JP6871266B2 - Copolymer for cleaning agent - Google Patents

Description

The present invention relates to a copolymer for a cleaning agent. More specifically, the present invention relates to a copolymer for a cleaning agent, which is preferably used as a cleaning agent for a laundry detergent or the like.

In recent years, due to increasing awareness of hygiene, products having an antibacterial effect in addition to a cleaning effect have been put on the market in laundry detergents. Conventionally, cationic bactericides such as bleaching agents and cationic surfactants have been used as active ingredients having an antibacterial effect. Chlorine-based and oxygen-based bleaching agents are known to have a high antibacterial effect, but when chlorine-based bleaching agents are added to laundry detergents, there is a problem of discoloration of colored patterns. Oxygen-based bleach does not have a problem of discoloration, but it is clear in the industry that it is difficult to stably mix it with a heavy liquid detergent for clothing, which is generally weakly alkaline, and it has excellent solubility and strength. It is desired that heavy liquid detergents for clothing, which can deal with various stains, also have an antibacterial effect. Cationic bactericides, which are widely used as cleaning agents in the hygiene field, have a wide antibacterial spectrum band and are characterized by quick-acting properties, so attempts have been made to incorporate them into liquid cleaning agents for clothing. For example, Patent Documents 1 to 4 disclose amine-based polymers as cationic bactericides.

JP-A-2002-60788 JP-A-2002-60791 Japanese Unexamined Patent Publication No. 2003-40719 Japanese Unexamined Patent Publication No. 2011-190368

As described above, various cationic bactericides are used as antibacterial agents in detergents, but conventional cationic bactericides have a problem that they do not exhibit sufficient antibacterial performance during washing. In addition to sufficient antibacterial performance during washing, there is a demand for an agent that maintains antibacterial performance even after washing and further exhibits not only antibacterial performance but also recontamination prevention ability during washing, and there is room for development.

The present invention has been made in view of the above situation, and provides a copolymer for a cleaning agent, which has excellent antibacterial performance during washing and sustainability of antibacterial performance after washing, and also has excellent anti-recontamination ability. The purpose.

As a result of various studies on copolymers used for cleaning agents, the present inventor has a structural unit derived from a cationic group-containing monomer having a specific structure and a structural unit derived from a specific hydrophobic monomer. However, it has been found that a copolymer having a weight average molecular weight in a specific range exhibits sufficient antibacterial performance during and after washing, and is also excellent in anti-recontamination ability, and the above-mentioned problems can be solved brilliantly. And arrived at the present invention.

That is, the present invention is a copolymer for detergents having a structural unit (a) derived from a cationic group-containing monomer (A) and a structural unit (b) derived from a hydrophobic monomer (B). , The above-mentioned copolymer for cleaning agent has the following formula (4) and / or (5) as the structural unit (a);

(In formulas (4) and (5), R ¹ and R ² represent the same or different hydrocarbon atoms or hydrocarbon groups having 1 to 12 carbon atoms. Z represents a hydrogen atom or a methyl group. Represents a divalent linking group. X ⁻ represents an anion.) Has a structural unit derived from the cationic group-containing monomer (A) represented by), and has a weight average molecular weight of 1000 to. The following formula (6) and / or (7) as the one million copolymer (α) or structural unit (a);

(In formulas (6) and (7), R ^{3 to} R ⁵ represent the same or different hydrocarbon groups having 1 to 12 carbon atoms. Z represents a hydrogen atom or a methyl group. Y represents 2 Represents a valent linking group. X ⁻ represents an anion. M and n are identical or different and are integers 1 to 3) derived from the cationic group-containing monomer (A). The hydrophobic monomer (B) has a solubility parameter of 15 or less as a homopolymer, and has a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, and a phosphoric acid group. , Halogeno group, epoxy group and carbonyl group may have at least one substituent selected from the group (meth) acrylates; unsaturated monocarboxylic acids; aromatic vinyl-based single amounts such as styrene. Body; Olefin-based monomer; Ester of unsaturated alcohol and carboxylic acid; Vinyl halide; Alkyl vinyl ethers; Unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms and an unsaturated monomer having 1 to 20 carbon atoms. Addition reaction product with alcohol; alkylene oxide adduct of unsaturated alcohol having 2 to 20 carbon atoms and their terminal hydrophobic modified product; at least one compound selected from the group consisting of cyclic vinyl-based monomers. The ratio of the structural unit (e) derived from the monomer (E) other than the cationic group-containing monomer (A) and the hydrophobic monomer (B) is 0 with respect to 100% by mass of the total structural unit. The other monomer (E) is 10% by mass, and the above-mentioned other monomer (E) is an ester of a hydroxyl group having two or more substitutions of a polyol and (meth) acrylic acid; a methacrylate ester having two substitutions or more of a polyol; Ethers of more than substituted hydroxyl groups and unsaturated alcohols; diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyethane, triallyl cyanurate, divinyl adipate, vinyl crotonate, 1,5-hexadiene, divinyl A cleaning agent which is at least one compound selected from the group consisting of benzene and unsaturated carboxylic acid heavy metal salts, and is a copolymer (β) having a weight average molecular weight of 1,000 to 200,000. It is a copolymer for use.
The present invention will be described in detail below.
A combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Copolymer for cleaning agent>
The cleaning agent copolymer of the present invention exhibits antibacterial performance, and the antibacterial performance includes sterilization (killing microorganisms), bacteriostatic (suppressing the growth of microorganisms), sterilization, disinfection, bacteriostatic, and eradication. It means that it has the performance of bacteria, antiseptic, antifungal, etc. The target microorganisms are bacteria and fungi.
Examples of the above-mentioned bacteria include Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, and Rezionella; and Gram-positive bacteria such as Staphylococcus aureus and Clostridium. Examples of the fungus include yeasts such as Candida, Rhodotorula, and baker's yeast; molds such as red mold and black mold.

The copolymer for cleaning agent of the present invention (hereinafter, also simply referred to as the copolymer of the present invention) has a structural unit (a) derived from the cationic group-containing monomer (A) and a hydrophobic monomer (B). ) Is a copolymer having a structural unit (b) derived from. The reason why such a copolymer exhibits antibacterial properties is presumed as follows. When the copolymer of the present invention is allowed to act on a microorganism, the cationic group derived from the cationic group-containing monomer (A) possessed by the copolymer is adsorbed on the surface of the microorganism having a negative charge. Furthermore, the hydrophobic group of the copolymer exhibits affinity with the cell membrane portion and interacts with the cell membrane to disrupt the interaction between lipids and the like constituting the cell membrane and / or bind to the membrane. It is presumed that by inhibiting the function of a protein or the like, the cell is destroyed and / or the physiological activity of the cell is inhibited and the microorganism is killed.
Further, the copolymer for cleaning agent of the present invention is also excellent in the ability to prevent recontamination, and the cationic group derived from the cationic group-containing monomer (A) possessed by the copolymer of the present invention is anionic. By adsorbing to hydrophilic particles such as hydrophilic stains and mud, and adsorbing hydrophobic groups derived from hydrophobic monomers to hydrophobic stains, the stain components are suppressed from adhering to the fibers, and recontamination is prevented. The ability will be demonstrated.

The copolymer of the present invention is a copolymer (α) or a copolymer (β). In the present specification, the term "copolymer" means a matter common to the copolymer (α) or the copolymer (β).
The weight average molecular weight of the copolymer (α) is 10 to 1,000,000. The weight average molecular weight of the copolymer (β) is 1,000 to 200,000. It is considered that the conventional cationic bactericidal agent cannot exhibit sufficient antibacterial performance at the time of washing due to the agent adhering to the clothes during washing. On the other hand, since the copolymer of the present invention has a weight average molecular weight in the range of 10 to 1,000,000, it sufficiently suppresses adsorption to fibers during washing and sufficiently suppresses washing away by rinsing. It can be made and has excellent adsorptivity to fibers after washing. As a result, it is possible to achieve both the antibacterial performance during washing and the sustainability of the antibacterial performance after washing. Further, the copolymer of the present invention tends to be more excellent in sustainability of antibacterial performance and antibacterial property during washing if the weight average molecular weight is in the following preferable range.
The weight average molecular weight of the copolymer (α) is preferably 20 to 800,000, more preferably 3000 to 600,000, further preferably 4000 to 400,000, still more preferably 5000 to 200,000. It is even more preferably 6,000 to 180,000, even more preferably 7,000 to 140,000, particularly preferably 8,000 to 100,000, even more preferably 10,000 to 80,000, and most preferably 14,000 to 75,000. Is.

The weight average molecular weight of the copolymer (β) is preferably 2,000 to 200,000, more preferably 3,000 to 200,000, further preferably 4,000 to 180,000, and even more preferably 5,000 to 160,000. It is even more preferably 6,000 to 140,000, even more preferably 7,000 to 120,000, particularly preferably 8,000 to 100,000, even more preferably 10,000 to 80,000, and most preferably 14,000 to 75,000. Is. The weight average molecular weight of the copolymer can be measured by the method described in Examples.

The copolymer for cleaning agent of the present invention has a structural unit (a) derived from the cationic group-containing monomer (A). The cationic group-containing monomer (A) is not particularly limited as long as it has at least one ethylenically unsaturated group and one cationic group. Here, the cationic group is a group having a cation or a group for generating a cation, for example, a neutralized product of a primary to tertiary amino group, a neutralized product of a primary to tertiary amino group with an acid, and a quaternary ammonium base. And so on. Examples of the cationic group include the following formulas (1) to (3);

(In formulas (1) and (2), R ¹ and R ² represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, which are the same or different. In formula (3), R ^{3 to} R ⁵ are. , The same or different, represents a hydrocarbon group having 1 to 12 carbon atoms ^{. X −} represents an anion.) It is preferable that the group is represented by any one of.
The hydrocarbon group may have a chain structure or a ring structure, but a chain structure is preferable. When the hydrocarbon group has a chain structure, it may be linear or have a branch.
The hydrocarbon group is preferably an alkyl group, an alkenyl group or an aryl group, more preferably an alkyl group or an alkenyl group, and even more preferably an alkyl group.
The number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, particularly preferably 1 to 5, and most preferably 1 to 2.
In the above formulas (1) and (2), ^{at least one of R 1} and R ² is preferably an alkyl group having 1 to 12 carbon atoms, and both ^{R 1} and R ^{2 have 1 to 12 carbon atoms.} It is more preferable that it is a hydrocarbon group of.
In the above formula (3), R ^{3 to} R ⁵ are preferably an alkyl group having 1 to 12 carbon atoms and an alkenyl group having 2 to 12 carbon atoms.
As ^{the alkyl group of R 1 to} R ⁵ , a methyl group, an ethyl group and a tert-butyl group are more preferable, and a methyl group or an ethyl group is most preferable.

^{X −} in the above formulas (2) and (3) is not particularly limited, and is, for example, a halide ion such as chlorine ion, bromine ion, or iodine ion; an alkyl sulfate ion such as methyl sulfate ion; an organic acid such as acetate ion. Ions and the like can be mentioned.
^{For X −} in the above formula (2), an ion of an organic acid is preferable.
^{The X −} in the above formula (3) is preferably a halide ion or an alkyl sulfate ion.

Examples of the cationic group include acids of tertiary amino groups and tertiary amino groups among neutralized products of primary to tertiary amino groups and primary to tertiary amino groups with acids and quaternary ammonium bases. A neutralized product of the above or a quaternary ammonium base is preferable. As the neutralized product of the tertiary amino group and the tertiary amino group with an acid, a dimethylamino group, a diethylamino group or a neutralized product of these with an acid such as hydrochloric acid or acetic acid is preferable.

The cationic group-containing monomer (A) has the following formulas (4) to (7);

(In formulas (4) and (5), R ¹ and R ² represent the same or different hydrocarbon atoms or hydrocarbon groups having 1 to 12 carbon atoms. In formulas (6) and (7), R ³ ~ R ⁵ represents the same or different hydrocarbon groups having 1 to 12 carbon atoms. Z represents a hydrogen atom or a methyl group. Y represents a divalent linking group. X ⁻ represents an anion. M and n are the same or different, and are preferably integers of 1 to 3).

X in the formula (6) and (7) ^- specific examples of, X in the formula (2) and (3) ^- are the same as. It is preferably a halide ion or an alkyl sulfate ion, and more preferably a chloride ion or a methyl sulfate ion.

From the viewpoint of antibacterial property and hydrolysis resistance, the Z is preferably a methyl group.
M and n in the above formula (7) are the same or different, and are integers of 1 to 3, preferably 1 or 2, and more preferably 1.

The divalent linking group in the above formulas (4) to (6) is not particularly limited, but for example, the following formula (8);

(In the formula, i represents an integer from 0 to 12.), The following formula (9);

(In the formula, j represents an integer of 1 to 10) and the following formula (10);

(In the formula, k represents an integer of 0 to 4).
As the divalent linking group, the structure represented by the above formula (8) or (9) is preferable.
I in the above formula (8) is preferably 1 to 6, and more preferably 1 to 4.
J in the above formula (9) is preferably 1 to 6, and more preferably 1 to 4.

Specific examples of the cationic group-containing monomer (A) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth). ) N, N-dialkylamino group-containing (meth) acrylates such as acrylates and N, N-diethylaminopropyl (meth) acrylates, monomers obtained by adding a quaternizing agent to the above monomers, or acids such as hydrochloric acid and acetic acid thereof. Neutralized by: N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide N, N-dialkylamino group-containing (meth) acrylamides such as, and monomers obtained by adding a quaternizing agent to the above monomers or neutralized products of these with acids such as hydrochloric acid and acetic acid; monomethylaminoethyl (meth) acrylate, Contains monoalkylamino groups such as monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, 2- (tert-butylamino) ethyl (meth) acrylate. Acrylates and neutralized products of these with acids such as hydrochloric acid and acetic acid; monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide, etc. Monoalkylamino group-containing (meth) acrylamides and neutralized products of these with acids such as hydrochloric acid and acetic acid; esters of (meth) acrylic acids such as -2-aminoethyl (meth) acrylate and alkanolamines and Neutralized products with acids such as hydrochloric acid and acetic acid; N, N-diallylmethylamine such as diallyldimethylammonium chloride and monomers added with a quaternizing agent, or neutralized with acids such as hydrochloric acid and acetic acid. Substances: Allylamine and its neutralized products with acids such as hydrochloric acid and acetic acid; 1-allyloxy-3-dibutylamino-2-ol, 1-allyloxy-3-diethanolamino-2-ol, etc. having 2 to 8 carbon atoms. An addition reaction product of an unsaturated monomer having a cyclic ether-containing group and an amine compound having 1 to 24 carbon atoms, a monomer having a quaternizing agent added thereto, or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid. Etc. ..

The amine compound having 1 to 24 carbon atoms is not particularly limited as long as it can react with the cyclic ether structure of an unsaturated monomer having an amino group and a cyclic ether-containing group having 2 to 8 carbon atoms. The amine compound having 1 to 24 carbon atoms preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms. Examples of the amine compound having 1 to 24 carbon atoms include primary amines and secondary amines, for example, (di) alkylamines having 1 to 24 carbon atoms, (di) alkanolamines having 1 to 24 carbon atoms, and the like. Examples thereof include alkylalkanolamines having 1 to 24 carbon atoms.
Examples of (di) alkylamines having 1 to 24 carbon atoms include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine and heptylamine. , Diheptylamine, octylamine, dioctylamine, dodecylamine, didodecylamine and the like are preferable.
As the (di) alkanolamine having 1 to 24 carbon atoms, methanolamine, ethanolamine, propanolamine, butanolamine, dimethanolamine, diethanolamine, dipropanolamine, dibutanolamine, hexanolamine and the like are preferable.
As the alkylalkanolamine having 1 to 24 carbon atoms, methylethanolamine or the like is preferable.
As the cationic group-containing monomer (A), preferably, N, N-dialkylamino group-containing (meth) acrylates, neutralized products of these with acids such as hydrochloric acid and acetic acid, and quaternizing agents are added thereto. Additions of monomers, N, N-dialkylamino group-containing (meth) acrylamides and neutralized products of these with acids such as hydrochloric acid and acetic acid, and monomers with a quaternizing agent added to them, especially N, N-dimethyl. Aminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, neutralized products of these with acids such as hydrochloric acid and acetic acid, and quaternizing agents. The added monomer is more preferable.
The quaternizing agent is not particularly limited, but is an alkyl halide such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate and the like. Examples thereof include general alkylating agents such as alkyl sulfate.

The copolymer for cleaning agent of the present invention has a structural unit (b) derived from the hydrophobic monomer (B). The hydrophobic monomer (B) has a solubility parameter of 15 or less with respect to the homopolymer obtained by homopolymerization. Even if the solubility parameter is 15 or less, those having a cationic group are included in the cationic group-containing monomer (A).
Here, the solubility parameter is a value calculated by the method described on pages 147 to 154 of "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2).
The method is outlined below. The solubility parameter (δ) (cal / cm ³ ) ^1/2 of the homopolymer is as follows, based on the evaporation energy (Δei) and molar volume (Δvi) of the constituent units forming the polymer. It is calculated by the calculation method of.
δ = (Δei / Δvi) ^1/2 (cal / cm ³ ) ^1/2

If the solubility parameter for the homopolymer obtained when the hydrophobic monomer (B) is polymerized alone is 15 or less, the hydrophobicity of the copolymer of the present invention is sufficient. Since the affinity of the polymer for the cell membrane is improved and the interaction with the cell membrane is increased, the physiological activity of the cell membrane is damaged, so that the antibacterial performance is superior to that of the conventional cationic bactericide. The solubility parameter is preferably 14 or less, more preferably 13 or less, and further preferably 12 or less. The solubility parameter is usually 5 or more.

The hydrophobic monomer (B) is not particularly limited as long as the solubility parameter in the homopolymer is 15 or less, but it is an ester of (meth) acrylic acid and an alcohol which may have a substituent. ((Meta) acrylate) types; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-allyloxyacrylic acid and salts thereof; aromatic vinyl-based monomers such as styrene; ethylene, propylene and the like. Olefin-based monomer; ester of unsaturated alcohol such as vinyl acetate and carboxylic acid; vinyl halide such as vinyl chloride; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; 1-allyloxy-3-butoxypropane-2 -Additional reaction product of unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms such as oar and alcohol having 1 to 20 carbon atoms; ethylene oxide adduct of allyl alcohol, ethylene oxide adduct of metallic alcohol, Examples thereof include alkylene oxide adducts of unsaturated alcohols having 2 to 20 carbon atoms such as ethylene oxide adducts of isoprenol and terminal hydrophobic modified products thereof; cyclic vinyl-based monomers such as N-vinylpyrrolidone.

Examples of the unsaturated monocarboxylic acid salt include metal salts. Examples of the metal of the metal salt include alkali metals such as lithium, sodium and potassium.

Examples of the substituent in the (meth) acrylate include a hydroxyl group; an alkoxy group having 1 to 18 carbon atoms such as a methoxy group and an ethoxy group; an oxo group-containing group such as an oxyalkylene group, a sulfonic acid group and a phosphoric acid group; a fluoro group and the like. Harogeno group; epoxy group such as glycidyl group; carbonyl group such as aldehyde group and the like.

Examples of the alkyl (meth) acrylate having no substituent as described above include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. ) Acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) ) Cycloalkyl (meth) acrylate such as acrylate, n-lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl methacrylate and the like.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxy. Examples thereof include hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in ester groups such as butyl (meth) acrylates.

Examples of the alkoxyalkyl (meth) acrylate include methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, and trimethylolpropane tripropoxy (meth) acrylate. Can be mentioned.

Examples of the oxo group-containing (meth) acrylate include (di) ethylene glycol (methoxy) such as ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. Meta) acrylate; alkoxypolyalkylene glycol (meth) acrylate having 1 to 100 repetitions of alkylene glycol such as alkoxypolyethylene glycol methacrylate (Antox LMA-10); sulfopropyl (meth) acrylate; (meth) acryloyloxyethyl phosphate And so on.

Examples of the fluorogroup-containing (meth) acrylate include fluorogroups having 2 to 6 carbon atoms in ester groups such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Alkyl (meth) acrylate and the like can be mentioned.

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, and glycidyl allyl ether.

Examples of the carbonyl group-containing (meth) acrylate include acetonyl (meth) acrylate, diacetone (meth) acrylate, 2-hydroxypropyl (meth) acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, and 2- (aceto). Examples thereof include acetoxy) ethyl (meth) acrylate and (meth) acryloyloxyalkylpropenal.

The hydrophobic monomer (B) preferably contains at least one (meth) acrylic acid ester. That is, the copolymer of the present invention preferably has a structural unit derived from at least one (meth) acrylic acid ester.
The (meth) acrylic acid ester is represented by the following formula (11);

(In the formula, R ⁶ represents a hydrogen atom or a methyl group. R ⁷ represents a hydrocarbon group having 1 to 30 carbon atoms.) It is preferable that the compound is represented by.
The hydrocarbon group preferably has 1 to 20 carbon atoms. It is more preferably 1 to 16, still more preferably 1 to 12, and particularly preferably 1 to 8.
When the number of carbon atoms of the hydrocarbon group is 1 to 20, the water solubility and viscosity of the polymer can be in a suitable range, and the handling is excellent. When the hydrocarbon group has 1 to 12 carbon atoms, the polymer can be easily produced, and the safety is excellent in addition to the antibacterial property.

The hydrocarbon group is not particularly limited, and examples thereof include a chain hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group, and a cyclic hydrocarbon group such as an aromatic hydrocarbon group, a cycloalkyl group, and a cycloalkenyl group. .. The above-mentioned hydrocarbon group may have a branch, and the number of carbon atoms of the hydrocarbon group when having a branch means the total number of carbon atoms of the main chain and the branched chain.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group. , Stearyl group, icosyl group and the like.
Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group and an icosenyl group. And so on.
Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group and an icocinyl group. And so on.

Examples of the aromatic hydrocarbon group include a phenyl group, a benzyl group, a tolyl group, an o-kisilyl group and the like.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like.
The hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
That is, as the (meth) acrylic acid ester, a (meth) acrylic acid alkyl ester (alkyl (meth) acrylate) is preferable.

The alkyl (meth) acrylate is preferably methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-. Butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, more preferably methyl (meth) acrylate, ethyl (meth) acrylate, n- With propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate is there.

The detergent copolymer of the present invention is also a group consisting of a structural unit (b-1) derived from a (meth) acrylic acid alkyl ester, a solubility parameter of 15 or less, and a carboxyl group, a hydroxyl group, and an ether group. It is preferable that it has a structural unit (b-2) derived from a monomer having at least one functional group selected from the above. Copolymers having such structural units are also one of the preferred embodiments of the present invention.
The monomer having at least one functional group selected from the group consisting of the carboxyl group, the hydroxyl group and the ether group has a solubility parameter of 15 or less and is functional to any one of the carboxyl group, the hydroxyl group and the ether group. Any group may be used, and even if it has a (meth) acrylic acid ester structure, at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group. It shall be classified into a monomer having.
When the copolymer of the present invention has a structural unit (b-2), the water solubility of the copolymer is improved, and the copolymer is precipitated due to a change in salt or pH, the antibacterial property is lowered, and the like. Since the influence can be more sufficiently mitigated, the copolymer can be used in a wide pH range, and can be preferably used with a cleaning agent which is often in the neutral to weak alkaline range. The copolymer of the present invention also has the above-mentioned structure, so that the hydrophilicity of the copolymer is improved and the ability to prevent recontamination is further improved. Examples of the monomer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group include the above-mentioned unsaturated monocarboxylic acids; hydroxyl group-containing (meth) acrylates; alkyl vinyl ethers; and carbon atoms. Examples thereof include an alkylene oxide adduct of 2 to 20 unsaturated alcohols; an addition reaction product of an unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms and an alcohol having 1 to 20 carbon atoms.

Examples of the monomer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group include unsaturated monocarboxylic acids; hydroxyl group-containing (meth) acrylates; unsaturated alcohols having 2 to 20 carbon atoms. Alkylene oxide adduct: An addition reaction product of an unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms and an alcohol having 1 to 20 carbon atoms is preferable.
As the unsaturated monocarboxylic acids, (meth) acrylic acid and salts thereof are preferable.
As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate is preferable.

The unsaturated alcohol having 2 to 20 carbon atoms preferably has 2 to 18 carbon atoms, and examples of the unsaturated alcohol having 2 to 20 carbon atoms include vinyl alcohol, allyl alcohol, and isoprenyl alcohol.
The alkylene oxide adduct of the unsaturated alcohol having 2 to 20 carbon atoms preferably has 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, and styrene oxide. Ethylene oxide, propylene oxide and butylene oxide are more preferable, and ethylene oxide and propylene oxide are more preferable.
The average number of moles of the alkylene oxide added is preferably 1 to 100. It is more preferably 1 to 80, still more preferably 1 to 70, and particularly preferably 1 to 50.
As the alkylene oxide adduct of the unsaturated alcohol having 2 to 20 carbon atoms, an ethylene oxide adduct of isoprenol is preferable.

Examples of the alcohol having 1 to 20 carbon atoms include alkyl alcohols such as methanol, ethanol, propanol, butanol, pentanol and hexanol. It is preferably an alkyl alcohol having 2 to 16 carbon atoms such as ethanol, propanol and butanol.
As the addition reaction product of the unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms and an alcohol having 1 to 20 carbon atoms, 1-allyloxy-3-butoxypropan-2-ol is preferable.

The copolymer of the present invention has a structural unit (e) derived from the monomer (E) other than the cationic group-containing monomer (A) and the hydrophobic monomer (B). May be good. The other monomer (E) is not particularly limited as long as it can be copolymerized with the cationic group-containing monomer (A) and the hydrophobic monomer (B). The solubility parameter of the other monomer (E) in the homopolymer may be 15 or less or more than 15, and the solubility parameter of the monomer (E-) is larger than 15. The 1) is not particularly limited, and examples thereof include acrylonitrile.
The solubility parameter of the monomer (E-1) is preferably larger than 15 and 20 or less, more preferably larger than 15 and 17 or less.
Regardless of whether the solubility parameter of the other monomer is 15 or less or more than 15, the hydrophobicity as a copolymer is as long as the above hydrophobic monomer is polymerized at a preferable ratio. It will be sufficiently maintained.
Further, from the viewpoint of adjusting the viscosity, a monomer having two or more ethylenically unsaturated groups may be contained regardless of the value of the solubility parameter. Examples of the monomer having two or more ethylenically unsaturated groups include ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, pentaerythritol, saccharose, sorbitol, 1, Esters of disubstituted or higher hydroxyl groups of polyols such as 4-butanediol and (meth) acrylic acid; disubstituted or higher methacrylic acid esters of the above polyols; disubstituted or higher hydroxyl groups of the polyols and allyl alcohols, vinyl alcohols Ethers with unsaturated alcohols such as diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyethane, triallyl cyanurate, divinyl adipate, vinyl crotonate, 1,5-hexadiene, divinylbenzene, etc. Can be mentioned. These other monomers may be used alone or in combination of two or more.
From the viewpoint of improving the antibacterial property, the copolymer of the present invention may be copolymerized with a polymerizable metal salt as another monomer. Examples of the polymerizable metal salt include heavy metal salts of unsaturated carboxylic acids such as zinc acrylate, zinc methacrylate, and zinc α-allyloxyacrylate.

In the copolymer of the present invention, the proportion of the structural unit (a) derived from the cationic group-containing monomer (A) is preferably 15 to 99.9% by mass with respect to 100% by mass of the total structural units. .. It is more preferably 20 to 99% by mass, further preferably 20 to 98% by mass, even more preferably 25 to 95% by mass, still more preferably 25 to 94% by mass, and even more preferably 25. It is ~ 93% by mass, further preferably 25 to 90% by mass, particularly preferably 30 to 88% by mass, and most preferably 30 to 85% by mass.
The lower limit of the above ratio may be 36% by mass, 40% by mass, 50% by mass, or 55% by mass.

When the cationic group-containing monomer (A) is a tertiary amino group-containing monomer and / or a neutralized product of these acids, that is, the structural unit (a) in the copolymer (α). The ratio is preferably 20 to 99.9% by mass with respect to 100% by mass of all structural units. It is more preferably 25 to 99.9% by mass, further preferably 30 to 99.9% by mass, and even more preferably 36 to 99.9% by mass. That is, the copolymer for cleaning agent in which the ratio of the structural unit (a) in the copolymer (α) is 36 to 99.9% by mass with respect to 100% by mass of the total structural unit is a preferred embodiment of the present invention. There is one. The above ratio is even more preferably 40 to 99.9% by mass, further preferably 45 to 99.9% by mass, even more preferably 45 to 95% by mass, and particularly preferably 45 to 93% by mass. Yes, most preferably 45-90% by mass.
The lower limit of the above ratio may be 50% by mass, 55% by mass, or 60% by mass.

On the other hand, when the cationic group-containing monomer (A) is a quaternary ammonium salt, that is, the ratio of the structural unit (a) in the copolymer (β) is 15 to 99 with respect to 100% by mass of the total structural unit. It is preferably 9.9% by mass. It is more preferably 20 to 99% by mass, further preferably 20 to 98% by mass, even more preferably 20 to 97% by mass, still more preferably 20 to 95% by mass, and even more preferably 25. It is ~ 90% by mass, more preferably 25 to 85% by mass, and particularly preferably 25 to 80% by mass.
The lower limit of the above ratio may be 51% by mass, 53% by mass, 55% by mass, or 60% by mass.

The copolymer of the present invention, that is, the copolymer (α) and / or (β) has a structure derived from the hydrophobic monomer (B) with respect to a total amount of 100% by mass of the structural units forming the copolymer. It is preferable to have the unit (b) in a proportion of 0.01 to 85% by mass. It is more preferably 0.01 to 75% by mass, and even more preferably 0.01 to 64% by mass. Even more preferably 0.01 to 60% by mass, still more preferably 0.01 to 50% by mass, even more preferably 0.01 to 48% by mass, and even more preferably 0.01 to 45% by mass. It is particularly preferably 0.1 to 40% by mass, and most preferably 1 to 30% by mass.

When the cationic group-containing monomer (A) is a tertiary amino group-containing monomer and / or a neutralized product of these acids, that is, a hydrophobic monomer in the copolymer (α) ( The ratio of the structural unit (b) derived from B) is preferably 0.01 to 80% by mass with respect to 100% by mass of the total structural unit. It is more preferably 0.01 to 70% by mass, further preferably 0.01 to 64% by mass, even more preferably 0.01 to 60% by mass, still more preferably 0.01 to 55% by mass. It is even more preferably 0.01 to 50% by mass, particularly preferably 0.01 to 45% by mass, and most preferably 0.01 to 40% by mass.

When the cationic group-containing monomer (A) is a quaternary ammonium salt, that is, the proportion of the structural unit (b) derived from the hydrophobic monomer (B) in the copolymer (β) is the total structural unit. The ratio is preferably 0.01 to 85% by mass with respect to 100% by mass. It is more preferably 0.1 to 80% by mass, further preferably 1 to 75% by mass, even more preferably 2 to 70% by mass, still more preferably 3 to 65% by mass, and even more preferably. Is 4 to 55% by mass, further preferably 5 to 49% by mass, particularly preferably 10 to 47% by mass, particularly still more preferably 15 to 45% by mass, and most preferably 20 to 40% by mass. It is mass%.

In the copolymer of the present invention, the content ratio of the structural unit (b) derived from the hydrophobic monomer (B) in the copolymer is the structural unit derived from the cationic group-containing monomer (A) in the copolymer. (A) It is preferably 0.01 to 567% by mass with respect to 100% by mass. It is more preferably 0.1 to 400% by mass, further preferably 1 to 300% by mass, still more preferably 1.01 to 200% by mass, still more preferably 2.05 to 100% by mass, and further. It is more preferably 5.3 to 80% by mass, and particularly preferably 11.1 to 60% by mass. When the content ratio of the structural unit (b) in the copolymer of the present invention is within such a range, the antibacterial performance of the copolymer tends to be improved. The upper limit of the above ratio may be 50% by mass, 40% by mass, 35% by mass, or 25% by mass.

When the structural unit (b) derived from the hydrophobic monomer (B) of the copolymer of the present invention has the structural unit (b-1) derived from the (meth) acrylic acid alkyl ester, the structural unit (b-1) Is preferably 0.01 to 80% by mass with respect to 100% by mass of the total amount of the structural units forming the copolymer. It is more preferably 0.015 to 75% by mass, further preferably 1 to 70% by mass, and particularly preferably 5 to 65% by mass. The upper limit of the above ratio may be 55% by mass, 49% by mass, 40% by mass, or 30% by mass.

As described above, the copolymer of the present invention has a structural unit (a) derived from the cationic group-containing monomer (A), a structural unit (b-1) derived from the (meth) acrylic acid alkyl ester, and a carboxyl group. It may have a structural unit (b-2) derived from a monomer having at least one functional group selected from the group consisting of a hydroxyl group and an ether group, and may have a structural unit (b-2) in the above-mentioned copolymer. The ratio of -2) is preferably 0 to 100% by mass with respect to 100% by mass of the structural unit (b-1) derived from the (meth) acrylic acid alkyl ester. More preferably, it is 0 to 50% by mass.

In the copolymer of the present invention, the content ratio of the structural unit (e) derived from the other monomer (E) is 0 to 10% by mass with respect to 100% by mass of the total amount of the structural units forming the copolymer. Is preferable. It is more preferably 0 to 8% by mass, still more preferably 0 to 5% by mass.
When the structural unit (e-1) is contained among other monomers, the ratio of the structural unit (e-1) is 0 to 1 with respect to 100% by mass of the total amount of the structural units forming the copolymer. It is preferably mass%. More preferably, it is 0 to 0.5% by mass.
Among the other monomers, the content ratio of the structural unit derived from the monomer having two or more ethylenically unsaturated groups is 0 to 1% with respect to 100% by mass of the total amount of the structural units forming the copolymer. It is preferably 0 to 0.5% by mass, and even more preferably 0 to 0.1% by mass.

As the copolymer of the present invention, a copolymer composed of only a structural unit (a) derived from a cationic group-containing monomer (A) and a structural unit (b) derived from a hydrophobic monomer (B) is also used. , Which is one of the preferred forms. In this case, the total ratio of the structural unit (a) and the structural unit (b) is 100% by mass, and the ratio of each of these structural units is from 100% by mass to the ratio or structure of the above-mentioned structural unit (a). The value is obtained by subtracting the ratio of the unit (b).

The structure of the copolymer of the present invention includes a random copolymer structure, a graft structure, a block copolymer structure, a gradient copolymer structure, a star-shaped structure, a dendrimer structure, and the like, but any structure may be used. ..

<Method for producing copolymer>
The production of the copolymer of the present invention is not particularly limited, but it can be produced by polymerizing the monomer components, and specific examples, preferable examples and preferable ratios of each monomer component are each in the copolymer. As described in the structural unit.

The copolymer is preferably produced by a method of polymerizing the monomer component in the presence of a polymerization initiator. When polymerizing the monomer component, a polymerization initiator can be appropriately used depending on the polymerization method. As the polymerization initiator, commonly used ones can be used, for example, hydrogen peroxide; persulfate such as sodium persulfate and ammonium persulfate; dimethyl 2,2'-azobis (2-methylpropionate). ), 2,2'-Azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (isobutyric acid) dimethyl, 4,4'-azobis (4) -Cyanovaleric acid), 2,2'-azobis (2-methylpropion amidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine] n hydrate, 2,2'-Azobisisobuty [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydration Azobisisobuty, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide] and other azo compounds; benzoyl peroxide, peroxide Organic peroxides such as lauroyl, peracetic acid, and di-t-butyl peroxide are suitable. Of these polymerization initiators, azo compounds are preferable. The polymerization initiator is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.

The amount of the polymerization initiator used is not particularly limited as long as it can initiate the polymerization of the monomer component, but is usually 0.01 to 50 parts by mass with respect to 100 parts by mass of all the monomer components. , It is preferably 0.05 to 30 parts by mass, and more preferably 0.05 to 20 parts by mass.

As a method of using the cationic group-containing monomer used in the present invention, it may be used as an acid neutralized product obtained by neutralizing them with an acid or as a quaternary ammonium salt quaternized with a quaternary agent.
The acid used for neutralizing the cationic group-containing monomer is not particularly limited, but is not particularly limited. Inorganic acids such as hydrochloric acid and sulfuric acid; acetic acid, citric acid, tartaric acid, toluenesulfonic acid, lactic acid, succinic acid and glycol. Examples include organic acids such as acids.
The quaternizing agent for the cationic group-containing monomer is as described above.

When the acid or the quaternizing agent is used, the amount of these used is not particularly limited as long as a part or all of the cationic group-containing monomer is neutralized or quaternized, but the polymerization reaction is not particularly limited. The acid or quaternizing agent is preferably 0.1 to 1 mol with respect to 1 mol of the cationic group-containing monomer used in.

In the above copolymerization method, as a method of adding the monomer component, the polymerization initiator, etc. to the reaction vessel, all the monomer components are charged in the reaction vessel, and the polymerization initiator is added into the reaction vessel. Method of performing polymerization: A part of the monomer component is charged into the reaction vessel, and the polymerization initiator and the remaining monomer component are added continuously or stepwise (preferably continuously) into the reaction vessel. Method of performing copolymerization by: A method of charging a polymerization solvent in a reaction vessel and adding the entire amount of the monomer component and the polymerization initiator; one of the monomers (for example, a monomer containing a cationic group). A method of carrying out copolymerization by charging the part into a reaction vessel and adding the polymerization initiator and the remaining monomer components into the reaction vessel (preferably continuously) is preferable. Among such methods, since the molecular weight distribution of the obtained copolymer can be narrowed (sharpened), the copolymerization is carried out by sequentially dropping the polymerization initiator and the monomer component into the reaction vessel. Is preferable.

The copolymerization method can be carried out by, for example, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, living polymerization, graft polymerization and the like, and is not particularly limited, but solution polymerization is preferable. The solvent that can be used at this time is preferably water. When only water is used, it is preferable in that the solvent removal step can be omitted.

The above copolymerization method can be carried out by either a batch method or a continuous method. In addition, known solvents can be used as the solvent used in the copolymerization as needed, and water; monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butanol, and THF (tetrahydrofuran); Polyhydric alcohols such as glycerin, (poly) ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-heptane; acetic acid Esters such as ethyl; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide; ethers such as diethyl ether and dioxane are suitable. These may be used alone or in combination of two or more. Among these, one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms may be used from the viewpoint of the solubility of the monomer component and the obtained copolymer. preferable. The solvent is relatively inexpensive, and the production method of the present invention is economically excellent. Further, in the above-mentioned copolymerization method, a polyhydric alcohol solvent such as propylene glycol or ethylene glycol may be added to water for polymerization. When the above polyhydric alcohol solvent is used in combination with water, the solubility of the polymer can be enhanced, and soap-free polymerization can be suppressed more sufficiently. As a result, the formation of a polymer having poor water solubility can be more sufficiently suppressed, and the transparency of the solution can be further improved.
When the polyhydric alcohol solvent and water are used in combination, the ratio of the polyhydric alcohol solvent to 100% by mass of water is preferably 0 to 200% by mass.
In the method for producing a copolymer of the present invention, any chain transfer agent, pH adjuster, buffer, or the like can be used, if necessary.

The temperature at the time of polymerization is not particularly limited, but is usually 50 to 120 ° C, preferably 60 to 110 ° C. When the temperature at the time of polymerization is within the above range, the residual monomer component tends to decrease. It is not necessary to keep the temperature at the time of polymerization constant during the progress of the polymerization reaction. For example, the polymerization is started from room temperature and the temperature is raised to a set temperature at an appropriate temperature rise time or rate. After that, the set temperature may be maintained, or the polymerization temperature may be changed (increased or lowered) with time during the progress of the polymerization reaction depending on the dropping method of the monomer component, the initiator, or the like. May be good. Further, when the monomer component is polymerized, it is preferable to appropriately stir the monomer component so that the monomer component is polymerized uniformly.

The polymerization time is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours. In the present invention, the "polymerization time" represents the time during which the monomer is heated and stirred before the dropping, the time during which the monomer is added, and the aging time after the dropping of the monomer.

The pressure in the reaction system may be normal pressure (atmospheric pressure), reduced pressure, or pressurized pressure. The atmosphere in the reaction system may be either an air atmosphere or an inert atmosphere.

The solid content concentration in the aqueous solution (that is, the polymerized solid content concentration of the monomer) at the time when the polymerization reaction in the above polymerization reaction system is completed is preferably 20% by mass or more, more preferably 25 to 80% by mass. .. As described above, when the solid content concentration at the end of the polymerization reaction is as high as 20% by mass or more, the polymerization can be carried out at a high concentration and in one step. Therefore, the copolymer can be efficiently obtained, for example, the concentration step which is necessary in some cases in the conventional production method can be omitted. Therefore, the production efficiency can be significantly increased, and as a result, the productivity of the copolymer of the present invention can be significantly improved, and the increase in production cost can be suppressed.

In the method for producing a copolymer of the present invention, an aging step may be provided for the purpose of increasing the polymerization rate of the monomer after the addition of all the raw materials used is completed. The aging time is usually 1-240 minutes, preferably 1-180 minutes, more preferably 1-120 minutes. If the aging time is less than 1 minute, the monomer component may remain due to insufficient aging, and toxicity and odor caused by the residual monomer become a problem.

The temperature of the polymer solution preferable in the aging step is in the same range as the above-mentioned polymerization temperature. Therefore, the temperature here may be maintained at a constant temperature (preferably the temperature at the time when the dropping is completed), or the temperature may be changed over time during aging.

<Detergent and detergent composition>
The present invention is also a cleaning agent containing the copolymer for cleaning agent of the present invention.
As described above, since the copolymer of the present invention exhibits antibacterial performance, the cleaning agent can also be said to be a cleaning agent containing an antibacterial agent. Further, a method of using the above-mentioned copolymer for cleaning agent as a detergent builder or a detergent composition is also one of the present inventions.
The cleaning agent may contain the copolymer of the present invention and other components other than the copolymer, and other components include a surfactant, an additive used in a detergent, a polymerization initiator residue, and the like. Residual monomers, by-products during polymerization, moisture and the like can be mentioned, and one or more of these can be contained.
Among these components, the surfactant is the main cleaning component, and the cleaning agent preferably contains a surfactant. That is, a detergent composition containing an antibacterial agent and a surfactant, which is a copolymer for a detergent of the present invention, is also one of the present inventions.
The detergent composition may contain the above other components other than the surfactant.
The content of the above-mentioned copolymer in the cleaning agent or the cleaning agent composition is not particularly limited, but is preferably 0.001 to 20% by mass, more preferably 0.001 to 20% by mass, based on 100% by mass of the total amount of the cleaning agent or the cleaning agent composition. It is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass.
The specific form of the surfactant or additive is not particularly limited, and findings generally known in the field of detergents can be referred to as appropriate.
The cleaning agent is not particularly limited, and examples thereof include powder detergents for clothing and liquid detergents.

As the surfactant, one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 50% by mass or more, based on 100% by mass of the total amount of the surfactant. It is 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by 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 and its ester salt, and alkane sulfonic acid. Salt, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester and its salt, alkenyl phosphate ester And its salt and the like are preferably mentioned. The alkyl group and alkenyl group in these anionic surfactants may be linear or branched.
When the cleaning agent or cleaning agent composition contains an anionic surfactant, the antibacterial performance against yellow staphylococcus is further improved, and the copolymer of the present invention can be used as the hydrophobic monomer (B). , (Meta) Acrylic acid alkyl ester-derived structural unit, and a monomer derived from a monomer having a solubility parameter of 15 or less and having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group. When it has a structural unit and / or a structural unit derived from a monomer having a solubility parameter larger than 15, the anti-recontamination ability and antibacterial performance can be more effectively exhibited.

Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides and their alkylene oxide adducts, sucrose fatty acid esters, alkyl glycolides, and fatty acid glycerin mono. Esters, alkylamine oxides and the like are preferably mentioned. The alkyl group and alkenyl group in these nonionic surfactants may be linear or branched chain.
As the cationic surfactant, a quaternary ammonium salt or the like is suitable. Further, as the amphoteric tenside, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are suitable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be linear or branched.

The blending (containing) ratio of the surfactant is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further, based on 100% by mass of the total amount of the detergent or the detergent composition. It is preferably 15 to 50% by mass, more preferably 20 to 45% by mass, and particularly preferably 25 to 40% by mass. If the blending ratio of the surfactant is less than 10% by mass, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is more than 60% by mass, the economic efficiency may be lowered and the stability may be reduced. It can get worse.

Additives include detergent builders, stain inhibitors (benzotriazole, ethylene-thiourea, etc.), soil release agents, color transfer inhibitors, fabric softeners, pH adjusting alkaline substances, fragrances, solubilizers, fluorescent agents, coloring agents. Preferable examples include agents, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes (proteas, lipases, cellulase, etc.), dyes, solvents and the like. Further, in the case of a powder detergent composition, it is preferable to add zeolite.
The cleaning composition preferably contains at least one additive selected from the group consisting of enzymes, fluorescent agents, solvents and detergent builders.

The detergent builder is not particularly limited, but for example, an alkaline builder such as carbonate, hydrogen carbonate, silicate, sulfate; tripolyphosphate, pyrophosphate, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, etc. Chelatebuilders such as diethylenetriamine pentaacetate, citrate, diglycolate, oxycarboxylate, (meth) acrylic acid copolymer salt, acrylic acid-maleic acid copolymer, fumarate, zeolite, etc. Examples thereof include carboxyl derivatives of polysaccharides such as methyl cellulose. Examples of the salt used in the builder include alkali metals such as sodium and potassium, ammonium, amines and the like.

As the above-mentioned enzyme, an enzyme usually used for clothes detergent applications and the like can be used, and examples thereof include protease, amylase, lipase, cellulase, and mannase.
The content of the enzyme in the detergent or the detergent composition is preferably 0.01 to 3% by mass with respect to 100% by mass of the total amount of the detergent or the detergent composition.

The total blending ratio of the above additives is preferably 0.1 to 50% by mass with respect to 100% by mass of the detergent or the detergent composition. It is more preferably 0.2 to 40% by mass, further preferably 0.3 to 35% by mass, particularly preferably 0.4 to 30% by mass, and most preferably 0.5 to 20% by mass. is there. If the total blending ratio of the additives is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 50% by mass, the economic efficiency may decrease.

The copolymer for a cleaning agent of the present invention has the above-mentioned structure, is excellent in sustainability of antibacterial performance during washing and antibacterial performance after washing, and is also excellent in anti-recontamination ability, and is therefore preferably used as a cleaning agent or the like. be able to.

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

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

<Minimum inhibitory concentration (MIC)>
An aqueous solution containing an antibacterial agent (copolymer) was sequentially diluted 2-fold in Mueller-Hinton medium to prepare a dilution series of the antibacterial agent-containing medium. Then, 50 μL of a medium containing each concentration of antibacterial agent was added to a polystyrene 96-well plate. Next, colonies of Escherichia coli (Escherichia coli, NBRC-3972, NBRC-15304) or Staphylococcus aureus (NBRC-12732, NBRC-15835) grown on Mueller-Hinton agar medium for 18 hours were subjected to butterfield buffer. To prepare a bacterial solution of about 10 × 10 ^{8 cells / mL. The prepared bacterial solution was diluted to about 10 × 10 6} cells / mL in Mueller-Hinton medium, and 50 μL was added to each dilution series prepared above. After standing at 35 ° C. for 20 hours, the minimum antibacterial agent concentration (ppm) in the medium in which the bacteria did not grow was determined as the minimum inhibitory concentration (MIC). The presence or absence of bacterial growth was visually determined by whether the turbidity had increased.

<Bactericidal test (time-kill test)>
A bactericidal test of an aqueous solution containing 10 ppm of a polymer obtained as an antibacterial agent, 100 ppm of a nonionic surfactant as a detergent, and 5 ppm of polyoxyethylene lauryl ether was carried out according to ASTM E-2315-03, with a contact time of 10 minutes. I went there. The bacterial species used in the test are Escherichia coli (NBRC-3972) and Staphylococcus aureus (NBRC-12732).
Shown a decrease in the viable count value bactericidal activity values shown in logarithm (log) as (A), viable cell count of the control antibacterial agent was not added is a ^107, the viable cell material obtained by adding antimicrobial agents if the number is 10 ^2, bactericidal activity value is 5. The bactericidal activity value was evaluated according to the following criteria, and the bactericidal property was judged.
A> 1: ◎
0.5 <A ≤ 1: 〇 0.2 <A ≤ 0.5: Δ
A ≤ 0.2: ×

<Sustainability evaluation (simulated washing test)>
Cotton cloth (Kanakin No. 3, Japanese Standards Association) was cut into 0.4 g portions, sterilized in a vial, and dried. Next, the sterilized and dried cloth was impregnated with 5 ml of an aqueous solution having the composition shown in Table 1 for 30 minutes to prepare a test cloth 1.
Then, the impregnated test cloth 1 was sandwiched between clean paper towels and dehydrated by applying pressure. Subsequently, rinsing and dehydration were performed three times each. For rinsing and dehydration, the cloth was stirred (rinsed) in a beaker containing 20 ml of ultrapure water, sandwiched between paper towels, and dehydrated by applying pressure. After rinsing and dehydrating three times, the test cloth 2 was divided into vials one by one and dried overnight.
The antibacterial property test of test cloths 1 and 2 was carried out in accordance with JIS L1902: 2008. Put test cloths 1 and 2 treated with the vial bottle, there E. coli the bacteria count was adjusted ^{10 5 CFU / ml (Escherichia coli} , NBRC-3972) bacteria or Staphylococcus aureus (Staphylococcus aureus, NBRC-12732) 0.2 ml of the solution was inoculated and statically cultured at 37 ° C. for 18 hours. To the vial after culturing, 20 ml of physiological saline containing 0.7% by weight of polysorbate 80 and 0.1% by weight of soybean lecithin was added and shaken. A dilution series was prepared by a 10-fold dilution method, applied to Mueller-Hinton medium, inoculated, and then cultured at 37 ° C. for 24 hours to measure the viable cell count. The number of bacteria sterilized is logarithmic compared to the number of bacteria obtained by subtracting the number of bacteria in the case of the test cloth subjected to the above treatment from the number of bacteria in the case of performing the same test as above on the cloth treated with water containing no antibacterial component. displayed.
The number of sterilized products on the test cloth 2 / the number of sterilized products on the test cloth 1 × 100 (%) was defined as the durability of the antibacterial agent, and was judged according to the following criteria.
70% or more: ◎
50% or more and less than 70%: 〇 20% or more and less than 50%: △
Less than 20%: ×

<Evaluation of carbon black (CB) recontamination prevention ability>
(1) A polyester cloth obtained from Test fabric was cut into 5 cm × 5 cm pieces to prepare a white cloth. The whiteness of this white cloth was measured in advance by the reflectance using a colorimetric color difference meter SE6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
(2) Pure water was added to 7.5 g of calcium chloride dihydrate to make 17 kg, and hard water was prepared.
(3) Pure water was added to 4.0 g of polyoxyethylene (8) lauryl ether to make 100.0 g, and an aqueous surfactant solution was prepared. The pH was adjusted to 8.5 with sodium hydroxide.
(4) The turgot meter was set at 25 ° C., 1 L of hard water, 1 g of an aqueous surfactant solution, 1 g of a 5% polymer aqueous solution in terms of solid content, and 0.1 g of carbon black were placed in a pot and stirred at 100 rpm for 1 minute. .. Then, 5 pieces of white cloth were put in and stirred at 100 rpm for 10 minutes.
(5) The water of the white cloth was drained by hand, 1 L of hard water at 25 ° C. was put into a pot, and the mixture was stirred at 100 rpm for 2 minutes.
(6) A cloth was applied to a white cloth and dried while smoothing wrinkles with an iron, and then the whiteness of the white cloth was measured again by the reflectance with the above colorimetric color difference meter.
(7) From the above measurement results, the recontamination prevention ability was determined by the following formula.
(8) Recontamination prevention ability (%) = [(whiteness after washing) / (whiteness of raw white cloth)] x 100
70% or more: ◎
50% or more and less than 70%: 〇 30% or more and less than 50%: △
Less than 30%: ×

<Example 1>
65.0 g of pure water and 24 g of propylene glycol were placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, 2- (dimethylamino) ethyl methacrylate (N, N-dimethylaminoethyl methacrylate) (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter also referred to as DAM) was placed in a polymerization reaction system at a constant state of 90 ° C. Monomer solution 1; 2,2'-azobis (2-methylpropionamidine) dihydrochloride consisting of 48.3 g, 17.5 g of acetate and 18.1 g of butyl acrylate (hereinafter also referred to as BA. Solubility parameter: 9.75) Initiator aqueous solution consisting of 30.1 g of 5% aqueous solution of salt (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter also referred to as V-50); monomer solution 2 consisting of 24.12 g of DAM and 8.77 g of acetic acid are separately added dropwise. Dropped from the nozzle. Regarding the dropping time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the initiator aqueous solution was dropped for 210 minutes. The monomer solution 2 was added dropwise over 60 minutes after the completion of the addition of the monomer solution 1.
After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 30 minutes for aging to complete the polymerization, and the copolymer 1 was obtained.
The solid content of the obtained copolymer 1 was 37.9%, the pH was 6.6, and the weight average molecular weight was 28,200.

<Example 2>
45.0 g of pure water was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution 1 composed of 39.3 g of DAM, 14.3 g of acetic acid and 6.54 g of ethyl methacrylate (hereinafter, also referred to as EMA; solubility parameter: 9.71); An initiator aqueous solution consisting of 22 g of a 10% aqueous solution of V-50; a monomer solution 2 composed of 19.6 g of DAM and 7.13 g of acetic acid was added dropwise from separate dropping nozzles.
Regarding the dropping start time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the initiator aqueous solution was dropped for 210 minutes. The monomer solution 2 was added dropwise over 60 minutes after the completion of the addition of the monomer solution 1. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 30 minutes for aging to complete the polymerization, and the copolymer 2 was obtained.
The solid content of the obtained copolymer 2 was 39.7%, the pH was 6.75, and the weight average molecular weight was 15,800.

<Example 3>
Polymerization was carried out in the same manner as in Example 2 except that the initiator aqueous solution was changed to 21.6 g of a 5% aqueous solution of V-50 to obtain a copolymer 3.
The solid content of the obtained copolymer 3 was 39%, the pH was 6.83, and the weight average molecular weight was 28,800.

<Example 4>
Polymerization was carried out in the same manner as in Example 3 except that the initiator aqueous solution was changed to 36.3 g of a 2.5% aqueous solution of V-50 to obtain a copolymer 4.
The solid content of the obtained copolymer 4 was 40.9%, the pH was 6.82, and the weight average molecular weight was 69,900.

<Example 5>
Polymerization was carried out in the same manner as in Example 3 except that N, N-dimethylaminoethyl methacrylate (DAM) in the monomer solutions 1 and 2 was changed to diethylaminoethyl methacrylate (hereinafter, also referred to as DEAM) to obtain the copolymer 5. Obtained.
The solid content of the obtained copolymer 5 was 36.9%, the pH was 6.7, and the weight average molecular weight was 28,400.

<Example 6>
A copolymer 6 was obtained in the same manner as in Example 5 except that the monomer solution 2 was changed to BA.
The solid content of the obtained copolymer 6 was 37.2%, the pH was 6.5, and the weight average molecular weight was 32,000.

<Example 7>
25 g of deionized water and 70 g of propylene glycol were charged in a separable flask, and 73.7 g of dimethylaminoethyl methacrylate quaternized product (hereinafter referred to as DQ-100, manufactured by Kyoeisha Chemical Co., Ltd.) was weighed as a monomer solution 1, and 50.9 g of deionized water The one dissolved in was used. The initiator aqueous solution was 25 g of a 2.5% aqueous solution of V-50, BA was 12.8 g as the monomer solution 2, and the dropping time was 180 minutes for the monomer solution 1, 180 minutes for the monomer solution 2, and 210 minutes for the initiator aqueous solution. A copolymer 7 was obtained in the same manner as in Example 1 except for the above.
The solid content of the obtained copolymer 7 was 37%, the weight average molecular weight was 25,600, and the pH was 5.5.

<Example 8>
20 g of deionized water and 70 g of propylene glycol were charged in a separable flask, 54.0 g of DQ-100 was weighed as the monomer solution 1, and the solution was dissolved in 37.8 g of deionized water. Polymerization was carried out in the same manner as in Example 5 except that the initiator aqueous solution was 35.9 g and the monomer solution 2 was EMA 36.0 g to obtain a copolymer 8.
The solid content of the obtained copolymer 8 was 37.7%, the weight average molecular weight was 19,500, and the pH was 5.0.

<Example 9>
The copolymer 9 was obtained in the same manner as in Example 6 except that 63 g of DQ-100 and 44.1 g of deionized water were used as the monomer solution 1 and 27 g of BA was used as the monomer solution 2.
The solid content of the obtained copolymer 9 was 37.7%, the weight average molecular weight was 14,300, and the pH was 5.5.

<Example 10>
65.0 g of pure water and 24 g of propylene glycol were placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution 1 consisting of 67.9 g of DAM, 13.6 g of BA, and 26 g of acetic acid; an aqueous initiator solution consisting of 26.9 g of a 5% aqueous solution of V-50; ethylene oxide in isoprenol. A monomer solution 2 consisting of 11.3 g of a monomer (hereinafter, also referred to as IPN10; solubility parameter: 8.17, solid content 80%) to which 10 mol of the mixture was added was added dropwise from separate dropping nozzles.
The dropping time was 180 minutes for the monomer solution 1, 90 minutes for the monomer solution 2, and 210 minutes for the initiator aqueous solution. Other polymerization methods were polymerized in the same manner as in Example 7 to obtain a copolymer 10.
The solid content of the obtained copolymer 10 was 37.3%, the pH was 6.7, and the weight average molecular weight was 38,100.

<Example 11>
50 g of pure water and 22 g of propylene glycol were placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution 1 consisting of 63 g of DAM, 24.1 g of acetic acid and 22.5 g of BA; an initiator aqueous solution consisting of 31.9 g of a 5% aqueous solution of V-50; 18% acrylic A monomer solution 2 composed of 25.6 g of an aqueous acid (solubility parameter: 14.1) aqueous solution was added dropwise from separate dropping nozzles. With respect to the dropping start time, the monomer solution 1 was dropped for 180 minutes, and the initiator aqueous solution and the monomer solution 2 were dropped for 210 minutes. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 30 minutes for aging to complete the polymerization, and the copolymer 11 was obtained.
The solid content of the obtained copolymer 11 was 34.9%, the pH was 6.15, and the weight average molecular weight was 49,500.

<Example 12>
14 g of pure water and 39 g of propylene glycol were placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, a monomer consisting of 34.0 g of 2- (tert-butylamino) ethyl methacrylate (hereinafter, also referred to as t-BDAM), 10.4 g of acetic acid, and 42.4 g of water was placed in a polymerization reaction system at a constant state of 90 ° C. Solution 1; an initiator aqueous solution consisting of 23.5 g of a 2.5% aqueous solution of V-50; and a monomer solution 2 consisting of 8 g of butyl acrylate were added dropwise from separate dropping nozzles. With respect to the dropping start time, the monomer solution 1 was dropped for 180 minutes, and the initiator aqueous solution and the monomer solution 2 were dropped for 210 minutes. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 30 minutes for aging to complete the polymerization, and a copolymer 12 was obtained.
The solid content of the obtained copolymer 12 was 21.7%, the pH was 6.03, and the weight average molecular weight was 21,600.

<Example 13>
14 g of pure water and 39 g of propylene glycol were placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution 1 consisting of 110.4 g of diallyldimethylammonium chloride (hereinafter, also referred to as DADMAC, manufactured by Osaka Soda Co., Ltd., solid content 65.2%); V-50. A starter solution consisting of 29.3 g of a 5% aqueous solution of the above; a monomer solution 2 consisting of 18 g of butyl acrylate was added dropwise from separate dropping nozzles. With respect to the dropping start time, the monomer solutions 1 and 2 were dropped for 180 minutes, and the initiator aqueous solution and the monomer solution 2 were dropped for 210 minutes. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 30 minutes for aging to complete the polymerization, and a copolymer 13 was obtained.
The solid content of the obtained copolymer 13 was 39%, the pH was 5.6, and the weight average molecular weight was 5,100.

<Example 14>
70 g of 1,3-butanediol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution consisting of 67.5 g of DAM and 18 g of EMA: an initiator aqueous solution consisting of 31.6 g of a V-50 5% aqueous solution and 15.6 g of a 29% acrylic acid aqueous solution. The monomer solution 2 was added dropwise from separate dropping nozzles.
With respect to the dropping start time, the monomer solutions 1 and 2 were dropped for 180 minutes, and the initiator aqueous solution and the monomer solution 2 were dropped for 210 minutes.
After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 90 minutes for aging to complete the polymerization. 113.8 g of pure water was added to obtain a copolymer 14.
The solid content of the obtained copolymer 14 was 27.7%, the pH was 9.0, and the weight average molecular weight was 29,100.

<Example 15>
60 g of 1,3-butanediol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution consisting of 81 g of DEAM and 28.1 g of a 5% aqueous solution of V-50 1: a monomer consisting of an initiator aqueous solution and 21.3 g of a 42.4% acrylic acid aqueous solution. The solution 2 was added dropwise from separate dropping nozzles. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 90 minutes for aging to complete the polymerization. 60 g of pure water was added to obtain a copolymer 15.
The solid content of the obtained copolymer 15 was 32.9%, the pH was 8.8, and the weight average molecular weight was 22,100.

<Example 16>
25 g of pure water and 50 g of propylene glycol were placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution 1 consisting of 45 g of DAM, 20.6 g of acetic acid and 42.3 g of BA; an initiator aqueous solution consisting of 26.2 g of a 10% aqueous solution of V-50; 20.3. The monomer solution 2 composed of 13.4 g of the% AA aqueous solution was added dropwise from separate dropping nozzles. Regarding the dropping start time, the monomer solution 1 and the monomer solution 2 were dropped for 140 minutes, and the initiator aqueous solution was dropped for 240 minutes. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 30 minutes for aging to complete the polymerization, and 50 g of pure water was added to obtain a copolymer 16. The solid content of the obtained copolymer 16 was 31.4%, the pH was 5.7, and the weight average molecular weight was 68,800.

<Example 17>
A copolymer 17 was obtained in the same manner as in Example 16 except that 75 g of propylene glycol was charged in a separable flask and the monomer solution 1 was 36 g of DAM, 16.5 g of acetic acid and 51.3 g of BA. The solid content of the obtained copolymer 17 was 32.1%, the pH was 5.7, and the weight average molecular weight was 18,700.

<Example 18>
Example 17 except that the monomer solution 1 was 27 g of DAM, 12.4 g of acetic acid, BA50.4, the monomer solution 2 was 14.5 g of a 24.8% AA aqueous solution, and the initiator aqueous solution was 24.6 g of a 10% V-50 aqueous solution. The copolymer 18 was obtained in the same manner as in the above. The solid content of the obtained copolymer 18 was 31%, the pH was 5.7, and the weight average molecular weight was 12,000.

<Example 19>
Example 18 except that the monomer solution 1 was DAM 45 g, acetic acid 20.6 g, 2EHA 41.4 g, the monomer solution 2 was 14.5 g of a 24.8% AA aqueous solution, and the initiator aqueous solution was 22.4 g of a 10% V-50 aqueous solution. The copolymer 19 was obtained in the same manner as in the above. The solid content of the obtained copolymer 19 was 31.1%, the pH was 5.6, and the weight average molecular weight was 15,000.

<Example 20>
The copolymer 20 was obtained in the same manner as in Example 19 except that the monomer solution 1 was 36 g of DAM, 16.5 g of acetic acid, 2EHA 49.5 g, and the monomer solution 2 was 15.6 g of a 28.7% AA aqueous solution. The solid content of the obtained copolymer 20 was 31.3%, the pH was 5.6, and the weight average molecular weight was 16,600.

<Example 21>
Monomer solution 1 is composed of 45 g of DAM, 24.1 g of citrate monohydrate, 18.1 g of ion-exchanged water and 42.3 g of BA. A copolymer 21 was obtained in the same manner as in Example 20 except that the -50 aqueous solution was 26.2 g, the dropping time of the monomer solution 2 was 100 minutes, and the dropping time of the monomer solution 3 was 140 minutes. The solid content of the obtained copolymer 21 was 33.6%, the pH was 5.8, and the weight average molecular weight was 16,500.

<Example 22>
80 g of ion-exchanged water is charged in a separable flask, the monomer solution 1 is composed of 81 g of DMAPAA, 24.9 g of acetic acid, and 45.4 g of water, and the monomer solution 2 is added to 9 g of N-vinylpyrrolidone (hereinafter, also referred to as NVP) as an initiator. The copolymer 22 was obtained in the same manner as in Example 1 except that the aqueous solution was composed of 20.9 g of a 10% V-50 aqueous solution and the dropping time of the monomers 1 and 2 solutions was 120 minutes from the start of polymerization. .. The solid content of the obtained copolymer 22 was 35.2%, the pH was 7.5, and the weight average molecular weight was 23,800.

<Example 23>
80 g of propylene glycol was charged in a separable flask, 36.0 g of DQ-100 was weighed as the monomer solution 1, and the solution was dissolved in 25.2 g of deionized water. The same as in Example 1 except that the initiator aqueous solution was 24.4 g of a 10% aqueous solution of V-50, BA was 54 g as the monomer solution 2, the dropping time of the monomer solution was 140 minutes, and the dropping time of the monomer solution was 100 minutes. The above was polymerized to obtain a copolymer 23.
The solid content of the obtained copolymer 23 was 31.2%, the pH was 5.4, and the weight average molecular weight was 10,100.

<Example 24>
100 g of propylene glycol was charged in a separable flask, 18.0 g of DQ-100 was weighed as the monomer solution 1, and the solution was dissolved in 12.6 g of deionized water. Polymerization was carried out in the same manner as in Example 23 except that the initiator aqueous solution was 26.2 g and the monomer solution 2 was BA 72 g to obtain a copolymer 24.
The solid content of the obtained copolymer 24 was 30.9%, the pH was 6.0, and the weight average molecular weight was 7,600.

<Example 25>
Polymerization was carried out in the same manner as in Synthesis Example 24 except that the monomer solution 2 was 54 g of 2EHA and the initiator aqueous solution was 19.3 g of a 10% aqueous solution of V-50 to obtain a copolymer 25.
The solid content of the obtained copolymer 25 was 33.4%, the pH was 4.9, and the weight average molecular weight was 8,000.

<Example 26>
Polymerization was carried out in the same manner as in Example 23 except that 72 g of 2EHA was used as the monomer solution 2, to obtain a copolymer 26. The obtained copolymer 26 had a solid content of 31.5%, a pH of 5.6, and a weight average molecular weight of 5,200.

<Example 27>
24 g of pure water and 72 g of propylene glycol were charged in a separable flask, the monomer solution 1 was DAM 54 g, acetic acid 20.6 g and BA 36 g, and the initiator aqueous solution was 2.5% V-50 32.5 g, and the monomer solution 2 The copolymer 27 was obtained in the same manner as in Example 1 except that the above was not used.
The solid content of the obtained copolymer 27 was 35.2%, the pH was 6.7, and the weight average molecular weight was 22,000.

<Example 28>
A copolymer 28 was obtained in the same manner as in Example 27 except that 39 g of pure water and 71 g of propylene glycol were charged in a separable flask, and the monomer solution 1 was 54 g of DAM, 20.6 g of acetic acid and 36 g of 2EHA. The solid content of the obtained copolymer 28 was 36.4%, the pH was 6.7, and the weight average molecular weight was 70,700.

<Example 29>
A copolymer 29 was obtained in the same manner as in Example 28 except that 26 g of pure water and 74 g of propylene glycol were charged in a separable flask, and the monomer solution 1 was 54 g of DAM, 20.6 g of acetic acid and 36 g of EMA. The solid content of the obtained copolymer 29 was 34.4%, the pH was 6.7, and the weight average molecular weight was 44,600.

<Example 30>
Performed except that 26 g of pure water and 74 g of propylene glycol were charged in a separable flask, the monomer solution 1 was 54.0 g of DAM, 20.6 g of acetic acid and 36.0 g of EMA, and the initiator aqueous solution was 65.9 g of a 15% V-50 aqueous solution. The copolymer 30 was obtained in the same manner as in Example 29.
The solid content of the obtained copolymer 30 was 30.3%, the pH was 6.6, and the weight average molecular weight was 6,900.

<Example 31>
26 g of pure water and 74 g of propylene glycol were charged in a separable flask, the monomer solution 1 was 51.3 g of DAM, 19.6 g of acetic acid and 36.0 g of EMA, the initiator aqueous solution was 68 g of a 15% V-50 aqueous solution, and the monomer solution 2 was 20.3. A copolymer 31 was obtained in the same manner as in Example 16 except that the amount was 13.4 g of the% AA aqueous solution.
The solid content of the obtained copolymer 31 was 30.3%, the pH was 6.7, and the weight average molecular weight was 7,000.

<Example 32>
75 g of propylene glycol and 26 g of ion-exchanged water were charged in a separable flask, the monomer solution 1 was 51.3 g of DAM, 20.6 g of acetic acid and 36.0 g of BA, 68 g of a 15% V-50 aqueous solution as an initiator aqueous solution, and 20. Polymerization was carried out in the same manner as in Example 16 except that the amount was 13.4 g of a 3% AA aqueous solution to obtain a copolymer 32. The solid content of the obtained copolymer 32 was 28.1%, the pH was 6.5, and the weight average molecular weight was 6,900.

Measurement of the minimum inhibitory concentration (MIC) of the copolymers 1 to 15 obtained in Examples 1 to 15 and benzalkonium chloride and hexadecyltrimethylammonium chloride (also referred to as HDAC) as Comparative Examples 1 and 2. , A bactericidal test (time-kill test) and a sustainability evaluation (simulated washing test) were performed. The results are shown in Table 2. In the table below, Ec represents Escherichia coli and Sa represents Staphylococcus aureus.

The minimum inhibitory concentration (MIC) was measured for the copolymers 16 to 32 obtained in Examples 16 to 32. The results are shown in Table 3.

Claims (9)

A laundry detergent builder containing a copolymer having a structural unit (a) derived from a cationic group-containing monomer (A) and a structural unit (b) derived from a hydrophobic monomer (B).
The copolymer has the following formulas (4) and / or (5) as the structural unit (a);

(In formulas (4) and (5), R ¹ and R ² represent the same or different hydrocarbon atoms or hydrocarbon groups having 1 to 12 carbon atoms. Z represents a hydrogen atom or a methyl group. Is the following formula (8) or (10);

(In the formula, i represents an integer of 0 to 12. k represents an integer of 0 to 4.). X ⁻ represents an anion. It has a structural unit derived from the cationic group-containing monomer (A) represented by), and the ratio of the structural unit (a) is 55 to 90% by mass with respect to 100% by mass of the total structural unit. , A copolymer (α) having a weight average molecular weight of 10 to 1,000,000 ( excluding those having a structural unit derived from a crosslinkable monomer) , or.
The following formula (6) as the structural unit (a);

(In the formula (6), R ^{3 to} R ⁵ represent the same or different hydrocarbon groups having 1 to 12 carbon atoms. Z represents a hydrogen atom or a methyl group. Y represents the above formula (8). Alternatively, it represents the structure represented by (10) ^{. X −} represents a cationic group-containing monomer (A) represented by) and has a structural unit derived from the cationic group-containing monomer (A).
The hydrophobic monomer (B) has a solubility parameter of 15 or less as a homopolymer, and has a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, a phosphoric acid group, a halogeno group, an epoxy group and the like. which it may have at least one substituent selected from the group consisting of carbonyl group-containing (meth) acrylate; unsaturated monocarboxylic acids; Kaoru aromatic vinyl monomer; olefin monomer; not Ester of saturated alcohol and carboxylic acid; vinyl halide; alkyl vinyl ethers; addition reaction product of unsaturated monomer having cyclic ether-containing group having 2 to 8 carbon atoms and alcohol having 1 to 20 carbon atoms; carbon number of carbon atoms An alkylene oxide adduct of 2 to 20 unsaturated alcohols and their terminal hydrophobic modified products; at least one compound selected from the group consisting of cyclic vinyl-based monomers.
The ratio of the structural unit (a) is 55 to 99.9% by mass with respect to 100% by mass of all structural units.
The ratio of the structural unit (e) derived from the monomer (E) other than the cationic group-containing monomer (A) and the hydrophobic monomer (B) is 0 with respect to 100% by mass of the total structural unit. It is 10% by mass,
The other monomer (E) is at least one compound selected from the group consisting of vinyl crotonic acid, unsaturated carboxylic acid heavy metal salt, and,
A detergent builder for laundry detergent, which is a copolymer (β) having a weight average molecular weight of 1,000 to 200,000. The copolymer (α) and / or (β) has a structural unit (b) derived from the hydrophobic monomer (B) of 0 with respect to a total amount of 100% by mass of the structural units forming the copolymer. The detergent builder for a laundry detergent according to claim 1, which has a ratio of 0.01 to 45% by mass. The detergent builder for laundry detergent according to claim 1 or 2, wherein the copolymer (α) and / or (β) has a structural unit derived from at least one (meth) acrylic acid ester. The copolymer (α) and / or (β) has a structural unit (b-1) derived from a (meth) acrylic acid alkyl ester and a solubility parameter of 15 or less, and has a carboxyl group, a hydroxyl group and an ether group. The detergent for laundry detergent according to any one of claims 1 to 3, which has a structural unit (b-2) derived from a monomer having at least one functional group selected from the group consisting of. builder. A laundry detergent containing a copolymer having a cationic group-containing monomer (A) derived structural unit (a) and the hydrophobic monomer (B) structural units derived from (b),
The copolymer has the following formulas (4) and / or (5) as the structural unit (a);

(In formulas (4) and (5), R ¹ and R ² represent the same or different hydrocarbon atoms or hydrocarbon groups having 1 to 12 carbon atoms. Z represents a hydrogen atom or a methyl group. Is the following formula (8) or (10);

(In the formula, i represents an integer of 0 to 12. k represents an integer of 0 to 4.). X ⁻ represents an anion. It has a structural unit derived from the cationic group-containing monomer (A) represented by), and the ratio of the structural unit (a) is 55 to 90% by mass with respect to 100% by mass of the total structural unit. , A copolymer (α) having a weight average molecular weight of 10 to 1,000,000 ( excluding those having a structural unit derived from a crosslinkable monomer) , or.
The following formula (6) as the structural unit (a);

(In the formula (6), R ^{3 to} R ⁵ represent the same or different hydrocarbon groups having 1 to 12 carbon atoms. Z represents a hydrogen atom or a methyl group. Y represents the above formula (8). Alternatively, it represents the structure represented by (10) ^{. X −} represents a cationic group-containing monomer (A) represented by) and has a structural unit derived from the cationic group-containing monomer (A).
The hydrophobic monomer (B) has a solubility parameter of 15 or less as a homopolymer, and has a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, a phosphoric acid group, a halogeno group, an epoxy group and the like. which it may have at least one substituent selected from the group consisting of carbonyl group-containing (meth) acrylate; unsaturated monocarboxylic acids; Kaoru aromatic vinyl monomer; olefin monomer; not Ester of saturated alcohol and carboxylic acid; vinyl halide; alkyl vinyl ethers; addition reaction product of unsaturated monomer having cyclic ether-containing group having 2 to 8 carbon atoms and alcohol having 1 to 20 carbon atoms; carbon number of carbon atoms An alkylene oxide adduct of 2 to 20 unsaturated alcohols and their terminal hydrophobic modified products; at least one compound selected from the group consisting of cyclic vinyl-based monomers.
The ratio of the structural unit (a) is 55 to 99.9% by mass with respect to 100% by mass of all structural units.
The ratio of the structural unit (e) derived from the monomer (E) other than the cationic group-containing monomer (A) and the hydrophobic monomer (B) is 0 with respect to 100% by mass of the total structural unit. It is 10% by mass,
The other monomer (E) is at least one compound selected from the group consisting of vinyl crotonic acid, unsaturated carboxylic acid heavy metal salt, and,
Laundry detergents, wherein the weight-average molecular weight of copolymer is 1000 to 200,000 (beta). A laundry detergent composition comprising the detergent builder for laundry detergent according to any one of claims 1 to 4 and a surfactant. The laundry detergent composition further comprises at least one additive selected from the group consisting of an enzyme, a fluorescent agent, a solvent, and a detergent builder other than the detergent builder for laundry detergent according to any one of claims 1 to 4. The laundry detergent composition according to claim 6, which comprises. The laundry detergent composition, laundry detergent composition according to claim 6 or 7, wherein the content of the surfactant is 5 to 70% by mass relative to the total amount 100% by weight of the laundry detergent composition .. An antibacterial agent for detergents containing a copolymer having a structural unit (a) derived from a cationic group-containing monomer (A) and a structural unit (b) derived from a hydrophobic monomer (B).
The copolymer has the following formulas (4) and / or (5) as the structural unit (a);

(In formulas (4) and (5), R ¹ and R ² represent the same or different hydrocarbon atoms or hydrocarbon groups having 1 to 12 carbon atoms. Z represents a hydrogen atom or a methyl group. Is the following formula (8) or (10);

(In the formula, i represents an integer of 0 to 12. k represents an integer of 0 to 4.). X ⁻ represents an anion. It has a structural unit derived from the cationic group-containing monomer (A) represented by), and the ratio of the structural unit (a) is 55 to 90% by mass with respect to 100% by mass of the total structural unit. , A copolymer (α) having a weight average molecular weight of 10 to 1,000,000, or
The following formula (6) as the structural unit (a);

(In the formula (6), R ^{3 to} R ⁵ represent the same or different hydrocarbon groups having 1 to 12 carbon atoms. Z represents a hydrogen atom or a methyl group. Y represents the above formula (8). Alternatively, it represents the structure represented by (10) ^{. X −} represents a cationic group-containing monomer (A) represented by) and has a structural unit derived from the cationic group-containing monomer (A).
The hydrophobic monomer (B) has a solubility parameter of 15 or less as a homopolymer, and has a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, a phosphoric acid group, a halogeno group, an epoxy group and the like. which it may have at least one substituent selected from the group consisting of carbonyl group-containing (meth) acrylate; unsaturated monocarboxylic acids; Kaoru aromatic vinyl monomer; olefin monomer; not Ester of saturated alcohol and carboxylic acid; vinyl halide; alkyl vinyl ethers; addition reaction product of unsaturated monomer having cyclic ether-containing group having 2 to 8 carbon atoms and alcohol having 1 to 20 carbon atoms; carbon number of carbon atoms An alkylene oxide adduct of 2 to 20 unsaturated alcohols and their terminal hydrophobic modified products; at least one compound selected from the group consisting of cyclic vinyl-based monomers.
The ratio of the structural unit (a) is 55 to 99.9% by mass with respect to 100% by mass of all structural units.
The ratio of the structural unit (e) derived from the monomer (E) other than the cationic group-containing monomer (A) and the hydrophobic monomer (B) is 0 with respect to 100% by mass of the total structural unit. It is 10% by mass,
The other monomer (E) is unsaturated with disubstituted or higher hydroxyl groups of polyol and (meth) acrylic acid; methacrylic acid esters with disubstituted or higher polyols; and disubstituted or higher hydroxyl groups of polyol. Ethers with alcohols; diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyethane, triallyl cyanurate, divinyl adipate, vinyl crotonate, 1,5-hexadiene, divinylbenzene, unsaturated carboxylic acid heavy metal At least one compound selected from the group consisting of salts, and
An antibacterial agent for detergents, which is a copolymer (β) having a weight average molecular weight of 1,000 to 200,000.