JP2019006913A - Hydrophobic group-containing copolymer - Google Patents

Abstract

To provide a Polymer that is excellent in dispersibility of hydrophobic dirt such as oil dirt.SOLUTION: Provided is a hydrophobic group-containing copolymer having (A) a structural unit derived from an ether bond-containing monomer represented by the formula (1), (B) a structural unit derived from an alkyl(meth)acrylate and (C) a structural unit derived from a carboxylic acid-type monomer (Ris H or a CHgroup; Ris a CHgroup, a CHCHgroup or a direct bond; AO is each independently a group derived from alkylene oxide of C2 to 8; Xis an integer of 1 to 200; Ris H or a C1-20 hydrocarbon group).SELECTED DRAWING: None

Description

The present invention relates to a hydrophobic group-containing copolymer. More specifically, the present invention relates to a hydrophobic group-containing copolymer useful for a cleaning agent or the like.

Conventionally, various types of detergents mainly composed of surfactants have been developed for clothes, tableware, etc., and research and development of ingredients to enhance the properties such as detergency has been actively conducted. ing.
For example, Patent Document 1 includes a structural unit derived from an acrylic acid monomer, a structural unit derived from an unsaturated monomer having an oxyalkylene group, and a structural unit derived from an alkyl (meth) acrylate monomer. It is disclosed that a (meth) acrylic acid-based copolymer having a detergent composition is used as a material for a detergent composition.

By the way, a copolymer having a structural unit derived from an acrylic acid-based monomer and a structural unit derived from an unsaturated monomer having an oxyalkylene group has been conventionally used as a cement dispersant. As a copolymer used in the above, a copolymer having a structure similar to the copolymer described in Patent Document 1 is disclosed (see Patent Documents 2 to 8).

JP 2007-231260 A JP 2010-1199 A JP 2010-120826 A JP2013-40100A JP 2014-24690 A JP 2012-171818 A JP 2014-205607 A JP-T-2006-525938

The dirt targeted by the cleaning agent includes hydrophilic dirt and hydrophobic dirt such as oil and hydrophobic fine particles, but the cleaning agent has the ability to remove hydrophobic dirt such as oil dirt that cannot be removed by simply washing with water. It is important to be excellent. Therefore, a detergent component having high dispersibility of hydrophobic dirt such as oil dirt is required, and development of a polymer that can be used as such a detergent ingredient (detergent builder) is required.

This invention is made | formed in view of the said present condition, and aims at providing the polymer excellent in the dispersibility of hydrophobic stain | pollution | contamination, such as oil stain | pollution | contamination.

The present inventor has made various studies on polymers excellent in dispersibility of hydrophobic soils. As a result, structural units derived from ether bond-containing monomers having a predetermined number of repeating oxyalkylene groups and derived from alkyl (meth) acrylates. In the hydrophobic group-containing copolymer having a structural unit and a structural unit derived from a carboxylic acid monomer, a predetermined alkyl (meth) acrylate is used, and the proportion of the structural unit derived from the alkyl (meth) acrylate and the carboxylic acid Copolymers that are excellent in dispersibility of hydrophobic stains such as oil stains and stains due to hydrophobic fine particles, and can be suitably used as a detergent builder when the proportion of structural units derived from system monomers is adjusted within a predetermined range And the present invention has been achieved.

That is, the present invention provides the following formula (1);

(In the formula, R ⁰ represents a hydrogen atom or a CH ₃ group. R ^a represents ^a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. AO is the same or different and has 2 to 8 carbon atoms. Represents a group derived from an alkylene oxide, X ¹ represents the average number of repeating units represented by AO, and is a number from 1 to 200. R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The structural unit (A) derived from the ether bond-containing monomer represented by the following formula (2);

(In the formula, R ² represents a hydrogen atom or a CH ₃ group. R ³ represents an alkyl group or a cycloalkyl group having 1 to 20 carbon atoms, and the total number of carbon atoms of R ² and R ³ is 2 or more. And a hydrophobic group-containing copolymer having a structural unit (B) derived from an alkyl (meth) acrylate and a structural unit (C) derived from a carboxylic acid monomer, The ratio of the structural unit (B) in the copolymer is 11 to 50% by mass with respect to 100% by mass of the structural unit derived from all monomers, and the ratio of the structural unit (C) in the copolymer is It is a hydrophobic group containing copolymer characterized by being 1-25 mass% with respect to 100 mass% of structural units derived from all monomers.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Hydrophobic group-containing copolymer>
In the hydrophobic group-containing copolymer of the present invention, the proportion of the structural unit (B) derived from the alkyl (meth) acrylate represented by the above formula (2) is 100% by mass of the structural unit derived from all monomers. 11 to 50% by mass, and the proportion of the structural unit (C) derived from the carboxylic acid monomer is 1 to 25% by mass with respect to 100% by mass of the structural unit derived from all monomers. And The structural unit (B) derived from an alkyl (meth) acrylate has a high affinity for hydrophobic soil, and the structural unit (C) derived from a carboxylic acid monomer exhibits an action of dispersing the hydrophobic soil. The hydrophobic group-containing copolymer of the present invention having the structural units (B) and (C) in such a ratio can exhibit an excellent effect in dispersibility of hydrophobic soils, especially oil soils.

The proportion of the structural unit (B) derived from the alkyl (meth) acrylate represented by the above formula (2) in the hydrophobic group-containing copolymer of the present invention is 100% by mass of the structural unit derived from all monomers. It is preferable that it is 11-40 mass%. More preferably, it is 11-35 mass%, More preferably, it is 12-30 mass%. When the proportion of the structural unit (B) derived from the alkyl (meth) acrylate is in such a range, it is preferable in that a hydrophobic group-containing copolymer can be produced by solution polymerization.

The proportion of the structural unit (C) derived from the carboxylic acid monomer in the hydrophobic group-containing copolymer of the present invention is 5 to 25% by mass with respect to 100% by mass of the structural unit derived from all monomers. Is preferred. More preferably, it is 5-22 mass%, More preferably, it is 10-20 mass%.
In the present invention, when the proportion of the structural unit (C) derived from the carboxylic acid monomer is calculated, it is calculated in terms of the corresponding acid. For example, when the structural unit (C) is a structural unit —CH ₂ —CH (COONa) — derived from sodium acrylate, the structural unit derived from acrylic acid which is the corresponding acid —CH ₂ —CH (COOH) — Calculate the mass ratio (mass%).
Similarly, when calculating the mass ratio (mass%) of the carboxylic acid monomer in the monomer component, it is calculated in terms of the corresponding acid. For example, if it is sodium acrylate, a mass ratio (mass%) is calculated as acrylic acid which is a corresponding acid.

The carboxyl group in the hydrophobic group-containing copolymer of the present invention may be acid type or salt type, but with respect to 100 mol% of all the carboxyl groups of the hydrophobic group-containing copolymer, It is preferable that 5-90 mol% of carboxyl groups are a salt type. More preferably, it is 7-80 mol% as a ratio of a salt type carboxyl group, More preferably, it is 10-70 mol%. In the production method described later, by performing a neutralization step during or after the polymerization reaction, or by using a carboxylic acid monomer in which a part of the carboxyl group is a salt type as a raw material, The ratio of groups can be within the above preferred range.

The proportion of the structural unit (A) in the hydrophobic group-containing copolymer of the present invention is preferably 25 to 88% by mass with respect to 100% by mass of the structural units derived from all monomers. In the structural unit (A), when R ¹ is a hydrogen atom, the structural unit (A) has a hydrophilic structure and exerts an action of dispersing hydrophobic dirt, and R ¹ is a hydrophobic group having 1 to 20 carbon atoms. In the case of a hydrophobic organic group, the affinity for the hydrophobic soil is increased, and the compatibility with the hydrophobic soil is improved. As described above, although the function of the structural unit (A) varies depending on the structure of the terminal, in any case, the hydrophobic group-containing copolymer of the present invention has the structural unit (A) in such a ratio. However, it is excellent due to the dispersibility of the hydrophobic soil.
The proportion of the structural unit (A) in the hydrophobic group-containing copolymer of the present invention is more preferably 40 to 85% by mass, and still more preferably 100% by mass of the structural unit derived from all monomers. It is 55-83 mass%, Most preferably, it is 60-80 mass%.

(Ether bond-containing monomer)
The hydrophobic group-containing copolymer of the present invention has a structural unit (A) derived from an ether bond-containing monomer represented by the above formula (1) (hereinafter also referred to as monomer (a)). 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 structural unit (A), in the above formula (1), the double bond of the vinyl group is a single bond (—CH ₂ —C (R ⁰ ) (R ^a —O— (AO) x ¹ — R ¹ )-) form.

When R ^{1 in the} above formula (1) is a hydrogen atom, it is effective for dispersion of hydrophobic soil.
When R ^{1 in the} above formula (1) is a hydrocarbon group having 1 to 20 carbon atoms, familiarity with hydrophobic soils is improved by hydrophobic interaction.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group. As said hydrocarbon group, an alkyl group, an alkenyl group, and an aryl group are preferable, More preferably, they are an alkyl group and an alkenyl group, More preferably, it is an alkyl group.
Moreover, as carbon number of the said hydrophobic organic group, 2-18 are preferable, More preferably, it is 3-12, More preferably, it is 4-8. If the number of carbon atoms is 4 or more, the hydrophobicity can be more sufficiently exhibited, and if it is 8 or less, the polymerizability can be sufficiently improved.

In the above formula (1), AO represents a group derived from an alkylene oxide having 2 to 8 carbon atoms. In this case, preferred examples of the alkylene oxide having 2 to 8 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.

X ¹ in the above formula (1) represents the average added mole number of AO, which is a group derived from the alkylene oxide having 2 to 8 carbon atoms, and is a number of 1 to 200. When X ¹ is ¹ to 200, the ether bond-containing monomer can further improve the hydrophilicity, and therefore has a characteristic that it is easily copolymerized even when a hydrophilic solvent such as water is used.
X ¹ is preferably 5 to 100, and most preferably 8 to 50. In the above formula (1), when X ¹ is 2 or more, the AOs present in one structural unit (b) may be the same or of different types. .
Since the hydrophobic group-containing copolymer of the present invention has a good balance between hydrophilicity and hydrophobicity, it can more fully exhibit the dispersion performance of hydrophobic stains. It is preferable to adjust the value of X ¹ according to the proportion of the structural units (B) and (C).

R ⁰ in the above formula (1) is a hydrogen atom or a CH ₃ group, preferably a CH ₃ group.
R ^a in the above formula (1) is a CH ₂ group, a CH ₂ CH ₂ group or a direct bond, preferably a CH ₂ CH ₂ group.

Examples of the monomer (a) include an adduct obtained by adding ethylene oxide to an alcohol having an unsaturated double bond such as vinyl alcohol, allyl alcohol, methallyl alcohol, and isoprenol, and further, the adduct has a carbon number. Examples thereof include compounds obtained by reacting 1 to 20 halogenated alkyls.

(Alkyl (meth) acrylate)
The hydrophobic group-containing copolymer of the present invention has a structural unit (B) derived from an alkyl (meth) acrylate represented by the above formula (2) (hereinafter also referred to as monomer (b)). In the present invention, the structural unit (B) may be present alone or in the form of a mixture of two or more. Further, the structural unit (B) is in the form (—CH ₂ —C (R ² ) (COOR ³ ) —) in which the double bond of the vinyl group is a single bond in the above formula (2).

In the above formula (2), the total number of carbon atoms of R ² and R ³ is 2 or more. Therefore, methyl acrylate is not included in the above formula (2).
R ³ is an alkyl group or cycloalkyl group having 1 to 20 carbon atoms, and the stability of the polymer obtained is higher when the carbon number of R ³ is somewhat large. On the other hand, when the carbon number of R ³ is too large, the polymerizability is remarkably lowered. More preferably, it has 4 to 8 carbon atoms.
Note that when ^{R 3} is a cycloalkyl group, the carbon number is 3-20.

The alkyl group having 1 to 20 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 -Linear or branched such as -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 -Like groups.
Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.
Of these, R ³ is preferably an n-butyl group, a 2-ethylhexyl group, or a dodecyl group, and more preferably an n-butyl group or a 2-ethylhexyl group.

Therefore, as the alkyl (meth) acrylate preferably used in the present invention, (meth) acrylic acid alkyl ester monomers such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, etc. Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and dodecyl (meth) acrylate are preferable, and butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and dodecyl (meth) acrylate are more preferable. In addition, as above-mentioned in this invention, alkyl (meth) acrylate may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.

(Carboxylic acid monomer)
The hydrophobic group-containing copolymer of the present invention has a structural unit (C) derived from a carboxylic acid monomer.
The carboxylic acid monomer (hereinafter also referred to as monomer (c)) is a monomer containing an unsaturated double bond (carbon-carbon double bond) and a carboxy group and / or a carboxylate group. is there.
By having the structural unit (C), the hydrophobic group-containing copolymer of the present invention has good water solubility and excellent dispersibility of hydrophobic soil.

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

Examples of the carboxylic acid monomer include unsaturated monocarboxylic acid monomers containing an unsaturated double bond and one carboxy group (or carboxylic acid base) in one molecule, and unsaturated in one molecule. An unsaturated dicarboxylic acid monomer containing a double bond and two carboxy groups (or carboxylate groups) is preferred.

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

Among the carboxylic acid monomers, (meth) acrylic acid, (meth) acrylate, maleic acid, and maleate are preferable. Among these, (meth) acrylic acid and (meth) acrylate which are (meth) acrylic monomers are more preferable.
That is, it is one of the preferred embodiments of the present invention that the carboxylic acid monomer is a (meth) acrylic acid monomer.

(Other monomers)
The hydrophobic group-containing copolymer of the present invention is a structural unit derived from another monomer (a monomer other than the above-mentioned ether bond-containing monomer, alkyl (meth) acrylate and carboxylic acid monomer) ( D) may be included.
At this time, the proportion of the structural unit (D) present in the hydrophobic group-containing copolymer is not particularly limited, but the effects of the structural units (A), (B) and (C), which are essential structural units, are obtained. In consideration of not inhibiting, the total composition of the structural units (A), (B) and (C) is 100% by mass, more than 0% by mass and 10% by mass or less, more preferably more than 0% by mass. The ratio is preferably 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) and (C), which are essential structural units, that is, the ability to disperse hydrophobic dirt can be maintained, and the effects of the structural unit (D) can be maintained. For example, it is preferable because chelating ability and viscosity adjusting ability are further imparted. When the proportion of the structural unit (D) 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 or a bad odor is emitted. There is a fear.

The other monomer (hereinafter also referred to as monomer (d)) is not particularly limited as long as it is copolymerizable with the monomers (a), (b), and (c). It is possible to select appropriately depending on the effect.
Examples of the other monomer (d) include vinyl aromatic monomers having an aromatic hydrocarbon group such as styrene, α-methylstyrene, o-chlorostyrene, vinyl toluene, vinyl naphthalene, and vinyl anthracene, and Vinyl aromatic monomers having a heterocyclic aromatic hydrocarbon group such as vinyl pyridine and vinyl imidazole; sulfonic acid monomers such as vinyl sulfonic acid and styrene sulfonic acid and their salts; N-vinyl pyrrolidone; N-vinyl monomers such as N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyloxazolidone; (meth) acrylamide, N, N- Amide monomers such as dimethylacrylamide and N-isopropylacrylamide; 3- (meth) Compounds obtained by adding 1 to 200 moles of ethylene oxide to ryloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane (3-allyloxy-1,2) -Di (poly) oxyethylene ether propane), allyl ether monomers such as (meth) allyl alcohol; isoprene monomers such as isoprenol;
Another monomer (d) may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.

In the hydrophobic group-containing copolymer of the present invention, the structural units (A), (B) and (C), and if necessary, the structural unit (D) are introduced at a specific ratio as described above. Each structural unit may exist in either a block shape or a random shape. Moreover, the weight average molecular weight of the hydrophobic group-containing copolymer of the present invention can be appropriately set and is not particularly limited. Specifically, the weight average molecular weight of the hydrophobic group-containing copolymer is preferably 2,000 to 200,000, more preferably 3,000 to 100,000, and most preferably 4,000 to 60. , 000. If it is less than 2,000, the dispersibility with respect to dirt decreases, and conversely, if it exceeds 200,000, the adhesion of dirt to the object to be cleaned may be promoted. In addition, in this specification, a weight average molecular weight is a measured value by GPC (gel permeation chromatography), and a specific measuring method is calculated according to the method described in an Example.

<Method for producing hydrophobic group-containing copolymer>
The method for producing the hydrophobic group-containing 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, as a method for producing the hydrophobic group-containing copolymer of the present invention, an ether bond-containing monomer (a), an alkyl (meth) acrylate (b), and a carboxylic acid monomer (c) are essential. It can manufacture by copolymerizing the monomer component contained as a component. Moreover, when copolymerizing a monomer component, you may further copolymerize the said other monomer (d) as needed.
The content ratio of the monomer (a), the monomer (b), the monomer (c) and the other monomer (d) in the monomer component is the above-described hydrophobic group-containing content of the present invention. This is the same as the proportion of structural units derived from these monomers in the copolymer.

In such a production method, the monomer component may be copolymerized using a polymerization initiator.
In the present invention, the copolymerization of the monomers (a) to (c) and, if necessary, another monomer (d) uses water in 50% by mass or more of the solvent used, and / or The reaction is preferably carried out in the presence of a chain transfer agent, more preferably 50% by weight or more of the solvent to be used, and more preferably 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 polymerization is completed. Moreover, when a chain transfer agent is used, there exists an advantage that it can suppress that the hydrophobic group containing copolymer manufactured becomes high molecular weight more than necessary. In particular, when sulfurous acid or sulfite is used as a chain transfer agent, the sulfonic acid group can be introduced quantitatively at the end of the resulting hydrophobic group-containing copolymer, improving gel resistance. can do.

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 60% by mass or more, and most preferably water alone (ie, 100% by mass) with respect to the total amount of solvent used.

The chain transfer agent is not particularly limited as long as it can adjust the molecular weight, and a known chain transfer agent can be used. Specifically, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 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, a sulfonic acid group can be quantitatively introduced into the main chain terminal of the obtained hydrophobic group-containing copolymer, and the gel resistance can be improved. In addition, the fact that the sulfonic acid group can be introduced quantitatively indicates that the sulfite is functioning very well as a chain transfer agent and the like. Thus, 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 method for producing a hydrophobic group-containing copolymer, the amount of chain transfer agent added is not limited as long as the monomer component is polymerized satisfactorily, but preferably with respect to 1 mol of all monomer components. 1-20 g, more preferably 2-15 g.

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, persulfate and azo compounds are preferred.
These polymerization initiators may be used alone or in the form of a mixture of two or more. At this time, alkali metal sulfite such as sodium hydrogen sulfite, metabisulfite, sodium hypophosphite, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride, thiourea, L-ascorbic acid (salt), erythorbine Accelerators such as acids (salts) can be used in combination. In addition, when using hydrogen peroxide, it is preferable to use in combination with promoters, such as L-ascorbic acid (salt).

The amount of the initiator used is not particularly limited as long as it is an amount capable of initiating copolymerization of monomer components, but is 10 g or less, more preferably 1 to 5 g, relative to 1 mol of all monomer components. Is preferred.

In the method for producing the hydrophobic group-containing copolymer, heavy metal ions may be used as a reaction accelerator.
The heavy metal ion used as a reaction accelerator 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 content of the heavy metal ion 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.

The total amount of the chain transfer agent, the initiator, and the reaction accelerator is preferably 2 to 20 g with respect to 1 mol of all monomer components. By setting it as such a range, the hydrophobic group containing copolymer of this invention can be produced efficiently, and the molecular weight distribution of a (meth) acrylic acid type copolymer may be made into a desired thing. it can. More preferably, it is 4-18g, More preferably, it is 5-16g.

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

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 in a reaction vessel, and a total amount of monomer components and a polymerization initiator is added; among monomers (a) to (c) (for example, monomer (a )) Is charged into the reaction vessel, the polymerization initiator and the remaining monomer components (the remainder of monomer (a) and monomers (b) and (c), and if necessary the monomer By adding all of (d)) into the reaction vessel (preferably continuously) The method performs the like.

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.

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.

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 50 degreeC or more, Most preferably, it is 60 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 time is preferably 30 to 360 minutes. More preferably, it is 60-330 minutes, More preferably, it is 120-240 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 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.

<Cleaning agent>
The hydrophobic group-containing copolymer of the present invention is a polymer having excellent dispersibility of hydrophobic soil such as oil soil and hydrophobic fine particle soil, and can be suitably used as a dispersant, particularly a dispersant for a cleaning agent. it can.
Such a dispersant containing the hydrophobic group-containing copolymer of the present invention and a cleaning agent containing the dispersant are also one aspect of the present invention.

Detergents usually include surfactants and additives used in detergents.
The cleaning agent of the present invention may contain one or more surfactants selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. it can.
In addition, as additives, alkali builder, chelate builder, anti-redeposition agent for preventing redeposition of contaminants such as sodium carboxymethyl cellulose, soil inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, Color transfer inhibitor, softener, alkaline substance for pH adjustment, fragrance, solubilizer, fluorescent agent, colorant, foaming agent, foam stabilizer, polish, bactericidal agent, bleaching agent, bleaching aid, enzyme , Dyes, solvents and the like, and one or more of these may be included.

The hydrophobic group-containing copolymer of the present invention has the above-described structure and is a copolymer excellent in dispersibility of hydrophobic soils such as oil soils and hydrophobic fine particle soils. Therefore, a detergent builder (dispersant) Can be suitably used.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

The weight average molecular weight (Mw) of the hydrophobic group-containing copolymer of the present invention, the lime soap dispersibility used to determine the oil stain dispersibility, and the carbon black dispersibility used to determine the hydrophobic fine particle stain dispersibility are: It measured by the method shown below.

<Measurement conditions of weight average molecular weight>
Both the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the hydrophobic machine-containing copolymer were measured by GPC (gel permeation chromatography). The measurement conditions and apparatus are as follows.
Device: HLC-8320 manufactured by Tosoh Corporation
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: POLYETHYLENE GLYCOL STANDARD made by GL Sciences Inc.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)

<Lime soap dispersibility test>
As oil stain dispersibility, lime soap dispersibility was measured by the following method.
First, in the measurement of lime soap dispersibility, hard water was prepared. Pure water was added to 8.20 g of calcium chloride dihydrate to make 100 g, and hard water was prepared.
Next, 0.3 g of a 1% aqueous polymer solution, 1.5 g of a 1% aqueous sodium oleate solution, and 14.1 g of pure water were put into a 20 ml sample tube and stirred. The prepared hard water 0.1g was added and stirred, and it was set as the test liquid. Thereafter, the sample tube was left in a dark place for 10 minutes. Ten minutes later, the absorbance of the test solution was measured with a UV spectrometer (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm). It shows that lime soap dispersibility is so high that this value is small.

<Carbon black (hydrophobic fine particle) dispersibility test>
As the hydrophobic fine particle dispersibility, the carbon black dispersibility was measured by the following method.
First, in the measurement of carbon black dispersibility, a dispersion was prepared. Pure water was added to 60.56 g of glycine, 52.6 g of sodium chloride, and 2.4 g of sodium hydroxide to make 600 g. (This is designated as buffer A.) 0.163 g of calcium chloride dihydrate was added to 60 g of buffer A, and pure water was further added to make 1000 g. (This is referred to as buffer B.) 36 g of buffer B was added to 4 g of 0.1% polymer aqueous solution in terms of solid content and stirred to obtain a dispersion.
Next, after putting 0.03 g of carbon black powder into a test tube (diameter 16 mm, height 180 mm), 30 g of the above dispersion is added and sealed. The test tube was shaken to uniformly disperse the carbon black, and then the test tube was left in a dark place for 20 hours. After 20 hours, 5 mL of the supernatant was taken, diluted 10 times, and then the absorbance was measured with a UV spectrometer (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm). It shows that carbon black dispersibility is so high that this value is large.

Example 1
In a 2.5 liter SUS separable flask equipped with a reflux condenser and a stirrer, an ion-exchanged water 225.0 g, isopropyl alcohol 225.0 g, and an 80% aqueous solution of 50 mol of isoprenol ethylene oxide adduct (hereinafter, Abbreviated as 80% IPN50.) Charged 425.6 g and 1.97 g of 70% paratoluenesulfonic acid monohydrate (hereinafter abbreviated as 70% PTS) and heated to 85 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 85 ° C., 80% aqueous acrylic acid solution (hereinafter abbreviated as 80% AA) 66.9 g, 100% butyl acrylate (hereinafter abbreviated as 100% BA) 56. 07.0, 10% 2,2′-azobis (2-amidinopropane) hydrochloride aqueous solution (hereinafter abbreviated as 10% V-50) 67.0 g was dropped from another nozzle. The dropping time of each solution was 180 minutes for 80% AA and 100% BA and 210 minutes for 10% V-50. Moreover, the dropping rate of each solution was made constant, and dropping was performed continuously.
After completion of the dropwise addition of 10% V-50, the reaction solution was kept at 85 ° C. for 30 minutes (ripening) to complete the polymerization. After completion of the polymerization, 12.4 g of a 48% aqueous sodium hydroxide solution (hereinafter abbreviated as 48% NaOH) was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool to neutralize the polymerization liquid. Thus, a polymer 1 having a solid content concentration of 43% and a weight average molecular weight of 11,000 was obtained.

Example 2
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 375.0 g of ion-exchanged water, 472.9 g of 80% IPN50, and 2.19 g of 70% PTS. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 80% AA 74.4 g, 100% BA 62.2 g, 10% V-50 74.5 g, and 50% isopropyl alcohol 30.0 g were put in separate nozzles in the polymerization reaction system maintained at 85 ° C. More dripped. The dropping time of each solution was 180 minutes for 80% AA, 100% BA and 50% isopropyl alcohol, and 210 minutes for 10% V-50. Moreover, the dropping rate of each solution was made constant, and dropping was performed continuously.
After completion of the dropwise addition of 10% V-50, the reaction solution was kept at 85 ° C. for 30 minutes (ripening) to complete the polymerization. After completion of the polymerization, 13.8 g of 48% NaOH was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization liquid. Thus, Polymer 2 having a solid content concentration of 46% and a weight average molecular weight of 46,000 was obtained.

Example 3
A 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with 375.0 g of ion-exchanged water, 472.9 g of 80% IPN50, and 2.19 g of 70% PTS. The temperature was raised to ° C. to obtain a polymerization reaction system. Next, 74.4 g of 80% AA, 62.2 g of 100% BA, and 74.5 g of 10% V-50 were dropped from different nozzles into the polymerization reaction system maintained at 85 ° C. The dropping time of each solution was 180 minutes for 80% AA and 100% BA and 210 minutes for 10% V-50. Moreover, the dropping rate of each solution was made constant, and dropping was performed continuously.
After completion of the dropwise addition of 10% V-50, the reaction solution was kept at 85 ° C. for 30 minutes (ripening) to complete the polymerization. After completion of the polymerization, 13.8 g of 48% NaOH was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization liquid. Thus, Polymer 3 having a solid content concentration of 48% and a weight average molecular weight of 70,000 was obtained.

Example 4
A glass separable flask equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube was charged with 233.0 g of 80% IPN50, 1.2 g of 70% PTS, and 1.8 g of 0.1% Mole salt, and stirred with stirring. The temperature was raised to 0 ° C., and 1.1 g of 35% aqueous hydrogen peroxide solution was added thereto to form a polymerization reaction system. Next, in the polymerization reaction system, a mixed solution of 29.4 g of 100% AA and 30.6 g of 100% BA, 0.1 g of L-ascorbic acid (hereinafter abbreviated as L-AS) was charged with 14.2 g of ion-exchanged water. An aqueous solution diluted with 9.8 g of 3-mercaptopropionic acid (hereinafter abbreviated as MPA) diluted with 9.8 g of ion-exchanged water was dropped from separate nozzles. The dropping time of each solution was 150 minutes for the mixed solution of 100% AA and 100% BA, 270 minutes for the L-AS aqueous solution, and 210 minutes for the MPA aqueous solution. Moreover, the dropping rate of each solution was made constant, and dropping was performed continuously.
After completion of the dropwise addition of the L-AS aqueous solution, the reaction solution was kept at 60 ° C. for 60 minutes (ripening) to complete the polymerization. After completion of the polymerization, 5.9 g of a 30% aqueous sodium hydroxide solution (hereinafter abbreviated as 30% NaOH) was gradually added dropwise while stirring and cooling the polymerization reaction solution to neutralize the polymerization solution. Further, 90.6 g of dilution water for concentration adjustment was added. In this way, a polymer 4 having a solid content concentration of 58% and a weight average molecular weight of 17,000 was obtained.

Example 5
A glass separable flask equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube was charged with 193.5 g of 80% IPN50, 1.1 g of 70% PTS, and 1.5 g of 0.1% Mole salt, and stirred while stirring. The temperature was raised to 0 ° C. and 1.2 g of 35% aqueous hydrogen peroxide solution was added thereto to form a polymerization reaction system. Next, in the polymerization reaction system, a mixed solution of 27.4 g of 100% AA and 47.6 g of 100% BA, an aqueous solution in which 0.1 g of L-AS was diluted with 15.6 g of ion-exchanged water, and 3.3 g of MPA were ionized. An aqueous solution diluted with 11.1 g of exchange water was dropped from different nozzles. The dropping time of each solution was 150 minutes for the mixed solution of 100% AA and 100% BA, 270 minutes for the L-AS aqueous solution, and 210 minutes for the MPA aqueous solution. Moreover, the dropping rate of each solution was made constant, and dropping was performed continuously.
After completion of the dropwise addition of the L-AS aqueous solution, the reaction solution was kept at 60 ° C. for 60 minutes (ripening) to complete the polymerization. After completion of the polymerization, 11.1 g of 30% NaOH was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization liquid. Further, 82.7 g of dilution water for concentration adjustment was added. Thus, a polymer 5 having a solid content concentration of 57% and a weight average molecular weight of 16,000 was obtained.

Example 6
A glass separable flask equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube was charged with 247.7 g of 80% IPN50, 1.4 g of 70% PTS, and 1.9 g of 0.1% Mole salt, and stirred. The temperature was raised to 0 ° C., and 1.3 g of 35% aqueous hydrogen peroxide solution was added thereto to form a polymerization reaction system. Next, in the polymerization reaction system, a mixed solution of 32.5 g of 100% AA and 42.5 g of 100% BA, an aqueous solution obtained by diluting 0.2 g of L-AS with 19.7 g of ion-exchanged water, and 3.7 g of MPA were ionized. Aqueous solutions diluted with 8.6 g of exchange water were dropped from different nozzles. The dropping time of each solution was 150 minutes for the mixed solution of 100% AA and 100% BA, 270 minutes for the L-AS aqueous solution, and 210 minutes for the MPA aqueous solution. Moreover, the dropping rate of each solution was made constant, and dropping was performed continuously.
After completion of the dropwise addition of the L-AS aqueous solution, the reaction solution was kept at 60 ° C. for 60 minutes (ripening) to complete the polymerization. After completion of the polymerization, while the polymerization reaction solution was stirred and allowed to cool, 45.8 g of 30% NaOH was gradually added dropwise to neutralize the polymerization solution. Further, 80.8 g of dilution water for concentration adjustment was added. In this way, a polymer 6 having a solid content concentration of 61% and a weight average molecular weight of 17,000 was obtained.

Comparative Example 1
In a 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer, 430 g of ion-exchanged water and 0.03 g of Mole salt were added, and the temperature was raised to 90 ° C. while stirring. did. Next, in a polymerization reaction system maintained at 90 ° C., a mixed solution of 315.3 g of 80% AA and 14.6 g of 48% NaOH, and an ethylene oxide 10 mol adduct of 100% isoprenol (hereinafter abbreviated as 100% IPN10). ) 227.0 g, 100% BA 25.2 g, 15% sodium persulfate aqueous solution (hereinafter abbreviated as 15% NaPS) 82.6 g, 35% sodium hydrogen sulfite aqueous solution (hereinafter abbreviated as 35% SBS) 70. 8g was dripped from another nozzle respectively. The dropping time of each solution was 180 minutes for a mixed solution of 80% AA and 48% NaOH, 170 minutes for 100% IPN10 and 100% BA, 210 minutes for 15% NaPS, and 175 minutes for 35% SBS. Moreover, the dropping rate of each solution was made constant, and dropping was performed continuously.
After completion of the dropwise addition of 15% NaPS, the reaction solution was kept at 90 ° C. (ripening) for 30 minutes to complete the polymerization. After completion of the polymerization, 247.9 g of 48% NaOH was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization liquid. Thus, Comparative Polymer 1 having a solid content concentration of 44% and a weight average molecular weight of 14,000 was obtained.

<Lime soap dispersibility test results>
The polymers obtained in Examples 1 to 6 and Comparative Example 1 were evaluated for lime soap dispersion performance according to the above method. The results are shown in Table 1.
As is clear from Table 1, the polymers 1 to 6 in the present invention have significantly superior lime soap dispersion performance with respect to the comparative polymer 1.

<Carbon black dispersibility test results>
The polymers obtained in Examples 1 to 6 and Comparative Example 1 were evaluated for carbon black dispersion performance according to the above method. The results are shown in Table 1.
As is clear from Table 1, the polymers 1 to 6 in the present invention have significantly superior carbon black dispersion performance with respect to the comparative polymer 1.

Claims (6)

Following formula (1);

(In the formula, R ⁰ represents a hydrogen atom or a CH ₃ group. R ^a represents ^a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. AO is the same or different and has 2 to 8 carbon atoms. Represents a group derived from an alkylene oxide, X ¹ represents the average number of repeating units represented by AO, and is a number from 1 to 200. R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The structural unit (A) derived from the ether bond-containing monomer represented by the following formula (2);

(In the formula, R ² represents a hydrogen atom or a CH ₃ group. R ³ represents an alkyl group or a cycloalkyl group having 1 to 20 carbon atoms, and the total number of carbon atoms of R ² and R ³ is 2 or more. A hydrophobic group-containing copolymer having a structural unit (B) derived from an alkyl (meth) acrylate and a structural unit (C) derived from a carboxylic acid monomer represented by:
In the copolymer, the proportion of the structural unit (B) in the copolymer is 11 to 50% by mass with respect to 100% by mass of the structural units derived from all monomers,
The hydrophobic group-containing copolymer, wherein the proportion of the structural unit (C) in the copolymer is 1 to 25% by mass with respect to 100% by mass of the structural units derived from all monomers. The proportion of the structural unit (A) in the copolymer is 25 to 88% by mass with respect to 100% by mass of the structural units derived from all monomers, containing the hydrophobic group according to claim 1. Copolymer. The hydrophobic group-containing monomer is characterized in that the proportion of structural units (C) in the copolymer is 5 to 25% by mass with respect to 100% by mass of structural units derived from all monomers. Item 3. The hydrophobic group-containing copolymer according to Item 1 or 2. The hydrophobic group-containing copolymer according to claim 1, wherein the carboxylic acid monomer is a (meth) acrylic acid monomer. The dispersing agent characterized by including the hydrophobic group containing copolymer in any one of Claims 1-4. A cleaning agent comprising the dispersant according to claim 5.