JP2020079239A - Antifungal agent - Google Patents

Abstract

To provide an antifungal agent containing a polymer excellent in antifungal performance.SOLUTION: The antifungal agent is an antifungal agent containing a cationic group-containing copolymer where the antifungal performance measured by a specific method using black mold is 2.0 or higher, the cationic group-containing copolymer has a structural unit (a) derived from a cationic group-containing monomer (A) and a structural unit (b) derived from a monomer (B), the ratio of the unit (a) is 36-99.9 mass% to 100 mass% of total structural units, the monomer (B) is one or more of monomer(s) selected from a monomer (B1) having a solubility parameter of a homopolymer of 10 or less, and a monomer (B2) having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an ether group, the weight average molecular weight of the cationic group-containing copolymer is 4,000-1,000,000, and the rate of the cationic group-containing copolymer is 10-100 mass% to 100 mass% of the antifungal agent.SELECTED DRAWING: None

Description

The present invention relates to antifungal agents. More specifically, detergents, cosmetics, paints, resins, wood preservatives, cement admixtures, water treatment agents, industrial water, paper pulp, plastics, fibers, food additives, medical equipment, optical equipment, modules, electronic products. The present invention relates to a useful antifungal agent.

In recent years, from the viewpoint of consumer's cleanliness and hygiene, various daily products and industrial products are required to be subjected to antibacterial treatment. As an antibacterial agent used for such an antibacterial treatment, for example, Patent Document 1 discloses an antibacterial agent containing a cationic group-containing copolymer, wherein the copolymer has a structure derived from a cationic group-containing monomer. Unit and a structural unit derived from a hydrophobic monomer, and the ratio of the structural unit derived from the cationic group-containing monomer is 36 to 99.9 mass% with respect to 100 mass% of all structural units. Disclosed is an antibacterial agent containing a cationic group-containing copolymer, wherein the hydrophobic monomer has a weight average molecular weight of 4000 to 1,000,000 and a homopolymer has a solubility parameter of 15 or less. Has been done.
In hot and humid Japan, it is important not only to suppress the growth of bacteria but also to suppress the growth of mold. Regarding the antifungal technique, for example, in Patent Document 2, agar medium is smeared with a composition of interest and a mold spore suspension, and after static culture, the number of mold colonies is counted, and the number of colonies is used as a control. The method for confirming the antifungal effect of the composition is disclosed, which is characterized in that
Patent Document 3 is a method for producing a polyacrylic acid (salt)-based water-absorbing agent, which comprises a step of polymerizing an aqueous solution of a monomer, a drying step, and a surface-crosslinking step, and is included in a monomer or a polymer thereof. Production of a polyacrylic acid (salt)-based water-absorbing agent, wherein the total amount of acetic acid and propionic acid is 200 to 2500 ppm, and further including a step of adding an aqueous liquid containing a bactericidal component to the surface-crosslinked water-absorbing resin particles. A method is disclosed.

JP, 2017-214346, A JP, 2013-162805, A JP, 2016-131902, A

As described above, although various antibacterial agents and the like have been conventionally developed, there is room for developing an antifungal agent that is particularly effective against fungi that are eukaryotes.

The present invention has been made in view of the above circumstances, and an object thereof is to provide an antifungal agent containing a polymer having excellent antifungal performance.

The present inventors have conducted various studies on polymers, and have a structural unit derived from a cationic group-containing monomer and a structural unit derived from a specific monomer, and a structure derived from a cationic group-containing monomer. The inventors have found that a copolymer having a unit ratio and a weight average molecular weight within a specific range has excellent antifungal performance, and thought that the above-mentioned problems could be solved satisfactorily, and thus arrived at the present invention.

That is, the present invention is an antifungal agent containing a cationic group-containing copolymer, wherein the antifungal agent has an antifungal ability of 2.0 or more as measured by the following method, The copolymer has a structural unit (a) derived from the cationic group-containing monomer (A) and a structural unit (b) derived from the monomer (B), and the cationic group-containing monomer ( The proportion of the structural unit (a) derived from A) is 36 to 99.9 mass% with respect to 100 mass% of all structural units, and the monomer (B) has a solubility parameter of a homopolymer of 10%. One or more monomers selected from the following monomers (B1) and monomers (B2) having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group. The cationic group-containing copolymer has a weight average molecular weight of 4000 to 1,000,000 and the ratio of the cationic group-containing copolymer contained in the antifungal agent is 100% by mass of the antifungal agent. The antifungal agent is 10 to 100% by mass.
<Measurement of antifungal ability>
1) Potato dextrose agar (PDA) slope medium is inoculated with black mold (Cladosporium cladosporioides), and precultured at 30° C. for 1 week.
2) A spore suspension is prepared from the grown black mold, and the number of spores is counted in a blood cell disc and appropriately diluted to adjust the concentration to about 5.0×10 ⁴ pores/ml. At this time, the adjusted spore suspension is appropriately diluted, applied to a PDA medium in an amount of 100 μL, and cultured at 30° C. for 3 days to obtain the actual viable cell count, which is used as the initial viable cell count α. ..
3) Into a 1.5 ml tube, 500 μL of a 20% aqueous solution of the cationic group-containing copolymer and 500 μL of the adjusted spore suspension are put and stirred with a twin mixer. 100 μl of the sample after 180 minutes of stirring is smeared on a PDA medium and cultured at 30° C. for 3 days to obtain the viable cell count, which is defined as the viable cell number β in the sample after 180 minutes of stirring.
4) The antifungal ability is calculated by the following formula (1).
Antifungal ability=2-log [(β/α)×100] (1)

The antifungal agent of the present invention has the above-mentioned constitution and is excellent in antifungal ability, so that it is a detergent, cosmetic, paint, resin, wood preservative, cement admixture, water treatment agent, industrial water, paper pulp, plastic. , Fibers, food additives, medical devices, optical devices, modules, electronic products and the like.

The preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied without changing the gist of the present invention. It should be noted that a combination of two or more individual preferred embodiments of the present invention described below also corresponds to the preferred embodiment of the present invention.

<<Antifungal agent>>
The antifungal agent in the present invention refers to an agent having antifungal properties. The antifungal performance means having properties such as suppressing the growth of mold, killing mold, and preventing mold. The target mold is not particularly limited, but includes, for example, microorganisms belonging to the genus Penicillium, microorganisms belonging to the genus Aspergillus, microorganisms belonging to the genus Cladosporium, and belonging to the genus Fusarium. Examples thereof include microorganisms, microorganisms belonging to the genus Alternaria, microorganisms belonging to the genus Rhizopus, and the like.

The cationic group-containing copolymer contained in the antifungal agent of the present invention (hereinafter also referred to as the copolymer of the present invention) has an antifungal ability of 2.0 or more as measured by the above method.
The antifungal activity is preferably 2.5 or more, more preferably 3.0 or more, and particularly preferably 3.5 or more.
The details of the method for measuring the antifungal ability are as described in the examples.

The cationic group-containing copolymer has the structural unit (a) derived from the cationic group-containing monomer (A) in a proportion of 36 to 99.9% by mass based on 100% by mass of all structural units. It is preferably 40 to 99% by mass, more preferably 45 to 99% by mass, further preferably 50 to 95% by mass, and further preferably 60 to 90% by mass.

When the cationic group-containing monomer (A) is a neutralized product of the primary to tertiary amino group-containing monomer (A1) and/or an acid thereof, the cationic group-containing copolymer is cationic. The proportion of the structural unit (a1) derived from the group-containing monomer (A1) is preferably 36 to 99.9 mass% with respect to 100 mass% of all structural units. That is, the cationic group-containing monomer (A) is a neutralized product of the primary to tertiary amino group-containing monomer (A1) and/or an acid thereof, and contains a primary to tertiary amino group. A cationic group-containing copolymer in which the proportion of the structural unit (a1) derived from the monomer (A1) and/or a neutralized product of these acids is 36 to 99.9% by mass based on 100% by mass of all structural units. A polymer is also one of the present inventions.
The above ratio is preferably 40 to 99% by mass, more preferably 45 to 99% by mass, further preferably 50 to 95% by mass, and further preferably 60 to 90% by mass.
When the amino groups in the structural units (a) and (a1) are neutralized products of an amine base with an acid, the masses of the structural units (a) and (a1) are converted into the structural units before neutralization. And calculate the mass.

When the cationic group-containing monomer (A) has a structure represented by the formula (4-1) or (4-2) described below and R ³ and R ⁴ are methyl groups, a structural unit The content ratio of (a) is preferably 40 to 95% by mass. It is more preferably 50 to 90% by mass, further preferably 60 to 90% by mass, and particularly preferably 70 to 90% by mass.
The above-mentioned cationic group-containing monomer (A) has a structure represented by the formula (4-1) or (4-2) described below, and R ³ and R ⁴ are hydrocarbon groups having 2 or more carbon atoms. When it is, the content ratio of the structural unit (a) is preferably 40 to 90 mass %. It is more preferably 45 to 85% by mass, further preferably 50 to 80% by mass, further preferably 55 to 80% by mass, particularly preferably 60 to 80% by mass, and most preferably 65 to 80% by mass. It is% by mass.

The cationic group-containing copolymer of the present invention preferably has the structural unit (b) derived from the monomer (B) in a proportion of 0.1 to 64 mass% with respect to 100 mass% of all the structural units. .. It is more preferably 1 to 60% by mass, still more preferably 1 to 55% by mass, still more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass.

In the copolymer of the present invention, the content ratio of the structural unit (b) derived from the monomer (B) in the copolymer is 100% by mass of the structural unit (a) derived from the cationic group-containing monomer (A). On the other hand, it is preferably 1 to 150% by mass. The amount is more preferably 1 to 120% by mass, further preferably 5 to 100% by mass, and further preferably 10 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 antifungal performance of the above copolymer tends to be improved.

In the copolymer, the content ratio of the structural unit (b1) derived from the monomer (B1) is preferably 0.1 to 64 mass% with respect to 100 mass% of all structural units. It is more preferably 1 to 60% by mass, still more preferably 1 to 55% by mass, still more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass.
In the above copolymer, the content ratio of the structural unit (b2) derived from the monomer (B2) is preferably 0 to 30 mass% with respect to 100 mass% of all structural units. It is more preferably 0 to 20% by mass, and further preferably 0 to 10% by mass.

As will be described later, the copolymer of the present invention has, as the monomer (B1), at least one structural unit derived from an alkyl (meth)acrylate ester, and at least one selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group. And a structural unit (b2) derived from the monomer (B2) having a functional group of at least one kind selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group in the above copolymer. The proportion of the structural unit (b2) derived from the monomer (B2) having a functional group is preferably 0 to 100% by mass based on 100% by mass of the structural unit derived from the (meth)acrylic acid alkyl ester. It is more preferably 0 to 50% by mass, further preferably 0 to 40% by mass, and particularly preferably 0.1 to 30% by mass.

When the copolymer of the present invention has a structural unit derived from (meth)acrylic acid alkyl ester as the monomer (B1), the proportion of structural units derived from (meth)acrylic acid alkyl ester is 100% by mass of all structural units. On the other hand, it is preferably 0.1 to 64% by mass. The amount is more preferably 1 to 60% by mass, still more preferably 1 to 55% by mass, still more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass.

As will be described later, the copolymer of the present invention has a structural unit (e) derived from another monomer (E) other than the above-mentioned cationic group-containing monomer (A) and monomer (B). The content ratio of the structural unit (e) derived from the other monomer (E) is preferably 0 to 10 mass% with respect to 100 mass% of all the structural units. It is more preferably 0 to 8% by mass, and further preferably 0 to 5% by mass.

As the copolymer of the present invention, a copolymer comprising only the structural unit (a) derived from the cationic group-containing monomer (A) and the structural unit (b) derived from the monomer (B) is also preferable. It is one of the forms. In this case, the total of the ratio of the structural unit (a) derived from the cationic group-containing monomer (A) and the structural unit derived from the monomer was 100% by mass, and the ratio of each of these structural units was 100. It is a value obtained by subtracting the ratio of the structural unit (a) derived from the cationic group-containing monomer (A) or the ratio of the structural unit (b) derived from the monomer (B) from mass %.

The cationic group-containing copolymer of the present invention has a weight average molecular weight of 4000 to 1,000,000. When the weight average molecular weight of the cationic group-containing copolymer is in such a range, the adsorption of the antifungal agent to the material using the antifungal agent is improved, so that it is sufficiently prevented from being washed off when washed. However, the antifungal effect on the above materials is improved.
The weight average molecular weight is preferably 4,000 to 800,000, more preferably 5,000 to 600,000, still more preferably 6,000 to 400,000, further preferably 7,000 to 200,000, and still more preferably 7,000 to 7,000. It is 100,000, and particularly preferably 7,000 to 80,000. The weight average molecular weight of the cationic group-containing copolymer can be measured by the method described in Examples.

The structure of the cationic group-containing copolymer of the present invention includes random copolymer structure, graft structure, block copolymer structure, gradient copolymer structure, star structure, dendrimer structure, etc. It may be.

The antifungal agent of the present invention preferably contains a cationic group-containing copolymer and an organic acid and/or an inorganic acid. This further improves the antifungal performance of the antifungal agent of the present invention.
Examples of the organic acid include acetic acid, citric acid, tartaric acid, toluenesulfonic acid, lactic acid, succinic acid, glycolic acid and the like. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like. Organic acids are preferable, acetic acid, citric acid and hydrochloric acid are more preferable, and acetic acid is particularly preferable.
The content ratio of the organic acid and/or the inorganic acid in the above antifungal agent is not particularly limited, but the content ratio of the organic acid and/or the inorganic acid is 1 relative to 1 unit of the structural unit (a) of the cationic group-containing copolymer. It is preferably 0.5 to 2 normal. It is more preferably 0.8 to 1.5, and even more preferably 1.0 to 1.2.

<Cationic group-containing monomer (A)>
The cationic group-containing copolymer contained in the antifungal agent of the present invention has the structural unit (a) derived from the cationic group-containing monomer (A). The cationic group-containing monomer is not particularly limited as long as it has at least one ethylenically unsaturated group and at least one cationic group. In addition, the “structural unit (a) derived from the cationic group-containing monomer (A)” is the same as the structural unit formed by the polymerization of the monomer (A), and it may be produced by another production method. It may be formed. The same applies to the monomer (B) and the monomer (E) described later. For example, when the monomer (A) is N,N-dimethylaminoethyl methacrylate, the structural unit (a) has —CH ₂ —C(CH ₃ )(COCH ₂ CH ₂ —N(CH ₃ ) ₂ ). It is a structural unit represented by-. Here, the cationic group is a group having a cation or a group generating a cation, and examples thereof include a primary to tertiary amino group and a neutralized product of the primary to tertiary amino group with an acid. As the primary to tertiary amino groups, the following formula (2);

(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms).
The hydrocarbon group may have a chain structure or a ring structure, but preferably has a chain structure. When the hydrocarbon group has a chain structure, it may be linear or branched.
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 in the hydrocarbon group is preferably 1-10, more preferably 1-8, particularly preferably 1-5, particularly preferably 1-2, and most preferably 1 Is.
At least one of R ¹ and R ² is preferably a hydrocarbon group having 1 to 12 carbon atoms, and both R ¹ and R ² are hydrocarbon groups having 1 to 12 carbon atoms. More preferable. That is, the tertiary amino group is preferable among the primary to tertiary amino groups.

Examples of the neutralized product of the above primary to tertiary amino groups with an acid include the following formula (3);

(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Y ⁻ represents an anion.) preferable. Specific examples and preferable forms of the hydrocarbon group are as described above.

The above-mentioned cationic group-containing copolymer is a structural unit containing at least one structural unit (a1) derived from a neutralized product of a primary to tertiary amino group (A1) and/or an acid thereof. Each of the alkyl groups bonded to the secondary or tertiary amino group of (a1) has the highest number of carbon atoms in at least one of the structural units (b) derived from the monomer (B). It is preferable that the number of carbon atoms is smaller than that of the alkyl group.
As a result, the hydrophobic balance between the structural unit (a) and the structural unit (b) is further improved, and the antifungal agent of the present invention tends to act more effectively on the fungal cell membrane and cell wall. Will exhibit better antifungal performance.
The above-mentioned cationic group-containing copolymer has a structural unit (a1) (hereinafter also referred to as a structural unit (a1′)) and a structural unit (b) (hereinafter also referred to as a structural unit (b′)) satisfying the above relationship. It suffices that each of the structural units (a1′) is 50 to 100 mol %, based on 100 mol% of the structural unit (a1). More preferably, it is 80 to 100 mol %. Further, the proportion of the structural unit (b′) in the cationic group-containing copolymer is preferably 50 to 100 mol% with respect to 100 mol% of the structural unit (b). More preferably, it is 80 to 100 mol %.

As the above-mentioned cationic group, among the neutralized products of the primary to tertiary amino group and the primary to tertiary amino group with an acid, a tertiary amino group and a neutralized product of the tertiary amino group with an acid are preferable. . As the tertiary amino group or the neutralized product of the tertiary amino group with an acid, a dimethylamino group, a diethylamino group or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid is preferable.

Examples of the cationic group-containing monomer include the following formulas (4-1) and/or (4-2);

(In formulas (4-1) and (4-2), R ^{5 to} R ⁷ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X is a direct bond or a divalent group. It represents a linking group, and R ³ and R ⁴ are preferably the structures represented by the above formula (2), which are the same as R ¹ and R ² .

The alkyl group having 1 to 5 carbon atoms in R ⁷ is preferably a methyl group. R ⁷ is preferably a hydrogen atom or a methyl group. From the viewpoint of antifungal properties and hydrolysis resistance, R ⁷ is more preferably a methyl group.
The above R ⁵ and R ⁶ are preferably hydrogen atoms.

The divalent linking group for X in the formulas (4-1) and (4-2) is not particularly limited, but examples thereof include an alkylene group having 1 to 12 carbon atoms and the following formula (5);

(In the formula, m represents an integer of 0 to 12), the following formula (6);

(In the formula, e represents an integer of 0 to 4) and the following formula (7);

(In the formula, k represents an integer of 1 to 10.).
M in the above formula (5) is preferably 1 to 8, and more preferably 1 to 5.
K in the above formula (7) is preferably 1 to 8, and more preferably 1 to 5.

As the cationic group-containing monomer, specifically, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dialkylaminopropyl (meth)acrylate-containing N,N-dialkylamino group-containing (meth)acrylates or their neutralized products with acids such as hydrochloric acid and acetic acid; N,N-dimethylaminoethyl (meth)acrylamide , N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dialkylaminopropyl(meth)acrylamide, or other N,N-dialkylamino group-containing (meth)acrylamides, or Neutralized products of these acids such as hydrochloric acid; monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, monoethylaminopropyl (meth)acrylate, (meth)acrylic acid Monoalkylamino group-containing (meth)acrylates such as 2-(tert-butylamino)ethyl and their neutralized products with acids such as hydrochloric acid; monomethylaminoethyl (meth)acrylamide, monoethylaminoethyl (meth)acrylamide, Monoalkylamino group-containing (meth)acrylamides such as monomethylaminopropyl (meth)acrylamide and monoethylaminopropyl (meth)acrylamide and their neutralized products with acids such as hydrochloric acid; (meth)acrylic acid-2-aminoethyl And the like, esters of (meth)acrylic acid and alkanolamine and their neutralized products with acids such as hydrochloric acid; allylamine and its neutralized products with acids such as hydrochloric acid; 1-allyloxy-3-dibutylamino-2- An addition reaction product of an unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms such as ol and 1-allyloxy-3-diethanolamino-2-ol with an amine compound having 1 to 24 carbon atoms, or an addition reaction product thereof. Examples include neutralized products with acids such as hydrochloric acid.

The amine compound having 1 to 24 carbon atoms is not particularly limited as long as it has an amino group and can react with a cyclic ether structure of an unsaturated monomer having a cyclic ether containing group having 2 to 8 carbon atoms. 1-20 are preferable and, as for carbon number of a C1-C24 amine compound, 1-16 are more preferable. Examples of the amine compound having 1 to 24 carbon atoms include primary amines and secondary amines. For example, (di)alkylamine having 1 to 24 carbon atoms, (di)alkanolamine having 1 to 24 carbon atoms, Examples thereof include alkylalkanolamines having 1 to 24 carbon atoms.
Examples of the (di)alkylamine having 1 to 24 carbon atoms include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, 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 and the like are preferable.

The structure represented by the above formula (5) is preferable as the divalent linking group for X in the above formulas (4-1) to (4-2).
In the above-mentioned cationic group-containing monomer, R ⁷ in the above formulas (4-1) and (4-2) is preferably a methyl group, and X is preferably a structure represented by the above formula (5). ..

The cationic group-containing monomer is preferably N,N-dialkylamino group-containing (meth)acrylates and their neutralized products with an acid such as hydrochloric acid, or a monomer obtained by adding a quaternizing agent to these. N,N-dialkylamino group-containing (meth)acrylamides and their neutralized products with acids such as hydrochloric acid, among them, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N , N-dimethylaminopropyl(meth)acrylamide and neutralized products thereof with an acid such as hydrochloric acid are more preferable. More preferred are N,N-diethylaminoethyl (meth)acrylate and their neutralized products with acids such as hydrochloric acid.

<Monomer (B)>
The monomer (B) is a monomer (B1) having a solubility parameter of 10 or less with respect to a homopolymer (homopolymer) obtained by homopolymerization, and a carboxyl group, a hydroxyl group and an ether group. One or more monomers selected from the monomer (B2) having at least one functional group selected from the group consisting of: The monomer (B) does not include the monomer corresponding to the cationic group-containing monomer (A). Further, even a monomer having a solubility parameter of 10 or less is classified as a monomer (B2) if it has at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group. I shall.
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 the molar volume (Δvi) of the structural units forming the polymer. It is calculated by the calculation method of.
δ=(Δei/Δvi) ^1/2 (cal/cm ³ ) ^1/2

When the copolymer of the present invention has the structural unit (a) derived from the cationic group-containing monomer (A) and the structural unit (b) derived from the above monomer (B), Since the affinity for the cell membrane or cell wall is improved and the interaction with the cell membrane or cell wall is increased, the physiological activity of the cell membrane or cell wall is damaged, resulting in excellent antifungal performance.

The solubility parameter of the monomer (B1) is preferably 10 or less, and the solubility parameter is usually 5 or more.

The monomer (B1) is not particularly limited as long as the solubility parameter in a homopolymer is 10 or less, but it has (meth)acrylic acid and a substituent other than a carboxyl group, a hydroxyl group and an ether group. Esters with alcohols ((meth)acrylates); aromatic vinyl monomers such as styrene; olefin monomers such as ethylene and propylene; esters of unsaturated alcohols such as vinyl acetate with carboxylic acids A vinyl halide such as vinyl chloride;
As the above-mentioned monomer (B1), it is preferable to include at least one kind or more of the above-mentioned monomers.
As the monomer (B1), those having an alkyl group having 2 or more carbon atoms are preferable among those having a solubility parameter of 10 or less. When the monomer (B1) has an alkyl group having 2 or more carbon atoms, the affinity for the fungal cell membrane or cell wall is increased, and the antifungal property is further improved.

Examples of the substituent other than the carboxyl group, the hydroxyl group and the ether group in the (meth)acrylate include a halogeno group such as a fluoro group.

Examples of the alkyl (meth)acrylate having no substituent as described above include, for example, 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, tridecyl (meth)acrylate, cyclohexyl (meth) ) Cycloalkyl (meth)acrylates such as acrylate, n-lauryl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl methacrylate and the like.

Examples of the fluoro group-containing (meth)acrylate include a fluoro group having a carbon number of 2 to 6 in the ester group such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate and the like. Alkyl (meth)acrylate etc. are mentioned.

The monomer (B1) preferably contains at least one (meth)acrylic acid ester.
The above (meth)acrylic acid ester has the following formula (8);

(In the formula, R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents a hydrocarbon group having 1 to 30 carbon atoms).
The hydrocarbon group preferably has 1 to 20 carbon atoms. It is more preferably 1-16, still more preferably 2-12, even more preferably 2-8, and particularly preferably 2-4.
When the number of carbon atoms in the hydrocarbon group is 1 to 20, the water solubility and viscosity of the polymer can be set within a suitable range, and handling becomes excellent. When the number of carbon atoms in the hydrocarbon group is 2 to 12, the production of the polymer becomes easy and, in addition to the antifungal property, the polymer also becomes excellent in safety. Further, when the number of carbon atoms of the above hydrocarbon group is 2 to 4, not only the production of the polymer is easy, but also the safety is excellent, and the affinity for the fungal cell membrane or cell wall is increased, and the antifungal property is increased. It will be improved.

The hydrocarbon group is not particularly limited, and examples thereof include chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, aromatic hydrocarbon groups, cyclic hydrocarbon groups such as cycloalkyl groups, and cycloalkenyl groups. .. The hydrocarbon group may have a branch, and the carbon number of the hydrocarbon group in the case of having a branch means the total carbon number of the main chain and the branched chain.
Examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, Examples thereof include nonyl group, decyl group, dodecyl (lauryl) group, stearyl group and icosyl group.
Examples of the alkenyl group include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, icosenyl group. Etc.
As the alkynyl group, for example, ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, dodecynyl group, octadecynyl group, icosinyl group. Etc.

Examples of the aromatic hydrocarbon group include a phenyl group, a benzyl group, a tolyl group, and an o-xylyl group.
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 above hydrocarbon group is preferably an alkyl group or an alkenyl group, 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-. 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 Yes, more preferably ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, and even more preferably ethyl (meth). Acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate are preferable, and ethyl methacrylate, isobutyl acrylate, and tert-butyl acrylate are particularly preferable.

The monomer (B2) is not particularly limited as long as it has at least one kind of functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group, and has two or more kinds of these functional groups. May be For example, the monomer having a carboxyl group may have a hydroxyl group or an ether group.
Examples of the monomer having a carboxyl group include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-allyloxyacrylic acid and salts thereof; maleic acid, itaconic acid, mesaconic acid, citraconic acid. Unsaturated dicarboxylic acids such as fumaric acid and salts thereof; and carboxyl group-containing (meth)acrylates such as 2-carboxyethyl acrylate. Among these, unsaturated monocarboxylic acids are preferable, and (meth)acrylic acid is more preferable. 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, and heavy metal salts such as zinc.

Examples of the monomer having a hydroxyl group include unsaturated alcohols having 2 to 20 carbon atoms such as the above-mentioned vinyl alcohol, allyl alcohol, and isoprenyl alcohol; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth). Examples thereof include a hydroxyl group-containing (meth)acrylate having an ester group having 1 to 18 carbon atoms such as acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. .. Of these, a hydroxyl group-containing (meth)acrylate is preferable, and 2-hydroxyethyl (meth)acrylate is more preferable.

Examples of the monomer having an ether group include methoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, and trimethylolpropane tripropoxy (meth)acrylate. Alkoxyalkyl (meth)acrylates; ethylene glycol (meth)acrylates, ethylene glycol methoxy (meth)acrylates, diethylene glycol (meth)acrylates, diethylene glycol methoxy (meth)acrylates and other (di)ethylene glycol (methoxy)(meth)acrylates; Alkoxypolyalkylene glycol (meth)acrylate in which the number of repeating alkylene glycols such as alkoxypolyethylene glycol methacrylate (ANTOX LMA-10) is 1 to 100; glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, glycidyl allyl ether. Epoxy group-containing (meth)acrylates such as; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; end-hydrophobic modified products of ethylene oxide adducts of allyl alcohol; End-hydrophobic modified products of alkylene oxide adducts of unsaturated alcohols having 2 to 20 carbon atoms. Among these, a monomer having one ether group is preferable.

As the monomer (B2), a monomer having a carboxyl group and/or a hydroxyl group is preferable. More preferably, it is a monomer having a carboxyl group (hereinafter, also referred to as a carboxyl group-containing monomer (B2-1)).
The form in which the cationic group-containing copolymer has the structural unit (b2-1) derived from the carboxyl group-containing monomer (B2-1) is one of the preferred embodiments of the present invention. When the cationic group-containing copolymer has a structural unit (b2-1) derived from a carboxyl group-containing monomer (B2-1), the structural unit (b2-1) is added to 100% by mass of all structural units. On the other hand, it is preferable to have the ratio of 1.0 to 30 mass %. It is more preferably 1.0 to 20% by mass, and particularly preferably 1.0 to 10% by mass.

The cationic group-containing copolymer contained in the antifungal agent of the present invention (hereinafter, also referred to as the copolymer of the present invention) also has, as the monomer (B), a structural unit derived from a (meth)acrylic acid alkyl ester. And a structural unit derived from the monomer (B2) having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group. A copolymer having such a structural unit is also one of the preferred embodiments of the present invention.
In the present invention, as the monomer (B), a monomer (B2) having the above (meth)acrylic acid alkyl ester and at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group, By copolymerizing the above, the water solubility of the resulting copolymer is improved, and the precipitation of the copolymer due to salt or pH, and the effect of reducing antifungal properties, etc. can be more sufficiently alleviated. The copolymer can be used in a wide pH range and can be suitably used for various applications such as cosmetics, which are often weakly acidic, and detergents, which are often neutral to weakly alkaline.

<Other monomers>
The copolymer of the present invention is, if necessary, derived from other monomers (E) other than the above-mentioned cationic group-containing monomer (A) and monomer (B) to the extent that they do not affect the antifungal performance. The structural unit (e) may be included. The other monomer (E) is not particularly limited as long as it has no cationic group and can be copolymerized with the cationic group-containing monomer (A) and the monomer (B). ..
Cyclic vinyl monomers such as acrylonitrile, acrylamide, N-vinylpyrrolidone and the like can be mentioned.
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 or the type of the functional group. As the monomer having two or more ethylenically unsaturated groups, ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, pentaerythritol, saccharose, sorbitol, 1, Esters of (meth)acrylic acid with 2- or more-substituted hydroxyl groups of polyols such as 4-butanediol; 2- or more-substituted methacrylic acid esters of the above polyols; diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyl Examples thereof include oxyethane, triallyl cyanurate, divinyl adipate, vinyl crotonate, 1,5-hexadiene and divinylbenzene. These other monomers may be used alone or in combination of two or more.

<Method for producing cationic group-containing copolymer>
The production of the copolymer of the present invention is not particularly limited, but it can be produced by polymerizing a monomer component, and specific examples of the monomer component, preferable examples and preferable ratios of the respective monomers are It is similar to the composition of the polymer.

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 above-mentioned polymerization initiator, those generally used can be used, and examples thereof include hydrogen peroxide; persulfates 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-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] n hydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate , 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(2,4- Azo compounds such as dimethyl valeronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, organic peroxides such as di-t-butyl peroxide, and the like are preferable. Of these polymerization initiators, azo compounds are preferable. The above-mentioned polymerization initiator is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more kinds.

The amount of the polymerization initiator used is not particularly limited as long as it can initiate the polymerization of the monomer components, 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, more preferably 0.05 to 20 parts by mass.

The cationic group-containing monomer used in the present invention may be used as an acid neutralized product obtained by neutralizing them with an acid.
The acid used for neutralizing the cationic group-containing monomer is not particularly limited, but inorganic acids such as hydrochloric acid and sulfuric acid; acetic acid, citric acid, tartaric acid, toluenesulfonic acid, lactic acid, succinic acid, glycol Examples thereof include organic acids such as acids.

When the above-mentioned acid is used, the amount thereof is not particularly limited as long as a part or all of the above-mentioned cationic group-containing monomer is neutralized or quaternized, but the cationic group-containing monomer used in the polymerization reaction is not particularly limited. The acid is preferably 0.5 to 2.0 N relative to 1 N of the monomer. It is more preferably 0.7 to 1.5, and particularly preferably 1.0 to 1.2.

In the above-mentioned copolymerization method, as a method of adding a monomer component, a polymerization initiator and the like to a reaction vessel, all of the monomer components are charged in the reaction vessel, and the polymerization initiator is added to the reaction vessel. Polymerization method: Part of a monomer component is charged into a reaction vessel, and a polymerization initiator and the remaining monomer component are continuously or stepwise (preferably continuously) added into the reaction vessel. Copolymerization method by charging the reaction vessel with a polymerization solvent and adding the total amount of the monomer component and the polymerization initiator; one of the monomers (for example, a cationic group-containing monomer) A method in which a part is charged into a reaction vessel and a polymerization initiator and the remaining monomer components are added (preferably continuously) into the reaction vessel to carry out copolymerization is suitable. Among these methods, it is possible to narrow (sharply) the molecular weight distribution of the obtained copolymer, and thus the copolymerization is carried out by the method of successively dropping the polymerization initiator and the monomer component into the reaction vessel. Preferably.

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

The above copolymerization method can be carried out batchwise or continuously. Known solvents can be used as necessary in the copolymerization, 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 Preferred are esters such as ethyl; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide; ethers such as diethyl ether and dioxane. These may be used alone or in combination of two or more. Among these, one or two or more solvents selected from the group consisting of water and a lower alcohol having 1 to 4 carbon atoms may be used from the viewpoint of solubility of the monomer component and the copolymer obtained. preferable. The solvent is relatively inexpensive and the production method of the present invention is economically excellent. In the above-mentioned copolymerization method, a polyhydric alcohol solvent such as propylene glycol, 1,3-butylene glycol or ethylene glycol may be added to water for polymerization. When the polyhydric alcohol solvent is used in combination with water, the solubility of the polymer can be increased, and soap-free polymerization can be more sufficiently suppressed. This makes it possible to more sufficiently suppress the production of a polymer having poor water solubility and further improve the transparency of the solution. 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.
The polyhydric alcohol solvent is more preferably 1,3-butylene glycol.
When 1,3-butylene glycol is used as a solvent, the obtained copolymer contains 1,3-butylene glycol, and in this case, it is more excellent in antifungal performance.
A form in which the antibacterial agent of the present invention contains 0 to 80% by mass of 1,3-butylene glycol based on 100% by mass of the copolymer is also one of preferred embodiments of the present invention.
The polymer obtained may be either one that is freely soluble in water or one that is optionally dispersed, but one that is freely soluble in water is particularly preferred. It is one of the preferred embodiments of the present invention that the copolymer of the present invention has an insoluble content of 1 g or less when dissolved in 10 g of 100 g of water at 25°C.
In the method for producing the copolymer of the present invention, any chain transfer agent, pH adjusting agent, buffering agent 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 in the above range, the residual monomer component tends to decrease. The temperature during the polymerization does not always have to be kept constant during the progress of the polymerization reaction, and for example, the polymerization is started from room temperature and the temperature is raised to a set temperature at an appropriate heating time or heating rate, After that, the set temperature may be maintained, or the polymerization temperature may be changed (increased or decreased) with time during the progress of the polymerization reaction, depending on the dropping method of the monomer component, the initiator and the like. Good. Further, when the monomer component is polymerized, it is preferable to appropriately stir so that the monomer component is uniformly polymerized.

The polymerization time is not particularly limited and may be appropriately set depending on the progress of the polymerization reaction, but is usually about 2 to 9 hours.
In addition, in this invention, "polymerization time" represents the time which heat-stirs before dropping of a monomer, the time of adding a monomer, and the aging time after dropping of a monomer.

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

20 mass% or more is preferable and, as for the solid content density|concentration (namely, polymerization solid content density of a monomer) in an aqueous solution at the time of the completion of the polymerization reaction in the said polymerization reaction system, it is more preferable that it is 25 to 80 mass %. . Thus, if 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 a single stage. Therefore, the antifungal agent containing the copolymer can be efficiently obtained, for example, the concentration step which is necessary in the conventional production method can be omitted. Therefore, the production efficiency can be significantly increased, and as a result, the productivity of the antifungal agent of the present invention can be significantly improved and the increase in production cost can be suppressed.

In the method for producing the copolymer of the present invention, an aging step may be provided after the addition of all the raw materials used, for the purpose of increasing the polymerization rate of the monomer. The aging time is usually 1 to 240 minutes, preferably 1 to 180 minutes, and more preferably 1 to 120 minutes. When the aging time is less than 1 minute, the monomer component may remain due to insufficient aging, which causes problems such as toxicity and odor due to the residual monomer.

Further, the preferable temperature of the polymer solution 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 finished), or the temperature may be changed with time during aging.

The antifungal agent of the present invention contains the copolymer of the present invention in an amount of 10 to 100% by mass based on 100% by mass of the antifungal agent.
The antifungal agent of the present invention may contain other components other than the copolymer of the present invention.
The above-mentioned other components are not particularly limited as long as they do not inhibit the antifungal performance of the antifungal agent, and examples thereof include alkali modifiers, anionic surfactants, additives such as compatibilizers and stabilizers, and the like. Be done.
Further, the antifungal agent of the present invention may further contain a metal salt, a metal oxide, a metal hydroxide or the like from the viewpoint of improving the antifungal property. As the metal in the metal salt or oxide or the metal hydroxide, heavy metals such as copper, zinc and silver are preferable.
The content of the other components is not particularly limited as long as it does not inhibit the antifungal performance of the antifungal agent, but is preferably 0 to 20% by mass relative to 100% by mass of the copolymer.

Since the antifungal agent of the present invention has the above-mentioned constitution and is excellent in antifungal performance, it is used as a detergent such as a laundry detergent, a softener, a household detergent, a dishwashing agent, a hard surface detergent; shampoo, rinse. , Lotions, emulsions, creams, sunscreens, foundations, cosmetics such as eye-makeup products, cosmetics such as antiperspirants; paints, wood preservatives, cement admixtures, industrial water (papermaking process water in papermaking process, various It can be suitably used for industrial applications such as industrial cooling water and washing water); medical devices, food additives, electronic device applications such as solar cell modules and organic element devices, and heat ray shielding films. The antifungal agent is preferably 0.1 to 20 mass% with respect to 100 mass% of the above-mentioned use product. More preferably, it is 1 to 10 mass %.

Among the above-mentioned uses, the use for cosmetics is preferable, and the cosmetic containing the antifungal agent of the present invention is also one of the present inventions. The content ratio of the antifungal agent in the cosmetic is preferably 0.1 to 20 mass% with respect to 100 mass% of the cosmetic. It is more preferably 1 to 10% by mass.

The cosmetic of the present invention may contain other components other than the antifungal agent of the present invention.
A cosmetic composition containing the antifungal agent of the present invention and other components other than the antifungal agent is also one aspect of the present invention. The content ratio of the antifungal agent in the cosmetic composition is preferably 0.1 to 20 mass% with respect to 100 mass% of the cosmetic composition. More preferably, it is 1 to 10 mass %.

The above-mentioned other components are not particularly limited, but include, for example, oily bases; humectants such as glycerin and propylene glycol; texture improvers; surfactants; polymers; thickening/gelling agents; solvents/propellants; oxidation. Inhibitors; reducing agents, oxidizing agents; antiseptics/antibacterial agents; chelating agents; pH adjusters/acids/alkalis; powders; inorganic salts; ultraviolet absorbers; whitening agents; vitamins and their derivatives; anti-inflammatory agents Anti-inflammatory agents; Hair-growth agents, blood circulation promoters, stimulants; Hormones; Anti-wrinkle agents, anti-aging agents, tightening agents, cooling agents, warming agents; Wound healing accelerators, stimulants, analgesics, cells Activator; Plant/Animal/Microbial extract; Antipruritic, Exfoliating/Solubilizing agent, Antiperspirant, Cooling agent, Astringent, Enzyme, Nucleic acid, Fragrance, Dye/colorant/Dye/Pigment, Water, etc. Can be mentioned. As specific examples of these components, those similar to those described in JP-A 2007-45776 can be used.

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

<Gel permeation chromatography (GPC)>
The weight average molecular weight (Mw) of the cationic group-containing copolymer was measured by GPC (gel permeation chromatography).
The measurement conditions and equipment are as follows.
Device: Tosoh EcoSEC HLC-8320GPC
Detector: Differential Refractive Index (RI) Detector Column: Tosoh TSKgel α-M, α-2500
Column temperature: 40°C
Flow rate: 0.8 mL/min
Injection volume: 10 μL (eluent preparation solution with a sample concentration of 0.4 wt%)
Calibration curve: GL Sciences polyethylene glycol GPC software: Tosoh EcoSEC-WS
Eluent: 0.5 M acetic acid + 0.2 M Na nitrate/acetonitrile = 50/50 (v/v)

<Measurement of antifungal ability>
1) Potato dextrose agar (PDA) slant medium was inoculated with black mold (Cladosporium cladosporioides NBRC30314) and precultured at 30° C. for 1 week.
2) A spore suspension was prepared from the grown Aspergillus niger, and the number of spores was counted by a blood cell disc and appropriately diluted to adjust the concentration to about 5.0×10 ⁴ pores/ml. At this time, the adjusted spore suspension was appropriately diluted, applied to a PDA medium in an amount of 100 μL, and cultured at 30° C. for 3 days to obtain the actual viable cell count, which was defined as the initial viable cell count α. ..
3) Into a 1.5 ml tube, 500 μL of a 20% aqueous solution of the copolymer containing a cationic group and 500 μL of the adjusted spore suspension were placed and stirred with a twin mixer. After 180 minutes of stirring, 100 μl of the sample was smeared on a PDA medium and cultured at 30° C. for 3 days. The viable cell count in the sample after 180 minutes of stirring was defined as β.
4) The antifungal ability was calculated by the following formula (1).
Antifungal ability=2-log [(β/α)×100] (1)

<Measurement of mycelium growth inhibition>
1) 45 g of pure water was added to 1.95 g of powder of potato dextrose agar (PDA) medium (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and then sterilized by autoclave at 121° C. for 20 minutes. The sterilized PDA medium was taken out and then cooled to about 60° C., 5 g of a 10% polymer aqueous solution was added and mixed, and the mixture was put into a plate and solidified to prepare an assay medium.
2) Another PDA medium was inoculated with Aspergillus brasiliensis NBRC9455 and cultured at 25°C for about 1 week.
3) A medium in which Aspergillus niger had grown was cut out with a cork borer having a diameter of 4 mm to prepare a flora disk, which was placed on the assay medium with the growth surface of mycelium facing down.
4) The cells were cultured at 25°C for 3 days, and the colony size (mm) including the flora disc was measured.
The colony size is shown in Table 3 below as mycelial growth inhibition (mm).

<Synthesis example 1>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 70.0 g of 1,3-butanediol (hereinafter abbreviated as BG), and the temperature was raised to 75°C with stirring. Then, under stirring, in a polymerization reaction system at a constant temperature of 75° C., 81.0 g of 2-(dimethylamino)ethyl methacrylate (hereinafter abbreviated as DAM), 31.0 g of acetic acid, ethyl methacrylate (hereinafter abbreviated as EMA). Solubility parameter: 9.7) 9.0 g of a 15% aqueous solution of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (hereinafter abbreviated as VA-044) 35. 0.7 g was dropped from separate dropping nozzles. With respect to the dropping time, the dropping was started at the same time, and DAM, acetic acid and EMA were dropped for 180 minutes, and a 15% aqueous solution of VA-044 was dropped for 210 minutes. After the completion of all droppings, the reaction solution was kept at 75° C. for 30 minutes for aging to complete the polymerization. After that, 45.8 g of pure water was added to obtain a copolymer 1.
The solid content of the obtained copolymer 1 was 33.4%, the pH was 6.4, and the weight average molecular weight was 11,000.

<Synthesis example 2>
A glass separable flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 70.0 g of BG and heated to 90° C. under stirring. Then, under stirring, in a polymerization reaction system at a constant temperature of 90° C., 81.0 g of DAM, 31.0 g of acetic acid, 9.0 g of EMA, 2,2′-azobis(2-methylpropionamidine) dihydrochloride (hereinafter, referred to as V- 27.3 g of a 5% aqueous solution (abbreviated as 50) was dropped from separate dropping nozzles. With respect to the dropping time, all of the dropping was started at the same time, DAM and acetic acid were added for 180 minutes, EMA was added for 170 minutes, and a 5% aqueous solution of V-50 was added for 210 minutes. After the completion of all droppings, the reaction solution was kept at 90° C. for another 30 minutes for aging to complete the polymerization. After that, 42.7 g of pure water was added to obtain a copolymer 2.
The solid content of the obtained copolymer 2 was 33.2%, the pH was 6.3, and the weight average molecular weight was 27,000.

<Synthesis example 3>
A glass separable flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 70.0 g of BG and heated to 75° C. under stirring. Then, with stirring, 72.0 g of DAM, 33.0 g of acetic acid, 18.0 g of EMA, and 36.7 g of a 5% aqueous solution of VA-044 were dropped into the polymerization reaction system at a constant temperature of 75° C. from separate dropping nozzles. With respect to the dropping time, the dropping was all started at the same time, and DAM, acetic acid and EMA were dropped for 180 minutes, and a 5% aqueous solution of VA-044 was dropped for 210 minutes. After the completion of all droppings, the reaction solution was kept at 75° C. for 30 minutes for aging to complete the polymerization. After that, 32.8 g of pure water was added to obtain a copolymer 3.
The solid content of the obtained copolymer 3 was 31.4%, the pH was 6.2, and the weight average molecular weight was 29,000.

<Synthesis example 4>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 50.0 g of pure water and 22.0 g of PG, and the temperature was raised to 90° C. with stirring. Then, under stirring, in a polymerization reaction system at a constant temperature of 90° C., DAM 63.0 g, acetic acid 24.1 g, BA 22.5 g, methacrylic acid (hereinafter abbreviated as MAA) 4.5 g, pure water 21.1 g, V- 31.4 g of 50% 5% aqueous solution was added dropwise from separate dropping nozzles. With regard to the dropping time, the dropping was all started simultaneously, and DAM, acetic acid and BA were dropped for 180 minutes, and MAA, pure water and a 5% aqueous solution of V-50 were dropped for 210 minutes. After the completion of all droppings, the reaction solution was kept at 90° C. for 90 minutes for aging to complete the polymerization, whereby a copolymer 4 was obtained.
The solid content of the obtained copolymer 4 was 34.9%, the pH was 6.0, and the weight average molecular weight was 27,000.

<Synthesis example 5>
A glass separable flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 70.0 g of BG and heated to 75° C. under stirring. Then, with stirring, in a polymerization reaction system at a constant temperature of 75° C., 81.0 g of DAM, 31.0 g of acetic acid, 9.0 g of lauryl methacrylate (hereinafter abbreviated as LMA. Solubility parameter: 9.0), VA-044. 36.7 g of 15% aqueous solution of was added dropwise from separate dropping nozzles. With respect to the dropping time, the dropping was all started at the same time, and DAM, acetic acid and LMA were dropped for 180 minutes, and a 15% aqueous solution of VA-044 was dropped for 210 minutes. After the completion of all droppings, the reaction solution was kept at 75° C. for 30 minutes for aging to complete the polymerization. After that, 45.2 g of pure water was added to obtain a copolymer 5.
The solid content of the obtained copolymer 5 was 32.6%, the pH was 6.3, and the weight average molecular weight was 11,000.

<Synthesis example 6>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 50.0 g of pure water and 30.0 g of BG, and the temperature was raised to 90° C. with stirring. Then, under stirring, in a polymerization reaction system at a constant temperature of 90° C., 72.0 g of DAM, 27.5 g of acetic acid, butyl acrylate (hereinafter abbreviated as BA, solubility parameter: 9.8) 18.0 g, V-50. 29.9 g of a 5% aqueous solution of was added dropwise from separate dropping nozzles. With respect to the dropping time, the dropping was all started at the same time, and DAM, acetic acid and BA were dropped for 180 minutes, and a 5% aqueous solution of V-50 was dropped for 240 minutes. After the completion of all droppings, the reaction solution was kept at 90° C. for further 60 minutes for aging to complete the polymerization. After that, 50.0 g of pure water was added to obtain a copolymer 6.
The solid content of the obtained copolymer 6 was 30.2%, the pH was 6.5, and the weight average molecular weight was 27,000.

<Synthesis example 7>
A glass separable flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 24.0 g of pure water and 72.0 g of propylene glycol (hereinafter abbreviated as PG), and the temperature was raised to 90° C. with stirring. Then, under stirring, 54.0 g of DAM, 20.6 g of acetic acid, 36.0 g of BA, and 33.3 g of a 3% aqueous solution of V-50 were dropped into the polymerization reaction system at a constant temperature of 90° C. from separate dropping nozzles. With respect to the dropping time, all of them were started at the same time, and DAM, acetic acid and BA were dropped for 180 minutes, and a 3% aqueous solution of V-50 was dropped for 210 minutes. After the completion of all droppings, the reaction solution was kept at 90° C. for 90 minutes for aging to complete the polymerization, whereby a copolymer 7 was obtained.
The solid content of the obtained copolymer 7 was 34.2%, the pH was 6.7, and the weight average molecular weight was 25,000.

<Synthesis example 8>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 18.0 g of pure water and 72.0 g of PG, and the temperature was raised to 90° C. with stirring. Then, under stirring, in a polymerization reaction system at 90° C., 72.0 g of 2-(diethylamino)ethyl methacrylate (hereinafter abbreviated as DEAM), 23.3 g of acetic acid, 18.0 g of BA, 5% of V-50. 31.7 g of the aqueous solution was dropped from separate dropping nozzles. With regard to the dropping time, all the dropping was started at the same time, and DEAM, acetic acid and BA were dropped for 180 minutes, and a 5% aqueous solution of V-50 was dropped for 210 minutes. After the completion of all droppings, the reaction solution was kept at 90° C. for 90 minutes for aging to complete the polymerization, whereby a copolymer 8 was obtained.
The obtained copolymer 8 had a solid content of 35.8%, a pH of 6.8 and a weight average molecular weight of 13,000.

<Synthesis example 9>
A glass separable flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 70.0 g of BG and heated to 80° C. under stirring. Then, with stirring, 45.0 g of DEAM, 14.6 g of acetic acid, 45.0 g of BA, and 35.6 g of a 5% aqueous solution of VA-044 were added dropwise from separate dropping nozzles into the polymerization reaction system at a constant temperature of 80°C. With respect to the dropping time, all of them were started at the same time, DEAM and acetic acid were added for 180 minutes, BA was added for 140 minutes, and a 5% aqueous solution of VA-044 was added for 240 minutes. After the completion of all droppings, the reaction solution was kept at 80° C. for 60 minutes for aging to complete the polymerization, and a copolymer 9 was obtained.
The solid content of the obtained copolymer 9 was 35.2%, the pH was 5.6, and the weight average molecular weight was 13,000.

<Synthesis example 10>
A glass separable flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 70.0 g of BG and heated to 80° C. under stirring. Then, under stirring, in a polymerization reaction system at a constant temperature of 80° C., 72.0 g of DEAM, 23.3 g of acetic acid, 18.0 g of isobutyl acrylate (hereinafter abbreviated as iso-BA), and a 7.5% aqueous solution of VA-044 31 0.7 g was dropped from separate dropping nozzles. With respect to the dropping time, all of them were started at the same time, DEAM and acetic acid were added for 180 minutes, iso-BA was added for 150 minutes, and a 7.5% aqueous solution of VA-044 was added for 240 minutes. After the completion of all droppings, the reaction solution was kept at 80° C. for 60 minutes for aging to complete the polymerization, and thus a copolymer 10 was obtained.
The solid content of the obtained copolymer 10 was 35.9%, the pH was 6.0, and the weight average molecular weight was 15,000.

<Synthesis example 11>
A glass separable flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 70.0 g of BG and heated to 80° C. under stirring. Then, with stirring, in a polymerization reaction system at a constant temperature of 80° C., 72.0 g of DEAM, 23.3 g of acetic acid, 18.0 g of t-butyl acrylate (hereinafter abbreviated as t-BA), and 7.5% of VA-044. 31.7 g of the aqueous solution was dropped from separate dropping nozzles. With respect to the dropping time, all the dropping was started at the same time, DEAM and acetic acid were added for 180 minutes, t-BA was added for 170 minutes, and a 7.5% aqueous solution of VA-044 was added for 240 minutes. After the completion of all droppings, the reaction solution was kept at 80° C. for further 60 minutes for aging to complete the polymerization, whereby a copolymer 11 was obtained.
The solid content of the obtained copolymer 11 was 35.5%, the pH was 6.1, and the weight average molecular weight was 13,000.

<Comparative Synthesis Example 1>
A glass separable flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 70.0 g of BG and heated to 90° C. under stirring. Then, under stirring, 90.0 g of DAM, 34.4 g of acetic acid, and 34.4 g of a 5% aqueous solution of V-50 were dropped from separate dropping nozzles into the polymerization reaction system at a constant temperature of 90°C. With regard to the dropping time, all of them were started at the same time, and DAM and acetic acid were added for 120 minutes, and a 5% aqueous solution of V-50 was added for 180 minutes. After the completion of all droppings, the reaction solution was kept at 90° C. for 60 minutes for aging to complete the polymerization, whereby Comparative Copolymer 1 was obtained.
The obtained comparative copolymer 1 had a solid content of 39.6%, a pH of 7.2, and a weight average molecular weight of 19,000.

<Comparative Synthesis Example 2>
A glass separable flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 90.0 g of BG and heated to 90° C. under stirring. Then, under stirring, 31.5 g of DAM, 12.0 g of acetic acid, 58.5 g of EMA, and 35.7 g of a 7% aqueous solution of V-50 were added dropwise to the polymerization reaction system at 90° C. under constant conditions. With respect to the dropping time, all of them were started at the same time, DAM, acetic acid and EMA were added for 120 minutes, and a 7% aqueous solution of V-50 was added for 180 minutes. After the completion of all droppings, the reaction solution was kept at 90° C. for further 60 minutes for aging to complete the polymerization. Then, 36.6 g of pure water was added to obtain Comparative Copolymer 2.
The obtained comparative copolymer 2 had a solid content of 35.5%, a pH of 6.6 and a weight average molecular weight of 33,000.

<Examples 1-1 to 1-11 and Comparative Examples 1-1 and 1-2>
Antifungal tests were conducted on the copolymers obtained in Synthesis Examples 1 to 11 and Comparative Synthesis Examples 1 and 2. The results are shown in Table 1.

<Example 2-1 and Comparative Example 2-1>
The copolymer obtained in Synthetic Example 3 was tested for antifungal properties in a lotion formulation.
In the measurement of the antifungal ability, the antifungal test was carried out using a 10% aqueous solution of glycerin/8% propylene glycol/8% cationic group-containing copolymer instead of the 20% aqueous solution of the cationic group-containing copolymer. .. The results are shown in Table 2.

<Examples 3-1 to 3-6 and Comparative Example 3-1>
For the copolymers obtained in Synthesis Examples 2, 3, 5, 6, 9, 10 and Comparative Synthesis Example 1, mycelium growth inhibition was measured. The results are shown in Table 3.

Claims (5)

An antifungal agent containing a cationic group-containing copolymer,
The antifungal agent has an antifungal ability of 2.0 or more as measured by the following method,
The cationic group-containing copolymer has the structural unit (a) derived from the cationic group-containing monomer (A) and the structural unit (b) derived from the monomer (B), and contains the cationic group. The proportion of the structural unit (a) derived from the monomer (A) is 36 to 99.9% by mass with respect to 100% by mass of all structural units, and the monomer (B) is a homopolymer dissolved therein. 1 selected from a monomer (B1) having a sex parameter of 10 or less, and a monomer (B2) having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group. One or more kinds of monomers, the weight average molecular weight of the cationic group-containing copolymer is 4000 to 1,000,000, and the ratio of the cationic group-containing copolymer contained in the antifungal agent is 100. An antifungal agent characterized by being 10 to 100% by mass relative to% by mass.
<Measurement of antifungal ability>
1) Potato dextrose agar (PDA) slant medium is inoculated with black mold (Cladosporium cladosporioides) and precultured at 30° C. for 1 week.
2) A spore suspension is prepared from the grown black mold, and the number of spores is counted in a blood cell plate and appropriately diluted to adjust the concentration to about 5.0×10 ⁴ pores/ml. At this time, the adjusted spore suspension is appropriately diluted, applied to a PDA medium in an amount of 100 μL, and cultured at 30° C. for 3 days to obtain the actual viable cell count, which is used as the initial viable cell count α. .
3) Into a 1.5 ml tube, 500 μL of a 20% aqueous solution of the cationic group-containing copolymer and 500 μL of the adjusted spore suspension are put and stirred with a twin mixer. 100 μl of the sample after 180 minutes of stirring is smeared on a PDA medium and cultured at 30° C. for 3 days to obtain the viable cell count, which is defined as the viable cell number β in the sample after 180 minutes of stirring.
4) The antifungal ability is calculated by the following formula (1).
Antifungal ability=2-log [(β/α)×100] (1) The cationic group-containing monomer (A) is a neutralized product of a primary to tertiary amino group-containing monomer (A1) and/or an acid thereof, and a primary to tertiary amino group-containing unit amount. The ratio of the structural unit (a1) derived from the body (A1) and/or a neutralized product of these acids is 36 to 99.9 mass% with respect to 100 mass% of all structural units. The antifungal agent according to 1. Regarding at least one of the structural unit (a1) derived from the neutralized product of the primary to tertiary amino group-containing monomer (A1) and/or acid, the second or third structural unit (a1) has The number of carbon atoms of each of all the alkyl groups bonded to the primary amino group is smaller than the number of carbon atoms of the alkyl group having the largest number of carbon atoms in at least one of the structural units (b) derived from the monomer (B). The antifungal agent according to claim 1 or 2, characterized in that. The monomer (B) contains at least one kind of a carboxyl group-containing monomer (B2-1),
The cationic group-containing copolymer contains 1.0 to 30% by mass of the structural unit (b2-1) derived from the carboxyl group-containing monomer (B2-1) based on 100% by mass of all structural units. The antifungal agent according to claims 1 to 3, wherein the antifungal agent is contained in a ratio. A cosmetic containing the antifungal agent according to any one of claims 1 to 4,
The cosmetic comprises an antifungal agent in a ratio of 0.1 to 20 mass% with respect to 100 mass% of the cosmetic.