JP2013203697A - Antibacterial and antifungal agent and antibacterial and antifungal product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial and antifungal agent having sufficient antibacterial and antifungal properties and being excellent in water resistance, heat discoloration resistance, and BHT/NOx gas discoloration resistance, and also to provide an antibacterial and antifungal product acquired by using the same.SOLUTION: An antibacterial and antifungal agent includes a cationic polymer obtained by polymerizing a composition containing a monomer represented by formula (1).

Description

  The present invention relates to an antibacterial and antifungal agent capable of imparting antibacterial and antifungal properties, and an antibacterial and antifungal product imparted with antibacterial and antifungal properties by the antibacterial and antifungal agent.

  In recent years, accidents caused by bacteria, such as nosocomial infections caused by methicillin-resistant Staphylococcus aureus (MRSA) and food poisoning caused by pathogenic E. coli O-157, etc., have become a social problem. In ordinary households, molds are easy to propagate due to the increase in airtightness of living spaces and the spread of air conditioning equipment, and problems such as allergic diseases caused by mold and discoloration of daily necessities are increasing. In order to deal with these problems, for example, an antibacterial agent for imparting antibacterial properties to the surface of a desired member, a fiber product or a resin product that has been antibacterial processed with an antibacterial agent in advance, and the like are on the market.

  Examples of the antibacterial agent include low molecular organic antibacterial agents such as benzalkonium chloride, cetylpyridinium chloride, chlorhexidine gluconate and 5-chloro-2- (2,4-dichlorophenoxyl) phenol, and Patent Document 1. Polyhexamethylene biguanide hydrochloride as described in Patent Document 2, poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] as described in Patent Document 2, and Patent Document 3 High molecular organic antibacterial agents such as condensation reaction products of cyanoguanidine and polyethylene polyamine have been used for a long time. In addition, inorganic antibacterial agents carrying silver, zinc, copper, etc., which are metals having antibacterial properties, such as zeolite and silica gel are also frequently used.

Japanese Examined Patent Publication No. 62-60509 Japanese Patent Laid-Open No. 5-310505 JP-A-9-195171

  The conventional low molecular weight organic antibacterial agent exhibits excellent antibacterial and antifungal properties, but has low water resistance, and even if it adheres to the surface of a member, it is easily removed by water. Therefore, there has been a problem that the provided antibacterial and antifungal properties cannot be sustained over a long period of time for textile products that repeat washing and washing such as kitchens, bathrooms, toilets, and toilets.

  On the other hand, the above-mentioned conventional polymer organic antibacterial agents have excellent water resistance and antibacterial properties, but have insufficient antifungal properties. And has a problem that it cannot prevent odors.

  By the way, a phenomenon in which packaged textiles are yellowed by an antioxidant such as 2,6-di-t-butyl-p-cresol (hereinafter referred to as BHT) contained in packaging materials has been reported. ing. This yellowing of the substrate due to BHT is considered to occur as follows. First, BHT in the packaging material sublimes with time and adheres to the fiber product. Next, the BHT is changed into a yellowing substance by nitration with nitrogen oxide gas (hereinafter referred to as NOx) in the air. The conventional high molecular weight organic antibacterial agent is a cationic polymer and is said to promote the adsorption of BHT or NOx to a substrate. The conventional polymer organic antibacterial agent also has the property of being easily discolored by heat. Therefore, in products antibacterial processed with the above-mentioned conventional polymer organic antibacterial agents, yellowing due to NOx and BHT (hereinafter referred to as BHT / NOx yellowing) occurs, and heat during product processing and use There was a problem of discoloration.

  The present invention has been made in view of the above circumstances, and has an antibacterial and antifungal property, an antibacterial and antifungal agent excellent in water resistance, heat discoloration resistance and BHT / NOx gas discoloration, and the same An object of the present invention is to provide an antibacterial and antifungal product obtainable using

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a cationic polymer obtained by polymerizing a monomer having a specific structure. The present invention has been completed.

［式（１）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、炭素数１〜２２のアルキル基若しくはヒドロキシアルキル基、炭素数２〜２２のアルケニル基若しくはヒドロキシアルケニル基、又は、−（ＡＯ）_ｋ−Ｈで表される基を示し、前記ＡＯは炭素数２〜４のアルキレンオキシ基を示し、ｋはＡＯの平均付加モル数を示し、２〜４であり、Ｒ^４は−Ｃ（Ｏ）−で表される基、−Ｒ^６−Ｏ−Ｃ（Ｏ）−で表される基又は炭素数１〜６のアルキレン基を示し、Ｒ^６は炭素数１〜６のアルキレン基を示し、Ｒ^５は水素又は炭素数１〜４のアルキル基を示し、Ｘ^ｎ−はｎ価のアニオンを示し、ｎは１〜３の整数であり、複数あるＡＯは同一であっても、異なってもよい。］ That is, this invention provides the antibacterial antifungal agent containing the cationic polymer obtained by polymerizing the composition containing the monomer represented by following General formula (1).

Wherein ^{(1), R 1, R} 2 and ^{R 3} are each independently an alkyl group or hydroxyalkyl group having 1 to 22 carbon atoms, an alkenyl group or hydroxy alkenyl group having 2 to 22 carbon atoms, or - ( a group represented by _AO) k -H, wherein AO represents an alkyleneoxy group having 2 to 4 carbon atoms, k represents an average addition mole number of AO, is 2-4, ^{R 4} is -C A group represented by (O) —, a group represented by —R ⁶ —O—C (O) — or an alkylene group having 1 to ⁶ carbon atoms, wherein R ⁶ represents an alkylene group having 1 to ⁶ carbon atoms. R ⁵ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, X ^n- represents an n-valent anion, n represents an integer of 1 to 3, and a plurality of AOs may be the same or different May be. ]

  The antibacterial and antifungal agent of the present invention has sufficient antibacterial and antifungal properties by containing a cationic polymer obtained by polymerizing a composition containing the monomer represented by the general formula (1). Moreover, it can be an antibacterial and antifungal agent having excellent water resistance, heat discoloration resistance, and BHT / NOx gas discoloration resistance.

  The present invention also provides an antibacterial and antifungal product imparted with antibacterial and antifungal properties by the above antibacterial and antifungal agent.

  According to the present invention, an antibacterial and antifungal agent having sufficient antibacterial and antifungal properties, and excellent in water resistance, heat discoloration resistance and BHT / NOx gas discoloration property, and antibacterial and antifungal properties obtained by using the same It becomes possible to provide products.

  The antibacterial and antifungal agent according to the present embodiment contains a cationic polymer obtained by polymerizing a composition containing a monomer represented by the following general formula (1).

In formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group or hydroxyalkyl group having 1 to 22 carbon atoms, an alkenyl group or hydroxyalkenyl group having 2 to 22 carbon atoms, or-( AO) is a group represented by _k- H.

  The alkyl group having 1 to 22 carbon atoms may be linear or branched. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl. Groups and docosyl groups.

  The hydroxyalkyl group having 1 to 22 carbon atoms may be linear or branched. Examples of such a hydroxyalkyl group include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and a 10-hydroxyoctadecyl group.

  The alkenyl group having 2 to 22 carbon atoms may be linear or branched. Examples of such alkenyl groups include propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, icosenyl and dococenyl. Groups.

  The C2-C22 hydroxyalkenyl group may be linear or branched. Examples of such a hydroxyalkenyl group include a 3-hydroxypropenyl group and a 12-hydroxy-9-octadecenyl group.

In the group represented by — (AO) _k —H, AO is an alkyleneoxy group having 2 to 4 carbon atoms. k shows the average addition mole number of AO, and is 2-4.

  Examples of AO include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group. A plurality of AOs may be the same or different. That is, the plurality of AOs may have a structure in which an alkylene oxide having 2 to 4 carbon atoms is addition-polymerized with only one kind, or a structure in which two or more kinds are subjected to block addition polymerization or random addition polymerization. May be. From the viewpoint of more excellent antibacterial and antifungal properties, the plurality of AOs are preferably a single addition structure of either an ethyleneoxy group or a propyleneoxy group, or a block addition structure or a random addition structure thereof.

From the viewpoint of more excellent antibacterial and antifungal properties, at least one of R ¹ , R ² and R ³ in formula (1) is an alkyl group, alkenyl group, hydroxyalkyl group and hydroxy group having 8 to 22 carbon atoms. A long-chain group (long-chain group) such as an alkenyl group, at least one of which is a short-chain group (short-chain group) such as an alkyl group having 1 to 4 carbon atoms, an alkenyl group, a hydroxyalkyl group, or a hydroxyalkenyl group Preferably there is. Furthermore, from the viewpoint of more excellent antibacterial and antifungal properties, the long chain group is preferably an alkyl group or alkenyl group having 8 to 18 carbon atoms, and the short chain group is an alkyl group having 1 to 4 carbon atoms or A hydroxyalkyl group is preferred.

R ⁴ is a group represented by —C (O) —, a group represented by —R ⁶ —O—C (O) —, or an alkylene group having 1 to 6 carbon atoms. R ⁶ is an alkylene group having 1 to 6 carbon atoms.

From the viewpoint of more excellent antibacterial properties and antifungal properties, R ⁴ represents a group represented by —C (O) —, a group represented by —R ⁶ —O—C (O) — (R ⁶ represents An alkylene group having 1 to 6 carbon atoms) or a methylene group is preferable.

R ⁵ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ⁵ is preferably a hydrogen atom or a methyl group from the viewpoint of more excellent antibacterial and antifungal properties.

X ⁿ⁻ is an n-valent anion, and n is an integer of 1 to 3. The anion is not particularly limited as long as it can form a counter ion with a quaternary ammonium compound. For example, formic acid, acetic acid, propionic acid, gluconic acid, lactic acid, fumaric acid, maleic acid, adipic acid, and the like Anion, alkyl phosphate ester anion, alkyl sulfate ester anion, alkyl sulfone anion, halogen anion, sulfate ion, nitrate ion, and phosphate ion produced by deprotonation of a monovalent or polyvalent carboxylic acid. Of these, chlorine ions, bromine ions, and sulfate ions are preferred because of their superior antibacterial and antifungal properties.

The monomer represented by the above formula (1) is, for example, a compound represented by the following general formula (2) and 3
It can be obtained by reacting with a neutralized product of a secondary amine. In formula (2), R ⁴ and R ⁵ are as described above.

Examples of the glycidyl compound in which R ⁴ in the formula (2) is a group represented by —C (O) — include glycidyl acrylate and glycidyl methacrylate.

Examples of the glycidyl compound in which R ⁴ in the formula (2) is a group represented by —R ⁶ —O—C (O) — include 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl methacrylate, 4- Examples thereof include hydroxybutyl acrylate glycidyl ether and 4-hydroxybutyl methacrylate glycidyl ether.

Examples of the glycidyl compound in which R ⁴ in the formula (2) is an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms include allyl glycidyl ether.

  Among these, glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether are preferable from the viewpoint that antibacterial properties and antifungal properties are more excellent.

The tertiary amine is a tertiary amine having groups corresponding to R ¹ , R ² and R ³ in the formula (1).

Acid used to obtain the neutralized product of the tertiary amine may be an acid that produce X ^n- in the formula (1), as such acids are, for example, hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid Inorganic acids such as formic acid, acetic acid, propionic acid, gluconic acid, lactic acid, fumaric acid, maleic acid and adipic acid, etc., alkylsulfonic acid, alkylsulfuric acid ester, alkylphosphoric acid, and alkyl A phosphate ester is mentioned.

  The reaction between the glycidyl compound represented by the formula (2) and the neutralized product of the tertiary amine is preferably performed while suppressing the polymerization reaction of the double bond portion of the acryloyl group or methacryloyl group of the glycidyl compound. As a method for this, the polymerization prohibition method in the manufacturing method of a conventionally well-known acrylate-type monomer or a methacrylic acid ester-type monomer is mentioned. That is, a method in which a polymerization inhibitor is added to the reaction system, and a method in which the reaction is not performed in an inert gas atmosphere such as nitrogen by passing a gas composition containing 5 to 10% by volume of oxygen, air, or the like. It is done. Examples of the polymerization inhibitor include known ones such as hydroquinone, hydroquinone monomethyl ether, and phenothiazine. The addition amount of a polymerization inhibitor is 0.01-5 mass% with respect to the total amount of a reaction material, Preferably it is the range of 0.05-1.0 mass%.

  The cationic polymer used for the antibacterial and antifungal agent according to the present embodiment can be obtained by polymerizing the composition containing the monomer represented by the formula (1). The cationic polymer may be a cationic polymer obtained by polymerizing the monomer represented by formula (1) alone, or may be obtained by copolymerizing with another monomer as necessary. It may be. Examples of the cationic polymer obtained by polymerizing the monomer represented by the formula (1) alone include a cationic polymer represented by the following general formula (3). Here, m represents the number of repeating units, is an integer of 2 or more, and is preferably an integer in a range calculated from the type of monomer used and the weight average molecular weight of the cationic polymer described later. When the cationic polymer is a copolymer, for example, a copolymer containing a structural unit in which m in the following general formula (3) is 1 can be mentioned. In this case, the copolymer preferably includes two or more of the structural units, and includes within a range calculated from the type of monomer used, the proportion of the monomer used, and the weight average molecular weight of the cationic polymer described below. In the present specification, the meaning of polymerizing the monomer represented by the formula (1) alone includes a case where two or more monomers represented by the formula (1) are polymerized. The meaning of copolymerizing the monomer represented by the formula (1) refers to the case where the monomer represented by the formula (1) is polymerized with a monomer other than the monomer.

  The monomer represented by the formula (1) has insufficient water resistance, but the cationic polymer obtained by polymerizing the monomer represented by the formula (1) alone, or the monomer represented by the formula (1) By using a cationic polymer obtained by copolymerizing a monomer with other monomers, an antibacterial and antifungal agent having excellent water resistance can be obtained.

  The other monomer to be copolymerized with the monomer represented by the formula (1) is not particularly limited as long as it is a monomer that can be copolymerized with the monomer represented by the formula (1). More than seeds may be used. When copolymerizing with another monomer, the monomer represented by Formula (1) can use 1 type (s) or 2 or more types.

  Examples of such other monomers include compounds having an unsaturated hydrocarbon group capable of radical polymerization. Examples of such a compound include α, β-unsaturation such as alkyl methacrylate having 2 to 18 carbon atoms in the alkyl group, alkyl acrylate having 1 to 18 carbon atoms in the alkyl group, acrylic acid, and methacrylic acid. Unsaturated divalent carboxylic acids such as acid, maleic acid, fumaric acid and itaconic acid and their alkyl esters, styrene, α-methylstyrene and aromatic vinyl compounds such as styrene having a substituent on the benzene ring, acrylonitrile and Vinyl cyanide compounds such as methacrylonitrile, amide compounds such as acrylamide and methacrylamide, and glycidyl compounds such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether can be suitably used.

  When the monomer represented by the formula (1) is copolymerized with another monomer to obtain the cationic polymer according to this embodiment, the monomer represented by the formula (1) is based on the total mass of all monomers. It is preferably 20% by mass or more, and more preferably 50% by mass or more. When the monomer represented by the formula (1) is less than 20% by mass with respect to the total mass of all monomers, sufficient antibacterial properties and antifungal properties tend not to be obtained. Moreover, there exists a tendency for the improvement of the antibacterial property with respect to the monomer usage-amount and antifungal property to be more excellent in it being 50 mass% or more.

  The weight average molecular weight of the cationic polymer according to this embodiment is not particularly limited, but is preferably 1000 or more. When the weight average molecular weight is less than 1000, the water resistance tends to be insufficient. The cationic polymer preferably has a weight average molecular weight of 100,000 or less. When the weight average molecular weight exceeds 100,000, the polymerization reaction time for obtaining the cationic polymer becomes longer, but further improvement in antibacterial and antifungal properties tends not to be expected. Also, the resulting cationic polymer tends to be too difficult to handle due to excessively high viscosity. From the balance of antibacterial property, antifungal property, water resistance, cost and ease of handling, the cationic polymer preferably has a weight average molecular weight of 1,000 to 50,000.

  The weight average molecular weight of the cationic polymer can be measured by gel permeation chromatography using polyethylene glycol having a known molecular weight as a standard substance.

  A conventionally known polymerization reaction can be applied to the reaction of polymerizing the monomer represented by the formula (1) alone or with other monomers. For example, the monomer represented by the formula (1) can be polymerized by mixing it alone or with other monomers, optionally adding water, a solvent or the like, and adding a polymerization initiator. That is, the cationic property according to the present embodiment is obtained by polymerizing the monomer represented by the formula (1) and, if necessary, another monomer, a solvent such as water, and a composition containing a polymerization initiator. A polymer can be obtained. As the polymerization initiator, for example, a known thermal polymerization initiator or photopolymerization initiator can be used.

  As the thermal polymerization initiator, conventionally known acrylic acid or methacrylic acid monomer polymerization initiators can be used. For example, inorganic peroxides such as sodium persulfate, potassium persulfate and ammonium persulfate, organic peroxides such as tert-hydroperoxide, benzoyl peroxide and di-tert-butyl peroxide, reduced to these peroxides Conjugated oxidation-reduction initiators combined with an agent, and active azo compounds such as azobisisobutyronitrile and 2,2′-azobis (2-methylpropionamidine) dihydrochloride. These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

  As the photopolymerization initiator, conventionally known photopolymerization initiators that decompose by light irradiation to generate radicals can be used. For example, benzoins such as benzoin and benzoin methyl ether, benzophenone, methylbenzophenone, 4, Benzophenones such as 4′-dichlorobenzophenone and 4,4′-bisdiethylaminobenzophenone, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, Acetophenones such as N, N-dimethylaminoacetophenone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-methylanthraquinone, 2-ethylanthraquinone, 1- Anthraquinones such as loloanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone, thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and 2-isopropylthioxanthone And ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

  In addition to these thermal photopolymerization initiators or photopolymerization initiators, chain transfer agents such as thiols, phosphines, benzoic acids and tertiary amines, polymerization accelerators and the like can be used in combination. Furthermore, in order to carry out the polymerization reaction by the combined use of heating and light irradiation, a thermal polymerization initiator, a photopolymerization initiator, a chain transfer agent for them, a polymerization accelerator and the like may be used in combination.

  The weight average molecular weight of the cationic polymer according to this embodiment can be adjusted by the reaction time, reaction temperature, reaction molar ratio, polymerization initiator, and the like.

  In particular, the amount of the polymerization initiator used often greatly affects the weight average molecular weight, and the larger the amount of the polymerization initiator, the smaller the weight average molecular weight of the resulting cationic polymer. Moreover, as reaction temperature of a polymerization reaction, 5-150 degreeC is mentioned, for example. The longer the reaction time of the polymerization reaction, the larger the weight average molecular weight of the resulting cationic polymer.

  In addition to the cationic polymer according to this embodiment, a conventionally known antibacterial and antifungal compound may be added to the antibacterial and antifungal agent according to the present embodiment. Examples of such compounds include low molecular organic antibacterial agents such as benzalkonium chloride and cetylpyridinium chloride, 5-chloro-2- [2,4-dichlorophenoxyl] phenol, and 3,4,4′- Examples include halogen antibacterial agents such as trichlorocarbanilide, inorganic antibacterial agents such as silver and zinc, and natural antibacterial agents such as chitosan and polylysine.

  The antibacterial and antifungal agent according to this embodiment is a surfactant such as a nonionic active agent, an anionic active agent, and a cationic active agent, an acrylic resin, a urethane resin, an epoxy resin, and a polyamide resin, depending on the application. And binder resins such as silicone resins, isocyanate compounds such as hexylene diisocyanate and toluene diisocyanate, cross-linking agents such as blocked isocyanate compounds obtained by blocking these, softeners, smoothing agents, penetrating agents, leveling agents, antistatic agents, Chelating agents, antioxidants, antifoaming agents, solvents, and other components such as water can be further contained.

  The solvent is not particularly limited, for example, lower alcohols such as methanol, ethanol, isopropyl alcohol and butanol, glycols such as ethylene glycol, diethylene glycol, propylene glycol, hexamethylene glycol and hexylene glycol, and Examples include polyhydric alcohols such as glycerin and sorbitol.

  The antibacterial and antifungal product according to the present embodiment can be obtained by imparting antibacterial and antifungal properties to various objects such as fibers and resin molded products using the antibacterial and antifungal agent according to the present embodiment. . Such antibacterial and antifungal products can exhibit effective antibacterial and antifungal properties against various bacteria and fungi. Moreover, such an antibacterial and antifungal product may be used for applying an antibacterial and antifungal process to a desired object.

  Antibacterial and antifungal products include, for example, liquid detergents, liquid soaps, spray liquids, other liquid products, adhesives, gel products, coating agents, resin additives, textile products, paper products and resin products. It is done.

  The liquid detergent of the present embodiment contains the antibacterial and antifungal agent of the present embodiment in such a ratio that the content of the cationic polymer according to the present invention is 0.1 to 5% by mass with respect to the total mass of the liquid detergent. Can do. When the content is less than 0.1% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even when the content exceeds 5% by mass, further improvement of the antibacterial and antifungal property is small and not economical. The liquid detergent of this embodiment has antibacterial and antifungal properties that are effective against various bacteria and fungi, and is used in kitchens, bathrooms, bathrooms, toilets, etc., and in washing machines. Discoloration and nasty smell caused by bacteria and fungi can be suppressed. Moreover, when a liquid detergent is a detergent for textiles, the discoloration and nasty smell resulting from the bacteria and mold | fungi in a fiber can be suppressed. Moreover, the liquid detergent of this embodiment can contain a conventionally well-known component used for a liquid detergent. Such components include, for example, surfactants, conventionally known antibacterial and antifungal compounds, softeners and bleaching agents.

  The liquid soap of this embodiment may contain the antibacterial and antifungal agent of this embodiment in a proportion such that the content of the cationic polymer according to the present invention is 0.1 to 5% by mass with respect to the total mass of the liquid soap. it can. When the content is less than 0.1% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even when the content exceeds 5% by mass, further improvement of the antibacterial and antifungal property is small and not economical. The liquid soap of this embodiment has antibacterial and antifungal properties effective against various bacteria and fungi, and can suppress discoloration and off-flavor caused by bacteria and fungi in the object to be cleaned. Examples of the use of liquid soap include household laundry, industrial laundry, face washing, hand washing, body washing (body soap, etc.) and the like. The liquid soap of this embodiment can contain conventionally known components used for liquid soap. Examples of such components include a surfactant, a compound having a conventionally known antibacterial and antifungal property as described above, a humectant, and a stabilizer.

  The liquid for spraying according to the present embodiment is an antibacterial antifungal agent according to the present embodiment at a ratio where the content of the cationic polymer according to the present invention is 0.1 to 90% by mass with respect to the total mass of the liquid for spraying. Can be included. When the content is less than 0.1% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even when the content exceeds 5% by mass, further improvement of the antibacterial and antifungal property is small and not economical. Such a spraying liquid can be obtained by diluting the cationic polymer according to the present invention with water, a lower alcohol such as ethanol or isopropanol, or a mixed solvent thereof. The liquid for spraying of the present embodiment is used for the walls, floors and articles, bedding, clothing, carpets, shoes, paper, plastic products, ceramics, filters, etc. in the kitchens, bathrooms, toilets and toilets. By spraying an appropriate amount on the area where there is a possibility of generation of bacteria and mold, discoloration and off-flavor caused by bacteria and mold can be suppressed. Moreover, according to the liquid for spraying of this embodiment, an antibacterial and antifungal process can be given to a target object.

  The spray liquid of this embodiment can be used, for example, as a deodorant, a fiber treatment agent, a paper treatment agent, a resin treatment agent, an antibacterial agent, and an antifungal agent.

  Moreover, as liquid products other than the above, for example, machine oils, fiber processing agents, and paper processing agents can be mentioned. These liquid products can contain the antibacterial and antifungal agent of the present embodiment in a proportion such that the content of the cationic polymer according to the present invention is 0.01 to 5% by mass with respect to the total mass of the liquid product. . When the content is less than 0.1% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even when the content exceeds 5% by mass, further improvement of the antibacterial and antifungal property is small and not economical. The liquid product of the present embodiment has antibacterial and antifungal properties effective against various bacteria and fungi, and can be unlikely to cause discoloration and off-flavor due to bacteria and fungi.

  The adhesive of the present embodiment includes the antibacterial and antifungal agent of the present embodiment at a ratio in which the content of the cationic polymer according to the present invention is 0.1 to 5% by mass with respect to the total mass of the adhesive. be able to. When the content is less than 0.1% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even when used in excess of 5% by mass, the effect of further improving the antibacterial and antifungal property is small and not economical. Such an adhesive of this embodiment can be obtained by mixing the antibacterial and antifungal agent of this embodiment with a known adhesive or the like. Examples of components used in known adhesives include conjugated diene copolymer latexes such as styrene / butadiene copolymers and methacrylate / butadiene polymers, polymers of acrylic acid esters or methacrylic acid esters, and copolymers thereof. Polymer-based vinyl polymer latex, polyamide resin, water-based polyurethane resin, petroleum resin, terpene resin, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, polyvinylpyrrolidone anhydrous Maleic acid resin, melamine resin, carboxymethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, modified starch such as oxidized starch, dextrin, gelatin, casein, In beauty, like soy protein. The adhesive of the present embodiment has antibacterial and antifungal properties effective against various bacteria and fungi, and can hardly cause discoloration and off-flavor caused by bacteria and fungi.

  As a gel-like product of this embodiment, a gel-like fragrance | flavor, a gel-like deodorant, a poultice, and a gel-like soap are mentioned, for example. These gel-like products contain the antibacterial and antifungal agent of the present embodiment in a proportion such that the content of the cationic polymer according to the present invention is 0.01 to 5% by mass with respect to the total mass of the gel-like product. Can do. If the content is less than 0.1% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even if it is used in excess of 5% by mass, further improvement in antibacterial and antifungal properties is small and not economical. The gel-like product of this embodiment has antibacterial and antifungal properties that are effective against various bacteria and fungi, and can be unlikely to cause discoloration and off-flavor due to bacteria and fungi.

The coating agent of the present embodiment contains the antibacterial and antifungal agent of the present embodiment in such a ratio that the content of the cationic polymer according to the present invention is 0.1 to 90% by mass with respect to the total mass of the coating agent. Can do. According to the coating agent of this embodiment, antibacterial and antifungal processing can be performed on an object by coating on the surface of hard materials such as textiles, paper products, plastics, and ceramics, and bacteria and fungi on the object can be applied. Discoloration and off-flavor caused by can be suppressed. As the coating method, a conventionally known method can be employed, and examples thereof include roll coating, brush coating, and spraying. Examples of other components contained in the coating agent of the present embodiment include binders such as acrylic resins and urethane resins, thickeners, antistatic agents, antioxidants, and dispersants. The amount of the coating agent applied to the object of the present embodiment is preferably such that the cationic polymer according to the present invention is 0.1 to 20 g / m ^{2 on the} object. If it is less than 0.1 g / m ^2, it is difficult to obtain sufficient antibacterial and antifungal properties, and even if it is used in excess of 20 g / m ² , further improvement in antibacterial and antifungal properties is small, which is not economical. The coating agent of this embodiment can be used as, for example, a fiber treating agent, a paper treating agent, and a resin treating agent.

  The additive for resin of the present embodiment includes the antibacterial and antifungal agent of the present embodiment so that the cationic polymer according to the present invention is added to the added resin at a ratio of 0.01 to 1% by mass. be able to. When the concentration of the cationic polymer according to the present invention added is less than 0.01% by mass with respect to the resin, sufficient antibacterial and antifungal effect is difficult to be exhibited. Difficult and not economical.

  According to the additive for resin of this embodiment, an antibacterial and antifungal process can be applied to a resin product by a method such as kneading into a resin composition containing resins. The resin to be used is not particularly limited. For example, acrylic resin, styrene resin, melamine resin, urethane resin, phenol resin, polyethylene resin, polypropylene resin, polyacetal, fluorine resin, silicone resin, vinyl acetate resin, vinyl chloride resin, epoxy resin , Polyester resin, polyamide resin, ABS resin, polycarbonate resin and cellulose acetate. Examples of other components contained in the resin additive of the present embodiment include antistatic agents, antioxidants, and dispersants.

  Examples of the resin product of this embodiment include a resin product that has been subjected to antibacterial and antifungal processing with the above coating agent or resin additive.

  The antibacterial and antifungal fiber product of the present embodiment is prepared by attaching the antibacterial and antifungal agent of the present embodiment to the fiber by a known method such as coating, spraying, dipping, and padding (dip-nip). It can be manufactured by processing. Examples of the antibacterial and antifungal fiber product of the present embodiment include various materials and various forms of fiber products. For example, textile materials include natural fibers such as cotton, hemp, wool and silk, regenerated cellulose fibers such as rayon, cupra and tencel (trademark), semi-synthetic fibers such as acetate and promix, polyamide fibers and polyester fibers. And synthetic fibers such as acrylic fiber, polyolefin fiber, polyvinyl chloride fiber, polyimide fiber and polyurethane fiber, and composite fibers of these fibers. Moreover, as a form of a textile product, a short fiber, a long fiber, a thread | yarn, a textile fabric, a knitted fabric, a nonwoven fabric, cotton, a sliver, and a top are mentioned, for example.

  When the antibacterial and antifungal process is a coating, for example, as an antibacterial and antifungal agent of the present embodiment, a fiber treatment agent in which the cationic polymer according to the present invention is mixed with a binder such as a urethane resin or an acrylic resin, a thickener, or the like. Can be used. In this case, the content of the cationic polymer according to the present invention in the fiber treatment agent is preferably 0.1 to 10% by mass with respect to the total mass of the fiber treatment agent. When the antibacterial and antifungal processing is spraying, for example, it is preferable to use a solution having a cationic polymer concentration of 10 to 90% by mass as the antibacterial and antifungal agent of the present embodiment. As the solvent at this time, water, lower alcohols such as methanol, ethanol, isopropyl alcohol and butanol, glycols such as ethylene glycol, diethylene glycol, propylene glycol, hexamethylene glycol and hexylene glycol, polyhydric alcohols such as glycerin and sorbitol, And ketones, such as acetone and methyl ethyl ketone, are mentioned.

When the textile product is coated or sprayed, the cationic polymer according to the present invention is preferably applied to the object so that the nonvolatile content is 0.1 to 20 g / m ² . If it is less than 0.1 g / m ^2, it is difficult to exhibit a sufficient antibacterial and antifungal effect, and even if it is used in excess of 20 g / m ² , the effect of further improving antibacterial and antifungal properties is small and not economical.

When the antibacterial and antifungal treatment is dipping or padding, for example, as the antibacterial and antifungal agent of the present embodiment, a method of preparing a treatment bath containing the cationic polymer according to the present invention and performing an antibacterial and antifungal treatment may be mentioned. . The concentration of the cationic polymer according to the present invention in the treatment bath is preferably a concentration at which the cationic polymer is applied to the object so that the non-volatile content is 0.1 to 20 g / m ² . If it is less than 0.1 g / m ^2, it is difficult to exhibit a sufficient antibacterial and antifungal effect. Even if it is used in excess of 20 g / m ² , the effect of further improving the antibacterial and antifungal properties is small and not economical.

  The antibacterial and antifungal paper product of the present embodiment can be produced by applying the antibacterial and antifungal agent of the present embodiment to paper. As an application method to the paper, for example, the antibacterial and antifungal agent of the present embodiment is added in a process of manufacturing paper such as a pulping process, a disaggregation process, a beating process, a preparation process in which chemicals are blended, and a papermaking process. And a method for applying a treatment agent for paper containing the antibacterial and antifungal agent of the present embodiment and applying the treatment agent to the finished paper by a method such as coating, spraying, impregnation treatment, padding treatment, etc. . From the viewpoint of more excellent antibacterial and antifungal properties, as a method for producing the antibacterial and antifungal paper product of this embodiment, a paper treatment agent containing the antibacterial and antifungal agent of this embodiment is prepared and coated on paper A method of applying the antibacterial and antifungal agent of the present embodiment by a method such as spraying, impregnation treatment or padding treatment is preferred. Examples of the paper processing agent include the paper processing agent as the liquid product described above.

  As an application amount of the antimicrobial and antifungal agent of the present embodiment to the paper, for example, when the antimicrobial and antifungal agent of the present embodiment is applied in the paper manufacturing process, the cationic polymer according to the present invention is added to the total mass of the pulp. The amount given to be 0.01 to 10% by mass is preferable, and the amount given to be 0.1 to 5% by mass is more preferable. Further, when the paper is subjected to coating, spraying, impregnation treatment or padding treatment, an amount given so that the cationic polymer according to the present invention is 0.01 to 10% by mass with respect to the total mass of the pulp is preferable. The amount given to be 0.1 to 1% by mass is more preferable. When the application method is coating on paper, the apparatus used for coating is not particularly limited. For example, air knife coater, roll coater, blade coater, reverse roll coater, bar coater, size press coater, curtain coater and gate roll coater Is mentioned.

  The pulp used for the antibacterial and antifungal paper product of the present embodiment is not particularly limited, and for example, synthetic fibers such as wood fiber, bagasse, kenaf and bamboo pulp obtained from hardwoods and conifers, rayon and polyester, etc. Examples include molecular fibers, fibrous inorganic materials, and recycled paper recycled pulp.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further, this invention is not limited at all by these Examples. In addition, solid content in a present Example means the residue after heating a sample at 105 degreeC for 3 hours.

I. Production of antibacterial and antifungal components Antibacterial and antifungal components such as cationic polymers were obtained by the methods shown in the following examples and comparative examples. The weight average molecular weight of the obtained polymer was determined using gel permeation chromatograph [Column: TSKgel G3000PW-CP] manufactured by Tosoh Corporation, using polyethylene glycol as a standard substance, and sodium nitrate as an eluent. Measured using 1M aqueous solution. The total amine value of the solid content of the composition containing the monomer was measured by the following method. That is, the above composition containing an appropriate amount (about 5 g) of solid content was weighed into 100 ml of a stoppered Erlenmeyer flask, and an acetylating agent (acetic anhydride (reagent grade 1) and glacial acetic acid (reagent grade 1) were added there. 50 ml of a mixture with a volume ratio of 3: 7) was added, lightly stoppered, and immersed in a 100 ° C. oil bath for 30 minutes with occasional shaking. It was titrated with N / 10 perchlorine standard solution, and the total amine value was calculated by the obtained titration value and the following formula. In the formula, A represents the amount (titration value) (ml) of the N / 10 perchlorine standard solution required for titration, and S represents the solid content (g) of the composition.
Total amine number = (A × 5.61) / S

[Example 1]
(Production of Monomer M-1 and Cationic Polymer P-1)
In a four-necked flask equipped with a thermometer and a cooling condenser, dimethylbehenylamine (total amine value: 157, molecular weight determined from total amine value: 357, 178.5 g, 0.5 mol) and isopropyl alcohol as a solvent (70 g) was added. Thereto, a 35% by mass aqueous solution of hydrochloric acid (53.1 g, hydrochloric acid 0.51 mol) was added dropwise to the reaction mixture with stirring, and neutralized. Next, hydroquinone monomethyl ether (0.015 g) as a polymerization inhibitor was added to the reaction mixture, stirred until it was uniformly dissolved, and air was blown into the liquid.

  Glycidyl methacrylate (71.1 g, 0.5 mol) was added dropwise to the reaction mixture over about 2 hours at a temperature of 70-75 ° C. After completion of dropping, the reaction was carried out at a temperature of 70 to 75 ° C. for about 4 hours to obtain a composition containing the monomer M-1. The total amine value of the solid content of the obtained composition was 4.0.

  Next, in a four-necked flask equipped with a thermometer and a cooling condenser, ion exchange water (300 g, first time) and the above composition containing 20 g of solid content are placed under a nitrogen gas stream. The mixture was heated to 35 to 45 ° C. with stirring. As a polymerization initiator, 2,2′-azobis (2-methylpropionamineamidine) dihydrochloric acid (0.05 g) was dissolved in ion-exchanged water (0.5 g), and the temperature was gradually increased while dropping it into the reaction mixture. It was raised. Ion exchange water (800 g, second time) was further added to the reaction mixture at about 48 ° C., and a polymerization reaction was performed at 48 to 52 ° C. for 3 hours to obtain a composition containing the cationic polymer P-1. The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-1 was 9000.

[Example 2]
(Production of Monomer M-2 and Cationic Polymer P-2)
Other than changing dimethylbehenylamine (178.5 g, 0.5 mol) to dimethylstearylamine (total amine value: 186.5, molecular weight determined from total amine value: 301, 150.5 g, 0.5 mol) Obtained a composition containing monomer M-2 in the same manner as in Example 1. The total amine value of the solid content of the obtained composition was 3.6.

  Next, the composition containing monomer M-1 was replaced with the composition containing monomer M-2, and the amount of ion-exchanged water added for the second time was changed from 800 g to 600 g, as in Example 1. Thus, a composition containing the cationic polymer P-2 was obtained. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-2 was 9,200.

[Example 3]
(Production of Monomer M-3 and Cationic Polymer P-3)
Dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethylpalmitylamine (total amine value: 205.5, molecular weight determined from total amine value: 273, 136.5 g, 0.5 mol). Except for this, a composition containing monomer M-3 was obtained in the same manner as in Example 1. The total amine value of the solid content of the obtained composition was 3.0.

  Next, the composition containing monomer M-1 was replaced with the composition containing monomer M-3, and the amount of ion-exchanged water added for the second time was changed from 800 g to 600 g, as in Example 1. Thus, a composition containing the cationic polymer P-3 was obtained. The resulting composition was a translucent high viscosity liquid, and the weight average molecular weight of the cationic polymer P-3 was 11,000.

[Example 4]
(Production of Monomer M-4 and Cationic Polymer P-4)
Example except that dimethyl behenylamine 178.5 g (0.5 mol) was replaced with dimethyl myristylamine (total amine value: 229, molecular weight determined from total amine value: 245, 122.5 g, 0.5 mol) In the same manner as in Example 1, a composition containing monomer M-4 was obtained. The total amine value of the solid content of the obtained composition was 3.2.

  Next, the composition containing monomer M-1 was replaced with the composition containing monomer M-4, and the amount of ion-exchanged water added for the second time was changed from 800 g to 600 g, as in Example 1. Thus, a composition containing the cationic polymer P-4 was obtained. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-4 was 11,000.

[Example 5]
(Production of Monomer M-5 and Cationic Polymer P-5-1)
Except for replacing dimethylbehenylamine (178.5 g, 0.5 mol) with dimethyllaurylamine (total amine value: 261, molecular weight determined from total amine value: 215, 107.5 g, 0.5 mol) In the same manner as in Example 1, a composition containing monomer M-5 was obtained. The total amine value of the solid content of the obtained composition was 2.8.

  Next, the composition containing monomer M-1 is replaced with the above composition containing monomer M-5, the amount of ion-exchanged water added for the second time is changed from 800 g to 400 g, and a polymerization initiator (2,2 ′ -A composition containing the cationic polymer P-5-1 in the same manner as in Example 1 except that the amount of azobis (2-methylpropionamineamidine) dihydrochloride) used was changed from 0.05 g to 0.025 g. Got. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-5-1 was 20,000.

[Example 6]
(Production of Cationic Polymer P-5-2)
In the same manner as in Example 1, except that the composition containing the monomer M-1 was replaced with the composition containing the monomer M-5, and the amount of ion-exchanged water added the second time was changed from 800 g to 400 g. A composition containing the functional polymer P-5-2 was obtained. The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-5-2 was 10900.

[Example 7]
(Production of cationic polymer P-5-3)
The composition containing the monomer M-1 is replaced with the composition containing the monomer M-5, and the amount of ion-exchanged water added in the second time is changed from 800 g to 400 g, and the polymerization initiator (2,2′-azobis (2 -A composition containing the cationic polymer P-5-3 was obtained in the same manner as in Example 1 except that the amount of methyl propionamine amidine) dihydrochloride) used was changed from 0.05 g to 0.1 g. The obtained compound was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-5-3 was 3900.

[Example 8]
(Production of cationic polymer P-5-4)
A composition containing the monomer M-5 obtained in Example 5 in an amount containing 30 g of isopropyl alcohol (90 g) and a solid content in a four-necked flask equipped with a thermometer and a cooling condenser under a nitrogen gas stream. And heated to 35-45 ° C. As a polymerization initiator, azobisisobutyronitrile (0.05 g) was dissolved in acetone (0.5 g), and the temperature was gradually raised while dropping it into the reaction mixture. Isopropyl alcohol (210 g) was further added to the reaction mixture at about 48 ° C., and a polymerization reaction was carried out at 48 to 52 ° C. for 3 hours to obtain a composition containing the cationic polymer P-5-4. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-5-4 was 19000.

[Example 9]
(Production of Monomer M-6 and Cationic Polymer P-6)
Dimethylbehenylamine (178.5 g, 0.5 mol) was obtained from dimethyl coconutamine (manufactured by Kao Corporation, trade name: Farmin DM-24C, total amine number: 246, molecular weight determined from total amine number: 228, 114 g, 0.5 mol) A composition containing the monomer M-6 was obtained in the same manner as in Example 1 except that the composition was changed. The total amine value of the solid content of the obtained composition was 3.0.

  Next, the composition containing monomer M-1 is replaced with the above composition containing monomer M-6, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-6 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 400 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-6 was 10,500.

[Example 10]
(Production of Monomer M-7 and Cationic Polymer P-7)
Example except that dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethyldecylamine (total amine value: 298, molecular weight determined from total amine value: 188, 94 g, 0.5 mol) In the same manner as in Example 1, a composition containing the monomer M-7 was obtained. The total amine value of the solid content of the obtained composition was 3.1.

  Next, the composition containing monomer M-1 is replaced with the composition containing monomer M-7, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-7 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 200 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-7 was 10200.

[Example 11]
(Production of Monomer M-8 and Cationic Polymer P-8)
Example except that dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethyloctylamine (total amine value: 351, molecular weight determined from total amine value: 160, 80 g, 0.5 mol) In the same manner as in Example 1, a composition containing monomer M-8 was obtained. The total amine value of the solid content of the obtained composition was 4.3.

  Next, the composition containing monomer M-1 is replaced with the composition containing monomer M-8, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-8 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 200 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-8 was 9,500.

[Example 12]
(Production of Monomer M-9 and Cationic Polymer P-9)
In the same manner as in Example 1, except that dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with trimethylamine (total amine value: 59.1, 29.5 g, 0.5 mol), monomer M- A composition containing 9 was obtained. The total amine value of the solid content of the obtained composition was 8.8.

  Next, the composition containing the monomer M-1 is replaced with a composition containing the monomer M-9 in an amount containing 23 g of solid content, and the amount of ion-exchanged water added for the first time is changed from 300 g to 200 g. A composition containing the cationic polymer P-9 was obtained in the same manner as in Example 1 except that the amount of ion-exchanged water added the second time was changed from 800 g to 200 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-9 was 4000.

[Example 13]
(Production of Monomer M-10 and Cationic Polymer P-10)
Example 1 was followed except that dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with N-methyldiethanolamine (total amine number: 119.2, 59.6 g, 0.5 mol). A composition containing monomer M-10 was obtained. The total amine value of the solid content of the obtained composition was 7.0 in solid content.

  Next, the composition containing the monomer M-1 is replaced with a composition containing the monomer M-10 in an amount containing 21 g of solid content, and the amount of ion-exchanged water added for the first time is changed from 300 g to 200 g. A composition containing the cationic polymer P-10 was obtained in the same manner as in Example 1 except that the amount of ion-exchanged water added the second time was changed from 800 g to 200 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-10 was 3700.

[Example 14]
(Production of Monomer M-11 and Cationic Polymer P-11)
Stearylamine (total amine value: 209, molecular weight determined from total amine value: 268.4, 268.4 g, 1 mol) was placed in a pressure-resistant reaction vessel, the inside was replaced with nitrogen gas, and the temperature was increased by heating. Thereafter, while maintaining the temperature of 140 to 150 ° C. and the pressure of 392 kpa or less, ethylene oxide (88 g, 2 mol) was blown into the pressure resistant reactor over about 2 hours to obtain dihydroxyethyl stearylamine.

  The obtained dihydroxyethyl stearylamine (178.2 g, 0.5 mol) and isopropyl alcohol (50 g) as a solvent were placed in a four-necked flask equipped with a thermometer and a cooling condenser. Further, a 35% by mass aqueous solution of hydrochloric acid (53.1 g, hydrochloric acid 0.51 mol) was added dropwise to the reaction mixture for neutralization. Hydroquinone monomethyl ether (0.015 g) was added to the reaction mixture as a polymerization inhibitor, stirred until it was uniformly dissolved, and air was blown into the liquid.

  Glycidyl methacrylate (71.1 g, 0.5 mol) was added dropwise to the reaction mixture over about 1.5 hours at a temperature of 70-75 ° C. After completion of the dropwise addition, the mixture was reacted at 70 to 75 ° C. for about 4 hours to obtain a composition containing monomer M-11. The total amine value of the solid content of the obtained composition was 5.4.

  Next, the composition containing monomer M-1 was replaced with the composition containing monomer M-11, and the amount of ion-exchanged water added the second time was changed from 800 g to 600 g, as in Example 1. Thus, a composition containing the cationic polymer P-11 was obtained. The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-11 was 5000.

[Example 15]
(Production of Monomer M-12 and Cationic Polymer P-12)
Monomer in the same manner as in Example 14 except that stearylamine (268.4 g, 1 mol) was changed to laurylamine (total amine value: 300, molecular weight determined from total amine value: 187, 187 g, 1 mol). A composition containing M-12 was obtained. The total amine value of the solid content of the obtained composition was 5.0.

  Next, the composition containing monomer M-1 is replaced with the above composition containing monomer M-12, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-12 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 400 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-12 was 4500.

[Example 16]
(Production of Monomer M-13 and Cationic Polymer P-13)
Stearylamine (268.4 g, 1 mol) was replaced with laurylamine (total amine value: 300, molecular weight determined from total amine value: 187, 187 g, 1 mol), and ethylene oxide (88 g, 2 mol) was replaced with propylene oxide (116 g). The composition containing the monomer M-13 was obtained in the same manner as in Example 14 except that the amount was changed to 2 mol). The total amine value of the solid content of the obtained composition was 6.0.

  Next, the composition containing monomer M-1 is replaced with the composition containing monomer M-13, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-13 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 400 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-13 was 4600.

[Example 17]
(Production of Monomer M-14 and Cationic Polymer P-14)
Laurylamine (total amine value: 300, molecular weight determined from total amine value: 187, 93.5 g, 0.5 mol) was placed in a pressure-resistant reaction vessel, the inside was replaced with nitrogen gas, and the temperature was raised. Thereafter, while maintaining the temperature of 140 to 150 ° C. and the pressure of 392 kpa or less, ethylene oxide (44 g, 1 mol) was blown into the pressure resistant reactor over about 2 hours to obtain dihydroxyethyl laurylamine.

  Next, the obtained dihydroxyethyl laurylamine was cooled, sodium hydroxide (0.2 g) was added, and dehydrated under reduced pressure at 120 ° C. for 30 minutes. Thereafter, the inside was replaced with nitrogen gas, and the temperature was raised by heating. Propylene oxide (58 g, 1 mol) was blown into the pressure-resistant reaction vessel over about 2 hours while maintaining the temperature of 140 to 150 ° C. and the pressure of 392 kpa or less, and ethylene oxide-propylene oxide block adduct of laurylamine (EOPO block adduct). )

  The resulting EOPO block adduct of laurylamine (97.8 g, 0.25 mol) and isopropyl alcohol (50 g) as a solvent were placed in a four-necked flask equipped with a thermometer and a cooling condenser. Thereafter, a 35% by mass aqueous solution of hydrochloric acid (26.6 g, hydrochloric acid 0.255 mol) was added dropwise to the reaction mixture to neutralize it. Hydroquinone monomethyl ether (0.015 g) was added to the reaction mixture as a polymerization inhibitor, stirred until it was uniformly dissolved, and air was blown into the liquid.

  Glycidyl methacrylate (35.6 g, 0.25 mol) was added dropwise to the reaction mixture over about 1.5 hours at a temperature of 70-75 ° C. After completion of the dropwise addition, the mixture was reacted at 70 to 75 ° C. for about 4 hours to obtain a composition containing monomer M-14. The total amine value of the solid content of the obtained composition was 6.2.

  Next, the composition containing monomer M-1 is replaced with the composition containing monomer M-14, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-14 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 400 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-14 was 5100.

[Example 18]
(Production of Monomer M-15 and Cationic Polymer P-15)
Dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethylstearylamine (total amine value: 186.5, molecular weight determined from amine value: 301, 150.5 g, 0.5 mol), and glycidyl methacrylate ( 71.1 g, 0.5 mol) was replaced with allyl glycidyl ether (57.1 g, 0.5 mol) in the same manner as in Example 1 to obtain a composition containing monomer M-15. The total amine value of the solid content of the obtained composition was 5.5.

  Next, the composition containing monomer M-1 was replaced with the composition containing monomer M-15, and the amount of ion-exchanged water added the second time was changed from 800 g to 600 g, as in Example 1. Thus, a composition containing the cationic polymer P-15 was obtained. The obtained compound was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-15 was 4500.

[Example 19]
(Production of Monomer M-16 and Cationic Polymer P-16)
Dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethylmyristylamine (total amine value: 229, molecular weight determined from total amine value: 245, 122.5 g, 0.5 mol), and glycidyl methacrylate (71 0.1 g, 0.5 mol) was changed to allyl glycidyl ether (57.1 g, 0.5 mol) in the same manner as in Example 1 to obtain a composition containing monomer M-18. The total amine value of the solid content of the obtained composition was 4.7.

  Next, the composition containing monomer M-1 was replaced with the composition containing monomer M-16, and the amount of ion-exchanged water added the second time was changed from 800 g to 600 g, as in Example 1. Thus, a composition containing the cationic polymer P-16 was obtained. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-16 was 4800.

[Example 20]
(Production of Monomer M-17 and Cationic Polymer P-17-1)
Dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethyllaurylamine (total amine value: 261, molecular weight determined from total amine value: 215, 107.5 g, 0.5 mol), and glycidyl methacrylate ( 71.1 g, 0.5 mol) was replaced with allyl glycidyl ether (57.1 g, 0.5 mol) in the same manner as in Example 1 to obtain a composition containing monomer M-17. The total amine value of the solid content of the obtained composition was 4.4.

  Next, the composition containing the monomer M-1 was replaced with the above composition containing the monomer M-17, and the amount of ion-exchanged water added the second time was changed from 800 g to 400 g, and the polymerization initiator (2,2 ′ -A composition containing the cationic polymer P-17-1 in the same manner as in Example 1 except that the amount of azobis (2-methylpropionamineamidine) dihydrochloride) used was changed from 0.05 g to 0.025 g. Got. The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-17-1 was 8,900.

[Example 21]
(Production of cationic polymer P-17-2)
Except that the composition containing the monomer M-1 was replaced with the above composition containing the monomer M-17 and the amount of ion-exchanged water added the second time was changed from 800 g to 400 g, the same as in Example 1, A composition containing the cationic polymer P-17-2 was obtained. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-17-2 was 5000.

[Example 22]
(Production of cationic polymer P-17-3)
The composition containing monomer M-1 was replaced with the above composition containing monomer M-17, and the amount of ion-exchanged water added the second time was changed from 800 g to 400 g, and the polymerization initiator (2,2′-azobis ( A composition containing the cationic polymer P-17-3 was obtained in the same manner as in Example 1 except that the amount of 2-methylpropionamine amidine) dihydrochloride) used was changed from 0.05 g to 0.1 g. . The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-17-3 was 3000.

[Example 23]
(Production of cationic polymer P-17-4)
In a four-necked flask equipped with a thermometer and a cooling condenser, under a nitrogen gas stream, isopropyl alcohol (30 g) and a composition containing the monomer M-17 in an amount containing 30 g of solid content are placed. Heated to 45 ° C. As a polymerization initiator, azobisisobutyronitrile (0.05 g) was dissolved in acetone (0.5 g), and the temperature was gradually raised while dropping it into the reaction mixture. Isopropyl alcohol (30 g) was further added to the reaction mixture at about 48 ° C., and a polymerization reaction was performed at 48 to 52 ° C. for 3 hours to obtain a composition containing the cationic polymer P-17-4. The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-17-4 was 7400.

[Example 24]
(Production of Monomer M-18 and Cationic Polymer P-18)
Dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethyldecylamine (total amine value: 298, molecular weight determined from total amine value: 188, 94 g, 0.5 mol), and glycidyl methacrylate (71. 1 g, 0.5 mol) was replaced with allyl glycidyl ether (57.1 g, 0.5 mol) in the same manner as in Example 1 to obtain a composition containing monomer M-18. The total amine value of the solid content of the obtained composition was 5.0.

  Next, the composition containing monomer M-1 is replaced with the above composition containing monomer M-18, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-18 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 400 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-18 was 3,500.

[Example 25]
(Production of Monomer M-19 and Cationic Polymer P-19)
Dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethyloctylamine (total amine value: 351, molecular weight determined from amine value: 160, 80 g, 0.5 mol), and glycidyl methacrylate (71.1 g). , 0.5 mol) was replaced with allyl glycidyl ether (57.1 g, 0.5 mol) in the same manner as in Example 1 to obtain monomer M-19. The total amine value of the solid content of the obtained composition was 6.4.

  Next, the composition containing monomer M-1 is replaced with the composition containing monomer M-19, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-19 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 200 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-19 was 3300.

[Example 26]
(Production of Monomer M-20 and Cationic Polymer P-20)
Laurylamine (total amine value: 300, molecular weight determined from total amine value: 187, 187 g, 1 mol) was placed in a pressure-resistant reaction vessel, the inside was replaced with nitrogen gas, and the temperature was raised. Thereafter, while maintaining the temperature of 140 to 150 ° C. and the pressure of 392 kpa or less, ethylene oxide (88 g, 2 mol) was blown into the pressure resistant reactor over about 2 hours to obtain dihydroxyethyl laurylamine.

  Into a four-necked flask equipped with a thermometer and a cooling condenser, the obtained dihydroxyethyl laurylamine (137.5 g, 0.5 mol) and isopropyl alcohol (50 g) as a solvent were placed, and 35% by mass of hydrochloric acid. An aqueous solution (53.1 g, hydrochloric acid 0.51 mol) was added dropwise for neutralization. Hydroquinone monomethyl ether (0.015 g) was added to the reaction mixture as a polymerization inhibitor, stirred until it was uniformly dissolved, and air was blown into the liquid.

  Allyl glycidyl ether (57.1 g, 0.5 mol) was added dropwise to the reaction mixture over about 1.5 hours at a temperature of 70-75 ° C. After completion of dropping, the mixture was reacted at 70 to 75 ° C. for about 4 hours to obtain a composition containing monomer M-20. The total amine value of the solid content of the obtained composition was 6.0.

  Next, the composition containing monomer M-1 is replaced with the above composition containing monomer M-20, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-20 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 400 g. The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-20 was 3000.

[Example 27]
(Production of Monomer M-21 and Cationic Polymer P-21)
Laurylamine (total amine value: 300, molecular weight determined from total amine value: 187, 93.5 g, 0.5 mol) and sodium hydroxide (0.2 g) are placed in a pressure-resistant reaction vessel, and the inside is filled with nitrogen gas The temperature was raised. Thereafter, a mixture of ethylene oxide (44 g, 1 mol) and propylene oxide (58 g, 1 mol) was blown into the pressure-resistant reaction vessel over about 2 hours while maintaining a temperature of 140 to 150 ° C. and a pressure of 392 kpa or less. An EOPO random adduct was obtained.

  In a four-necked flask equipped with a thermometer and a cooling condenser, the EOPO random adduct of laurylamine (97.8 g, 0.25 mol) and isopropyl alcohol (50 g) as a solvent were placed. A 35 mass% aqueous solution (26.6 g, hydrochloric acid 0.255 mol) was added dropwise for neutralization. Hydroquinone monomethyl ether (0.015 g) was added to the reaction mixture as a polymerization inhibitor, stirred until it was uniformly dissolved, and air was blown into the liquid.

  Allyl glycidyl ether (28.5 g, 0.25 mol) was added dropwise to the reaction mixture over about 1.5 hours at a temperature of 70-75 ° C. After completion of dropping, the mixture was reacted at 70 to 75 ° C. for about 4 hours to obtain a composition containing the monomer M-21. The total amine value of the solid content of the obtained composition was 6.3.

  Next, the composition containing monomer M-1 is replaced with the above composition containing monomer M-21, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-21 was obtained in the same manner as the cationic polymer P-1, except that the amount of was changed from 800 g to 400 g. The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-21 was 3,500.

[Example 28]
(Production of Monomer M-22 and Cationic Polymer P-22)
Dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethyllaurylamine (total amine value: 261, molecular weight determined from total amine value: 215, 107.5 g, 0.5 mol), and glycidyl methacrylate ( 71.1 g, 0.5 mol) was replaced with 4-hydroxybutyl acrylate glycidyl ether (72 g, 0.5 mol) in the same manner as in Example 1 to obtain a composition containing monomer M-22. It was. The total amine value of the solid content of the obtained composition was 8.1.

  Next, the composition containing monomer M-1 is replaced with the above composition containing monomer M-22, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-22 was obtained in the same manner as in Example 1 except that the amount of was changed from 800 g to 400 g. The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-22 was 9800.

[Example 29]
(Production of Monomer M-23 and Cationic Polymer P-23)
Dimethylbehenylamine (178.5 g, 0.5 mol) was replaced with dimethyllaurylamine (total amine value: 261, molecular weight determined from total amine value: 215, 107.5 g, 0.5 mol), and 35 mass of hydrochloric acid. % Aqueous solution (53.1 g, hydrochloric acid 0.51 mol) was replaced with a concentrated sulfuric acid 98% product (50 g, sulfuric acid 0.5 mol) in the same manner as in Example 1 except for the composition containing monomer M-23 I got a thing. The total amine value of the solid content of the obtained composition was 3.3.

  Next, the composition containing monomer M-1 is replaced with the above composition containing monomer M-23, and the amount of ion-exchanged water added at the first time is changed from 300 g to 200 g, and ion-exchanged water added at the second time. A composition containing the cationic polymer P-23 was obtained in the same manner as the cationic polymer P-1, except that the amount of was changed from 800 g to 400 g. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-23 was 11100.

[Example 30]
(Production of Cationic Polymer P-24)
In a four-necked flask equipped with a thermometer and a cooling condenser, in a nitrogen gas stream, ion exchange water (300 g, first time), a composition containing monomer M-2 and a composition containing monomer M-5 Were added (amount containing 10 g of each solid content) and heated to 35-45 ° C. with stirring.

  As a polymerization initiator, 2,2′-azobis (2-methylpropionamineamidine) dihydrochloric acid (0.05 g) was dissolved in ion-exchanged water (0.5 g), and the temperature was gradually increased while dropping it into the reaction mixture. It was raised. Ion exchange water (600 g, second time) was further added to the reaction mixture at about 48 ° C., and a polymerization reaction was performed at 48 to 52 ° C. for 3 hours to obtain a composition containing the cationic polymer P-24. The resulting composition was a translucent high viscosity liquid, and the weight average molecular weight of the cationic polymer P-24 was 9,200.

[Example 31]
(Production of cationic polymer P-25)
As in Example 29, except that the composition containing monomer M-2 and the composition containing monomer M-5 were replaced with a composition containing monomer M-16 and a composition containing monomer M-17, A composition containing the cationic polymer P-25 was obtained. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-25 was 4900.

[Example 32]
(Production of cationic polymer P-26)
The composition containing the monomer M-2 and the composition containing the monomer M-5 were replaced with the composition containing the monomer M-2 (containing 10 g of solid content) and methyl acrylate (10 g), and added for the first time. A composition containing the cationic polymer P-26 in the same manner as in Example 29 except that the amount of ion-exchanged water was changed from 300 g to 150 g and the amount of ion-exchanged water added the second time was changed from 600 g to 300 g. Got. The obtained composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-26 was 33,000.

[Example 33]
(Production of cationic polymer P-27)
The composition containing the monomer M-2 and the composition containing the monomer M-5 are replaced with the composition containing the monomer M-5 and methyl acrylate (10 g) in an amount containing 10 g of solids and added for the first time. A composition containing the cationic polymer P-27 in the same manner as in Example 29 except that the amount of ion-exchanged water was changed from 300 g to 100 g and the amount of ion-exchanged water added the second time was changed from 600 g to 300 g. Got. The resulting composition was a translucent high viscosity liquid, and the weight average molecular weight of the cationic polymer P-27 was 34,000.

[Example 34]
(Production of cationic polymer P-28)
The composition containing monomer M-2 and the composition containing monomer M-5 are replaced with the composition containing monomer M-12 and methyl acrylate (10 g) in an amount containing 10 g of solids, and added first time. A composition containing the cationic polymer P-28 in the same manner as in Example 29 except that the amount of ion-exchanged water was changed from 300 g to 100 g and the amount of ion-exchanged water added the second time was changed from 600 g to 300 g. Got. The resulting composition was a translucent high viscosity liquid, and the weight average molecular weight of the cationic polymer P-28 was 12,000.

[Example 35]
(Production of cationic polymer P-29)
Example except that the composition containing monomer M-2 and the composition containing monomer M-5 were replaced with a composition containing monomer M-16 in an amount containing 10 g of solid content and methyl acrylate (10 g). In the same manner as in Example 29, a composition containing the cationic polymer P-29 was obtained. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-29 was 9700.

[Example 36]
(Production of cationic polymer P-30)
The composition containing the monomer M-2 and the composition containing the monomer M-5 are replaced with the composition containing the monomer M-17 and the methyl acrylate (10 g) in an amount containing 10 g of solids, and added first time. A composition containing the cationic polymer P-30 in the same manner as in Example 29 except that the amount of ion-exchanged water was changed from 300 g to 100 g and the amount of ion-exchanged water added the second time was changed from 600 g to 300 g. Got. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-30 was 12,000.

[Example 37]
(Production of cationic polymer P-31)
The composition containing monomer M-2 and the composition containing monomer M-5 are added to the composition containing monomer M-20 and methyl acrylate (10 g) in an amount containing 10 g of solids and added for the first time. A composition containing the cationic polymer P-31 in the same manner as in Example 29 except that the amount of ion-exchanged water was changed from 300 g to 100 g and the amount of ion-exchanged water added the second time was changed from 600 g to 300 g. Got. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-31 was 11,000.

[Example 38]
(Production of cationic polymer P-32)
The composition containing monomer M-2 and the composition containing monomer M-5 are replaced with the composition containing monomer M-5 and methyl acrylate (5 g) in an amount containing 15 g of solids, and added for the first time. A composition containing the cationic polymer P-32 in the same manner as in Example 29 except that the amount of ion-exchanged water was changed from 300 g to 150 g and the amount of ion-exchanged water added the second time was changed from 600 g to 450 g. Got. The resulting composition was a translucent high viscosity liquid, and the weight average molecular weight of the cationic polymer P-32 was 22,000.

[Example 39]
(Production of cationic polymer P-33)
The composition containing the monomer M-2 and the composition containing the monomer M-5 are replaced with the composition containing the monomer M-17 in an amount containing 15 g of solid content and methyl acrylate (5 g), and added for the first time. A composition containing the cationic polymer P-33 in the same manner as in Example 29 except that the amount of ion-exchanged water was changed from 300 g to 150 g and the amount of ion-exchanged water added the second time was changed from 600 g to 450 g. Got. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-33 was 8,000.

[Example 40]
(Production of cationic polymer P-34)
Ion added for the first time by replacing the composition containing monomer M-2 and the composition containing monomer M-5 with the composition containing monomer M-5 and methacrylic acid (5 g) in an amount of 15 g of solid content. A composition containing the cationic polymer P-34 was prepared in the same manner as in Example 29 except that the amount of exchange water was changed from 300 g to 150 g and the amount of ion exchange water added the second time was changed from 600 g to 450 g. Obtained. The resulting composition was a translucent high viscosity liquid, and the weight average molecular weight of the cationic polymer P-34 was 24,000.

[Example 41]
(Production of cationic polymer P-35)
Ion added for the first time by replacing the composition containing monomer M-2 and the composition containing monomer M-5 with the composition containing monomer M-17 and methacrylic acid (5 g) in an amount containing 15 g of solid content. A composition containing the cationic polymer P-35 was prepared in the same manner as in Example 29 except that the amount of exchange water was changed from 300 g to 150 g and the amount of ion exchange water added the second time was changed from 600 g to 450 g. Obtained. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-35 was 8100.

[Example 42]
(Production of cationic polymer P-36)
The composition containing monomer M-2 and the composition containing monomer M-5 are added to the composition containing monomer M-5 and methyl acrylate (10 g) in an amount containing 5 g of solids, and added for the first time. A composition containing the cationic polymer P-36 in the same manner as in Example 29 except that the amount of ion-exchanged water was changed from 300 g to 150 g and the amount of ion-exchanged water added the second time was changed from 600 g to 300 g. Got. The resulting composition was a translucent high-viscosity liquid, and the weight average molecular weight of the cationic polymer P-36 was 89000.

[Comparative Example 1]
(Monomer M-7)
Monomer M-7 obtained in Example 7 was used as an antibacterial and antifungal component.

[Comparative Example 2]
(Monomer M-12)
Monomer M-12 obtained in Example 15 was used as an antibacterial and antifungal component.

[Comparative Example 3]
(Monomer M-13)
Monomer M-13 obtained in Example 16 was used as an antibacterial and antifungal component.

[Comparative Example 4]
(Monomer M-17)
Monomer M-17 obtained in Example 20 was used as an antibacterial and antifungal component.

[Comparative Example 5]
(Production of poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] (abbreviated as P ′ in the table))
N, N, N ′, N′-tetramethyl-1,2-ethylenediamine (116 g, 1 mol) and bis (2-chloroethyl) ether (143 g, 1 mol) were mixed and reacted at 95 ° C. for 20 hours. To obtain poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride]. The obtained poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] had a weight average molecular weight of 10,000.

[Comparative Example 6]
(Benzalkonium chloride)
Benzalkonium chloride was used as an antibacterial and antifungal component.

[Comparative Example 7]
(Polyhexamethylene biguanide hydrochloride)
Polyhexamethylene biguanide hydrochloride was used as an antibacterial antifungal component.

[Comparative Example 8]
(Zinc pyrithione)
Zinc pyrithione was used as an antibacterial antifungal ingredient.

II. The following test bacteria and test fungi were used for evaluation of antibacterial and antifungal ingredients .
(Test bacteria)
Staphylococcus aureus ATCC 6538P
Klebsiella pneumoniae (Klebsiella pneumoniae NBRC13277)
E. coli (Escherichia coli NBRC3301)
Pseudomonas aeruginosa (Pseudomonase areruginosa NBRC3080)
Methicillin-resistant Staphylococcus aureus (Methicillin-resistant Staphylococcus aureus IID1677, abbreviated as MRSA in Tables 1-4)

(Test mold)
Black persimmon (Aspergillus niger NBRC105650)
Black Panther (Cladosporium cladosporiodes NBRC6348)
Blue fox (Penicillium citrinum NBRC6352)
Trichophyton mentagrophytes NBRC3240

(Evaluation 1. Anti-antifungal agent minimum inhibitory concentration test)
As an antibacterial and antifungal agent, an aqueous solution containing the antibacterial and antifungal component obtained in Examples 1, 4, 6, 10, 15, 18, 19, 21, 24, 26, 28 or 42, or Comparative Example 5 or 6. Were prepared. Regarding these antibacterial and antifungal ingredients and water, “Easy-to-understand fungus test method and anti-contamination measures (Techno System Co., Ltd.), Part II Easy-to-understand fungus test method, Chapter 6 Antifungal test, Section 4 Based on “Efficacy test of fungicides”, the minimum inhibitory concentration (mg / L) for the above-mentioned test bacteria and test fungi was measured.

  Prepare an aqueous solution in which the concentration of the antibacterial antifungal component is 2.5, 5, 10, 25, 50, 125, 250, 500 or 1000 mg / L, in which the growth of the test bacteria or test fungus is completely The lowest concentration that was inhibited was taken as the minimum growth inhibitory concentration. In addition, the density | concentration in the aqueous solution of the cationic polymer obtained in the Example is a density | concentration in conversion of solid content. The results are shown in Tables 1-4. The smaller the minimum inhibitory concentration, the more antibacterial and antifungal. In addition, the concentration of the cationic polymer of the examples in the antibacterial and antifungal agent is the solid content, and the culture conditions of the test bacteria or the test fungus were as follows.

Culture condition test bacteria: 37 ° C., 48 hours, normal agar medium test mold: 25 ° C., 2 or 7 days, potato dextrose agar medium

(Evaluation 2. Antibacterial test and water resistance test of cotton products and polyester fiber products)
An aqueous solution having a concentration of the antibacterial and antifungal component obtained in Examples and Comparative Examples (concentration of solid content in the cationic polymers of Examples and Comparative Examples 5) of 0.2% by mass was prepared and used as a treatment liquid. . A polyester ponji white cloth or cotton knitted white cloth was dipped in the obtained treatment liquid, and wrung with a pickle at 70%. The application amount of the antibacterial and antifungal component was 0.14% by mass with respect to the polyester ponji white cloth or the cotton knitted white cloth. Next, the polyester ponge white cloth was heat-dried at 120 ° C. for 2 minutes and further heat-treated at 180 ° C. for 30 seconds to obtain a processed cloth. On the other hand, the cotton knitted white cloth was heat-dried at 120 ° C. for 2 minutes and further heat-treated at 150 ° C. for 1 minute to obtain a processed cloth.

  The bacteriostatic activity value of Staphylococcus aureus before washing (L-0) of the obtained processed fabric was determined according to the quantitative test method of JIS L 1902 (2008), and the antibacterial property was examined. The results are shown in Tables 5 and 6. When the bacteriostatic activity value was larger than 2.2, it was determined that there was an antibacterial effect. In addition, the bacteriostatic activity value of Staphylococcus aureus 10 times after washing the processed cloth (L-10) was also measured to examine the water resistance. The results are shown in Tables 5 and 6. In the measurement of the bacteriostatic activity value, S. aureus was used as a test bacterium, and the washing method was in accordance with method 103 of JIS L 0217 (1995) Appendix Table 1.

(Evaluation 3. Antifungal test of cotton products)
Example 1, 4, 6, 10, 15, 18, 19, 21, 24, 26, 28 or 42, or the concentration of the antibacterial and antifungal component of Comparative Example 5 or 6 (solid in the cationic polymer of the examples) An aqueous solution having a concentration of 0.2% by mass was prepared as a treatment solution. A cotton knitted white cloth was soaked in the resulting treatment solution and wrung with a mangle at a pickup of 70%. The amount of the antibacterial and antifungal component applied to the cotton knitted white fabric was 0.14% by mass. Subsequently, it heat-dried at 120 degreeC for 2 minutes, and also heat-processed at 150 degreeC for 1 minute, and obtained the work cloth. The antifungal activity value of the obtained processed cloth was determined by the following method. The results are shown in Tables 7-10. When the antifungal activity value was larger than 2.0, it was determined that there was an antifungal effect.

(Calculation method of antifungal activity value)
This was carried out as follows in accordance with JIS F301 “Anti-fungal processed fiber product certification standards” of the Japan Textile Evaluation Technology Council.
Luminometer (Kikkoman Foods Co., Ltd. product) shows the amount of ATP produced by black cocoon immediately after inoculation and the amount of ATP produced by black cocoon after 42 hours of inoculation in processed and unprocessed cloth. , Trade name: Lumitester C-110), and the common logarithm of the measured ATP amount was determined. This test was repeated three times, and the antifungal activity value was calculated by the following formula using the average value of three common logarithmic values. When the antifungal activity value was larger than 2.0, it was determined that there was an antifungal effect.
Antifungal activity value = (F _b −F _a ) − (F _c −F ₀ )
F _a : Average value of common logarithm values of ATP amount produced by black camellia (3 samples) immediately after inoculating black cloth on untreated cloth
F _b : Average value of the common logarithm of the amount of ATP produced by black candy after inoculating black candy on a raw cloth and culturing for 42 hours (3 samples)
F ₀ : Average value of common logarithm values of the amount of ATP produced by black shark immediately after inoculation of black candy on processed cloth (3 samples)
F _c : Average value of common logarithm values of ATP amount produced by black camellia after inoculating black straw on a processed cloth and culturing for 42 hours (3 samples)

(Evaluation 4. Thermal discoloration test of cotton products)
Work cloth was obtained in the same manner as in Evaluation 3. The obtained processed cloth and a cotton knitted white cloth not subjected to antibacterial and antifungal treatment were heat-treated at 120 ° C. or 180 ° C. for 1 minute, and the whiteness was measured. Whiteness was measured using a spectrocolorimeter (Minolta Co., Ltd., CM-3700d) under conditions of a light source D65 and a visual field of 10 degrees. The results are shown in Tables 7-10. It was determined that there was discoloration as the whiteness was smaller than that of an untreated cotton knitted white fabric.

(Evaluation 5. BHT / NOx discoloration test of cotton products)
Work cloth was obtained in the same manner as in Evaluation 3. The obtained processed cloth and a white cotton cloth that has not been antibacterial and antifungal processed are placed in a 2 L sealed system containing BHT (0.05 g) and left at 50 ° C. for 24 hours. BHT was attached to the surface. The obtained processed fabric with BHT and unprocessed fabric were tested in accordance with JIS L 0855 (2005) (weak test (1 cycle test)). NOx was exposed to BHT treated or untreated fabric for 24 hours at room temperature. Then, it measured on condition of the light source D65 and the visual field of 10 degree | times about the processed cloth with BHT, and a non-processed cloth using the spectrocolorimeter (Minolta Co., Ltd. make, CM-3700d). The b value in the L ^* a ^* b ^* color system was obtained, and the difference (Δb value) between the b value of the processed cloth and the unprocessed cloth was calculated. The results are shown in Tables 7-10. It was determined that discoloration was suppressed as the Δb value was smaller.

(Evaluation 6. Antibacterial and antifungal test of antibacterial and antifungal polyester film)
Example 1, 4, 6, 10, 15, 18, 19, 21, 24, 26, 28, 42 or isopropyl alcohol solution containing the antibacterial and antifungal component obtained in Comparative Example 5 or obtained in Comparative Example 6 An aqueous solution containing the antibacterial and antifungal component thus prepared was prepared. Spray application of the isopropyl alcohol solution or aqueous solution containing the above antibacterial and antifungal component onto a polyester film (Teijin DuPont Films Co., Ltd., trade name: Teijin Tetron Film, Brand G2) to 0.5 g / m ² did. In addition, in the cationic polymer of an Example, it is the coating amount in solid content. After spray coating, the polyester film coated with an isopropyl alcohol solution containing an antibacterial and antifungal component was dried at room temperature for 30 minutes to obtain a processed polyester film. On the other hand, about the polyester film which apply | coated the aqueous solution of the antibacterial antifungal component, it dried for 30 minutes at 100 degreeC, and obtained the process polyester film.

  The antibacterial activity value against Staphylococcus aureus of the obtained processed polyester film and the unprocessed polyester film not subjected to antibacterial and antifungal processing was determined according to JIS Z 2801 (2010), and the antibacterial property was examined. The results are shown in Tables 7-10. When the antibacterial activity value was larger than 2.0, it was determined that there was an antibacterial effect. Moreover, the antifungal activity value with respect to black shark was calculated | required by said method, and antifungal property was investigated. The results are shown in Tables 7-10. When the antifungal activity value was larger than 2.0, it was determined that there was an antifungal effect.

(Evaluation 7. Thermal discoloration test of antibacterial and antifungal polyester film)
In the same manner as in Evaluation 6, a processed polyester film was obtained. The obtained processed polyester film and an unprocessed polyester film not subjected to antibacterial and antifungal processing were heat-treated at 100 ° C. or 180 ° C. for 1 minute, and then subjected to colorimetry, and b in the L ^* a ^* b ^* color system The value was calculated | required and the difference ((DELTA) b value) of b value of a process polyester film and an unprocessed polyester film was computed. The results are shown in Tables 7-10. The smaller the Δb value, the more the color change is suppressed. Color measurement was performed using a spectrocolorimeter (CM-3700d, manufactured by Minolta Co., Ltd.) with a light source D65 and a visual field of 10 degrees.

(Evaluation 8. Water resistance test of antibacterial and antifungal polyester film)
The isopropyl alcohol solution containing the antibacterial and antifungal component obtained in Examples 6, 21, 28 and 42 or Comparative Example 5 or the aqueous solution containing the antibacterial and antifungal component obtained in Comparative Example 6 was prepared. An isopropyl alcohol solution or an aqueous solution containing the antibacterial and antifungal component is applied to a polyester film (manufactured by Teijin DuPont Films Co., Ltd., trade name: Teijin Tetron Film, Brand G2) at a solid content of 0.5 g / m ^2. Was spray applied. In addition, in the cationic polymer of an Example, it is the coating amount in solid content. After spray coating, the polyester film coated with the isopropyl alcohol solution containing the antibacterial and antifungal component obtained in Examples 6, 21, 28, 42 or Comparative Example 5 is dried at room temperature for 30 minutes to obtain a processed polyester film. It was. On the other hand, the polyester film coated with the aqueous solution containing the antibacterial and antifungal component obtained in Comparative Example 6 was dried at 100 ° C. for 30 minutes to obtain a processed polyester film.

  The obtained processed polyester film was immersed in water for 1 hour and then dried at room temperature. Thereafter, an antibacterial and antifungal test was conducted in the same manner as the antibacterial and antifungal test of the polyester film in Evaluation 6. The results are shown in Tables 7-10.

(Evaluation 9. Antibacterial, antifungal and thermal discoloration test of antibacterial and antifungal component kneaded resin products)
Antibacterial and antifungal component (1 part by mass) obtained in Examples 6, 21, 28, 42 or Comparative Example 5 and polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumitomo Nobrene H-501, 100 mass) Part) was kneaded at 210 ° C. for 5 minutes using a lab plast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.). In addition, in the cationic polymer of an Example, it is the quantity in solid content. Thereafter, a processed resin product of 150 mm (length) × 150 mm (width) × 0.5 mm (thickness) was produced with a small molding machine. In addition, a raw resin product was prepared in the same manner as described above using only the polypropylene resin without adding the antibacterial and antifungal component. These processed resin products or unprocessed resin products were subjected to antibacterial and antifungal tests in the same manner as in the above-mentioned “(6) Antibacterial and antifungal test of polyester film”. The results are shown in Tables 7-10. Moreover, the obtained processed resin product or unprocessed resin product was visually observed, and thermal discoloration was evaluated based on the following criteria. The results are shown in Tables 7-10.
A: Same color as raw resin product B: Colored compared to raw resin product

  With the antibacterial and antifungal agent of the present invention, an antibacterial and antifungal product having excellent and durable antibacterial and antifungal properties can be obtained. This makes it possible to apply antibacterial and antifungal treatments to floors and walls around water, such as kitchens, bathrooms, toilets, and toilets, and textile products, thereby preventing problems such as discoloration and off-flavors due to fungi and fungi.

  In addition, since the antibacterial and antifungal agent of the present invention can suppress discoloration due to heat and discoloration due to BHT / NOx gas, it has a problem of discoloration when processed into a light-colored fiber or kneaded into a light-colored resin. Can be prevented.

Claims (2)

The antibacterial antifungal agent containing the cationic polymer obtained by polymerizing the composition containing the monomer represented by following General formula (1).

Wherein ^{(1), R 1, R} 2 and ^{R 3} are each independently an alkyl group or hydroxyalkyl group having 1 to 22 carbon atoms, an alkenyl group or hydroxy alkenyl group having 2 to 22 carbon atoms, or - ( a group represented by _AO) k -H, wherein AO represents an alkyleneoxy group having 2 to 4 carbon atoms, k represents an average addition mole number of AO, is 2-4, ^{R 4} is -C A group represented by (O) —, a group represented by —R ⁶ —O—C (O) — or an alkylene group having 1 to ⁶ carbon atoms, wherein R ⁶ represents an alkylene group having 1 to ⁶ carbon atoms. R ⁵ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, X ^n- represents an n-valent anion, n represents an integer of 1 to 3, and a plurality of AOs may be the same or different May be. ] An antibacterial and antifungal product, which has been given antibacterial and antifungal properties by the antibacterial and antifungal agent according to claim 1.