to neutralize the polymerization reaction liquid. In this way, an aqueous solution of a comparative polymer having a solid content concentration of 45% and a weight average molecular weight of 10,000 was obtained. The compositions of the structural units (a) and (b) in the comparative polymer thus obtained were 73% by mass and 27% by mass, respectively.

Example 2
In Example 2, each polymer obtained in Examples 1-1, 1-4, 1-6, 1-8, 1-13 and Comparative Example 1 was another subject of the present invention. In order to evaluate as a detergent composition characterized by containing the composition, the anti-staining property was evaluated according to the above method. In Table 1 below, for the sake of reference, the results of similar experiments conducted without adding a polymer are also listed (in the column of “No addition of polymer” in Table 1 below).

  As is apparent from Table 1, the polymers 1, 4, 6, 8 and 13 in the present invention are significantly superior in recontamination as compared with the comparative polymer consisting only of the structural units (a) and (b). Has the ability to prevent.

Claims (9)

30 mass% or more and less than 95 mass% of following formula (1):
In the formula, R ¹ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group.
The structural unit (a) derived from the (meth) acrylic acid monomer (A) represented by the following formula (2) of 5% by mass or more and less than 70% by mass:
In the formula, R ² represents an alkenyl group having 2 to 5 carbon atoms; AO represents the same or different group derived from an alkylene oxide having 2 to 20 carbon atoms; R ³ represents a hydrogen atom or a carbon number Represents an alkyl group of 2 to 5; n is an integer of 1 to 200;
The structural unit (b) derived from the unsaturated monomer (B) represented by the following formula (3): more than 0% by mass and 50% by mass or less:
In the formula, R ⁴ represents a hydrogen atom or a methyl group, and Y represents an n-butyl group, a 2-ethylhexyl group, a dodecyl group, a hydroxypropyl group, a hydroxyisopropyl group, or a hydroxybutyl group.
The structural unit (c) derived from the alkyl (meth) acrylate monomer (C) and / or the structural unit (d) derived from the vinyl aromatic monomer (D) (however, the structural unit ( a), (b), possess as essential structural units, the (c) and (a total of the composition of d) is 100 wt%), the weight average molecular weight of 2,000 to 100,000, ( (Meth) acrylic acid copolymer. In the above formula (2), R ² is CH ₂ ═C (CH ₃ ) CH ₂ CH ₂ —, CH ₂ ═CHCH ₂ — or CH ₂ ═C (CH ₃ ) CH ₂ —, and R ³ is a hydrogen atom. The (meth) acrylic acid copolymer according to claim 1, wherein   The (meth) acrylic acid copolymer according to claim 1 or 2, wherein the structural unit (d) derived from the vinyl aromatic monomer (D) has an aromatic hydrocarbon group.   The (meth) acrylic acid-based copolymer further comprises a structural unit (e) derived from another monomer in a total composition of 100 mass% of the structural units (a), (b), (c) and (d). The (meth) acrylic acid-based copolymer according to any one of claims 1 to 3, which is contained in a proportion of more than 0% by mass and 10% by mass or less.   The (meth) acrylic acid copolymer for detergents according to any one of claims 1 to 4.   The (meth) acrylic acid copolymer according to claim 5, wherein the recontamination prevention rate is 65.0% or more. 10 mass% or more and less than 95 mass% of following formula (1):
In the formula, R ¹ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group.
(Meth) acrylic acid monomer (A) represented by the following formula (2) of 5 mass% or more and less than 90 mass%:
In the formula, R ² represents an alkenyl group having 2 to 5 carbon atoms; AO represents the same or different group derived from an alkylene oxide having 2 to 20 carbon atoms; R ³ represents a hydrogen atom or a carbon number Represents an alkyl group of 2 to 5; n is an integer of 1 to 200;
And an unsaturated monomer (B) represented by the following formula (3) exceeding 0% by mass and not more than 50% by mass:
In the formula, R ⁴ represents a hydrogen atom or a methyl group, and Y represents an n-butyl group, a 2-ethylhexyl group, a dodecyl group, a hydroxypropyl group, a hydroxyisopropyl group, or a hydroxybutyl group.
(Meth) acrylic acid monomer (C) and / or vinyl aromatic monomer (D) represented by the formula (However, monomers (A), (B), (C) and (D) ) Is a polymer having a weight average molecular weight of 2,000 to 100,000 , including a step of polymerizing in a solvent containing 50% by mass or more of water in the presence of a chain transfer agent. A method for producing a (meth) acrylic acid copolymer.   The method for producing a (meth) acrylic acid copolymer according to claim 7, wherein the chain transfer agent contains at least one of sulfite and sulfite.   A detergent composition comprising the (meth) acrylic acid copolymer according to any one of claims 1 to 6.