JP2022076342A - Antibacterial and antiviral agent composition, article, and method for producing article - Google Patents

Abstract

To disclose a composition that can give an article antibacterial durability and antiviral durability as well as water repellency.SOLUTION: An antibacterial and antiviral agent composition contains a water repellent and an antibacterial and antiviral agent, the antibacterial and antiviral agent having a quaternary ammonium cation group.SELECTED DRAWING: None

Description

The present application discloses an antibacterial / antiviral agent composition, an article, and a method for producing the article.

Patent Documents 1 and 2 disclose a method of applying an antibacterial deodorant having a quaternary ammonium cation group to a fiber and then performing curing at a high temperature. Patent Document 3 discloses a method for producing an antibacterial deodorant fiber by applying a treatment agent containing a quaternary ammonium salt and a melamine resin to the synthetic fiber. Patent Document 4 discloses a method of imparting antibacterial properties to synthetic fibers by treating the synthetic fibers with a quaternary ammonium salt in the presence of a sulfate surfactant. Patent Document 5 describes that a cloth is treated with a composition containing an antiviral agent containing a methoxysilane-based quaternary ammonium salt, an acrylic acid / acrylic acid ester copolymer polymer, a lower alcohol, and water. A method for producing an antibacterial / antiviral fabric is disclosed. Patent Document 6 describes a method for imparting antibacterial properties to an article containing at least a resin component having a carboxyl group on the surface by imparting an antibacterial agent containing an ethoxysilane quaternary ammonium salt to the article. It has been disclosed.

Japanese Unexamined Patent Publication No. 1-085367 Japanese Unexamined Patent Publication No. 4-034075 Japanese Unexamined Patent Publication No. 4-241171 Japanese Unexamined Patent Publication No. 62-177284 Japanese Unexamined Patent Publication No. 2019-07638 International Publication No. 2013/047642

In the prior art, when an antibacterial / antiviral article is washed with water or the like, the antibacterial / antiviral agent is likely to fall off from the article. That is, there is room for improvement in the durable antibacterial property and the durable antiviral property of the article. In particular, the durable antiviral property has not been sufficiently investigated. Further, in the prior art, the water repellency of antibacterial and antiviral articles has not been sufficiently studied. There is a need for new compositions capable of imparting durable antibacterial, durable antiviral and water repellency to the article.

The present application is one of the means for solving the above problems.
An antibacterial / antiviral agent composition containing a water repellent agent and an antibacterial / antiviral agent.
The antibacterial / antiviral agent has a quaternary ammonium cation group.
Disclose antibacterial / antiviral agent compositions.

In the antibacterial / antiviral agent composition of the present disclosure,
The antibacterial / antiviral agent is at least one compound of the compound represented by the following general formula (1), the compound represented by the following general formula (2), and the compound represented by the following general formula (3). May be good.

式（１）において、
Ｒ_１は炭素数１０～２２のアルキル基であり、
Ｒ_２はメチル基、エチル基、プロピル基又はブチル基であり、
Ｒ_３はメチル基、エチル基、プロピル基又はブチル基であり、
Ｒ_４は炭素数２～４のアルキレン基であり、
Ｒ_５はメチル基又はエチル基であり、
Ｒ_６はメチル基又はエチル基であり、
Ｒ_７はメチル基又はエチル基であり、
Ｚ_１はハロゲンである。

In equation (1)
R ₁ is an alkyl group having 10 to 22 carbon atoms.
_R2 is a methyl group, an ethyl group, a propyl group or a butyl group.
R ₃ is a methyl group, an ethyl group, a propyl group or a butyl group.
_R4 is an alkylene group having 2 to 4 carbon atoms.
_R5 is a methyl group or an ethyl group
R ₆ is a methyl group or an ethyl group
R ₇ is a methyl group or an ethyl group
Z ₁ is a halogen.

式（２）において、
Ｒ_８は炭素数１０～２０のアルキル基又はアリール基であり、
Ｒ_９はメチル基、エチル基、プロピル基、ブチル基又は（ＡＯ）_ｐＨで表される基であり、ＡＯは炭素数２～４のアルキレンオキサイドであり、ｐは１～１０の整数であり、
Ｒ_１０はメチル基、エチル基、ベンジル基又は炭素数２～４のヒドロキシアルキル基であり、
ｎは１又は２であり、
ｍは１又は２であり、
ｎ＋ｍは３であり、
ｌは１又は２であり、
Ｚ_２はモノアルキルリン酸、ジアルキルリン酸、ハロゲン、メチル硫酸、エチル硫酸又は芳香族アニオンである。

In equation (2)
R ₈ is an alkyl group or an aryl group having 10 to 20 carbon atoms.
R ₉ is a methyl group, an ethyl group, a propyl group, a butyl group or a group represented by (AO) pH, AO is an alkylene oxide having 2 to 4 carbon atoms, and _p is an integer of 1 to 10. ,
R ₁₀ is a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group having 2 to 4 carbon atoms.
n is 1 or 2
m is 1 or 2
n + m is 3
l is 1 or 2
Z ₂ is monoalkylphosphoric acid, dialkylphosphoric acid, halogen, methylsulfuric acid, ethylsulfuric acid or aromatic anion.

式（３）において、
Ｒ_２１は炭素数１～４のアルキレン基であり、
Ｒ_２２はメチル基又はエチル基であり、
Ｒ_２３はメチル基又はエチル基であり、
Ｒ_２４は炭素数１～４のアルキレン基であり、
Ｒ_２５はメチル基又はエチル基であり、
Ｒ_２６はメチル基又はエチル基であり、
Ｒ_２７は炭素数１～４のアルキレン基であり、
Ｚ_３はハロゲンであり、
ｋは任意の自然数である。

In equation (3)
R ₂₁ is an alkylene group having 1 to 4 carbon atoms.
R ₂₂ is a methyl group or an ethyl group.
R ₂₃ is a methyl group or an ethyl group.
R ₂₄ is an alkylene group having 1 to 4 carbon atoms.
R ₂₅ is a methyl group or an ethyl group
R ₂₆ is a methyl group or an ethyl group
R ₂₇ is an alkylene group having 1 to 4 carbon atoms.
Z ₃ is a halogen,
k is an arbitrary natural number.

In the antibacterial / antiviral agent composition of the present disclosure,
The water repellent is at least one selected from a polymer containing a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 12 to 24 carbon atoms, a silicone resin, a silicone oil, and a fluorine compound. You may.

The present application is one of the means for solving the above problems.
Disclosed is an article to which the antibacterial / antiviral agent composition of the present disclosure is attached.

The present application is one of the means for solving the above problems.
To obtain an article having antibacterial / antiviral properties by adhering the antibacterial / antiviral agent composition of the present disclosure to an object to which antibacterial / antiviral properties are imparted.
Disclose the manufacturing method of the article including.

The antibacterial / antiviral agent composition of the present disclosure can impart excellent durable antibacterial property, durable antiviral property and water repellency to an article.

1. 1. Antibacterial / antiviral agent composition The antibacterial / antiviral agent composition of the present disclosure contains a water repellent agent and an antibacterial / antiviral agent. Here, the antibacterial / antiviral agent has a quaternary ammonium cation group.

1.1 Water-repellent agent The water-repellent agent may be any antibacterial / antiviral agent composition that can coexist with a predetermined antibacterial / antiviral agent and exhibit water repellency, and is a non-fluorine compound and a fluorine compound. Any of these may be adopted. The water repellent agent may be an acrylic water repellent agent, a silicone water repellent agent, or a fluorine compound water repellent agent. For example, the alkyl group has 12 carbon atoms. It may be at least one selected from a polymer containing a structural unit derived from a (meth) acrylic acid alkyl ester of ~ 24, a silicone resin, a silicone oil and a fluorine compound. Only one type of water repellent may be used alone, or two or more types may be used in combination. Hereinafter, an example of the water repellent agent will be described.

1.1.1 Acrylic water repellent The acrylic water repellent is a (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1) (hereinafter, "component (A)". It may also contain a polymer (hereinafter, may be referred to as “non-fluorine acrylic polymer”) containing a structural unit derived from (also referred to as “non-fluorine acrylic polymer”).

式（Ａ－１）において、Ｒ_１１は水素又はメチル基であってよく、Ｒ_１２は置換基を有していてもよい炭素数１２以上の１価の炭化水素基であってよい。

In the formula (A-1), R ₁₁ may be a hydrogen or a methyl group, and R ₁₂ may be a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.

Here, "(meth) acrylic acid ester" means "acrylic acid ester" or "methacrylic acid ester" corresponding thereto, and is synonymous with "(meth) acrylic acid", "(meth) acrylamide" and the like. be.

The (meth) acrylic acid ester monomer (A) represented by the general formula (A-1) has a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. You may. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may have an alicyclic or aromatic ring. You may be doing it. Among these, when the acrylic water repellent is a polymer containing a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 12 to 24 carbon atoms, it exhibits more excellent water repellency. .. Alternatively, those in which the hydrocarbon is linear, particularly those in which the hydrocarbon is a linear alkyl group, also exhibit better water repellency. When the hydrocarbon group has a substituent, the substituent includes one or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, a (meth) acryloyloxy group and the like. Can be mentioned. In the above general formula (A-1), R ₁₂ may be an unsubstituted hydrocarbon group.

When the hydrocarbon group has 12 to 24 carbon atoms, the following effects can be expected. That is, when a non-fluorine-based acrylic polymer is attached to a textile product or the like, excellent water repellency can be easily obtained. Further, when a non-fluorine acrylic polymer is attached to a textile product or the like, the texture of the textile product tends to be soft and good. The hydrocarbon group may have 12 to 22 carbon atoms. When the number of carbon atoms is in this range, the water repellency and texture are particularly excellent. Particularly preferred as the hydrocarbon group is an alkyl group having 12 to 24 carbon atoms, particularly an alkyl group having 12 to 22 carbon atoms, particularly a linear alkyl group having 12 to 18 carbon atoms.

Examples of the component (A) include stearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, and (meth) acrylic acid. Pentadecyl, (meth) heptadecyl acrylate, (meth) nonadecylate acrylate, (meth) eicosyl acrylate, (meth) hen-eicosyl acrylate, behenyl (meth) acrylate, ceryl (meth) acrylate, mericyl (meth) acrylate Can be mentioned.

The component (A) may have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group that can react with the cross-linking agent. In this case, the durable water repellency of the obtained textile product can be further improved. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, when the component (A) has an amino group, the texture of the obtained textile product can be further improved.

The component (A) may be a monofunctional (meth) acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

As the component (A), one type may be used alone, or two or more types may be used in combination.

In terms of durable water repellency, the component (A) is preferably used in combination with the acrylic acid ester monomer (a1) and the methacrylic acid ester monomer (a2). The ratio (a1) / (a2) of the mass of the component (a1) to be blended to the mass of the component (a2) may be 30/70 to 90/10, or 40/60 to 85/15. It may be 50/50 to 80/20. When (a1) / (a2) is within the above range, more excellent durable water repellency is exhibited.

The non-fluorine-based acrylic polymer has a structural unit derived from the above component (A) and a monomer (E) of at least one of vinyl chloride and vinylidene chloride (hereinafter, also referred to as “component (E)”). It may have a structural unit derived from.). For example, when the component (E) is vinyl chloride, the water repellency and the peel strength are further excellent.

The ratio of the structural unit derived from the component (A) and the structural unit derived from the component (E) in the non-fluorine acrylic polymer is not particularly limited. From the viewpoint of emulsion stability of the non-fluorinated polymer, even if the ratio (A) / (E) of the mass of the component (A) to the mass of the component (E) is 40/60 to 90/10. It may be 50/50 to 85/15 or 60/40 to 80/20. If (A) / (E) is too large, the peel strength tends to decrease. If (A) / (E) is too small, the emulsification stability tends to decrease.

Further, the total mass of the mass of the component (A) and the mass of the component (E) may be 80 to 100% by mass with respect to the total amount of the monomer components constituting the non-fluorinated acrylic polymer. , 85-99% by mass, or 90-98% by mass.

The weight average molecular weight of the non-fluorinated acrylic polymer may be, for example, 100,000 or more, or 500,000 or more. In this case, even better water repellency is exhibited. The upper limit of the weight average molecular weight of the non-fluorine acrylic polymer is not particularly limited, and may be, for example, 5 million or less.

The melt viscosity of the non-fluorine acrylic polymer at 105 ° C. may be 1000 Pa · s or less, or 500 Pa · s or less. If the melt viscosity of the non-fluorine acrylic polymer is too high, the non-fluorine acrylic polymer may precipitate or settle when the non-fluorine acrylic polymer is emulsified or dispersed to form a composition. The storage stability of the composition tends to decrease.

"Melting viscosity at 105 ° C." means using an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation) and putting 1 g of a non-fluorine polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm). Viscosity measured by holding at 105 ° C. for 6 minutes and applying a load of 100 kg ・ f / cm ² with a plunger.

When the weight average molecular weights of the non-fluorine acrylic polymers are the same, the higher the blending ratio of the non-fluorine (meth) acrylic acid ester monomer, the higher the water repellency of the adhered article tends to be. Further, by copolymerizing a copolymerizable non-fluorine-based monomer, it is possible to improve the durable water repellency, texture, etc. of the adhered article.

The non-fluoroacrylic polymer has the following general formula (I-1) in which (B1) HLB is 7 to 18 in addition to the component (A) or in addition to the component (A) and the component (E). , (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18, and (B3) a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. As a monomer component, at least one reactive emulsifier (B) (hereinafter, also referred to as “(B) component”) selected from compounds in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil or fat having the above is used as a monomer component. It may be included.

式（Ｉ－１）において、Ｒ_１３は水素又はメチル基であってよく、Ｘは炭素数１～６の直鎖もしくは分岐のアルキレン基であってよく、Ｙ１は炭素数２～４のアルキレンオキシ基を含む２価の基であってよい。

In formula (I-1), R ₁₃ may be a hydrogen or methyl group, X may be a linear or branched alkylene group having 1 to 6 carbon atoms, and Y1 may be an alkyleneoxy having 2 to 4 carbon atoms. It may be a divalent group containing a group.

式（ＩＩ－１）において、Ｒ_１４は重合性不飽和基を有する炭素数１３～１７の１価の不飽和炭化水素基であってよく、Ｙ_２は炭素数２～４のアルキレンオキシ基を含む２価の基であってよい。

In formula (II-1), R ₁₄ may be a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ₂ may be an alkyleneoxy group having 2 to 4 carbon atoms. It may be a divalent group containing.

A "reactive emulsifier" is an emulsion dispersant having radical reactivity, that is, a surfactant having one or more polymerizable unsaturated groups in the molecule, such as a (meth) acrylic acid ester. It can be copolymerized with a monomer.

The "HLB" is an HLB value calculated by the Griffin method, where the ethyleneoxy group is regarded as a hydrophilic group and all the other groups are regarded as lipophilic groups.

The HLB of the compounds (B1) to (B3) may be 7 to 18, and the emulsion stability during the emulsion polymerization or dispersion polymerization of the non-fluoroacrylic polymer and in the composition after the polymerization (hereinafter). , Simply referred to as emulsion stability), may be 9-15. Furthermore, two or more reactive emulsifiers (B) having different HLBs within the above range may be used in combination in terms of storage stability of the composition.

In the reactive emulsifier (B1) represented by the general formula (I- ₁ ), when R13 is a methyl group, the copolymerizability with the component (A) becomes better. X may be a linear or branched alkylene group having 1 to 6 carbon atoms, and may be a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability. Y ₁ may be a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination and _number of alkyleneoxy groups in Y1 may be appropriately selected so as to be within the above range of HLB. Further, when there are two or more types of alkyleneoxy groups, they may have a block addition structure or a random addition structure.

Examples of the compound represented by the general formula (I-1) include compounds represented by the following general formula (I-2).

式（Ｉ－２）において、Ｒ_１３は水素又はメチル基であってよく、Ｘは炭素数１～６の直鎖もしくは分岐のアルキレン基であってよく、Ａ_１Ｏは炭素数２～４のアルキレンオキシ基であってよく、ｍは上記ＨＬＢの範囲内になるように適宜選択されてよく、具体的には、１～８０の整数であってよく、ｍが２以上のときｍ個のＡ_１Ｏは互いに同一であっても異なっていてもよい。

In formula (I-2), R ₁₃ may be a hydrogen or methyl group, X may be a linear or branched alkylene group having 1 to 6 carbon atoms, and A ₁ O may be a linear or branched alkylene group having 2 to 4 carbon atoms. It may be an alkyleneoxy group, m may be appropriately selected so as to be within the above range of HLB, and specifically, it may be an integer of 1 to 80, and when m is 2 or more, m A. ₁ O may be the same as or different from each other.

In the compound represented by the general formula ( _I -2), the type and combination of A1O and the number of m may be appropriately selected so as to be within the range of the above HLB. From the viewpoint of the emulsion stability of the non-fluorinated acrylic polymer, m may be an integer of 1 to 80 or an integer of 1 to 60. When there are two or more types of A ₁ O, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the general formula (I-2) can be obtained by a conventionally known method. It can also be obtained from a commercially available product, and examples thereof include "Latemuru PD-420", "Latemuru PD-430", and "Latemuru PD-450" manufactured by Kao Corporation.

In the reactive emulsifier (B2) represented by the general formula (II-1), R14 may be a monovalent unsaturated hydrocarbon group having ₁₃ to 17 carbon atoms and having a polymerizable unsaturated group, and may be a specific material. Examples thereof include a tridecenyl group, a tridecazienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatorienyl group, a heptadecenyl group, a heptadecadienyl group, a heptadecatrienyl group and the like. From the viewpoint of emulsion stability of the non-fluorinated acrylic polymer, R ₁₄ may be a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms. Y ₂ may be a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination and number of alkyleneoxy groups in Y ₂ may be appropriately selected so as to be within the above range of HLB. When there are two or more alkyleneoxy groups, they may have a block addition structure or a random addition structure. From the viewpoint of emulsion stability of the non-fluorinated acrylic polymer, the alkyleneoxy group may be an ethyleneoxy group.

Examples of the compound represented by the general formula (II-1) include compounds represented by the following general formula (II-2).

式（ＩＩ－２）において、Ｒ_１４は重合性不飽和基を有する炭素数１３～１７の１価の不飽和炭化水素基であってよく、Ａ_２Ｏは炭素数２～４のアルキレンオキシ基であってよく、ｎは上記ＨＬＢの範囲内になるように適宜選択されてもよく、具体的には、１～５０の整数であってもよく、ｎが２以上のときｎ個のＡ_２Ｏは互いに同一であっても異なっていてもよい。

In the formula (II-2), R ₁₄ may be a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and A ₂ O may be an alkylene oxy group having 2 to 4 carbon atoms. The n may be appropriately selected so as to be within the range of the above HLB, and specifically, it may be an integer of 1 to 50, and when n is 2 or more, n A _2s may be used. O may be the same as or different from each other.

In the above general formula (II- ₂ ), A2O may be an alkyleneoxy group having 2 to 4 carbon atoms. From the viewpoint of the emulsion stability of the non-fluorinated acrylic polymer, the type and combination of A2O and the number of _n may be appropriately selected so as to be within the above HLB range. Further, from the viewpoint of the emulsion stability of the non _- fluorinated acrylic polymer, A2O may be an ethyleneoxy group, n may be an integer of 1 to 50, and may be an integer of 5 to 20. It may be an integer of 8 to 14. When there are two or more types of A ₂ O, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B2) represented by the general formula (II-2) can be synthesized by adding an alkylene oxide to a phenol having an unsaturated hydrocarbon group. For example, it can be synthesized by adding a predetermined amount of alkylene oxide at 120 to 170 ° C. under pressure using an alkaline catalyst such as caustic soda or caustic potassium.

Phenol having an unsaturated hydrocarbon group includes not only industrially produced pure products or mixtures, but also pure products or mixtures extracted and purified from plants and the like. For example, 3- [8 (Z), 11 (Z), 14-pentadecatrienyl] phenol, 3- [8 (Z), 11 (Z), extracted from cashew nut shells and the like and collectively referred to as cardanol. -Pentadecazienyl] phenol, 3- [8 (Z) -pentadecenyl] phenol, 3- [11 (Z) -pentadecenyl] phenol and the like can be mentioned.

The reactive emulsifier (B3) may be a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. The fats and oils having a hydroxyl group and a polymerizable unsaturated group include hydroxy unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.). Examples include mono or diglycerides of fatty acids, and triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (lysynolic acid, lysinoelysinic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of the emulsion stability of the non-fluoroacrylic polymer, it may be an alkylene oxide adduct of triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid, and castor oil (triglyceride of fatty acid containing ricinoleic acid). It may be an alkylene oxide adduct having 2 to 4 carbon atoms, or it may be an ethylene oxide adduct of castor oil. Further, the number of moles of alkylene oxide added can be appropriately selected so as to be within the above range of HLB, and may be 20 to 50 moles from the viewpoint of emulsion stability of the non-fluorinated acrylic polymer. , 25-45 mol. Further, when two or more kinds of alkylene oxides are used, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B3) can be synthesized by adding an alkylene oxide to a fat or oil having a hydroxyl group and a polymerizable unsaturated group. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to triglyceride of a fatty acid containing ricinoleic acid, that is, castor oil using an alkaline catalyst such as caustic soda or caustic potassium at 120 to 170 ° C. under pressure. ..

The composition ratio of the monomer of the component (B) in the non-fluoroacrylic polymer is the total amount of the monomer components constituting the non-fluorine acrylic polymer from the viewpoint of improving water repellency and emulsion stability. It may be 0.5 to 20% by mass, 1 to 15% by mass, or 3 to 10% by mass.

From the viewpoint of improving the durable water repellency of the article, the non-fluorine acrylic polymer has the following components (C-1), (C-2) and (C-3) in addition to the components (A) and (E). And at least one second (meth) acrylic acid ester monomer (C) (hereinafter, also referred to as “C component”) selected from the group consisting of (C-4) is contained as a monomer component. May be.

式（Ｃ－１）において、Ｒ_１５は水素又はメチル基であってよく、Ｒ_１６はヒドロキシル基、アミノ基、カルボキシル基、エポキシ基、イソシアネート基及び（メタ）アクリロイルオキシ基からなる群より選ばれる少なくとも１種の官能基を有する炭素数１～１１の１価の鎖状炭化水素基であってよい。ただし、分子内における（メタ）アクリロイルオキシ基の数は２以下である。

In formula (C-1), R ₁₅ may be a hydrogen or methyl group, and R ₁₆ is selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group. It may be a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group. However, the number of (meth) acryloyloxy groups in the molecule is 2 or less.

式（Ｃ－２）において、Ｒ_１７は水素又はメチル基であってよく、Ｒ_１８は置換基を有していてもよい炭素数１～１１の１価の環状炭化水素基であってよい。

In the formula (C-2), R ₁₇ may be a hydrogen or a methyl group, and R ₁₈ may be a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.

式（Ｃ－３）において、Ｒ_１９は無置換の炭素数１～４の１価の鎖状炭化水素基であってよい。

In formula (C-3), R ₁₉ may be an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.

式（Ｃ－４）において、Ｒ_２０は水素又はメチル基であってよく、ｐは２以上の整数であってよく、Ｓは（ｐ＋１）価の有機基であってよく、Ｔは重合性不飽和基を有する１価の有機基であってよい

In formula (C-4), R ₂₀ may be a hydrogen or methyl group, p may be an integer of 2 or more, S may be a (p + 1) -valent organic group, and T may be a non-polymerizable group. It may be a monovalent organic group having a saturated group.

The monomer of (C-1) has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group in the ester moiety. It may be a (meth) acrylic acid ester monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms. The monovalent chain hydrocarbon group having 1 to 11 carbon atoms is at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group because it can react with a cross-linking agent. It may have a functional group. When a non-fluorinated acrylic polymer containing a (C-1) monomer having a group capable of reacting with these cross-linking agents was treated with a cross-linking agent into an article, the texture of the obtained article was maintained. As it is, durable water repellency can be improved. The isocyanate group may be a blocked isocyanate group protected by a blocking agent.

The chain hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the chain hydrocarbon group may further have a substituent in addition to the above functional group. Above all, when it is linear and / or when it is a saturated hydrocarbon group, the durable water repellency is further improved.

Specific examples of the monomer of (C-1) include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and 1,1-bis (acryloyloxymethyl). ) Ethyl isocyanate and the like. One of these monomers may be used alone, or two or more of these monomers may be used in combination. Among them, when the monomer of (C-1) is 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, or 1,1-bis (acryloyloxymethyl) ethyl isocyanate, the durable water repellency is further improved. improves. Further, from the viewpoint of improving the texture of the obtained article, the monomer of (C-1) may be dimethylaminoethyl (meth) acrylate.

The composition ratio of the monomer of the above (C-1) in the non-fluorine acrylic polymer is based on the total amount of the monomer components constituting the non-fluorine acrylic polymer from the viewpoint of water repellency and texture. It may be 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass.

The monomer (C-2) may be a (meth) acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety. Examples of the cyclic hydrocarbon group include an isobornyl group, a cyclohexyl group, a dicyclopentanyl group and the like. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group having a total of 11 or less carbon atoms of the substituent and the cyclic hydrocarbon group is selected. Further, from the viewpoint of improving durable water repellency, these cyclic hydrocarbon groups may be directly bonded to the ester bond. The cyclic hydrocarbon group may be an alicyclic group or an aromatic group, and in the case of an alicyclic group, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific examples of the monomer include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like. One of these monomers may be used alone, or two or more of these monomers may be used in combination. When the monomer of (C-2) is isobornyl (meth) acrylate or cyclohexyl methacrylate, particularly when it is isobornyl methacrylate, the durable water repellency is further improved.

The composition ratio of the above-mentioned (C-2) monomer in the non-fluorine acrylic polymer is the total amount of the monomer components constituting the non-fluorine polymer from the viewpoint of water repellency and texture of the obtained textile product. On the other hand, it may be 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass.

The monomer (C-3) may be a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. .. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t-butyl group. Specific examples of the monomer of (C-3) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and t-butyl methacrylate. Be done. One of these monomers may be used alone, or two or more of these monomers may be used in combination. When the monomer of (C-3) is methyl methacrylate, isopropyl methacrylate or t-butyl methacrylate, particularly when it is methyl methacrylate, the durable water repellency is further improved.

The composition ratio of the monomer of the above (C-3) in the non-fluorine acrylic polymer is based on the total amount of the monomer components constituting the non-fluorine acrylic polymer from the viewpoint of water repellency and texture. It may be 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass.

The monomer (C-4) may be a (meth) acrylic acid ester monomer having 3 or more polymerizable unsaturated groups in one molecule. The monomer is a polyfunctional (meth) acrylic acid ester having 3 or more (meth) acryloyloxy groups in one molecule in which T in the above general formula (C-4) is a (meth) acryloyloxy group. It may be a monomer. In the formula (C-4), the p Ts may be the same or different. Specific examples of the monomer of (C-4) include, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, and pentaerythritol. Examples thereof include triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. One of these monomers may be used alone, or two or more of these monomers may be used in combination. When the monomer of (C-4) is tetramethylolmethanetetraacrylate or ethoxylated isocyanuric acid triacrylate, the durable water repellency is further improved.

The composition ratio of the monomer of the above (C-4) in the non-fluorine acrylic polymer is based on the total amount of the monomer components constituting the non-fluorine acrylic polymer from the viewpoint of water repellency and texture. It may be 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass.

The total composition ratio of the monomers of the above component (C) in the non-fluorine acrylic polymer is the total amount of the monomer components constituting the non-fluorine acrylic polymer from the viewpoint of water repellency and texture. It may be 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass.

The non-fluorine acrylic polymer is composed of a monofunctional monomer (D) copolymerizable with the component (A), the component (E), the component (B) and the component (C). It may have a unit.

Examples of the monomer of (D) include (meth) acryloylmorpholine, (meth) acrylic acid ester having a hydrocarbon group other than the components (A) and (C), (meth) acrylic acid, and fumaric acid. Ester, maleic acid ester, fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene and other fluorine-free vinyl monomers other than the (E) component Can be mentioned. The (meth) acrylic acid ester having a hydrocarbon group other than the component (A) and the component (C) has a vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group, a blocked isocyanate group and the like as the hydrocarbon group. It may have a substituent, or may have a substituent other than a group that can react with a cross-linking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, a urethane bond, or the like. You may have. Examples of the (meth) acrylic acid ester other than the component (A) and the component (C) include methyl acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate and the like. Can be mentioned.

The composition ratio of the monomer of (D) in the non-fluorine acrylic polymer is 10 mass by mass with respect to the total amount of the monomer components constituting the non-fluorine acrylic polymer from the viewpoint of water repellency and texture. It may be less than or equal to%.

The non-fluoroacrylic polymer has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group capable of reacting with a cross-linking agent from the viewpoint of durable water repellency. May be. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, when the non-fluorine acrylic polymer has an amino group, the texture of the article is likely to be improved.

The non-fluorine acrylic polymer can be produced by a radical polymerization method. From the viewpoint of the performance of the obtained water repellent and the environment, it may be polymerized by an emulsion polymerization method or a dispersion polymerization method.

For example, in a medium, in the presence of the component (E), the (meth) acrylic acid ester monomer (A) represented by the general formula (A-1) is emulsion-polymerized or dispersedly polymerized to be non-fluorinated. Acrylic polymers can be obtained. More specifically, for example, the component (A), the component (E), and, if necessary, the component (B), the component (C) and the component (D), and an emulsifying aid or dispersion in the medium. Auxiliaries may be added and the mixture emulsified or dispersed to give an emulsion or dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction is started, and the monomer and the reactive emulsifier can be polymerized. Examples of the means for emulsifying or dispersing the above-mentioned mixed solution include a homomixer, a high-pressure emulsifier, ultrasonic waves, and the like.

Examples of the emulsification aid or dispersion aid (hereinafter, also referred to as “emulsification aid, etc.”) include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants other than the reactive emulsifier (B). One or more selected from surfactants can be used. The content of the emulsifying aid and the like may be 0.5 to 30 parts by mass, 1 to 20 parts by mass, or 1 to 10 parts by mass with respect to 100 parts by mass of the total monomer. There may be. If the content of the emulsifying aid or the like is too small, the dispersion stability of the mixed solution tends to decrease, and if the content of the emulsifying auxiliary or the like is too large, the water repellency of the non-fluorinated acrylic polymer tends to decrease. It is in.

Water is preferable as the medium for emulsion polymerization or dispersion polymerization, and water and an organic solvent may be mixed if necessary. The organic solvent at this time is not particularly limited, but for example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, and the like, propylene glycol, and the like. Examples thereof include glycols such as dipropylene glycol and tripropylene glycol. The ratio of water to the organic solvent is not particularly limited.

As the polymerization initiator, known polymerization initiators such as azo type, peroxide type, and redox type can be appropriately used. The content of the polymerization initiator may be 0.01 to 2 parts by mass with respect to 100 parts by mass of all the monomers. When the content of the polymerization initiator is within the above range, a non-fluorinated acrylic polymer having a weight average molecular weight of 100,000 or more can be efficiently produced.

Further, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent may be 0.3 parts by mass or less or 0.1 parts by mass or less with respect to 100 parts by mass of all the monomers. If the content of the chain transfer agent is too high, the molecular weight of the non-fluorinated acrylic polymer will decrease.

A polymerization inhibitor may be used for adjusting the molecular weight. By adding a polymerization inhibitor, a non-fluorinated acrylic polymer having a desired weight average molecular weight can be easily obtained.

The temperature of the polymerization reaction may be, for example, 20 ° C to 150 ° C. If the temperature is too low, the polymerization tends to be insufficient, the temperature is too high, and it may be difficult to control the heat of reaction.

The weight average molecular weight of the non-fluoroacrylic polymer obtained after the polymerization reaction can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent, and polymerization inhibitor, and the melt viscosity at 105 ° C. is high. It can be adjusted by increasing or decreasing the content of the functional monomer and the content of the polymerization initiator. For example, in order to reduce the melt viscosity at 105 ° C., the content of the monomer having two or more polymerizable functional groups may be reduced, or the content of the polymerization initiator may be increased.

The content of the non-fluoroacrylic polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is 10 with respect to the total amount of the emulsion or dispersion from the viewpoint of storage stability and handleability of the composition. It may be up to 50% by mass, or 20 to 40% by mass.

1.1.2 Silicone-based water repellent As the silicone-based water repellent, silicone resin, silicone oil and the like can be adopted. Silicone resin is an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT or MDTQ as constituents, solid at 25 ° C. and having a three-dimensional structure. Here, M, D, T and Q represent (R'') 3SiO 0.5 unit, (R'') 2SiO unit, R''SiO 1.5 unit and SiO2 unit, respectively. R'' may be a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

Silicone resins are commonly known as MQ resins, MT resins or MDT resins and may also have moieties labeled MDQ, MTQ or MDTQ.

Silicone resin can also be obtained as a solution in which it is dissolved in a suitable solvent. Examples of the solvent include relatively low molecular weight methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane and a mixture of these solvents. And so on.

Examples of the silicone resin solution include KF7312J (trimethylsilyl group-containing polysiloxane: decamethylcyclopentasiloxane = 50:50 mixture) and KF7312F (trimethylsilyl group-containing polysiloxane: octamethyl) commercially available from Shin-Etsu Chemical Industry Co., Ltd. Cyclotetrasiloxane), KF9021L (trimethylsilyl group-containing polysiloxane: low-viscosity methylpolysiloxane = 50:50 mixture), KF7312L (trimethylsilyl group-containing polysiloxane: low-viscosity methylpolysiloxane = 50:50 mixture) and the like.

Examples of the silicone resin alone include MQ-1600 solid Resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 Flake Resin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane) commercially available from Dow Corning Toray Co., Ltd. And so on. The commercially available product contains a trimethylsilyl group-containing polysiloxane and contains MQ, MDQ, MT, MTQ, MDT or MDTQ.

The silicone oil is a linear organopolysiloxane, and may have an organic group at at least one of the side chains and the ends of the organopolysiloxane. As such silicone oil, hydrophobic silicone oil, functionalized silicone oil and the like can be used, and for example, straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil and methylhydrogen silicone oil; amino-modified. Silicone oil, epoxy modified silicone oil, carbinol modified silicone oil, mercapto modified silicone oil, carboxyl modified silicone oil, polyether modified silicone oil, alkyl modified silicone oil, aralkyl modified silicone oil, alkyl aralkyl modified silicone oil, higher fatty acid ester modified Examples thereof include modified silicone oils such as silicone oils and higher aliphatic amide-modified silicone oils.

Among such silicone-based water repellents, silicone oil is preferable from the viewpoint of water repellency and dispersibility of the composition in an aqueous medium, and methylhydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, and carbinol-modified. More preferred are silicone oils, carboxyl-modified silicone oils, mercapto-modified silicone oils, alkyl-modified silicones, and alkyl aralkyl-modified silicone oils.

Examples of the amino-modified silicone oil include compounds having an organic group containing an amino group and / or an imino group at at least one of the side chain and the terminal of the organopolysiloxane. Examples of such an organic group include an organic group represented by -R-NH2 and an organic group represented by -R-NH-R'-NH2. Examples of R and R'include divalent groups such as an ethylene group and a propylene group. A part or all of the amino group and / or the imino group may be a closed amino group and / or an imino group. The blocked amino group and / or imino group can be obtained, for example, by treating the amino group and / or the imino group with a sealing agent. Examples of the sequestering agent include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms. Can be mentioned.

The functional group equivalent of the amino-modified silicone oil is preferably 100 to 20000 g / mol, more preferably 150 to 12000 g / mol, and even more preferably 200 to 4000 g / mol from the viewpoint of water repellency.

The amino-modified silicone oil is preferably liquid at 25 ° C. The kinematic viscosity of the amino-modified silicone oil at 25 ° C. is preferably 10 to 100,000 mm ² / s, more preferably 10 to 30,000 mm ² / s, and 10 to 5,000 mm ² / s. It is more preferable to have. When the kinematic viscosity at 25 ° C. is larger than 100,000 mm ² / s, the viscosity tends to be too high and the workability tends to be poor. The kinematic viscosity at 25 ° C. means the value measured by the method described in JIS K 2283: 2000 (Ubbelohde viscometer).

As the amino-modified silicone oil, it can be easily obtained as a commercially available product. Examples of commercially available products include KF8005, KF-868, KF-864, KF-393, and KF-8021 (all manufactured by Shin-Etsu Chemical Co., Ltd., trade names), TSF-4709, and XF42-B1989 (momentive. Performance Materials Japan (combined), product name), BY16-872, SF-8417, BY16-853U, BY16-892 (all manufactured by Toray Dow Corning Co., Ltd., product name), etc. ..

Further, silicone oils other than amino-modified silicone oil can also be easily obtained as commercial products. Examples of commercially available products include KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, epoxy-modified silicone oil) and X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, carboxyl-modified silicone oil). , SF8428 (manufactured by Toray Dow Corning Co., Ltd., trade name, carbinol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, methylhydrogen silicone oil), X-22-715 ( Shin-Etsu Chemical Co., Ltd., trade name, higher fatty acid ester-modified silicone oil), KF-96-3000cp (Shin-Etsu Chemical Co., Ltd., trade name, dimethyl silicone oil), SF8416 (Toray Dow Corning Co., Ltd.) , Trade name, alkyl modified silicone oil), SH203 (Tole Dow Corning Co., Ltd., trade name, alkyl aralkyl modified silicone oil), SF8410 (Toray Dow Corning Co., Ltd., trade name, polyether-modified silicone) Oil) and the like.

The silicone resin may be used alone or in combination of two or more.

1.1.3 Fluorine compound-based water repellent The type of fluorine compound as a water repellent is not particularly limited. For example, a water repellent agent having a perfluoroalkyl group having 6 or less carbon atoms can be mentioned. Specific examples of such a water repellent agent include those shown in the following (i) to (vi).

(I) A copolymer of a (meth) acrylate having a perfluoroalkyl group having 6 or less carbon atoms and another monomer copolymerizable with the (meth) acrylate.

The number of carbon atoms of the perfluoroalkyl group contained in the acrylate and / or methacrylate constituting the above-mentioned copolymer may be 3 to 6. Examples of the acrylate and methacrylate having such a perfluoroalkyl group include the following compounds.
CF ₃ (CF ₂ ) ₄ CH ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₂ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₂ CH ₂ CH ₂ OCOCH = CH ₂
CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂
CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ OCOCH = CH ₂
CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH = CH ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (CH ₂ ) ₂ OCOCH = CH ₂
CF ₃ CF ₂ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ OCOCH = CH ₂
(CF ₃ ) 2CF (CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂
CF ₃ (CF ₂ ) ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH = CH ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₄ OCOCH = CH ₂
CF ₃ (CF ₂ ) ₅ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₅ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCH = CH ₂
CF ₃ (CF ₂ ) ₅ CONHCH ₂ CH ₂ OCOCH = CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₃ CH ₂ CH ₂ CH ₂ OCOCH = CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₃ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₃ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂
CF ₃ (CF ₂ ) ₅ CONHCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ CF (CF ₂ Cl) (CF ₂ ) ₃ CONHCH ₂ CH ₂ OCOCH = CH ₂
CF ₃ CF (CF ₂ Cl) (CF ₂ ) ₃ CONHCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂
H (CF ₂ ) ₆ CH ₂ OCOCH = CH ₂
CF ₂ Cl (CF ₂ ) ₅ CH ₂ OCOC (CH ₃ ) = CH ₂
C ₆ F ₁₃ CH = CH ₂

Examples of other monomers copolymerizable with acrylates and / or methacrylates having a perfluoroalkyl group include, for example.
Lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, benzyl acrylate, benzyl methacrylate, glycidyl acrylate, glycidyl methacrylate, aziridinyl acrylate, aziridinyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-2-hydroxypropyl (Meta) acrylic acid esters such as methacrylate, alkylene diol acrylate, alkylene diol dimethacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
(Meta) acrylamides such as acrylamide, methacrylamide, N-methyllol acrylamide, N-methylol methacrylamide, diacetone acrylamide, diacetone methacrylamide, methylolated diacetone acrylamide, etc.
Maleic anhydride alkyl esters such as dibutyl maleate, phthalic acid alkyl esters, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, styrene, α-methylstyrene, β-methylstyrene, alkylvinyl ethers, halogenated alkylvinyl ethers, alkylvinyl ketones, Maleic anhydride, butadiene, isoprene, chloroprene and the like can be mentioned.

The composition ratio of the acrylate and / or methacrylate having a perfluoroalkyl group and other monomers copolymerizable with these is the composition ratio of the acrylate and methacrylate having a perfluoroalkyl group among all the monomers used for the copolymerization. The total may be 40% by mass or more, and may be 50 to 80% by mass.

These copolymers can be produced by a known method of vinyl polymerization, and may be produced by emulsion polymerization.

The medium for emulsion polymerization is not particularly limited, and for example, an aqueous solvent obtained by adding a water-soluble organic solvent to water may be used. When an aqueous solvent obtained by adding a water-soluble organic solvent to water is used, the monomers and copolymers are less likely to aggregate, and a stable emulsion can be obtained. The emulsifier used for emulsion polymerization is not particularly limited, and almost all nonionic, anionic, cationic and amphoteric emulsifiers can be used. In emulsion polymerization, acrylate and / or methacrylate having a perfluoroalkyl group, other monomers copolymerizable with these, emulsifiers, etc. are added to an aqueous solvent, and ultrasonic waves are transmitted in some cases while stirring. This may be carried out by emulsifying and dispersing the monomer mixture, adding a water-soluble polymerization initiator, and heating to polymerize. The water-soluble polymerization initiator used is not particularly limited, and examples thereof include various polymerization initiators such as organic peroxides, azo compounds, and persulfates, and further, ionizing radiation such as γ-rays initiates polymerization. It may be used in place of the agent.

(Ii) A (poly) ester of a monohydric or polyhydric alcohol containing a perfluoroalkyl group having 6 or less carbon atoms and a monovalent or polyvalent carboxylic acid which may be fluorinated, and may be fluorinated. A (poly) ester of a monohydric or polyhydric alcohol and a monovalent or polyvalent carboxylic acid having a perfluoroalkyl group having 6 or less carbon atoms.

(Iii) A fluorine-containing polyester copolymer as shown in JP-A No. 58-103550.

(Iv) A monohydric or polyhydric alcohol having a perfluoroalkyl group having 6 or less carbon atoms (in some cases, a monohydric or polyhydric alcohol containing no fluorine may be mixed) and a monovalent or polyhydric isocyanate (poly). ) Urethane.

The (poly) urethane may have a molecular weight of 700 or more.

(V) A compound having a reactive group (hydroxyl group, amino group, carboxyl group, etc.) capable of reacting with isocyanate and a perfluoroalkyl group having 6 or less carbon atoms.

Examples of such compounds include C ₆ F ₁₃ CH ₂ CH ₂ OH, C ₆ F ₁₃ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OH, C ₆ F ₁₃ SO ₂ N (CH ₂ CH ₃ ) CH. ₂ CH ₂ OH, C ₆ F ₁₃ COOH, C ₆ F ₁₃ CONNHC ₃ H ₆ NHCH ₃ , C ₆ F ₁₃ SO ₂ NHCH ₃ and the like can be mentioned.

(Vi) A fluorinated aliphatic polycarbonate having a perfluoroalkyl group having 6 or less carbon atoms.

The compounds shown in (ii) to (vi) may be used in an emulsified and dispersed form using an emulsifier.

1.2 Antibacterial / Antiviral Agent The antibacterial / antiviral agent composition of the present disclosure includes the above-mentioned water repellent agent and antibacterial / antiviral agent. Antibacterial and antiviral agents have a quaternary ammonium cation group.

Compounds having a quaternary ammonium cation group can exhibit antibacterial and antiviral properties on the surface of the article. Examples of the quaternary ammonium cation group having antibacterial and antiviral properties include a silane-based ammonium cation group, a polyoxyalkylene alkylammonium cation group, and an alkylammonium cation group. The antibacterial / antiviral agent may have at least one quaternary ammonium cation group, and may be a low molecular weight compound or a high molecular weight compound. Specific examples of the compound having a quaternary ammonium cation group will be described later.

The type of anion that is the counter ion of the quaternary ammonium cation group is not particularly limited. For example, it may be monoalkyl phosphoric acid, dialkyl phosphoric acid, halogen, methyl sulfuric acid, ethyl sulfuric acid or aromatic anion. Examples of the aromatic anion include p-toluenesulfonic acid, xylenesulfonic acid, benzoic acid, alkylbenzenesulfonic acid and the like.

The antibacterial / antiviral agent may be at least one compound of the compound represented by the following general formula (1), the compound represented by the following general formula (2), and the compound represented by the following general formula (3). .. From the viewpoint of ensuring higher performance, the antibacterial / antiviral agent may be at least one compound of the compound represented by the following general formula (1) and the compound represented by the following general formula (2).

In formula (1), R ₁ is an alkyl group having 10 to 22 carbon atoms, R ₂ is a methyl group, an ethyl group, a propyl group or a butyl group, and R ₃ is a methyl group, an ethyl group, a propyl group or a butyl group. Group, R ₄ is an alkylene group having 2 to 4 carbon atoms, R ₅ is a methyl or ethyl group, R ₆ is a methyl or ethyl group, and R ₇ is a methyl or ethyl group. , Z ₁ is a halogen.

Specific examples of R ₁ include dodecyl group, tridecylic group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecylic group, eikosyl group, uneicosyl group, doeikosyl group, trieicosyl group, tetraeicosyl group and the like. Can be mentioned. R ₂ and R ₃ may be the same group as each other. Further, R ₅ to R ₇ may be the same group as each other. Z ₁ may be chlorine, bromine, or a halogen other than this, but high performance can be expected especially when it is chlorine. The same applies to the halogen in the formula (2) and the halogen in the formula (3).

Among the silane-based quaternary ammonium salts represented by the formula (1), specific examples of the methoxysilane-based quaternary ammonium salt include octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and dodecyldimethyl (3-). Trimethoxysilylpropyl) ammonium chloride, dodecyldiisopropyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyldiethyl (3-trimethoxysilylpropyl) ammonium chloride, Tetradecyldi-n-propyl (3-trimethoxysilylpropyl) ammonium chloride, pentadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, pentadecyldiethyl (3-trimethoxysilylpropyl) ammonium chloride, pentadecyldi-n-propyl ( 3-Trimethoxysilylpropyl) ammonium chloride, hexadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, hexadecyldiethyl (3-trimethoxysilylpropyl) ammonium chloride, hexadecyldi-n-propyl (3-trimethoxysilylpropyl) ) Ammonium chloride, octadecyldiethyl (3-trimethoxysilylpropyl) ammonium chloride, octadecyldi-n-propyl (3-trimethoxysilylpropyl) ammonium chloride and the like. Among them, tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride has good antibacterial and antiviral properties.

Among the silane-based quaternary ammonium salts represented by the formula (1), as a specific example of the ethoxysilane-based quaternary ammonium salt, in those exemplified as the above-mentioned methoxysilane-based quaternary ammonium salt, trimethoxysilyl. Examples thereof include those in which the group is replaced with a triethoxysilyl group.

In the formula (2), R ₈ is an alkyl group or an aryl group having 10 to 20 carbon atoms, and R ₉ is a methyl group, an ethyl group, a propyl group, a butyl group or a group represented by (AO) _pH . , AO is an alkylene oxide having 2 to 4 carbon atoms, p is an integer of 1 to 10, R ₁₀ is a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group having 2 to 4 carbon atoms, and n is. 1 or 2, m is 1 or 2, n + m is 3, l is 1 or 2, Z ₂ is monoalkyl phosphate, dialkyl phosphate, halogen, methyl sulfate, ethyl sulfate or aromatic. It is an anion.

_In the formula (2), if the carbon number of R8 is too small or too large, the antibacterial / antiviral property tends to decrease. The carbon number of R ₈ may be 10 or more or 12 or more, and may be 20 or less or 18 or less.

In the formula (2), when R ₉ is a methyl group, it is more excellent in antibacterial and antiviral properties.

In the formula (2), when R ₁₀ is a hydroxyalkyl group having 2 to 4 carbon atoms, particularly a hydroxyethyl group, the antibacterial and antiviral properties are further excellent.

In the formula (2), when Z ₂ is monoalkyl phosphoric acid or dialkyl phosphoric acid, it is more excellent in antibacterial and antiviral properties. Examples of the alkyl group of monoalkyl phosphoric acid and dialkyl phosphoric acid include an alkyl group having 1 to 12 carbon atoms. Among them, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 2 to 4 carbon atoms is more preferable.

Specific examples of the aromatic anion that can be Z ₂ in the formula (2) include paratoluene sulfonic acid, xylene sulfonic acid, benzoic acid, alkylbenzene sulfonic acid and the like.

Specific examples of the compound represented by the formula (2) include dodecyldimethylhydroxyethylammonium-butyl phosphate ester salt, tetradecyldimethylhydroxyethylammonium-butylphosphate ester salt, dodecyldimethylhydroxyethylammonium-ethylphosphate ester salt, and tetra. Examples thereof include decyldimethylhydroxyethylammonium-ethylphosphate ester salt. Above all, when dodecyldimethylhydroxyethylammonium-butyl phosphate ester salt is adopted, antibacterial and antiviral properties are further improved.

The antibacterial / antiviral agent may be a polymer compound having a plurality of quaternary ammonium cations. For example, a polymer compound as represented by the above formula (3) can be adopted as an antibacterial / antiviral agent.

In formula (3), R ₂₁ may be an alkylene group having 1 to 4 carbon atoms, R ₂₂ may be a methyl group or an ethyl group, R ₂₃ may be a methyl group or an ethyl group, and R ₂₄ may be. May be an alkylene group having 1 to 4 carbon atoms, R ₂₅ may be a methyl group or an ethyl group, R ₂₆ may be a methyl group or an ethyl group, and R ₂₇ may be an alkylene group having 1 to 4 carbon atoms. It may be a group, Z ₃ may be halogen, and k may be any natural number. The weight average molecular weight of the polymer compound represented by the formula (3) may be, for example, 2,000 or more or 6,000 or more, and may be 200,000 or less or 80,000 or less.

1.3 Composition ratio In the antibacterial / antiviral agent composition of the present disclosure, the ratio of the water repellent agent to the antibacterial / antiviral agent is not particularly limited. For example, the total content of the water repellent and the antibacterial / antiviral agent may be 100% by mass, and the content of the water repellent may be 10% by mass or more or 20% by mass or more, and 95% by mass or less or 80% by mass. It may be as follows.

1.4 Adhesion amount In the antibacterial / antiviral agent composition of the present disclosure, the ratio of the article to the total of the water repellent agent and the antibacterial / antiviral agent adhering to the article is not particularly limited. For example, the total amount of the water repellent agent and the antibacterial / antiviral agent may be attached to 100 parts by mass of the article by 0.1 part by mass or more, or 5 parts by mass or less.

1.5 Optional Ingredients The antibacterial / antiviral agent composition of the present disclosure may contain other ingredients in addition to the above water repellent and antibacterial / antiviral agents. For example, the antibacterial / antiviral agent composition of the present disclosure may contain a surfactant and water, and may contain a surfactant, an organic solvent and water. Further, the antibacterial / antiviral agent composition of the present disclosure includes an acid component, an alkaline component, a surfactant, a silicone component, an organic solvent, a chelating agent, a softener, an antistatic agent, a penetrant, an antifoaming agent, and a cross-linking agent. It may contain a preservative or the like.

2. 2. Articles Articles to which the antibacterial / antiviral agent composition of the present disclosure is attached are excellent in durable antibacterial and durable antiviral properties and also excellent in water repellency.

The type of the article is not particularly limited, and may be any one that requires durable antibacterial property, durable antiviral property, and water repellency. Specific examples of articles include textile products. Alternatively, the antibacterial / antiviral agent composition of the present disclosure may be applied to articles other than textile products.

When the article is a textile product, the type of fiber constituting the textile product is not particularly limited, and may be a natural fiber or a chemical fiber. Specific examples of the fibers include natural fibers such as cotton, linen, silk and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon etc.), polyester, polyurethane and polypropylene, and composite fibers thereof. Examples include blended fibers. Examples of the polyamide include nylon 6, nylon 6, 6 and the like. Examples of polyester include polyethylene terephthalate, polytrimethylene terephthalate, polylactic acid and the like. The fibers may be in the form of yarn, knitted fabric (including mixed knitting), woven fabric (including mixed weaving), non-woven fabric, paper, wood and the like. The fibers may be dyed. The fiber may have some modification treatment on its surface.

3. 3. Method of Manufacturing Articles The techniques of the present disclosure also have aspects as a method of manufacturing articles having antibacterial and antiviral properties. That is, the method for producing the article of the present disclosure is to attach the antibacterial / antiviral agent composition of the present disclosure to an object to which the antibacterial / antiviral property is imparted to obtain an article having the antibacterial / antiviral property. ,including. As described above, the object may be a fiber and the article may be a textile product.

The method for adhering the above antibacterial / antiviral agent composition to the article is not particularly limited. For example, in the method of the present disclosure, an object is brought into contact with a treatment liquid (which may be a solution or a dispersion) containing an antibacterial / antiviral agent composition, whereby the object is brought into contact with the object. An antibacterial / antiviral agent composition may be attached. The timing of the treatment with the treatment liquid is not particularly limited.

The treatment liquid may be, for example, one containing the above-mentioned water repellent agent and the above-mentioned antibacterial / antiviral agent. Further, the treatment liquid may contain other components such as an acid component, an alkaline component, a surfactant, an organic solvent, a chelating agent, a softening agent, an antistatic agent, a penetrant, and an antifoaming agent. The pH of the treatment liquid is not particularly limited, but may be, for example, 2 or more and 7 or less. If it is desired to improve the durability, in the above-mentioned step of treating the object with a treatment liquid containing an antibacterial / antiviral agent composition, one or more melamine resin, glioxal resin, isocyanate group or blocked isocyanate group is used. It is preferable to treat the object by a method including a step of adhering the treatment liquid to the object and heating the object in combination with a cross-linking agent typified by the compound having the substance.

Specific examples of the method for treating an object with a treatment liquid include a padding treatment, a dipping treatment, a spray treatment, a coating treatment and the like. The concentration of the treatment liquid at this time and the treatment conditions such as the heat treatment after the application may be appropriately adjusted in consideration of various conditions such as the purpose and performance. After treating the object with the treatment liquid, a cleaning treatment such as washing with water may be performed in order to remove excess antibacterial / antiviral agent. Further, when the treatment liquid contains water, a drying treatment may be performed in order to remove the water after adhering the treatment liquid to the object. The drying method is not particularly limited and may be either a dry heat method or a wet heat method. The drying temperature and drying time are not particularly limited, and for example, drying may be performed at room temperature to 200 ° C. for 10 seconds to several days. It is more preferably 20 seconds to 10 minutes at 40 to 130 ° C. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 190 ° C. for about 10 seconds to 5 minutes. It is more preferably 30 seconds to 5 minutes at 130 to 190 ° C.

4. Effect As described above, the antibacterial / antiviral agent composition of the present disclosure contains a water repellent agent together with a predetermined antibacterial / antiviral agent, so that the antibacterial / antiviral agent composition has excellent durable antibacterial property, durable antiviral property and repellent property to the article. It can be water-based.

Hereinafter, the effects and the like of the disclosed technique will be described in more detail while showing examples, but the technique of the present disclosure is not limited to the following examples.

1. 1. Preparation of water repellent 1.1 Acrylic water repellent Acrylic water repellent was obtained by polymerizing the monomers at the mass ratios shown in Table 1 below. Specifically, it is as follows.

1.1.1 Synthesis Example 1
Stearyl acrylate 270 parts by mass, Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7) 5 parts by mass, Neugen XL-60 (Daiichi Kogyo Pharmaceutical Co., Ltd.) in a reaction vessel. Co., Ltd., Polyoxyalkylene branched decyl ether, HLB = 12.5) 10 parts by mass, Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Polyoxyalkylene branched decyl ether, HLB = 10.5) 5 parts by mass, 13 parts by mass of stearyltrimethylammonium sulfate, 150 parts by mass of tripropylene glycol and 545.5 parts by mass of water were added, and the mixture was mixed and stirred at 45 ° C. to prepare a mixed solution. The mixed solution was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 1.5 parts by mass of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and the mixture was reacted at 61 ° C. for 6 hours to obtain an acrylic resin dispersion containing 27% by mass of acrylic resin.

1.1.2 Synthesis Example 2
In a reaction vessel, 200 parts by mass of stearyl acrylate, 5 parts by mass of Neugen XL-100 (polyoxyalkylene branched decyl ether, HLB = 14.7) manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., Neugen XL-60 (stock of Daiichi Kogyo Pharmaceutical Co., Ltd.) Co., Ltd., Polyoxyalkylene branched decyl ether, HLB = 12.5) 10 parts by mass, Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Polyoxyalkylene branched decyl ether, HLB = 10.5) 5 parts by mass, 13 parts by mass of stearyltrimethylammonium sulfate, 150 parts by mass of tripropylene glycol and 545.5 parts by mass of water were added, and the mixture was mixed and stirred at 45 ° C. to prepare a mixed solution. The mixed solution was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 1.5 parts by mass of azobis (isobutylamidin) dihydrochloride was added to the mixed solution, and 70 parts by mass of vinyl chloride was continuously pressed in so that the internal pressure of the autoclave was maintained at 0.3 MPa under a nitrogen atmosphere. The temperature was kept at 61 ° C. and the reaction was carried out for 6 hours to obtain an acrylic resin dispersion containing 27% by mass of acrylic resin.

1.1.3 Synthesis Examples 3 to 7
Acrylic resin dispersions according to Synthesis Examples 3 to 7 were obtained in the same manner as in Synthesis Example 2 except that the compounding ratio of the monomers was changed as shown in Table 1 below.

In Table 1 below, "C6 fluorogroup-containing methacrylate" is represented by C _n F _{2n + 1} CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , and is a mixture in which the average value of n is 6. Further, "Neugen XL-100" is a polyoxyalkylene branched decyl ether (HLB = 14.7) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and "Neugen XL-60" is a polyoxy alkylene branched by Dai-ichi Kogyo Seiyaku Co., Ltd. It is an alkylene branched decyl ether (HLB = 12.5), and "Neugen XL-40" is a polyoxyalkylene branched decyl ether (HLB = 10.5) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

1.2 Silicone-based water repellent The silicone-based water repellent according to Preparation Examples 1 to 4 was obtained by the following procedure.

1.2.1 Preparation Example 1 (Dimethyl Silicone Dispersion)
KF-96-3000cs (dimethyl silicone, manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name) 20 parts by mass, 0.3 parts by mass of glycolic acid, and 5 mol adduct of branched alcohol having 12 to 14 carbon atoms 4 5 parts by mass of butyl diglycol and 5 parts by mass of butyl diglycol were mixed. Then, 70.7 parts by mass of water was added to the obtained mixture little by little while mixing to obtain a dispersion liquid containing 20% by mass of dimethyl silicone.

1.2.2 Preparation Example 2 (Silicone Resin Dispersion)
MQ-1600 silicone resin (polysiloxane containing trimethylsilyl group, trade name, manufactured by Toray Dow Corning Co., Ltd.), 15 parts by mass of dimethyl silicone (6cs, manufactured by Toray Dow Corning Co., Ltd., trade name) It was added and mixed until the silicone resin was dissolved to give a mixture. 18.5 parts by mass of the obtained mixture and 0.5 parts by mass of an adduct of 5 mol of ethylene oxide of a branched alcohol having 12 to 14 carbon atoms were mixed. Then, 81 parts by mass of water was added little by little while mixing to obtain a dispersion liquid containing 18.5% by mass of silicone resin and dimethyl silicone in total.

1.2.3 Preparation Example 3 (Amino Modified Silicone Dispersion)
Ethylene oxide 5 of a branched alcohol having 20 parts by mass of TSF-4709 (amino-modified silicone oil, manufactured by Momentive Performance Materials Japan LLC, trade name), 0.3 parts by mass of glycolic acid, and 12 to 14 carbon atoms. 4 parts by mass of the molar adduct and 5 parts by mass of butyl diglycol were mixed. Then, 70.7 parts by mass of water was added to the obtained mixture little by little while mixing to obtain a dispersion liquid containing 20% by mass of amino-modified silicone oil.

1.2.4 Preparation Example 4 (alkyl-modified silicone)
SF 8416 (alkyl-modified silicone, manufactured by Toray Dow Corning Co., Ltd., trade name) 20 parts by mass, 0.3 parts by mass of glycolic acid, and 4 parts by mass of ethylene oxide 5 mol adduct of branched alcohol having 12 to 14 carbon atoms. And 5 parts by mass of butyl diglycol were mixed. Then, 70.7 parts by mass of water was added to the obtained mixture little by little while mixing to obtain a dispersion liquid containing 20% by mass of alkyl-modified silicone.

2. 2. Preparation of antibacterial / antiviral agents The antibacterial / antiviral agents used in this example are as follows.

Compound A: In the following general formula (2), R ₈ is an alkyl group having 12 carbon atoms, R ₉ is a methyl group, R ₁₀ is a hydroxy ethyl group, n is 1, and m is 2. The compound A1 in which l is 1 and Z ₂ is dibutyl phosphate, and in the following general formula (2), R ₈ is an alkyl group having 12 carbon atoms, R ₉ is a methyl group, and R ₁₀ is. A mixture of compound A2 which is a hydroxyethyl group, n is 1, m is 2, l is 2, and Z ₂ is butyl phosphate (the molar ratio of compound A1 to compound A2 is 1: 1). ).

Compound B: In the following general formula (2), R ₈ is an alkyl group having 16 carbon atoms, R ₉ is a methyl group, R ₁₀ is a methyl group, n is 1, and m is 2. , L is 1 and Z ₂ is methyl sulfate.

Compound C: In the following general formula (2), R ₈ is an alkyl group having 10 carbon atoms, R ₉ is a methyl group, R ₁₀ is a methyl group, n is 1, and m is 2. , L is 1 and Z ₂ is chlorine.

Compound D: In the following general formula (1), R ₁ is an alkyl group having 14 carbon atoms, R ₂ is a methyl group, R ₃ is a methyl group, R ₄ is a propylene group, and R ₅ is. A compound in which R ₆ is a methyl group, R ₇ is a methyl group, and Z ₁ is chlorine.

Compound E: In the following general formula (1), R ₁ is an alkyl group having 18 carbon atoms, R ₂ is a methyl group, R ₃ is a methyl group, R ₄ is a propylene group, and R ₅ is. A compound which is an ethyl group, R ₆ is an ethyl group, R ₇ is an ethyl group, and Z ₁ is chlorine.

Compound F: In the following general formula (1), R ₁ is an alkyl group having 18 carbon atoms, R ₂ is a methyl group, R ₃ is a methyl group, R ₄ is a propylene group, and R ₅ is. A compound in which R ₆ is a methyl group, R ₇ is a methyl group, and Z ₁ is chlorine.

The conditions for synthesizing compounds A to F were as follows. The compounds A to C were used as a solution containing 15% by weight of the compound, and the compounds D to F were used as a solution containing 40% by weight of the compound.

2.1 Synthetic conditions for compound A 143 parts by mass of an alkyl phosphate ester and 500 parts by mass of water having a mixing ratio of about 1/1 mono- / di-form adjusted from 3 mol of n-butanol and 1 mol of anhydrous phosphate. It was charged in a reaction vessel and neutralized by adding 260 parts by mass of dodecyldimethylamine. 100 parts by mass of ethylene oxide was charged in this neutralized product and reacted at 100 ° C. for 3 hours to obtain 1000 parts by mass of a composition containing 50.0% by mass of dodecyldimethylhydroxyethylammonium-butyl phosphate ester salt. This was adjusted so that the amount of dodecyldimethylhydroxyethylammonium-butyl phosphate ester salt was 15% by weight.

2.2 Synthesis conditions of compound B 216 parts by mass of hexadecyldimethylamine was charged in the reaction vessel. While cooling the reaction vessel to 50 ° C., 100 parts by mass of dimethyl sulfate was added dropwise. After the reaction was carried out at 50 ° C. for 1 hour after the completion of the dropping, 684 parts by mass of water was added to obtain 1000 parts by mass of a composition containing 31.6% by mass of hexadecyltrimethylammonium-methylsulfate. This was adjusted so that the amount of hexadecyltrimethylammonium-methylsulfate was 15% by weight.

2.3 Synthesis conditions of compound C 311 parts by mass of didecylmethylamine was charged into the reaction vessel. After charging 50.5 parts by mass of methyl chloride and reacting at 80 ° C. for 2 hours, 638 parts by mass of water was added to obtain 1000 parts by mass of a composition containing 36.2% by mass of didecyldimethylammonium chloride. This was adjusted so that didecyldimethylammonium chloride was 15% by weight.

2.4 Synthesis conditions of compound D 199 parts by mass of trimethoxysilylpropyl chloride, 240 parts by mass of dimethyltetradecylamine, and 539 parts by mass of triethylene glycol monomethyl ether are placed in a reaction vessel and reacted at 150 ° C. for 20 hours under a nitrogen atmosphere. , Tetradecyl [3- (trimethoxysilyl) propyl] dimethylammonium chloride to give 1100 parts by weight of a solution of 40% by weight.

2.5 Synthesis conditions of compound E 240 parts by mass of triethoxysilylpropyl chloride, 298 parts by mass of dimethyloctadecylamine and 606 parts by mass of ethanol were placed in a reaction vessel and reacted at 150 ° C. for 20 hours under a nitrogen atmosphere to octadecyl [3- (Triethoxysilyl) propyl] dimethylammonium chloride was obtained in an amount of 1342 parts by mass of a solution of 40% by mass.

2.6 Synthesis conditions of compound F 199 parts by mass of trimethoxysilylpropyl chloride, 298 parts by mass of dimethyloctadecylamine, and 744 parts by mass of ethanol were placed in a reaction vessel and reacted at 150 ° C. for 20 hours under a nitrogen atmosphere to produce octadecyl [3-. (Trimethoxysilyl) propyl] 1204 parts by mass of a solution containing 40% by mass of dimethylammonium chloride was obtained.

3. 3. Preparation of isocyanate compound (crosslinking agent) In a reaction vessel, 239 parts by mass of a hexamethylene diisocyanate nurate (Duranate 24A-100, manufactured by Asahi Kasei Chemicals, 3, number of isocyanate groups, 100% content) and 5 parts by mass of methyl isobutyl ketone were added. Was added and heated to 60-70 ° C. Then, 144 parts by mass of 3,5-dimethylpyrazole was slowly charged and reacted at 60 to 70 ° C. until the isocyanate content confirmed by the infrared spectrophotometer became zero to obtain 98 pyrazole-blocked polyisocyanates. A colorless transparent viscous liquid composition containing 0.7% by mass was obtained. 180 parts by mass of the obtained composition, 140 parts by mass of dibutyldiglycol as an organic solvent, and 20 parts by mass of the above nonionic surfactant were mixed and homogenized. After gradually charging water with stirring, a homogenizer treatment was carried out at 30 MPa to obtain a pyrazole-blocked polyisocyanate aqueous dispersion having a non-volatile content of 20% by mass. The average particle size of the particles in this aqueous dispersion was 0.35 μm.

4. Preparation of treatment liquid (antibacterial / antiviral agent composition) The dispersion liquid containing the above water repellent agent, the above antibacterial / antiviral agent solution, the penetrant, and the above cross-linking agent are shown in Table 2 below. A treatment liquid was obtained by mixing at a predetermined ratio shown in 3.

5. Granting antibacterial and antiviral properties to articles 5.1 Examples 1 to 15
Antibacterial and anti-virus by immersing polyester knit (weight 120 g / m ² , manufactured by Color Dyeing Co., Ltd.) in the above treatment liquid, treating at a drawing ratio of 110%, and then heat-treating at 130 ° C. for 2 minutes. A textile product having sex was obtained.

5.2 Comparative Example 1
The treatment was carried out in the same manner as in Example 1 except that the water repellent was not mixed in the preparation of the treatment liquid to obtain a textile product having antibacterial and antiviral properties.

5.3 Comparative Example 2
The treatment was carried out in the same manner as in Example 3 except that the antibacterial / antiviral agent was not mixed in the preparation of the treatment liquid to obtain a textile product having antibacterial / antiviral properties.

5.4 Comparative Example 3
A fiber product having antibacterial properties was obtained according to the method described in Patent Document 3 (Japanese Unexamined Patent Publication No. 4-241171). Specifically, the treatment liquid is prepared so that the compound A is 30 g / L, the unicaresin 380-K (melamine resin: manufactured by Union Chemical Co., Ltd.) is 1.5 g / L, and the unicacatalist P-3 (catalyst) is 0.5 g / L. Adjusted and prepared a treatment bath. The polyester knit was immersed in a treatment bath, treated at a drawing ratio of 110%, and then heat-treated at 130 ° C. for 2 minutes to obtain antibacterial and antiviral fibers.

5.5 Comparative Example 4
A fiber product having antibacterial properties was obtained according to the method described in Patent Document 4 (Japanese Unexamined Patent Publication No. 62-177284). Specifically, the treatment liquid was adjusted so that the compound D was 30 g / L and the sulfate ester Na salt of the lauryl alcohol ethylene oxide 3 mol adduct was 5 g / L, and the treatment bath was prepared. The polyester knit was immersed in a treatment bath, treated at a drawing ratio of 110%, and then heat-treated at 130 ° C. for 2 minutes to obtain antibacterial and antiviral fibers.

5.6 Comparative Example 5
A fiber product having antibacterial properties was obtained according to the method described in Patent Document 5 (Japanese Unexamined Patent Publication No. 2019-077683). Specifically, the treatment liquid was adjusted so that the compound D was 30 g / L and the acrylic acid / acrylic acid ester copolymer was 30 g / L, and a treatment bath was prepared. The polyester knit which had not been pretreated was immersed in a treatment bath, treated at a drawing ratio of 110%, and then heat-treated at 130 ° C. for 2 minutes to obtain antibacterial and antiviral fibers.

6. Washing Textile products were washed according to the JIS L1930 (2014) C4G method. As the detergent, JAFET standard compound detergent (manufactured by the Textile Evaluation Technology Council) was used, and the detergent concentration of the washing liquid was 1.33 g / L. Under the above conditions, washing was repeated 10 times.

7. Evaluation of durable antibacterial properties The antibacterial activity value was measured by the JIS L1902 (2015) quantitative test (8.2 bacterial solution absorption method), and the antibacterial performance of textile products before and after washing was evaluated. Staphylococcus aureus NBRC12732 and Klebsiella pneumoniae NBRC13277 were used as the bacteria used. The results are shown in Tables 2 and 3 below. The higher the activity value shown in Tables 2 and 3, the better the antibacterial property.

8. Evaluation of durable antiviral property The antiviral activity value was measured by JIS L1922 (2016), and the antiviral performance of textile products was evaluated. Influenza A virus (H3N2) ATCC VR-1679 was used as the virus used. It was evaluated as antiviral activity value = log (Va) -log (Vc). The results are shown in Tables 2 and 3 below. Similar to the antibacterial property, the higher the activity value shown in Tables 2 and 3, the better the antiviral property. In JIS, it is considered effective when the antiviral activity value is 2.0 or more, but the virus decreases even when the activity value is 2.0 or less. In this example, it is determined that even if the activity value is 1.5, it has an antiviral effect.

9. Evaluation of water repellency The test was conducted with the shower water temperature set to 20 ° C. by the same method as the spray method of JIS L1092 (2009).
Water repellency: Condition 5: No wetness adhered to the surface 4: Slightly adhered to the surface Wetness 3: Partial wetness on the surface 2: Wetness on the surface 1: Wetness on the entire surface Item 0: Both front and back sides are completely moist.

As is clear from the results shown in Tables 2 and 3, when the textile product is treated with a composition containing a water repellent agent and a predetermined antibacterial / antiviral agent, the textile product has antibacterial and antiviral properties before and after washing. It can maintain a high activity value for any of the viral properties, has high durable antibacterial and durable antiviral properties, and has high water repellency (Examples 1 to 16). In Examples 1 to 16, not only the antibacterial / antiviral effect of the antibacterial / antiviral agent but also the water absorption / moisture absorption of the article is lowered by the water repellent agent, so that the growth of bacteria and viruses can be suppressed. It is considered that more excellent antibacterial and antiviral effects were exhibited.

On the other hand, when the antibacterial / antiviral agent composition does not contain a water repellent agent, the antiviral property of the textile product is significantly reduced before and after washing, and water repellency cannot be ensured (Comparative Example 1).

Further, when the antibacterial / antiviral agent composition does not contain the antibacterial / antiviral agent, the antibacterial and antiviral properties are not exhibited in the textile product (Comparative Example 2).

Further, when a melamine resin, a sulfate surfactant, or a polyacrylic acid / acrylic ethyl copolymer is used instead of the water repellent, the durable antiviral property is inferior and the water repellency is not ensured (Comparative Examples 3 to 5). ).

From the above, it can be said that an antibacterial / antiviral agent composition satisfying the following requirements can impart excellent durable antibacterial property, durable antiviral property and water repellency to an article.
(1) The antibacterial / antiviral agent composition contains a water repellent agent.
(2) The antibacterial / antiviral agent composition contains an antibacterial / antiviral agent having a quaternary ammonium cation group.

Claims (5)

An antibacterial / antiviral agent composition containing a water repellent agent and an antibacterial / antiviral agent.
The antibacterial / antiviral agent has a quaternary ammonium cation group.
Antibacterial / antiviral agent composition. The antibacterial / antiviral agent is at least one compound of the compound represented by the following general formula (1), the compound represented by the following general formula (2), and the compound represented by the following general formula (3).
The antibacterial / antiviral agent composition according to claim 1.

In equation (1)
R ₁ is an alkyl group having 10 to 22 carbon atoms.
_R2 is a methyl group, an ethyl group, a propyl group or a butyl group.
R ₃ is a methyl group, an ethyl group, a propyl group or a butyl group.
_R4 is an alkylene group having 2 to 4 carbon atoms.
_R5 is a methyl group or an ethyl group
R ₆ is a methyl group or an ethyl group
R ₇ is a methyl group or an ethyl group
Z ₁ is a halogen.

In equation (2)
R ₈ is an alkyl group or an aryl group having 10 to 20 carbon atoms.
R ₉ is a methyl group, an ethyl group, a propyl group, a butyl group or a group represented by (AO) pH, AO is an alkylene oxide having 2 to 4 carbon atoms, and _p is an integer of 1 to 10. ,
R ₁₀ is a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group having 2 to 4 carbon atoms.
n is 1 or 2
m is 1 or 2
n + m is 3
l is 1 or 2
Z ₂ is monoalkylphosphoric acid, dialkylphosphoric acid, halogen, methylsulfuric acid, ethylsulfuric acid or aromatic anion.

In equation (3)
R ₂₁ is an alkylene group having 1 to 4 carbon atoms.
R ₂₂ is a methyl group or an ethyl group.
R ₂₃ is a methyl group or an ethyl group.
R ₂₄ is an alkylene group having 1 to 4 carbon atoms.
R ₂₅ is a methyl group or an ethyl group
R ₂₆ is a methyl group or an ethyl group
R ₂₇ is an alkylene group having 1 to 4 carbon atoms.
Z ₃ is a halogen,
k is an arbitrary natural number. The water repellent is at least one selected from a polymer containing a (meth) acrylic acid alkyl ester having an alkyl group having 12 to 24 carbon atoms, a silicone resin, a silicone oil, and a fluorine compound.
The antibacterial / antiviral agent composition according to claim 1 or 2. The antibacterial / antiviral agent composition according to any one of claims 1 to 3 is attached.
Goods. To obtain an article having antibacterial / antiviral properties by attaching the antibacterial / antiviral agent composition according to any one of claims 1 to 3 to an object to which antibacterial / antiviral properties are imparted.
A method of manufacturing an article, including.