KR20100125261A - Sterile/antibacterial cmposition - Google Patents

Abstract

[식(I) 중, R¹은 탄소수 8 내지 22의 알킬기, A¹는 수소 원자, (CH₂)_m-COOX², X¹, X²는 수소 원자, 알칼리 금속 원자, 알칼리토류 금속 원자, 카티온성 암모늄기, n은 1 내지 3, m은 1 내지 3을 나타낸다.]

[식(Ⅱ) 중, R²은 탄소수 8 내지 22의 알킬기 또는 아실기, Q는 (NH-(CH₂)_m), r은 1, 0이고, r이 0일 때, A², A³는 수소 원자, 메틸기, r이 1일 때, A²는 수소 원자, A³는 수소 원자, CH₂COOX³, X³은 수소 원자, 알칼리 금속 원자, 알칼리토류 금속 원자, 카티온성 암모늄기, n는 1 내지 3, m는 1 내지 3을 나타낸다.](A1) component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt, (B1) component: Long-chain alkylamine compound selected from the group which consists of the following general formula (I) and (II), and / or A mixture with an anion generated from the long-chain alkylamine compound, or a complex formed from the component (A1) and the component (B1), which comprises a bactericidal / antibacterial composition, a liquid detergent composition and a treatment composition for a textile product.

[Wherein in the formula (I), R ¹ is an alkyl group having 8 to 22, A ¹ is a hydrogen ^{_{atom, (CH 2) m -COOX 2}} , X 1, X 2 is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, Cationic ammonium group, n represents 1 to 3, m represents 1 to 3.]

Equation (Ⅱ) of, R ² is an alkyl group or an acyl group having 8 to 22 carbon atoms, Q is _{(NH- (CH 2) m)} , r is 1, 0, when r is 0, A ^2, A ³ Is a hydrogen atom, a methyl group, r is 1, A ² is a hydrogen atom, A ³ is a hydrogen atom, CH ₂ COOX ³ , X ³ is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a cationic ammonium group, n is 1 to 3 and m represent 1 to 3.]

Description

Antibacterial, antimicrobial composition {STERILE / ANTIBACTERIAL CMPOSITION}

The present invention relates to a disinfectant composition, an antibacterial composition, a liquid detergent composition and a treatment composition for a textile product.

This application is Japanese Patent Application No. 2008-057847, filed in Japan on March 7, 2008, Japanese Patent Application No. 2009-029164, filed in Japan on February 10, 2009, and Japanese Patent Application No. 2009 in February 10, 2009. Priority is claimed based on Japanese Patent Application No. 029165 and Japanese Patent Application No. 2009-029166 filed on February 10, 2009, the contents of which are incorporated herein.

As a bactericidal and antibacterial composition in the field of daily necessities including detergents, organic compounds mainly based on quaternary ammonium salts have been used. However, since an organic compound has a low effect on Gram negative bacteria (E. coli, etc.), an inorganic compound has attracted attention in recent years. As an inorganic compound, it has a photocatalytic effect, and metal compounds containing metals, such as silver, copper, and zinc (for example, silver sulfate, zinc sulfate, etc.), a metal, and a multidentate ligand. And complexes (metal complexes) and the like. Especially, the conventional metal complex by the metal which has an antibacterial and antibacterial effect tends to act on microbe in a very small amount.

In recent years, as a result of the increase in the cleanliness orientation, the effect of washing a textile product requires not only a visible state of deterioration but also a cleaning effect (deodorant effect) and deodorization effect against odor contamination. have. As one of the causes of odors from clothes after washing, it is known that contamination of sebum or the like remaining without being completely removed by washing is decomposed by microorganisms.

Specifically, as an example of using a metal compound having a bactericidal / antibacterial effect, a bactericidal / antimicrobial liquid composition containing a bactericidal / antimicrobial inorganic metal-containing component and a cationic polymer and / or an alkaline polymer has been proposed (Patent Document 1). Reference).

Examples of the metal complex having an antibacterial and antibacterial effect include at least one compound selected from the group consisting of hydrogen peroxide, hydrogen peroxide adducts of alkali metal atom carbonates, and perborates, and groups consisting of Groups 3 to 12 of the periodic table. A composition containing a complex of a metal selected from the group and a multidentate ligand has been proposed (see Patent Document 2).

Further, in Patent Documents 1 to 4, methods for obtaining deodorizing effects by acting on bacteria such as microorganisms using inorganic metal compounds having bactericidal and antibacterial properties have been studied, and Patent Documents 5 and 6 disclose bactericidal and antimicrobial agents. Softener compositions incorporating inorganic metal compounds having properties have been proposed. As an inorganic metal compound, it is common to use the compound containing metals, such as silver, copper, and zinc, the complex (metal complex) of these metals with a multidentate ligand, etc. to use.

Patent Document 1: Japanese Patent Application Laid-Open No. 2006-151907

Patent Document 2: Japanese Patent Application Laid-Open No. 9-132797

Patent Document 3: Japanese Patent Application Laid-Open No. 2007-176985

Patent Document 4: Japanese Patent Application Laid-Open No. 3-141205

Patent Document 5: Japanese Patent Application Laid-Open No. 2001-192967

Patent Document 6: Japanese Patent Application Laid-Open No. 2001-200473

However, in the antibacterial and antimicrobial liquid composition proposed in Patent Literature 1, the metal content of the inorganic metal-containing component having the antibacterial and antibacterial effect is high, and especially when silver is used, economic problems arise.

In addition, the cationic polymer and / or the alkaline polymer in the bactericidal / antimicrobial liquid composition of Patent Document 1 are blended for the purpose of stably blending the inorganic metal-containing component so as not to cause coloring or sedimentation, and to the bactericidal / antibacterial effect. There is no impact.

In addition, when the inorganic metal compound is blended into the cleaning agent for textile products, since the cleaning agent is diluted with a large amount of water at the time of washing, it is necessary to blend a large amount of the inorganic metal compound in order to express a sufficient disinfecting effect and an antibacterial effect. It was disadvantageous in economics.

In addition, especially in the case of a liquid detergent, it is required to mix | blend detergent components, such as an inorganic metal compound, in liquid stably, and to maintain the storage stability of a detergent.

By the way, by simply incorporating an inorganic metal compound into the cleaning agent, a sufficient disinfection effect, an antibacterial effect, and a deodorizing effect are hardly obtained, and further improvement of the disinfection effect or the antibacterial effect and the deodorizing effect is required.

On the other hand, in patent document 2, the extremely small amount of metal complex which has an antibacterial and antibacterial effect, and peroxides, such as hydrogen peroxide and sodium percarbonate, are used together. Metal complexes having bactericidal and antibacterial effects exhibit high bactericidal and antibacterial effects on gram-negative bacteria, but tend to have weaker bactericidal and antibacterial effects on Gram-positive bacteria (such as yellow staphylococci) in contrast to the organic compounds described above.

By the way, peroxides, such as hydrogen peroxide and sodium percarbonate, show improvement of the antibacterial and antibacterial effect by using together with a metal. Therefore, the method which uses a metal complex and a peroxide together may be used in order to acquire the antibacterial and antibacterial effect to both gram negative bacteria and gram positive bacteria.

However, when a metal complex and a peroxide are used together, a peroxide may decompose | disassemble by a metal complex and the antibacterial and antibacterial effect may be reduced. Therefore, in order to use a metal complex and a peroxide together and to act on bacteria more effectively as an antibacterial and antimicrobial composition, it is preferable to mix a solid or liquid metal complex and a peroxide just before use, and a mixture of a metal complex and a peroxide Silver was inadequate for the preservation of organs.

Moreover, even if a metal complex and a peroxide were used together, the bactericidal and antibacterial effect on gram positive bacteria was not necessarily sufficient.

The present invention has been made in view of the above circumstances, and while maintaining the stability of the bactericidal / antibacterial composition which can exert an excellent bactericidal / antibacterial effect against both gram-positive bacteria and gram-negative bacteria with a small amount of metal without using a peroxide. It is an object of the present invention to provide a liquid detergent composition capable of expressing an excellent bactericidal effect or an antimicrobial effect, and a treatment composition for a textile product that can express an excellent bactericidal or antibacterial effect and a deodorizing effect.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, in order to acquire the deodorizing effect using the bactericidal / antibacterial effect of an inorganic metal compound by washing, it was necessary that the inorganic metal compound needs to adsorb | suck to the textile product after washing. However, most of the inorganic metal compound in the cleaning agent or the treatment agent easily flows in a washing process such as rinsing, and the inorganic metal compound is adsorbed and retained in the textile product after washing only by blending the inorganic metal compound in the cleaning agent or the treatment agent. It was difficult. Therefore, the present inventors have paid attention to the adsorption residual property of the inorganic metal compound and, as a result, have found that by using a specific component in combination with the inorganic metal compound, it is possible to improve the adsorption residual property of the inorganic metal compound to the textile product after washing. The invention has been completed.

[1] The bactericidal / antibacterial composition of the present invention is characterized by containing a complex formed from the following (A1) component and (B1) component or (A1) component and (B1) component.

(A1) Component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt.

(B1) component: The long-chain alkylamine compound selected from the group which consists of the following general formula (I) and (II), and / or an anion formed from this long-chain alkylamine compound.

[In formula (I), R <^1> represents a C8-C22 alkyl group. A ¹ represents a hydrogen atom or any of (CH ₂ ) _m -COOX ² . X ¹ and X ² may be the same or different and represent one kind selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]

[In formula (II), R <^2> represents either the C8-C22 alkyl group and the C8-C22 acyl group. Q is (NH- (CH ₂ ) _m ) and r represents 1 or 0. When r is 0, A <^2> , A <^3> may be same or different and is chosen from either a hydrogen atom or a methyl group. When r is 1, one of A ² and A ³ is a hydrogen atom, and the other is a hydrogen atom or any one of CH ₂ COOX ³ . X <^3> represents 1 type chosen from the group which consists of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]

[2] In the bactericidal / antibacterial composition of the present invention, R ¹ is preferably an alkyl group having 12 to 18 carbon atoms.

[3] In the bactericidal / antibacterial composition of the present invention, it is preferable that R ² is either an alkyl group having 12 to 18 carbon atoms or an acyl group having 12 to 18 carbon atoms.

[4] A liquid detergent composition comprising the following (A2) component, (B2) component and (C) component.

(A2) Component: Water-soluble zinc salt, water-soluble copper salt, or water-soluble silver salt.

(B2) Component: Polyethylenimine or an anion formed from the long-chain alkylamine compound and / or the said long-chain alkylamine compound (However, the said long-chain alkylamine compound is 1 from the group which consists of following General formula (I) and (II). More than one species).

(C) component: surfactant.

[In formula (I), R <^1> represents a C8-C22 alkyl group. A ¹ represents a hydrogen atom or any of (CH ₂ ) _m -COOX ² . X ¹ and X ² may be the same or different and represent one kind selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]

[In formula (II), R <^2> represents either the C8-C22 alkyl group and the C8-C22 acyl group. Q is (NH- (CH ₂ ) _m ) and r represents 1 or 0. When r is 0, A <^2> , A <^3> may be same or different and is chosen from either a hydrogen atom or a methyl group. When r is 1, one of A ² and A ³ is a hydrogen atom, and the other is a hydrogen atom or any one of CH ₂ COOX ³ . X <^3> represents 1 type chosen from the group which consists of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]

[5] A treating agent composition for a textile product, comprising a mixture of the following (A3) component and (B3) component or a complex formed from the (A3) component and the (B3) component and the following (D) component.

(A3) Component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt.

(B3) Component: Polyethylenimine or an anion formed from a long chain alkylamine compound and / or the said long chain alkylamine compound (However, the said long chain alkylamine compound is 1 from the group which consists of following General formula (I) and (II). More than one species).

(D) component: A cationic surfactant or a cationic high molecular compound.

[In formula (I), R <^1> represents a C8-C22 alkyl group. A ¹ represents a hydrogen atom or any of (CH ₂ ) _m -COOX ² . X ¹ and X ² may be the same or different and represent one kind selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]

[In formula (II), R <^2> represents either the C8-C22 alkyl group and the C8-C22 acyl group. Q is (NH- (CH ₂ ) _m ) and r represents 1 or 0. When r is 0, A <^2> , A <^3> may be same or different and is chosen from either a hydrogen atom or a methyl group. When r is 1, one of A ² and A ³ is a hydrogen atom, and the other is a hydrogen atom or any one of CH ₂ COOX ³ . X <^3> represents 1 type chosen from the group which consists of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]

According to the bactericidal composition or the antimicrobial composition of the present invention, a bactericidal / antibacterial composition capable of exerting an excellent bactericidal / antibacterial effect against both gram positive bacteria and gram negative bacteria with a small amount of metal without the use of a peroxide is maintained. In addition, an object of the present invention is to provide a liquid detergent composition capable of expressing an excellent bactericidal effect or an antibacterial effect, and a treatment composition for a textile product that can exhibit an excellent bactericidal or antibacterial effect and a deodorizing effect.

Hereinafter, the present invention will be described in detail.

The bactericidal and antimicrobial composition of the present invention is characterized by containing a mixture of the following (A1) component and (B1) component or a complex formed from (A1) component and (B1) component.

(A1) Component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt.

(B1) component: An anion formed from the long chain alkylamine compound selected from the group consisting of the general formulas (I) and (II) and / or the long chain alkylamine compound.

The liquid detergent composition of this invention contains the following (A2) component, (B2) component, and (C) component, It is characterized by the above-mentioned.

(A2) Component: Water-soluble zinc salt, water-soluble copper salt, or water-soluble silver salt.

(B2) Component: Polyethylenimine or an anion formed from the long-chain alkylamine compound and / or the said long-chain alkylamine compound (However, the said long-chain alkylamine compound is 1 from the group which consists of said general formula (I) and (II). More than one species).

(C) component: surfactant.

As for the processing agent composition for textile products of this invention, the processing agent composition for textile products (henceforth only a "processing agent composition") of this invention is a mixture of following (A3) component and (B3) component, or (A3 A complex formed from the component and the component (B3), and the following component (D).

(A3) Component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt.

(B3) Component: Polyethylenimine or an anion formed from the long-chain alkylamine compound and / or the said long-chain alkylamine compound (However, the said long-chain alkylamine compound is 1 from the group which consists of said general formula (I) and (II). More than one species).

(D) component: A cationic surfactant or a cationic high molecular compound.

[(A1) component]

[Eradication and Antibacterial Composition]

(A1) component in the antibacterial and antimicrobial composition of this invention is used in order to provide an antibacterial effect and an antibacterial effect. In addition, the germicidal effect shows the effect of reducing the number of bacteria present in the cleaning liquid or on the surface of the object, and the antibacterial effect shows the effect of inhibiting the growth of bacteria adhered to the surface of the object.

(A1-1: Water Soluble Silver Salt)

The water-soluble silver salt is not particularly limited as long as it dissolves in water and releases silver ions at that time. Examples of the water-soluble silver salt include silver sulfate, silver nitrate, silver acetate, silver fluoride, silver perchlorate, and the like, but silver sulfate is preferable in view of handleability and smell.

The water-soluble silver salt is not particularly limited, but is preferably formulated so that silver ions are at least 0.000001 mass% (0.01 ppm) in the bactericidal / antibacterial composition, more preferably at least 0.000002 mass%, particularly preferably at least 0.000003 mass%. .

If silver ion is mix | blended 0.000001 mass% or more in an antibacterial and antimicrobial composition, sufficient antibacterial effect and antibacterial effect can be acquired.

(A1-2: Water Soluble Copper Salt)

The water-soluble copper salt is not particularly limited as long as it dissolves in water and releases copper ions at that time. Examples of water-soluble copper salts include copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, ammonium chloride, copper gluconate, copper stannate, copper perchlorate, and the like. Copper sulfate, copper chloride, copper gluconate are preferable at these points, and copper sulfate is suitable among these.

The water-soluble copper salt is not particularly limited, but is preferably blended so that copper ions are 0.000025% by mass (0.25 ppm) or more in the bactericidal / antibacterial composition, more preferably 0.000076% by mass or more, particularly preferably 0.00015% by mass or more. Do.

When 0.000025 mass% or more of copper ions are mix | blended in an antibacterial and antimicrobial composition, sufficient antibacterial effect and antimicrobial effect can be acquired.

(A1-3: water soluble zinc salt)

The water-soluble zinc salt is not particularly limited as long as it dissolves in water and releases zinc ions at that time. Examples of the water-soluble zinc salt include zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, ammonium zinc chloride, zinc gluconate, zinc stannate, and zinc perchlorate. In view of these, zinc sulfate, zinc chloride and gluconate are preferable, and zinc sulfate is particularly suitable.

The water-soluble zinc salt is not particularly limited, but is preferably formulated so that the zinc ions are at least 0.000046 mass% (0.46 ppm) in the bactericidal / antibacterial composition, more preferably at least 0.00014 mass%, particularly preferably at least 0.00023 mass%. Do.

When 0.000046 mass% or more of zinc ions are mix | blended in an antibacterial and antimicrobial composition, sufficient antibacterial effect and antibacterial effect can be acquired.

LIQUID CLEANER COMPOSITION

(A2) A component is used in order to provide a disinfecting effect or an antibacterial effect to a liquid detergent composition.

(A2-1: water soluble silver salt)

The water-soluble silver salt is not particularly limited as long as it dissolves in water and releases ions at that time. Examples of the water-soluble silver salt include silver sulfate, silver nitrate, silver acetate, silver fluoride, silver perchlorate, and the like, but silver sulfate is preferable in view of handleability and smell.

Although the compounding quantity of the water-soluble silver salt in a liquid detergent composition is not specifically limited, It is preferable to mix | blend so that it may become 0.01 mass% or more, It is more preferable if it is 0.05 mass% or more, It is especially preferable if it is 0.09 mass% or more. When 0.01 mass% or more of water-soluble silver salts are mix | blended in a cleaning composition, sufficient antibacterial effect or antibacterial effect can be acquired. On the other hand, although it does not specifically limit about the upper limit of the compounding quantity of water-soluble silver salt, 5 mass% or less is preferable and 3 mass% or less is more preferable.

When the compounding quantity of water-soluble silver salt is 5 mass% or less, the favorable composition of stability can be obtained. Moreover, even if the compounding quantity of water-soluble silver salt exceeds 5 mass%, the effect of improving the bactericidal or antibacterial property suitable for it is hard to be acquired, and also it becomes economically disadvantageous.

(A2-2: Water Soluble Copper Salt)

The water-soluble copper salt is not particularly limited as long as it dissolves in water and releases copper ions at that time. Examples of the water-soluble copper salts include copper nitrate, copper sulfate, copper sulfide, copper chloride, copper acetate, copper cyanide, ammonium chloride, copper stannate, copper perchlorate, and the like. Copper sulfate is preferred.

Although the compounding quantity of the water-soluble copper salt in a liquid detergent composition does not specifically limit, It is preferable to mix | blend so that it may become 0.1 mass% or more, It is more preferable if it is 0.3 mass% or more, It is especially preferable if it is 0.5 mass% or more. When 0.1 mass% or more of water-soluble copper salts are mix | blended in the cleaning composition, sufficient antibacterial effect or antibacterial effect can be acquired. On the other hand, although it does not specifically limit about the upper limit of the compounding quantity of water-soluble copper salt, 5 mass% or less is preferable and 3 mass% or less is more preferable.

If the compounding quantity of water-soluble copper salt is 5 mass% or less, the favorable composition of stability can be obtained. Moreover, even if the compounding quantity of water-soluble copper salt exceeds 5 mass%, the effect of improving the bactericidal or antimicrobial property suitable for it is hard to be obtained, and also it becomes economically disadvantageous.

(A2-3: water soluble zinc salt)

The water-soluble zinc salt is not particularly limited as long as it dissolves in water and releases zinc ions at that time. Examples of water-soluble zinc salts include zinc nitrate, zinc sulfate, zinc sulfide, zinc chloride, zinc acetate, zinc cyanide, ammonium zinc chloride, zinc stannate, zinc perchlorate, and the like. Zinc sulfate is preferred.

Although the compounding quantity of the water-soluble zinc salt in a liquid detergent composition does not specifically limit, It is preferable to mix | blend so that it may become 0.2 mass% or more, It is more preferable if it is 0.7 mass% or more, It is especially preferable if it is 1.0 mass% or more. When 0.2 mass% or more of water-soluble zinc salts are mix | blended in the cleaning composition, sufficient antibacterial effect or antibacterial effect can be acquired. On the other hand, the upper limit of the blending amount of the water-soluble zinc salt is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less.

When the compounding quantity of water-soluble zinc salt is 5 mass% or less, the favorable composition of stability can be obtained. Moreover, even if the compounding quantity of water-soluble zinc salt exceeds 5 mass%, the effect of improving the bactericidal or antimicrobial property suitable for it is hard to be acquired, and also it becomes economically disadvantageous.

[Treatment Composition for Textile Products]

(A3) A component is used in order to provide a disinfecting effect or an antibacterial effect, and deodorizing effect to a processing agent composition. In addition, the germicidal effect shows the effect of reducing the number of bacteria present in the cleaning liquid or on the surface of the object, and the antibacterial effect shows the effect of inhibiting the growth of bacteria adhered to the surface of the object.

(A3-1: water soluble silver salt)

The water-soluble silver salt is not particularly limited as long as it dissolves in water and releases ions at that time, but a silver salt that dissolves 0.5 g or more with respect to 100 ml of water at 20 ° C is preferable. As an example of such a water-soluble silver salt, silver sulfate, silver nitrate, silver acetate, silver fluoride, silver perchlorate, etc. are mentioned, but silver sulfate is preferable at the point of handleability and odor.

Although the compounding quantity of the water-soluble silver salt in a processing agent composition does not specifically limit, 0.03-10 mass% is preferable, 0.1-5 mass% is more preferable, 0.16-3 mass% is especially preferable. If the compounding quantity of water-soluble silver salt is 0.03 mass% or more, sufficient antibacterial effect or antibacterial effect and deodorization effect can be acquired. When the compounding quantity of water-soluble silver salt is less than 0.03 mass%, there exists a tendency for the antimicrobial effect to E. coli to fall especially. On the other hand, when the compounding quantity of water-soluble silver salt is 10 mass% or less, the favorable composition of stability can be obtained. Even if the compounding quantity of water-soluble silver salt exceeds 10 mass%, the effect of improving the bactericidal and antimicrobial properties suitable for it is hard to be obtained, and it also becomes disadvantageous economically.

(A3-2: Water Soluble Copper Salt)

The water-soluble copper salt is not particularly limited as long as it dissolves in water and releases copper ions at that time, but a copper salt that dissolves 0.5 g or more with respect to 100 ml of water at 20 ° C is preferable. Examples of such water-soluble copper salts include copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, ammonium chloride, copper gluconate, copper stannate, copper perchlorate, and the like. In view of supplyability, copper sulfate, copper chloride and copper gluconate are preferred, and copper sulfate is particularly preferred.

Although the compounding quantity of the water-soluble copper salt in a processing agent composition does not specifically limit, 0.07-10 mass% is preferable, 0.2-5 mass% is more preferable, 0.4-3 mass% is especially preferable. If the compounding quantity of water-soluble copper salt is 0.07 mass% or more, sufficient antibacterial effect or antibacterial effect and deodorization effect can be acquired. When the compounding quantity of water-soluble copper salt is less than 0.07 mass%, it exists in the tendency for the antimicrobial effect to E. coli to fall especially. On the other hand, when the compounding quantity of water-soluble copper salt is 10 mass% or less, the favorable composition of stability can be obtained. Even if the compounding quantity of water-soluble copper salt exceeds 10 mass%, the effect of improving the bactericidal and antimicrobial properties suitable for it is hard to be obtained, and it also becomes disadvantageous economically.

(A3-3: water soluble zinc salt)

The water-soluble zinc salt is not particularly limited as long as it dissolves in water and releases zinc ions at that time, but a zinc salt that dissolves 0.5 g or more in 100 ml of water at 20 ° C is preferable. Examples of such water-soluble zinc salts include zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, ammonium zinc chloride, zinc gluconate, zinc stannate, and zinc perchlorate. Zinc sulfate, zinc chloride, zinc gluconate are preferable at the point of supplyability, and zinc sulfate is suitable among these.

Although the compounding quantity of the water-soluble zinc salt in a processing agent composition does not specifically limit, 0.13-10 mass% is preferable, 0.4-5 mass% is more preferable, 0.6-3 mass% is especially preferable. If the compounding quantity of water-soluble zinc salt is 0.13 mass% or more, sufficient antibacterial effect or antibacterial effect and deodorization effect can be acquired. When the compounding quantity of water-soluble zinc salt is less than 0.13 mass%, it exists in the tendency for the antimicrobial effect to E. coli to fall especially. On the other hand, when the compounding quantity of water-soluble zinc salt is 10 mass% or less, the favorable composition of stability can be obtained. Even if the compounding quantity of water-soluble zinc salt exceeds 10 mass%, the effect of improving the bactericidal and antimicrobial properties suitable for it is hard to be obtained, and it also becomes disadvantageous economically.

[(B1) component]

[Eradication and Antibacterial Composition]

The component (B1) is a long chain alkylamine compound selected from the group consisting of the general formulas (I) and (II), and / or an anion generated from the long chain alkylamine compound. In the bactericidal / antibacterial composition of the present invention, by using the component (B1) in combination with the component (A1), the bactericidal effect and antibacterial effect to both gram positive bacteria and gram negative bacteria are exhibited.

LIQUID CLEANER COMPOSITION

The component (B2) is an anion generated from polyethyleneimine or a long chain alkylamine compound and / or the long chain alkylamine compound, provided that the long chain alkylamine compound is selected from the group consisting of general formulas (I) and (II). One or more will be selected.). (B2) A component is used in order to improve the adsorption | suction residual property of (A2) component to the textile product (Hereinafter, it may be called "clothing.") After washing.

(B2-1: Polyethyleneimine)

As polyethyleneimine, what is marketed can be used, For example, "Epomin (P-1000), molecular weight 70000" by the Japan Catalyst Corporation, etc. are mentioned.

As for the compounding quantity of polyethyleneimine, 0.01-10 mass% is preferable with respect to the gross mass of a liquid detergent composition, More preferably, it is 0.05-5 mass%, Especially preferably, it is 0.09-3 mass%. If the compounding quantity of polyethyleneimine is 0.01 mass% or more, antibacterial and antimicrobial property can be provided to the medical care after washing. On the other hand, even if it mix | blends more than 10 mass% of polyethyleneimine, the improvement effect of the antibacterial and antimicrobial property suitable for it is hard to be acquired, and it also becomes economically disadvantageous.

(B2-2: An anion resulting from the long chain alkylamine compound and / or the long chain alkylamine compound)

The long-chain alkylamine compound is a compound selected from the group consisting of the general formulas (I) and (II).

[Treatment Composition for Textile Products]

The component (B3) is an anion formed from (B3-1) polyethyleneimine or (B3-2) long-chain alkylamine compound and / or the long-chain alkylamine compound.

(B3) A component is used in order to improve the adsorption residual of the (A3) component to the garment after washing. By using together with the above-mentioned (A3) component, the antibacterial effect or antibacterial effect to both Staphylococcus aureus and Escherichia coli can be acquired.

(B3-1: Polyethyleneimine)

As polyethyleneimine, a commercially available thing can be used, For example, "Epomin (P-1000), molecular weight 70000" by the Japan Catalyst Co., Ltd., etc. are mentioned.

As for the compounding quantity of polyethyleneimine, 0.1-20 mass% is preferable with respect to the gross mass of a processing agent composition, More preferably, it is 0.2-17 mass%, Especially preferably, it is 0.4-14 mass%. If the compounding quantity of polyethyleneimine is 0.1 mass% or more, antibacterial or antimicrobial property and deodorization property can be provided to the medical care after washing.

When the compounding quantity of polyethyleneimine is less than 0.1 mass%, it exists in the tendency for the antimicrobial effect to Staphylococcus aureus to fall especially. On the other hand, even if it mix | blends more than 20 mass% of polyethyleneimine, the improvement effect of the antibacterial and antimicrobial property suitable for it is hard to be acquired, and it also becomes disadvantageous economically.

(B3-2: An anion resulting from the long chain alkylamine compound and / or the long chain alkylamine compound)

The long-chain alkylamine compound is a compound selected from the group consisting of the general formulas (I) and (II).

In said general formula (I), R <^1> is a C8-C22 alkyl group and is more preferable if it is C12-C18. When carbon number in an alkyl group is 8 or more, an alkyl group will adsorb | suck to a bacterium, and there exists a tendency for metal ion to contact a microbe. On the other hand, when the number of carbon atoms in the alkyl group is 22 or less, there is no problem of solubility in water, and bactericidal activity and antibacterial activity are also maintained. In particular, when R ¹ is an alkyl group having 12 to 18 carbon atoms, the balance between hydrophobicity (that is, adsorption to bacteria) and hydrophilicity (that is, solubility in water) becomes good, so that the bactericidal activity and the antibacterial activity are more effectively achieved. Can be expressed.

A ¹ is either a hydrogen atom or (CH ₂ ) _m -COOX ² .

X ¹ and X ² may be the same or different and are one kind selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom and a cationic ammonium group. Examples of the alkali metal atom include sodium and potassium, and examples of the alkaline earth metal atom include magnesium and calcium. Examples of the cationic ammonium group include trimethylammonium and tetramethylammonium.

n is any one of 1-3, and when n is this range, the complex formed from (A1) and (B1) component, (A2) and (B2) component or (A3) and (B3) component exists stably. I think.

In addition, m is any one of 1-3, and when m is this range, it is thought that a complex exists more stably.

General formula (I) can be represented by general formula (I-1) and general formula (I-2) as follows. In addition, in each formula, a symbol shows the same thing as said general formula (I).

As a specific example represented by general formula (I-1), Alkyl imino diacetic acid salt, Octyl imino di, etc., such as sodium octylimino diacetic acid, sodium lauryl imino diacetic acid, sodium myristylimino diacetic acid, sodium palmitolimino diacetate, Alkyl imino dipropionate, such as sodium propionate, sodium lauryl imino dipropionate, sodium myristyl imino dipropionate, and sodium palmitylimino dipropionate, etc. are mentioned.

As a specific example represented by general formula (I-2), sodium lauryl amino acetate, sodium myristyl amino acetate, sodium palmityl amino acetate, sodium lauryl amino propionate, sodium myristyl amino propionate, sodium palmityl aminopropionate, etc. Can be mentioned.

In these, the alkylimino diacetic acid salt is preferable in view of stability of a complex.

In said general formula (II), R <^2> is either the C8-C22 alkyl group and the C8-C22 acyl group. Moreover, also in an alkyl group, also in an acyl group, it is more preferable that carbon number is 12-18. When the carbon number of the alkyl group or acyl group is 8 or more, the alkyl group tends to adsorb to the bacteria and the metal ions tend to easily contact the bacteria. On the other hand, when the carbon number in the alkyl group or acyl group is 22 or less, there is no problem of solubility in water, and the bactericidal activity and the antibacterial activity are also maintained. In particular, when R ² is either an alkyl group having 12 to 18 carbon atoms or an acyl group having 12 to 18 carbon atoms, the balance between hydrophobicity (that is, adsorption to bacteria) and hydrophilicity (that is, solubility in water) becomes good. Therefore, the antibacterial ability and the antibacterial ability can be expressed more effectively.

Q is (NH- (CH ₂ ) _m ), where r is 1 or 0 (single bond). If r is 1 or less, it is considered that metal ions tend to be in contact with the bacteria.

In addition, when r is 0 (single bond), A <^2> , A <^3> may be same or different and is selected from either a hydrogen atom or a methyl group.

On the other hand, when r is 1, one of A ² and A ³ is a hydrogen atom, and the other is a hydrogen atom or any one of CH ₂ COOX ³ . At this time, X <^3> is 1 type chosen from the group which consists of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. Moreover, the thing similar to the said General formula (I) is mentioned as a specific example of alkali metal atom, alkaline earth metal atom, and cationic ammonium.

n is any one of 1-3, and when n is this range, it is thought that a complex exists stably.

m is any one of 1-3, and when m is this range, a complex is considered to exist more stably.

General formula (II) can be represented by general formula (II-1) and general formula (II-2) as described below. In addition, in each formula, a symbol shows the same thing as said general formula (II).

As a specific example represented by general formula (II-1), Cocoalkyl propylene diamine, tallow alkyl propylene diamine, lauryl ethylene diamine, myristyl ethylene diamine, palmityl ethylene diamine, lauric acid dimethylaminopropylamide, previously Styric acid dimethylaminopropylamide, parmitic acid dimethylaminopropylamide, etc. are mentioned.

As a specific example represented by general formula (II-2), lauryl diethylene triamine, myristyl diethylene triamine, palmityl diethylene triamine, lauryl dipropylene triamine, myristyl dipropylene triamine, palmityl dipropylene Triamine, alkyl diamino ethyl glycine, etc. are mentioned.

Among these, in view of the stability of the complex, alkyldiaminoethylglycine is preferable.

In addition, in the long-chain alkylamine compound represented by general formula (I) and the long-chain alkylamine compound represented by general formula (II), the longer-chain alkylamine compound represented by general formula (II) has more bactericidal effect, and / Or antibacterial effect tends to be large. This is considered to be based on the following reasons.

In the long-chain alkylamine compound represented by the general formula (I), the charge of the metal ion is reduced or disappeared by the carboxyl group of the terminal group. On the other hand, in the long-chain alkylamine compound represented by the general formula (II), since the amino group interacts with the metal ions, the charge of the metal ions is maintained as it is, and thus, the bacteria which are negatively charged, in particular, E. coli It is thought to show high action.

Thereby, the metal ion derived from the corresponding (A1-3) component which forms a complex with (B1-3) components, respectively, can come into contact with a bacterium without distinguishing between E. coli and Staphylococcus aureus, and a small amount of metal ion Even if it can show more excellent bactericidal effect or antimicrobial effect with respect to both bacteria.

The component (B1) in the bactericidal / antibacterial composition of the present invention is not particularly limited, but is preferably blended so as to be 0.000001 mass% (0.01 ppm) or more in the bactericidal / antibacterial composition, and if it is 0.000002 mass% or more, It is preferable and it is especially preferable if it is 0.000003 mass% or more.

If (B1) component is 0.000001 mass% or more in an antibacterial and antimicrobial composition, it will become easy to form a complex with (A1) component, and antibacterial and antimicrobial property will be maintained.

In addition, the compounding quantity of (B1) component in an antibacterial and antimicrobial composition is molar ratio [B1] / [M1 of mole number [B1] of (B1) component and mole number [M1] of metal ion in (A1) component. ] Is preferable. At this time, [B1] / [M1] is preferably 1.0 to 50, more preferably 1.5 to 45, particularly preferably 2.0 to 40, based on the number of moles [M1] of the metal ions in the component (A1) to be blended. desirable.

It is preferable that molar number [B1] of (B1) component is excessive from a viewpoint of the stability of a metal, and if it is in the said range, disinfection performance and antibacterial performance will be maintained.

In addition, in the liquid detergent composition, the compounding quantity of the anion (henceforth these may be called "(B2-2) component") formed from the long-chain alkylamine compound and / or the said long-chain alkylamine compound is a thing of a liquid detergent composition. 0.01-10 mass% is preferable with respect to gross mass, More preferably, it is 0.05-7 mass%, Especially preferably, it is 0.09-5 mass%.

If the compounding quantity of (B2-2) component is 0.01 mass% or more, antibacterial and antimicrobial property can be provided to the medical care after washing. On the other hand, even if it mix | blends more than 10 mass% of (B2-2) components, the improvement effect of the antibacterial and antimicrobial property suitable for it is hard to be acquired, and it also becomes disadvantageous economically.

Moreover, in a liquid detergent composition, it is preferable that the mass ratio of (A2) component and (B2) component is (B2) component / (A2) component = 1.75 / 1-10/1, and it is 2/1-10/1 It is more preferable that is. When mass ratio is less than 1.75 / 1, the ratio of (A2) component which exists independently increases, without forming a complex with (B2) component in a liquid detergent composition. As a result, since it adversely affects the hydration state of the hydrophilic group of (C) component mentioned later (that is, since the hydration water of a hydrophilic group vicinity dehydrates, it becomes difficult to ensure stability as a formulation) of the liquid detergent composition There exists a tendency for storage stability to fall. On the other hand, even if the mass ratio exceeds 10/1, the effect of improving bactericidal and antimicrobial properties commensurate with it is difficult to be obtained, which is disadvantageous economically.

In the processing agent composition for textile products, the compounding quantity of the anion (henceforth these may be called "(B3-2) component") formed from the long-chain alkylamine compound and / or this long-chain alkylamine compound is the total of a processing agent composition. 0.1-20 mass% is preferable with respect to mass, More preferably, it is 0.2-17 mass%, Especially preferably, it is 0.4-14 mass%. If the compounding quantity of (B3-2) component is 0.1 mass% or more, bactericidal or antibacterial property and deodorization property can be provided to the medicine after washing. When the compounding quantity of (B3-2) component is less than 0.1 mass%, it exists in the tendency for the antimicrobial effect to Staphylococcus aureus to fall especially. On the other hand, even if it mix | blends more than 20 mass% (B3-2) component, the improvement effect of antibacterial and antimicrobial property suitable for it is hard to be acquired, and it also becomes disadvantageous economically.

In the treatment agent composition, the amount of the component (B3) is a molar ratio [B3] / [M3] between the number of moles [B3] of the component (B3) and the number of moles of metal ions [M3] in the component (A3). It is preferable if it is displayed. At this time, based on the number-of-moles [M3] of the metal ions in the compound (A3) to be blended, [B3] / [M3] is preferably 0.1 to 50, more preferably 0.15 to 45, particularly preferably 0.2 to 40. Do. If the compounding quantity of (B3) component based on the number-of-moles [M3] of the metal ion in (A3) component is in the said range, while disinfection performance or antimicrobial performance will improve remarkably, (A3) component and detail are mentioned later. The complex which is stable with (D) component can be formed in a processing agent composition. In addition, a good composition of stability can be obtained.

In the bactericidal / antibacterial composition of the present invention, the above-mentioned (A1) component and (B1) component may be mixed to prepare a bacteriostatic / antibacterial composition, and the complex formed from the component (A1) and the component (B1) may be mixed to sterilize. Antimicrobial composition may be prepared.

In addition, although the detail is mentioned later, when using the antibacterial and antimicrobial composition of this invention, a liquid detergent composition, and a processing agent composition as a liquid composition, (A1) and (B1) component, (A2) and (B2) component, or (A3) It is thought that () and (B3) component form a complex.

In the processing agent composition for textile products, the above-mentioned (A3) component and (B3) component may mix each individually, and may prepare a processing agent composition, and in the shape of a complex formed from (A3) component and (B3) component You may mix | blend and prepare a processing agent composition.

As above-mentioned, the antibacterial effect or the antibacterial effect to both Staphylococcus aureus and Escherichia coli can be acquired by using together (B1-3) components corresponding to each of (A1-3) components. The combination of the component (A3) and the component (B3) is not particularly limited, but considering the storage stability such as discoloration of the treatment composition, zinc sulfate or zinc chloride as the component (A3) and alkyldiaminoethyl as the component (B3) Combinations with glycine are suitable.

Thus, the complex formed from (B1-3) component corresponding to each of (A1-3) component is mix | blended, or (A1-3) component in the processing agent composition for textile products in a liquid detergent composition in an antibacterial and antimicrobial composition. If the (B1-3) component corresponding to each of the above forms a complex, the (B1-3) component improves the adsorption of the metal ions derived from the corresponding (A1-3) component to the clothes or the bacteria. You can. Thus, a small amount of metal can provide better bactericidal and / or antimicrobial effects without the use of peroxides.

[(C) component]

LIQUID CLEANER COMPOSITION

(C) component is surfactant and is used in order to provide a cleaning power to a liquid detergent composition.

As surfactant, it is preferable to use nonionic surfactant (C-I) and / or anionic surfactant (C-II).

(C-I: nonionic surfactant)

Although it does not specifically limit as a nonionic surfactant, For example, the polyoxyalkylene type nonionic surfactant represented by following General formula (III) is used suitably.

In formula (III), R <^3> is a C8-C22, preferably 10-18 hydrophobic group, and may be linear or branched chain. Examples of the hydrophobic group include primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.

-X ² -is a functional group such as -O-, -COO-, or -CONH-.

EO is ethylene oxide and PO is propylene oxide.

s and t represent the average added mole number, s is an integer of 3-20, Preferably it is 5-18, t is an integer of 0-6, Preferably it is 0-3.

R ⁴ is a hydrogen atom or an alkyl or alkenyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl or alkenyl group having 1 to 3 carbon atoms.

When the average molar number s of EO exceeds 20, since the HLB value becomes too high and it becomes disadvantageous for sebum washing, there exists a tendency for the washing function to fall. On the other hand, when the average molar number s of EO is less than 3, there exists a tendency for the effect of the prevention of deterioration of an odor to fall.

When the molar number t of the average part of PO exceeds 6, there exists a tendency for the storage stability under high temperature of a liquid detergent composition to fall.

The added mole number distribution of EO or PO is not specifically limited, It is easy to fluctuate by the reaction method at the time of manufacturing a nonionic surfactant. For example, the added mole number distribution of EO or PO tends to be relatively wide when the ethylene oxide or propylene oxide is added to the hydrophobic raw material using an alkali catalyst such as sodium hydroxide or potassium hydroxide. In addition, Al ^{+ 3} as described in Unexamined Japanese Patent Publication Hei 6-15038 Ho, Ga ^3+, In ^{+ 3,} Tl ^{+ 3,} Co ^{+ 3,} Sc ^{+ 3,} La ^{+ 3,} the addition of metal ions such as Mn ^{+ 2} When ethylene oxide and propylene oxide are added to a hydrophobic group raw material using specific alkoxylation catalysts, such as magnesium oxide, it exists in the tendency to become a comparatively narrow distribution.

In formula (III), when -X ² -is -O-, the nonionic surfactant is alcohol ethoxylate. In this case, carbon number of the linear or branched alkyl group or alkenyl group of R <^3> is 10-22, Preferably it is 10-20, More preferably, it is 10-18. R ³ may have an unsaturated bond. In this case, R ⁴ is preferably a hydrogen atom.

In the formula (III), when -X ² -is -COO-, the nonionic surfactant is a fatty acid ester type nonionic surfactant. In this case, carbon number of the alkyl group or alkenyl group of the linear or branched state of R <^3> is 9-21, Preferably it is 11-21. R ³ may have an unsaturated bond. In this case, R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms.

As a specific example of the nonionic surfactant represented by Formula (III), Mitsubishi Chemical Corporation: brand name Diadol (C13, C represents carbon number is the same below), Shell company brand name Neodol (C12 / C13), brand name Sasol: brand name Safol23 ( 12 mol equivalent or 15 mol equivalent of ethylene oxide is added with respect to alcohol, such as C12 / C13), P & G company make: 12 mol equivalent, or 15 mol equivalent to natural alcohol, such as brand name CO-1214 and CO-1270 Ethylene oxide was added, C12 alkene obtained by trimerizing butene was added to the C13 alcohol obtained by the oxo method, and 7 mol equivalent of ethylene oxide was added (BASF: trade name Lutensol TO7), pentanol 7 mol equivalent of ethylene oxide was added to the C10 alcohol obtained by the reaction (BASF Corporation: trade name Lutensol XL70), and 6 mol equivalent of ethylene oxide was added to the C10 alcohol obtained by providing pentanol to the Gabet reaction. (Product made in BASF Corporation: a product Lutensol XA60), having a carbon number of 12 to 14 of a secondary alcohol to a molar equivalent to adding the 9, or 15 moles of ethylene oxide equivalent (Japan catalyst Co.: trade name, and the like soap or soap tanol tanol 90 150). Furthermore, 15 mol of ethylene oxide is added to the palm fatty acid methyl (lauric acid / myristic acid = 8/2) using the alkoxylation catalyst.

A nonionic surfactant may be used individually by a single type of nonionic surfactant, and may be used in combination of multiple types of nonionic surfactant.

As for the compounding quantity of a nonionic surfactant, 10-60 mass% is preferable with respect to the gross mass of a liquid detergent composition, More preferably, it is 10-50 mass%. When the compounding quantity of a nonionic surfactant is 10 mass% or more, high cleaning power can be provided to a liquid detergent composition. When the compounding quantity of a nonionic surfactant is 60 mass% or less, high storage stability can be provided to a liquid detergent composition.

(C-II: anionic surfactant)

As an anionic surfactant, a well-known anionic surfactant can be used and can be obtained easily in a market.

As anionic surfactant, For example, linear alkylbenzene sulfonic acid or its salt; α-olefin sulfonate; Linear or branched alkyl sulfate ester salts; Alkyl ether sulfate ester salt or Alkenyl ether sulfate ester salt; Alkanesulfonate which has an alkyl group; (alpha)-sulfo fatty acid ester salt, etc. are mentioned.

As these salts, alkali metal salts, such as sodium and potassium, alkaline-earth metal salts, such as magnesium, alkanolamine salts, such as monoethanolamine and diethanolamine, etc. are mentioned.

Moreover, as these anionic surfactant, the following are specifically preferable. As linear alkylbenzenesulfonic acid or its salt, the C8-C16 thing of a linear alkyl group is preferable, and the C10-C14 thing is especially preferable.

As (alpha)-olefin sulfonate, a C10-20 thing is preferable.

As an alkyl sulfate ester salt, a C10-20 thing is preferable.

As alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt, it has a C10-C20 linear or branched alkyl group or alkenyl group, and adds 1-10 mol ethylene oxide on average (that is, polyoxyethylene alkyl ether Sulfuric acid ester salts or polyoxyethylene alkenyl ether sulfate ester salts).

As alkanesulfonate, it has a C10-C20, preferably 14-17 alkyl group, and a secondary alkanesulfonate is especially preferable.

As (alpha)-sulfo fatty acid ester salt, a C10-20 thing is preferable.

Among these, linear alkylbenzene sulfonic acid or its salt, alkanesulfonate, polyoxyethylene alkyl ether sulfate, and (alpha)-olefin sulfonate are especially preferable.

Anionic surfactant may be used individually by a single type of anionic surfactant, and may be used in combination of multiple types of anionic surfactant.

It is preferable that the compounding quantity of an anionic surfactant is 0-20 mass% with respect to the gross mass of a liquid detergent composition.

Moreover, when mix | blending anionic surfactant, the value of the mass ratio (C-II) / (B2) component of (B2) component and anionic surfactant is preferably 1.05 or more, and particularly preferably 1.10 or more. If the value of the mass ratio is 1.05 or more, the hydrophilicity is maintained without losing the anionic charge of the anionic surfactant, so that the storage stability of the liquid detergent composition is further improved. Moreover, 6000 or less are preferable and, as for the upper limit of the value of a mass ratio, 1000 or less are more preferable.

[(D) component]

[Treatment Composition for Textile Products]

(D) component is a cationic surfactant or a cationic high molecular compound.

(D) component is used in order to improve flexibility and antimicrobial property, and adsorption residual property of (A3) component to the textile product (Hereinafter, it may be called "clothing.") To a processing agent composition.

(Cationic surfactant)

As the cationic surfactant, a tertiary amine having one or more long-chain hydrocarbon groups having 10 to 24 carbon atoms in the molecule, or a neutralized or quaternized thereof is preferable. The long-chain hydrocarbon group having 10 to 24 carbon atoms may be divided into an amide group, an ester group and / or an ether group (hereinafter, these are referred to as "linking groups").

As such cationic surfactant, the amine compound represented by the following general formula (IV-1)-(IV-8), the neutralization of these amine compounds by organic acid or inorganic acid, and the quaternized substance of these amine compounds are mentioned. Can be. Hereinafter, the amine compound represented by the following general formula (IV-1) is described as compound (IV-1). Other amine compounds are similarly described.

These cationic surfactants can be used as 1 type or in mixture of 2 or more types. When using as a 2 or more types of mixture, when the mass ratio of the cationic surfactant which has two or three long-chain hydrocarbon groups in 100 mass% of mixtures is 50 mass% or more, the fiber processed using the treatment agent composition of this invention and finishing it It is preferable because it can give a good flexibility to a product.

In addition, from the viewpoint of imparting biodegradability after disposal in a natural environment after use, cationic surfactants containing an ester group in the middle of the long-chain hydrocarbon group (that is, the long-chain hydrocarbon group is divided into ester groups) are preferable, For example, compounds (IV-2) to (IV-6) and compound (IV-8) are suitable.

In addition, in the compound (IV-2), the compound (IV-3), the compound (IV-7), and the compound (IV-8), at least one of the long-chain hydrocarbon groups of the compound (IV-1) is divided into a linking group. Amine compound.

In formula (IV-1), R <^3> , R <^4> may be same or different, It is a C10-C24 long-chain hydrocarbon group and it is preferable that it is 12-20. In addition, R <^3> , R <^4> may be saturated, unsaturated, may be linear, and may be branched.

As R <^3> , R <^4> , a linear alkyl group or alkenyl group is preferable.

R <^5> -R <^7> may be same or different in formula (IV-2)-(IV-8), It is a residue remove | excluding the carboxyl group from a C10-20 fatty acid, Saturated fatty acid, Unsaturated fatty acid, Straight chain It is derived from either fatty acids or branched fatty acids. In the case of an unsaturated fatty acid, a cis body and a trans body exist, and the mass ratio is preferably cis body / trans body = 25/75 to 100/0, more preferably 40/60 to 80/20.

Examples of fatty acids having 10 to 20 carbon atoms include stearic acid, partic acid, myristic acid, lauric acid, oleic acid, ellidic acid, partially hydrogenated palm oil fatty acids (iodines 10 to 60), and partially hydrogenated fatty acid (iodine). And 10 to 60). Among these, a combination of stearic acid, parmitic acid, myristic acid, oleic acid, and ellidic acid in predetermined amounts, specifically, the mass ratio of saturated fatty acid / unsaturated fatty acid is 95/5 to 50/50, and that of cis / trans body. The mass ratio is 40/60 to 80/20, the iodine number is 10 to 50, the proportion of fatty acids having 18 carbon atoms is 80 mass% or more, the proportion of fatty acids having 20 carbon atoms is 2 mass% or less, and the proportion of fatty acids having 22 carbon atoms is 1 mass. It is preferable to use the fatty acid composition adjusted so that it may become% or less.

It is preferable to use the above-mentioned amine compound as neutralized neutralized with an acid (amine salt) or quaternized quaternized with the quaternization agent.

Examples of the acid used for neutralization include organic acids and inorganic acids, and among them, hydrochloric acid, sulfuric acid, and methyl sulfuric acid are preferable. In the neutralization step, neutralizing the tertiary amine compound in advance may be dispersed in water, or the tertiary amine compound may be introduced in a liquid or solid phase in an aqueous solution of acid. The tertiary amine compound and the acid may be added at the same time.

As a quaternization agent used for quaternization, methyl chloride, dimethyl sulfate, etc. are mentioned. A quaternization process can apply a well-known method.

Compound (IV-2) and compound (IV-3) can be synthesized by, for example, a condensation reaction between the fatty acid composition or the fatty acid methyl ester composition described above and methyldiethanolamine. In that case, the ratio of compound (IV-2) and compound (IV-3) is 99/1-mass ratio {compound (IV-3) / compound (IV-2)} from a viewpoint of making dispersion stability favorable. It is preferable to synthesize | combine to be 50/50.

In addition, in order to obtain the quaternized compound (IV-2) and the compound (IV-3), it is preferable to use methyl chloride from the point which is low molecular weight and the usage-amount can be reduced.

At that time, from the viewpoint of improving the dispersion stability, the abundance ratio of the quaternized compounds of the compound (IV-2) and the compound (IV-3) is the quaternary compound / compound (IV-) of the mass ratio {compound (IV-3). It is preferable to synthesize | combine so that it may become 99/1-50/50 by the quaternary substance of 2).

In addition, when quaternizing compound (IV-2) and compound (IV-3), generally unquaternized esteramine remains. These mass ratios are preferably 99/1 to 70/30 in terms of mass ratio (quaternary quaternized esteramine) from the viewpoint of hydrolysis stability of the ester group.

Compounds (IV-4) to (IV-6) can be synthesized, for example, by a condensation reaction between the fatty acid composition or the fatty acid methyl ester composition described above and triethanolamine. In that case, the ratio of compound (IV-4) to compound (IV-6) is mass ratio {[compound (IV-5) + compound (IV-6)] / compound (IV) from a viewpoint of making dispersion stability favorable. -4)} is preferably 99/1 to 50/50.

In order to obtain quaternized compounds (IV-4) to (IV-6), it is preferable to use dimethyl sulfuric acid as a quaternizing agent from the viewpoint of reactivity.

At that time, from the viewpoint of improving dispersion stability, the abundance ratio of the quaternized compounds of the compounds (IV-4) to (IV-6) is the mass ratio {[quadrant + compound (IV of compound (IV-5)) -6) quaternized compound] / compound (IV-4) quaternized product}, preferably from 99/1 to 50/50.

In addition, when quaternizing compounds (IV-4) to (IV-6), generally unquaternized esteramine remains. These mass ratios are preferably 99/1 to 70/30 in terms of mass ratio (quaternary quaternized esteramine) from the viewpoint of hydrolysis stability of the ester group.

Compound (IV-7) and compound (IV-8) can be synthesized by the condensation reaction of the fatty acid composition described above with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine. have. In that case, it is preferable to synthesize | combine so that the existence ratio of compound (IV-7) and compound (IV-8) may be 99/1-50/50 by mass ratio {compound (IV-8) / compound (IV-7)}. Do. In addition, N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine is a "J. N-methylethanolamine and the addition product of acrylonitrile. Org. Chem., VOL. 26 (1960) page 3409 ”.

In addition, in order to obtain the quaternized compound (IV-7) and compound (IV-8), it is preferable to use methyl chloride. At that time, the abundance ratio of the quaternized compounds of the compound (IV-7) and the compound (IV-8) is 99 in the mass ratio {the quaternized compound of the compound (IV-8) / quaternary compound of the compound (IV-7)}. It is preferable to synthesize | combine so that it is / 1-50/50.

In addition, when quaternizing compound (IV-7) or compound (IV-8), generally unquaternized esteramine remains. These mass ratios are preferably 99/1 to 70/30 in terms of mass ratio (quaternary quaternized esteramine) from the viewpoint of hydrolysis stability of the ester group.

As the cationic surfactant, among the amine compounds described above, quaternized compounds of compound (IV-4), quaternized compounds of compound (IV-5) and quaternized compounds of compound (IV-6) are particularly preferable. When synthesize | combining a compound (IV-4)-a compound (IV-6), from a viewpoint of providing flexibility, each content rate with respect to these total mass is 5-98 mass% of compound (IV-4), It is preferable to synthesize | combine compound (IV-5) so that 1-60 mass% and compound (IV-6) may be 0.1-40 mass%, More preferably, compound (IV-4) 10-55 mass% The compound (IV-5) is 30 to 60 mass%, and the compound (IV-6) is 5 to 35 mass%.

In addition, when synthesize | combining the quaternized compounds of the compounds (IV-4) to (IV-6), from the viewpoint of providing flexibility, the respective content ratio to the total mass of these compounds is the compound (IV-4). It is preferable to synthesize | combine so that a quaternized material may be 5-98 mass%, the quaternized compound (IV-5) is 1-60 mass%, and the quaternized compound (IV-6) is 0.1-40 mass%, More preferably, the quaternized compound of compound (IV-4) is 10-55 mass%, the quaternized compound of compound (IV-5) is 30-60 mass%, the quaternized compound of compound (IV-6) Is 5-35 mass%.

As the cationic surfactant, a commercially available one may be used. For example, "Lion Softer EQ", "Akado 2HT-75", "Akado 210-85E", and "Akado T-800" by Lion Arc Research Co .; "ARMOSOFT TEQ-E" by AKZO NOBEL company, etc. are mentioned.

1-40 mass% is preferable, as for the compounding quantity of the cationic surfactant in a treating agent composition, 3-25 mass% is preferable, and 8-20 mass% is especially preferable. When the compounding quantity of a cationic surfactant is 1 mass% or more, sufficient flexibility provision performance can be obtained, and antibacterial property and the adsorption | suction residual property to the clothing of (A3) component mentioned later can be improved. On the other hand, when the compounding quantity of a cationic surfactant is 40 mass% or less, the favorable composition of stability can be obtained.

(Cationic High Polymer Compound)

As a cationic high molecular compound, when melt | dissolving in water, what has cationic property can be used, For example, the water-soluble high molecular compound which has a cationic group chosen from the group which consists of an amino group, an amine group, and a quaternary ammonium group is preferable. The cationic polymer compound can be used as one kind or a mixture of two or more kinds.

In addition, in this invention, a cationic group means the monomer which has a positively charged atom. In addition, water solubility means that the liquid does not become turbid and transparent when 100 g of water of 25 degreeC adds the target compound 1g.

It is preferable that a cationization degree is 0.1% or more, as for a cationic high molecular compound, 0.1 to 35% is more preferable, 2.5 to 15% is especially preferable. If the degree of cationization is 0.1% or more, the adsorption residual property on the clothes of the component (A3) described later can be further improved.

Here, the degree of cationization means that a polymer compound is one in which a polymer of a cationic monomer, a copolymer of a cationic monomer and a nonionic monomer, and a part of a nonionic polymer are modified or substituted with a cationic group (for example, cationized cellulose Etc.), it is a value computed by following formula (i). In addition, when a high molecular compound is a copolymer of a cationic monomer and an anionic monomer, and a copolymer of a cationic monomer, an anionic monomer, and a nonionic monomer, it is a value computed by following formula (ii).

Cation degree (%) = S × T × 100. (i)

Cation degree (%) = S x (T-U) x 100. (Ii)

S: The atomic weight of the cationized atom (nitrogen etc.) in the cationic group of a high molecular compound.

T: The number-of-moles of cationic groups contained in 1 g of high molecular compounds.

U: number of moles of anionic groups contained in 1 g of the polymer compound (anionic group is a carboxyl group, sulfonic acid group, etc. contained in the monomer unit in the polymer chain. Specifically, carboxylic acid in acrylic acid, etc.) It does not include the zwitterionic diion).

In addition, the cationic polymer compound preferably has a mass average molecular weight of 1,000 to 5,000,000, more preferably 3,000 to 1,000,000, particularly preferably 5,000 to 500,000, based on polyethylene glycol as a standard. Do. If mass average molecular weight is in the said range, since the raise of the viscosity of a processing agent composition can be suppressed, handling property will become favorable.

As a cationic high molecular compound, you may use a commercially available thing. For example, such as "MERQUAT100" made by NALCO company, "ADEKAKACHIOS PD-50" made by ADEKA company, "DAIDORU EC-004" made by Daidosei Kogyo, "DAIDORU HEC", "DAIDORU EC", etc. Polymers of dimethyldiallyl ammonium chloride; Dimethyldiallyl ammonium acrylamide copolymer, such as "MERQUAT550 JL5" by NALCO company; Dimethyl diallyl ammonium acrylic acid copolymers, such as "MERQUAT280" by NALCO company; Cationized cellulose, such as "Leogado KGP" by Lion Corporation; Imidazolinium chloride vinylpyrrolidone copolymers, such as "LUVIQUAT-FC905" by B.A.S.F Co .; Polyethylene imines, such as "LUGALVAN-G15000" by B.A.S.F Corporation; Cationized polyvinyl alcohol, such as "foam M318" by Kuraresa; Natural polymer derivatives having amino groups such as chitosan; Although a copolymer with the vinyl monomer which has a hydrophilic group to which diethylamino methacrylate, ethylene oxide, etc. were added is mentioned, What is necessary is just a high molecular compound which has cationicity when melt | dissolved in water, and is not limited to this example.

Among these cationic high molecular compounds, the polymer of dimethyldiallylammonium chloride can be reduced from the viewpoint of reducing the stiffness imparted to the clothes when adsorbed to the clothes by the cationic high molecular compound alone, and suppressing the disturbance of the touch such as flexibility. Is preferred. The polymer of dimethyl diallyl ammonium chloride is obtained by superposing | polymerizing the methyl diallyl ammonium salt represented with the following general formula (V).

In formula (V), Xa <^-> represents arbitrary negative ions, such as a chloride ion and a bromide ion.

The structural unit of the polymer of dimethyldiallyl ammonium chloride is usually represented by the following general formula (VI) or (iii). In the polymer of dimethyldiallyl ammonium chloride, the structural unit represented by the following general formula (VI), or the structural unit represented by the following general formula (VII) may be contained alone, or these structural units may be included together. good.

In formula (VI) and (iii), Xa <^-> represents arbitrary negative ions, such as a chloride ion and a bromide ion. In addition, a and b are average polymerization degrees, respectively, It is preferable that it is the range of 6-30000, More preferably, it is 20-6000, More preferably, it is 30-3000.

1-40 mass% is preferable, as for the compounding quantity of the cationic high molecular compound in a treating agent composition, 3-25 mass% is preferable, and 8-20 mass% is especially preferable. When the amount of the cationic high molecular compound is 1% by mass or more, sufficient flexibility-providing performance can be obtained, and the adsorption resistance to the clothing of the antibacterial property and the (A3) component described later can be improved. On the other hand, when the compounding quantity of a cationic high molecular compound is 40 mass% or less, the favorable composition of stability can be obtained.

[Other Ingredients]

[Eradication and Antibacterial Composition]

Other arbitrary components can be mix | blended with the antibacterial and antimicrobial composition of this invention in the range which does not impair the effect of this invention.

As an example of an arbitrary component, what is shown below is mentioned.

((E) component)

In this invention, you may use together hydrogen peroxide or the peroxide which melt | dissolves in water and produces hydrogen peroxide as (E) component. When the (E) component is used in combination, the bactericidal effect and the antibacterial effect on both the gram positive bacteria and the gram negative bacteria can be further improved.

As a specific example of the peroxide which melt | dissolves in water and produces hydrogen peroxide, sodium percarbonate, sodium perborate, sodium perborate trihydrate, etc. are mentioned.

Although (E) component does not specifically limit, It is preferable to mix | blend 0.0001-20 mass% in an antibacterial and antimicrobial composition, and it is more preferable if it is 0.0005-5 mass%.

If the (E) component is 0.0001 mass% or more in an antibacterial and antimicrobial composition, sufficient antibacterial effect and antibacterial effect can be acquired. On the other hand, when (E) component is 20 mass% or less, damage to a to-be-processed object can be suppressed.

In addition, (E) component may decompose | disassemble by the complex formed from (A1) component and (B1) component. Therefore, when mix | blending (E) component with an antibacterial and antimicrobial composition, it is preferable to mix | blend it immediately before using an antibacterial and antimicrobial composition.

(Bleach activator)

In the present invention, in order to increase sterilization power, a bleach activator may be used in combination. Examples of the bleach activator include sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, octanoyloxybenzoic acid and nonano Iloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, decanoyloxybenzene, undecanoyloxybenzene, dodecanoyloxybenzene, etc. Can be mentioned.

(Surfactants)

As surfactant, anionic surfactant, a nonionic surfactant, cationic surfactant, an amphoteric surfactant, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types as appropriate.

As an anionic surfactant, the following are mentioned, for example.

(1) Straight or branched chain alkylbenzenesulfonate having an alkyl group having 8 to 18 carbon atoms ((LAS) or (ABS)).

(2) Alkanesulfonates having 10 to 20 carbon atoms.

(3) α-olefinsulfonate (AOS) having 10 to 20 carbon atoms.

(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.

(5) An average of 0.5 to 10 moles of any one of alkylene oxides having 2 to 4 carbon atoms or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) were added. Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.

(6) An average of 3 to 30 moles of any one of alkylene oxides having 2 to 4 carbon atoms or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) were added. Alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.

(7) An average of 0.5 to 10 moles of any one of alkylene oxides having 2 to 4 carbon atoms or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) were added. Alkyl (or alkenyl) ether carbonate having a straight or branched chain alkyl (or alkenyl) group having 10 to 20 carbon atoms.

(8) Alkyl polyhydric alcohol ether sulfates, such as C10-C20 alkyl glyceryl ether sulfonic acid.

(9) Saturated or unsaturated α-sulfofatty acid salt (α-SF) having 8 to 20 carbon atoms or methyl, ethyl or propyl ester thereof (MES).

(10) long-chain monoalkyl, dialkyl or seskialkyl phosphates.

(11) polyoxyethylene monoalkyl, dialkyl or seskialkyl phosphates.

(12) C10-C20 higher fatty acid salt (soap).

These anionic surfactants are alkali metal salts such as sodium and potassium, amine salts,

It can be used as an ammonium salt or the like. In addition, you may use these anionic surfactant as a mixture.

As a nonionic surfactant, if it is conventionally used as a washing | cleaning agent, it will not specifically limit, Various nonionic surfactant can be used. As a nonionic surfactant, the following are mentioned, for example.

(1) An average of 3 to 30 moles, preferably 4 to 20 moles, and more preferably 5 to 17 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ethers. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are suitable. As an aliphatic alcohol used here, a primary alcohol and a secondary alcohol are mentioned. In addition, the alkyl group may have a branched chain. As aliphatic alcohol, primary alcohol is preferable.

(2) polyoxyethylene alkyl (or alkenyl) phenyl ether.

(3) Fatty acid alkyl ester alkoxylate which the alkylene oxide added between the ester bonds of long-chain fatty acid alkyl ester, for example represented by the following general formula (i).

In formula (VIII), R <^3> CO represents a C6-C22, Preferably 8-18 fatty acid residue. OA ⁴ represents an additional unit of alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide. n represents the number-of-moles of the average addition of alkylene oxide, and is generally a number of 3-30, Preferably it is 5-20. R ⁴ is a lower alkyl group which may have a substituent having 1 to 3 carbon atoms.

(4) polyoxyethylene sorbitan fatty acid ester.

(5) polyoxyethylene sorbitan fatty acid ester.

(6) polyoxyethylene fatty acid ester.

(7) polyoxyethylene hardened castor oil.

(8) glycerin fatty acid esters.

(9) fatty acid alkanolamides.

(10) polyoxyethylene alkylamine.

(11) alkylglycosides.

(12) alkylamine oxides.

As the cationic surfactant, various cationic surfactants can be used without particular limitation as long as they are conventionally used in cleaning agents. As a cationic surfactant, the following are mentioned, for example.

(1) Di long-chain alkyl di short-chain alkyl type quaternary ammonium salt.

(2) Mono long-chain alkyl trishort-chain alkyl type quaternary ammonium salt.

(3) Tri-chain alkyl mono short-chain alkyl type quaternary ammonium salt.

(The said long chain alkyl represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18. The short chain alkyl has 1 to 4 carbon atoms, preferably 1 to 2 alkyl groups, benzyl groups and 2 to 4 carbon atoms, preferably 2 Or a hydroxyalkyl group or a polyoxyalkylene group.)

As an amphoteric surfactant, if it is conventionally used with a washing | cleaning agent, various amphoteric surfactant can be used without a restriction | limiting in particular.

In addition, surfactant used by this invention is not limited to the said surfactant, In addition, you may use the said surfactant suitably 1 type, or 2 or more types.

(Inorganic salts)

As inorganic salts, neutral salts, such as alkaline salts, such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate, sodium metasilicate, crystalline sodium sodium silicate, amorphous sodium silicate, and sodium sulfate , Phosphates such as oxophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and phosphate salts, crystalline aluminosilicates represented by the following general formula (Ⅸ), represented by the following general formulas (X) and (XI) And inorganic ammonium salts such as amorphous aluminosilicate, ammonium sulfate, and ammonium chloride.

In formula (M), M represents alkali metal atoms, such as sodium and potassium, (alpha) ¹ , (beta) ^1, and (gamma) ¹ shows the number-of-moles of each component, and, in general, (alpha) ¹ is 0.7-1.5 and (beta) ¹ is 0.8-6 , Γ ¹ represents an arbitrary integer.

In formula (X), M represents alkali metal atoms, such as sodium and potassium, (alpha) ² , (beta) ^2, and (gamma) ² shows the number-of-moles of each component, and, in general, (alpha) ² is 0.7-1.2, (beta) ² is 1.6-2.8 , γ ² represents 0 or an arbitrary integer.

Formula (XI) in, M is an alkali metal atom, α ^3, β ^3, η ^1, and γ ^3, such as sodium, potassium, represents a molar number of each component, in general, α ³ from 0.2 to 1.1, β ³ is 0.2-4.0, (eta) ¹ is 0.001-0.8, (gamma) ³ represents 0 or arbitrary integer.

Organic Acids

As organic acid salts, For example, amino carboxylic acid salts, such as a nitrilo triacetate, ethylenediamine tetraacetic acid salt, (beta) -alanine diacetic acid salt, aspartic acid diacetate, methylguricin diacetic acid salt, and imino diacetic acid salt; Hydroxyaminocarboxylic acid salts such as serine diacetate, hydroxyiminodihomic acid salt, hydroxyethyl ethylenediamine triacetate, and dihydroxyethylglycine salt; Hydroxy carbonates such as hydroxyacetate, tartarate, citrate and gluconate; Cyclocarbonates such as pyromellitate, benzopolycarbonate, and cyclopentane tetracarboxylic acid; Ether carboxylates such as carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, stannic acid mono or disuccinate, sodium p-toluenesulfonate, sodium xylene sulfonate, sodium cumene sulfonate Benzene sulfonate having short-chain alkyl, sodium benzoate, sodium benzene sulfonate and the like.

(Polymer compound)

Examples of the polymer compound include polymers or copolymers such as acrylic acid polymer compounds, polyacetal carbonates, itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid and aspartic acid, cellulose such as polyethylene glycol and carboxymethyl cellulose. Derivatives, polyvinylpyrrolidone and derivatives thereof, silicone oils and the like.

(Water soluble organics)

D-glucose, urea, sucrose, etc. are mentioned as water-soluble organic substance.

(Swellable water insoluble substance)

Examples of the swellable water-insoluble substance include clay minerals such as smectite.

LIQUID CLEANER COMPOSITION

The component normally used for a liquid detergent can be mix | blended with the liquid detergent composition of this invention as needed in the range which does not impair the effect of this invention.

As another component, what is shown below is mentioned.

(Surfactants)

In the liquid detergent composition of this invention, nonionic surfactants other than (C-I) mentioned above, anionic surfactants other than (C-II), cationic surfactant, and an amphoteric surfactant can be mix | blended according to a use.

As nonionic surfactant other than (CI), For example, Alkylene oxide adducts, such as an alkylphenol, a higher fatty acid, or a higher amine, a polyoxyethylene polyoxypropylene block copolymer, fatty acid alkanolamine, fatty acid alkanol amide, Polyhydric alcohol fatty acid ester or its alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hardened castor oil, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkylglyco Seed etc. are mentioned.

As anionic surfactants other than (C-II), for example, higher fatty acid salts, alkyl ether carbonates, polyoxyalkylene ether carbonates, alkyl (or alkenyl) amide ether carbonates, and acylaminocarboxes Phosphoric acid ester type anionic surfactant, such as a carboxylic acid type, such as a main acid salt, an alkyl phosphate ester salt, a polyoxyalkylene alkyl phosphate ester salt, a polyoxyalkylene alkyl phenyl phosphate ester salt, a glycerin fatty acid ester monophosphate ester salt, etc. Can be mentioned.

As cationic surfactant, the cationic surfactant of an alkyl trimethylammonium salt, a dialkyl dimethyl ammonium salt, an alkyl benzyl dimethyl ammonium salt, an alkyl pyridinium salt, etc. are mentioned, for example.

As the amphoteric surfactant, for example, an alkylbetaine type, an alkylamide betaine type, an imidazoline type, an alkylaminosulfone type, an alkylaminocarboxylic acid type, an alkylamidecarboxylic acid type, an amideamino acid type or a phosphoric acid type amphoteric interface Activators and the like.

(Water miscible organic solvent)

As a water miscible organic solvent, For example, alcohols, such as ethanol, 1-propanol, 2-propanol, 1-butanol, glycols, such as propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, triethylene glycol , Tetraethylene glycol, polyethylene glycol with an average molecular weight of about 200, polyethylene glycol with an average molecular weight of about 400, polyethylene glycol with an average molecular weight of about 1000, polyglycols such as dipropylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether Alkyl ether, such as these, etc. are mentioned.

As for the compounding quantity of the water miscible organic solvent, 0.1-15 mass% is preferable with respect to the gross mass of a liquid detergent composition.

(Optional ingredient)

The liquid detergent composition of this invention may contain the component illustrated below as an arbitrary component.

As a viscosity reducing agent and a solubilizer, 0.01-30 mass% of paratoluene sulfonic acid, benzoate (it also has an effect as a preservative), and urea etc. can be contained.

As a metal ion antifoaming agent, malonic acid, a succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, etc. can contain 0.1-20 mass%, for example.

As antioxidant, 0.01-2 mass% of butylhydroxytoluene, the distylated cresol, sodium sulfite, sodium hydrogen sulfite, etc. can be contained, for example.

As the preservative, for example, the product may be contained, for example, 0.001 to 1% by mass of the Rohm and House company.

Moreover, the liquid detergent composition of this invention is an alkali builder, pH adjusters, hydrotropes, such as an enzyme (protease, a lipase, a cellulase, etc.), a touch improving agent, an alkanolamine, etc., for the purpose of a washing performance improvement, storage stability improvement, etc. May contain a fluorescent agent, an anti-inflammatory agent, an anti-contamination agent, a pearl (pearl) agent, a soy-release agent, or the like.

In addition, the liquid detergent composition of this invention may contain extracts, such as a flavoring agent, a coloring agent, an emulsifier, a natural product, etc., for the purpose of the value added improvement etc. of a product.

As a flavoring agent, the perfume composition A, B, C, D etc. which are described in Table 11-18 of Unexamined-Japanese-Patent No. 2002-146399 can be used.

As for the compounding quantity of a flavoring agent, 0.1-1 mass% is preferable with respect to the gross mass of a liquid detergent composition.

As a coloring agent, general-purpose pigment | dyes and pigments, such as Asdre 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue 1, Blue 205, Green 3, Turquoise P-GR (all brand names), are mentioned. have.

As for the compounding quantity of a coloring agent, about 0.00005-0.005 mass% is preferable with respect to the gross mass of a liquid detergent composition.

Examples of the emulsion include polystyrene emulsion, polyvinyl acetate emulsion, and the like. Usually, an emulsion having a solid content of 30 to 50% by mass is suitably used.

As a specific example, a polystyrene emulsion (trade name: Cybinol RPX-196 PE-3 manufactured by Siden Chemical Co., Ltd., 40 mass% of solid content), etc. are mentioned.

As for the compounding quantity of an emulsion, 0.01-0.5 mass% is preferable with respect to the gross mass of a liquid detergent composition.

Examples of extracts such as natural products include elm tree, Uva-Ursi, Echinacea, golden, yellow bark, barberry, allspice, oregano, painting tree, chamomile, and copper , Red ginseng, hedgehog, cassia, laurel, Japanese magnolia, burdock, comfrey, casualty, cucumber grass, barn, ginger, sheep smell, elderberry (Elderberry), Salvia, Mistletoe, Creation, Thyme, Timothy, Clove, Wenzhou Citrus, Tea Tree, Barberry, Wild Wheat, Namcheon, Frankincense, Copper , Birch, windproof, pagoji, hop. Rosewood, hornnamcheon, purple railroad tree, melissa, pandan, breeze, eucalyptus, lavender, rose, rosemary, foliar, cedar, balsam tree, ringworm, daphnia, node of grass, orgy Plant extracts such as beggar, licorice and water. As for the compounding quantity of extracts, such as a natural product, about 0-0.5 mass% is preferable with respect to the gross mass of a liquid detergent composition.

[Treatment Composition for Textile Products]

In the treating agent composition of the present invention, a component usually used in treating agents such as a softening agent can be blended as necessary within a range that does not impair the effects of the present invention.

As another component, what is shown below is mentioned.

(Silicon compound)

The treating agent composition of the present invention may contain a silicone compound for the purpose of improving the activity. The silicone compound is not particularly limited as long as it can provide smoothness when adsorbed onto clothing, and examples thereof include dimethyl silicone, polyether-modified silicone, methylphenylsilicone, alkyl-modified silicone, higher fatty acid-modified silicone, methylhydrodiene silicone, and fluorine. Modified silicone, epoxy modified silicone, carboxy modified silicone, polyglycerol modified silicone, carbinol modified silicone, amino modified silicone and the like. These silicone compounds can be used as 1 type or in mixture of 2 or more types.

The molecular structure of the silicone compound may be linear, or may be branched or crosslinked. In addition, the modified silicone compound may be modified by one type of organic functional group, or may be modified by two or more types of organic functional groups.

It is preferable that it is 10-100,000,000 mm <2> / s, and, as for the dynamic viscosity in 25 degreeC of a silicone compound, it is more preferable that it is 1,000-100,000 mm <2> / s. When kinematic viscosity exists in such a range, the ease of mixing | blending and the activity of the clothing processed by the processing agent composition of this invention improve.

The silicone compound can be used as an oil and can also be used as an emulsion dispersed by any emulsifier. Moreover, it is preferable that it is nonionic from the point which has a high adsorption effect to clothing, and improves flexibility and smoothness, As a more preferable example, dimethyl silicone, carbinol modified silicone, polyglycerol modified silicone, epoxy modified silicone, polyether modified silicone Can be mentioned.

Among these, as a particularly preferable silicone compound, polyether modified silicone and dimethylsilicon are mentioned from a viewpoint of flexibility provision. Compared with the low molecular weight dimethylsilicone which does not have a polyether group, these silicone compounds are less sticky and have favorable flexibility.

As a preferable polyether modified silicone, the copolymer of alkyl (C1-C3) siloxane and polyoxyalkylene (C2-C5 of an alkylene group is preferable) is mentioned. Among them, a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, random or block copolymer of polyoxyethylene and polyoxypropylene, etc.) is preferable.

As a specific example of polyether modified silicone oil, "SH3772M", "SH3775M", "SH3748", "SH3749", "SF8410", "SF8416", "SH8700", "SH200C-5000CS", "made by Toray Dow Corning Corporation", " BY16-849 '', `` BY22-008 '', `` SF8421 '', `` SILWET L-7001 '', `` SILWET L-7002 '', `` SILWET L-7602 '', `` SILWET L-7604 '', `` SILWET FZ-2104 '', `` SILWET FZ-2120 '', `` SILWET FZ-2161 '', `` SILWET FZ-2162 '', `` SILWET FZ-2164 '', `` SILWET FZ-2171 '', `` ABN SILWET FZ-F1-009-01 '', `` ABN SILWET FZ-F1-009-02 '', `` ABN SILWET FZ-F1-009-03 '', `` ABN SILWET FZ-F1-009-05 '', `` ABN SILWET FZ-F1-009-09 '', `` ABN SILWET FZ- F1-009-11 "," ABN SILWET FZ-F1-009-13 "," ABN SILWET FZ-F1-009-54 "," ABN SILWET FZ-2222; "KF352A", "KF6008", "KF615A", "KF6016", "KF6017" by Shin-Etsu Chemical Co., Ltd .; "TSF4450", "TSF4452" by GE Toshiba Silicone Co., etc. are mentioned. These polyether modified silicone oils can be used as 1 type or in mixture of 2 or more types.

Although the compounding quantity of the silicone compound in a treating agent composition is not specifically limited, 0.05-20 mass% is preferable, 0.2-10 mass% is more preferable, 0.5-5 mass% is especially preferable.

(Water)

The treating agent composition of the present invention is preferably an aqueous composition, and as water that can be used, all of tap water, ion-exchanged water, pure water, distilled water, and the like can be used. Water from which heavy metals are removed is preferred, and ion exchange water is most preferred in consideration of cost.

(Water soluble solvent)

As the water-soluble solvent, a water-soluble solvent selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol polyoxyethylene phenyl ether, and a compound represented by the following general formula (XII) It may contain.

In formula (XII), R <^8> is a C1-C8 alkyl group or alkenyl group. Moreover, also in an alkyl group and also in an alkenyl group, it is preferable that carbon number is 2-6.

c and d are molar numbers of average parts, c is 2-20, and 2-10 are preferable. On the other hand, d is 0-5, and 0-3 are preferable.

Among these, ethanol, ethylene glycol, propylene glycol, butyl carbitol, diethylene glycol monopropylene glycol monobutyl ether and the like are suitable as water-soluble solvents. 0.1-30 mass% is preferable, and, as for the compounding quantity of the water-soluble solvent in a processing agent composition, 2-20 mass% is more preferable.

(Term)

In the present invention, a perfume may be added for the orientation of the treatment composition. Although it does not specifically limit as a coating agent, The list of the coating raw material which can be used is various documents, for example, "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994), "Composite and Chemicals of Commodity Chemicals", Indeung Won Il, Chemical Industry Daily (1996), Perfume and Flavor Materials of Natural Origin, Steffen Arctander, Allured Pub. Co. (1994), Encyclopedia of Fragrances, Japan Pharmaceutical Association, Chochang Bookstore (1989), Perfumery Material Performance V.3.3, Boelens Aroma Chemical Information Service (1996), Flower oils and Floral Compounds In Perfumery, ”Danute Lajaujis Anonis, Allured Pub. Co. (1993) and the like.

(Antioxidant)

In this invention, antioxidant can be added in order to improve the fragrance stability and color tone stability of a processing agent composition. As antioxidant, generally known natural antioxidant and synthetic antioxidant can be used. Specifically, ascorbic acid, ascorbic acid palmitate, a mixture of phosphate propyl, BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), a mixture of phosphate, and citric acid, hydroquinone, 3 Tertiary butylhydroquinone, natural tocopherol compounds, long chain esters of molar acids (8 to 22 carbon atoms), for example monobasic compounds, available from molar dodecyl, chivas specialty chemicals, citric acid and / or citric acid isopropyl, 4, 5-dihydroxy-m-benzenesulfonic acid / sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoid, francs, amino acids, etc. are mentioned.

Among these, BHT (butylated hydroxytoluene), a methoxy phenol, a tocopherol compound etc. are preferable from a viewpoint of the storage stability of a processing agent composition.

As for the compounding quantity of antioxidant in a processing agent composition, 0.01-1 mass% is preferable.

(antiseptic)

Preservatives are mainly used to maintain the preservatives during long-term storage. Examples of the preservative include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitropropane-1,3-diol and the like.

Examples of isothiazolone-based organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone and 2-benzyl-3-isothiazolone , 2-phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazoline-3- Warm and mixtures thereof. Among these, water-soluble mixtures of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferable, and more preferably about 77% by mass Water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one with about 23% by mass of 2-methyl-4-isothiazolin-3-one.

Examples of the benzisothiazoline-based organic sulfur compound include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and the like. . Moreover, dithio-2, 2-bis (benzmethylamide) etc. can also be used as a flexible compound, These can be used in arbitrary mixing ratios. Among these, 1, 2- benzisothiazolin-3-one is especially preferable.

Examples of benzoic acids include benzoic acid or salts thereof, parahydroxy benzoic acid or salts thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate and the like.

As for the compounding quantity of the preservative in a processing agent composition, 0.0001-1 mass% is preferable.

(dyes)

Addition of dye is arbitrary and it does not specifically limit even if it adds. When dye is added, a water-soluble dye is preferable for the ease of addition, and it is preferable that it is 1 type, or 2 or more types of water-soluble dye selected from acidic dye and direct dye especially.

Specific examples of the dye that can be added include, for example, a dye handbook (Organic Synthetic Chemistry Association, July 20, 1970 issuance, Circulation Co., Ltd.), Dye notebook 22nd edition (Color Dye Co., Ltd.) ) And the Statutory Coloring Handbook (Japan Cosmetics Industry Association, published on November 28, 1988, Pharmacist Daily).

0.01-50 ppm is preferable and, as for the compounding quantity of the dye in a processing agent composition, 0.1-30 ppm is more preferable. By setting it as such a compounding quantity, the color colored in the treatment agent composition can be prevented from becoming very thin, and the coloring effect can be made sufficient, while the coloring of the treatment agent composition can be prevented from becoming too dark.

(Defoamer, other additives)

Defoamers, other additives, etc. which are used for processing agents, such as a normal household softener, can be used for the treating agent composition of this invention in the range which does not prevent the effect of this invention. As antifoaming agents and other additives, for example, salts, water-soluble salts such as ammonium chloride, calcium chloride, magnesium chloride, potassium chloride, sodium citrate, emulsions such as liquid paraffin, higher alcohols, urea, hydrocarbons, nonionic cellulose derivatives, ultraviolet rays An absorbent, a fluorescent brightener, the pH adjuster mentioned later, etc. are mentioned.

[Physical Properties of Antibacterial and Antimicrobial Compositions]

(PH of Antibacterial and Antimicrobial Compositions)

The pH at the time of use of the bactericidal / antibacterial composition of the present invention is preferably pH 4 or more from the point of effect, more preferably pH 6 or more, and particularly preferably pH 7 to pH 12 from the point of effect and handleability.

In the bactericidal / antibacterial composition of the present invention, the deterioration of the bactericidal effect and the antibacterial effect is observed in the acidic side region. Moreover, the area of strong alkali is unpreferable in the handleability at the time of work.

The pH of the antibacterial and antimicrobial composition can be adjusted using a pH adjuster. As a pH adjuster, hydrochloric acid, sulfuric acid, nitric acid, citric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium citrate, sodium phosphate, sodium hydrogen phosphate and the like are suitably used. It can mix.

(Formulation of antibacterial and antimicrobial composition)

The formulation of the bactericidal / antibacterial composition of the present invention is not particularly limited, and as described above, the component (A1) and the component (B1) may be mixed to produce a powder form or granulated composition and to be used. It may be used as a liquid composition by dissolving or dispersing in a solvent such as water.

In addition, the complex formed from the component (A1) and the component (B1) may be blended to prepare and use a powder or granulated composition, or may be dissolved or dispersed in a solvent such as water and used as a liquid composition. .

In addition, the liquid composition can be used as it is, or diluted with a solvent, and applied or sprayed.

The antibacterial and antimicrobial compositions of the present invention described above can obtain antibacterial and antibacterial effects without using peroxides, and can be used for all applications requiring antibacterial and antibacterial effects, and the use thereof is not particularly limited.

As an example, the washing | cleaning agent for cloth | clothes, clothing | clothes, etc., the disinfecting and antibacterial effect imparting agent, the residential detergent used for living rooms, a toilet, a bathroom, a kitchen, a washroom, etc. are mentioned.

Since the alkyl group or acyl group of (B1) component in the antibacterial and antimicrobial composition of this invention has 8-22 carbon atoms, it exists in the tendency to adsorb | suck to gram negative bacteria. Thereby, the metal ion derived from (A1) component which forms the complex with (B1) component can contact a microbe without distinguishing between a gram negative microbe and a gram positive microbe, Even if a small amount of metal is high in both microbes. It is thought that the bactericidal and antimicrobial effects can be exhibited.

Physical Properties of Liquid Detergent Composition

(PH of the liquid detergent composition)

It is preferable that pHs in 25 degreeC are 4-9, and, as for the liquid detergent composition of this invention, it is more preferable that it is pH 4-8. If pH is in such a range, the storage stability of a liquid detergent composition can be kept favorable.

PH of a liquid detergent composition can be adjusted using a pH adjuster. As a pH adjuster, although it is mercury unless the effect of this invention is impaired, sulfuric acid, sodium hydroxide, potassium hydroxide, an alkanolamine, etc. are preferable at the point of stability.

[Preparation of Liquid Detergent Composition]

The liquid detergent composition of this invention dissolves or disperse | distributes the above-mentioned (A2) component, (B2) component, (C) component, and other components as needed in a solvent, such as water, and also a pH adjuster as needed. It obtains by adjusting pH so that it may become a desired value. There is no restriction | limiting in particular about the mixing order of each component.

Since the liquid detergent composition of this invention demonstrated above contains a specific (A2) component, (B2) component, and (C) component, (A2) component (inorganic metal compound) with respect to a textile product, maintaining a storage stability. Adsorption residual of () can be improved. Therefore, the liquid detergent composition of this invention can express the outstanding bactericidal effect or antibacterial effect. Since the bactericidal effect or the antimicrobial effect acts on bacteria such as microorganisms, even if contamination of sebum or the like remains on the garment after washing, decomposition by microorganisms can be suppressed. Therefore, the liquid detergent composition of this invention can reduce generation | occurrence | production of an odor, and can also expect the outstanding deodorizing effect.

[Physical Properties of Treatment Agent Compositions for Textile Products]

(PH of Treatment Composition for Textile Products)

Although the pH of the treating agent composition of the present invention is not particularly limited, the pH at 25 ° C. is in the range of 1 to 6 for the purpose of suppressing hydrolysis of the ester group contained in the molecule of the component (D) accompanying the storage days. It is preferable to adjust to and it is more preferable to adjust to the range of 2-4.

For pH adjustment, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, paratoluene sulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethanediphosphonic acid, phytic acid, ethylenediamine tetraacetic acid, triethanolamine, diethanol Short-chain amine compounds, such as amine, dimethylamine, N-methylethanolamine, and N-methyl diethanolamine, alkali metal hydroxides, such as sodium hydroxide, alkali metal carbonate, alkali metal silicates, etc. can be used.

(Viscosity of Treatment Composition for Textile Products)

It is preferable that the treating agent composition of this invention is 1000 mPa * s in the viscosity measured at 25 degreeC using a B-type clay system (made by TOKIMEC company). In consideration of the increase in viscosity due to the elapsed storage days, the viscosity immediately after the mixing of each component is more preferably less than 500 mPa · s, and particularly preferably less than 300 mPa · s. When the viscosity of the treating agent composition is within the above range, the usability such as handling property when feeding into the washing machine is good, and therefore, the amount is preferable.

When adjusting the viscosity of the treating agent composition, inorganic or organic water-soluble salts can be used. Specifically, calcium chloride, magnesium chloride, sodium chloride, sodium p-toluene sulfonate, and the like can be used. Among them, calcium chloride and magnesium chloride are preferable. These water-soluble salts can be mix | blended in about 0-1 mass% in a processing agent composition, and you may mix | blend in any process at the time of manufacturing a processing agent composition.

(Formulation of Treatment Composition for Textile Products)

The formulation of the treatment agent composition of the present invention is not particularly limited, and (D) component, (A3) component, (B3) component, and other components are mixed as necessary to form a powder or granulated composition. It may be prepared and used, or may be dissolved or dispersed in a solvent such as water and used as a liquid composition.

In addition, the complex formed from the component (A3) and the component (B3), the component (D), and other components may be blended as necessary to produce a powder form or a granulation composition, and may also be used. It may be used as a liquid composition by dissolving or dispersing in a solvent.

In addition, the liquid composition can also be used as it is or diluted with a solvent and applied or sprayed.

Since the treating agent composition of the present invention described above contains the specific (A3) component and (B3) component, the adsorption residual of the (A3) component (inorganic metal compound) with respect to a fiber product can be improved. In particular, when blending the complex formed from the component (A3) and the component (B3), or using the treatment composition as a liquid composition, the component (A3) and the component (B3) tend to form complexes in water. , The adsorption residual of the (A3) component can be improved more. Moreover, by containing a specific (D) component, while providing flexibility to a processing agent composition, the adsorption | suction residual of (A3) component can also be improved.

Therefore, the treating agent composition of the present invention can express excellent bactericidal effect or antibacterial effect. Since the bactericidal effect or the antimicrobial effect acts on bacteria such as microorganisms, even if contamination of sebum or the like remains on the garment after washing, decomposition by microorganisms can be suppressed. Therefore, the processing agent composition of this invention can reduce generation | occurrence | production of an odor, and can express the outstanding deodorizing effect.

[Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these.

[Eradication and Antibacterial Composition]

[Used raw materials]

As the starting materials, the reagents and compounds shown below were used.

As the component (A1), the reagents shown below were used.

(A1-1): silver sulfate; Hwagwang Pure Pharmaceutical Co., Limited

(A1-2): copper sulfate pentahydrate; Kanto Chemical Corp., Limited Express

(A1-3): zinc sulfate heptahydrate; Pure Chemistry, Limited

Copper chloride dihydrate: manufactured by Kanto Chemical.

Copper gluconate: Tokyo Chemical Co., Ltd. make.

Zinc chloride: manufactured by Kanto Chemical.

Zinc gluconate: manufactured by Tokyo Chemical Co., Ltd.

As the component (B1), the following reagents and compounds were used.

(B1-1): 2.5 g (19.5 mmol) of octylamine (manufactured by Hwagwang Pure Chemical Co., Ltd.), an alkylamine, and 5.0 g (52.9 mmol) of monochloroacetic acid (manufactured by Hwagwang Pure Chemical Co., Ltd.), 5 ml of water, ethanol (Kanto Chemical Co., Limited.) It was added to 32 ml of a mixed solution and stirred under reflux for 6 hours. During the reflux stirring, 7.8 ml of an aqueous sodium hydroxide solution (5.0 mol / L) prepared with sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to adjust the pH. The solution was then cooled to 4 ° C. and a precipitate formed. The resulting precipitate was washed with ethanol, filtered, dried under reduced pressure to recover a solid, and sodium octyliminodiacetic acid (carbon number of alkyl group (R): 8 in formula (1)) was obtained.

(B1-2): Except using 3.6 g (19.5 mmol) of lauryl amines (manufactured by Hwagwang Pure Chemical Co., Ltd., the highest grade) as an alkyl amine, it operates by the same compound as (B1-1), and shows the lauryl iminodi which is shown below. Sodium acetate (C12 of alkyl group (R) in Formula (1)) was obtained.

(B1-3): Except using 4.2 g (19.5 mmol) of myristylamine (made by Tokyo Chemical Industry Co., Ltd.) as alkylamine, operation is carried out by the same compound as (B1-1), and the myristyliminodie shown below. Sodium acetate (carbon number of alkyl group (R): 14) in Formula (1) was obtained.

(B1-4): Other than using 4.7 g (19.5 mmol) of palmithyl amine (manufactured by Tokyo Chemical Industry Co., Ltd.) as the alkyl amine, the same procedure as in (B1-1) was carried out to give sodium palmitriimino diacetate. (The carbon number of the alkyl group (R): 16) was obtained by Formula (1).

(B1-5): Except using 5.3 g (19.5 mmol) of stearylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as the alkyl amine, the compound was operated in the same manner as in (B1-1), and sodium stearyliminodiacetate was shown below. (The number of carbon atoms of the alkyl group (R): 18) was obtained in formula (1).

(B1-6): According to eicosylamine (synthesis; Langmuir, 1994, No. 10, p. 1226) as an alkylamine, arachidic acid is reacted with thionyl chloride to give carboxylic acid chloride, which is ammonia. Was added to obtain eicosanamide, and then reduced to lithium aluminum hydride to synthesize eicosylamine. The same procedure as in (B1-1) was carried out except that 5.8 g (19.5 mmol) of eicosylamine was used. Sodium imino diacetate (carbon number of the alkyl group (R) in Formula (1): 20) was obtained.

(B1-7): 40.4 g (0.33 mol) of sodium monochloroacetate dissolved in 5 ml of laurylamine (manufactured by Hwagwang Pure Chemical Co., Ltd., the highest grade), which is an alkylamine, in 100 ml of ethanol, and 50 ml of water therein. Was added to prepare a mixed liquid. After heating this mixed liquid to 60 degreeC, the sodium hydroxide aqueous solution (12.5 mol / L) was dripped, adjusting so that pH might not be 9 or less. After dropping, the mixture was allowed to react for 5 hours, and the precipitated salt was filtered off, washed, and the resulting filtrate was removed under reduced pressure to obtain sodium laurylaminoacetate (carbon number of alkyl group: 12) represented by the formula (2).

(B1-8): Cocoalkyl propylene diamine (Lion arc irradiating agent, duomin) represented by Formula (3) (The alkyl group (R) in Formula (3) has a C12 and 14 thing centered.) Was used. .

(B1-9): 224 g (1.1 mol) of lauric acid (made by Tokyo Chemical Industry Co., Ltd.) was added to four ball | basket | frames, and nitrogen substitution was performed twice at 80 degreeC. Thereafter, 173 g (1.7 mol) of dimethylaminopropylamine (manufactured by Kanto Chemical Co., Ltd., rust-express) was dropped in two hours while heating up at 170 ° C and removing water to be replicated. Again, it maintained at 170 degreeC-180 degreeC, and aged for 7 hours.

After aging, the reaction mixture was dried under reduced pressure to remove unreacted amine and water, thereby obtaining lauric acid dimethylaminopropylamide (acyl group having 12 carbon atoms) represented by formula (4).

(B1-10): 10.3 g (100 mmol) of diethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.0 g (10 mmol) of 1-yodododecane (manufactured by Hwagwang Pure Chemical Co., Ltd.) were stirred at 40 ° C for 5 hours. Then, 2.4 ml of sodium hydroxide aqueous solution (5.0 mol / L) was added, and also it stirred for a while. After cooling, the extraction operation was performed five times with diethyl ether / water using a separating lot, and the organic layer was removed under reduced pressure. The obtained organic layer was subjected to a column (manufactured by Nakarai Tetsu Co., silica gel 60, spherical form, neutral), eluent: chloroform (manufactured by Kanto Chemical Co., Ltd.) / Methanol (manufactured by Kanto Chemical Co., Limited) = 1/1, or more with column chromatography After purification by chromatography, dried under reduced pressure to recover a solid, to obtain lauryldiethylenetriamine (carbon number of alkyl group: 12) represented by formula (5).

(B1-11): Alkyldiaminoethylglycine represented by Formula (6) (for light photopharmaceuticals, reagents, antibacterial and antibacterial mold research) (Alkyl group (R) in Formula (6) has Center) was used.

(B1-12 (comparative product)): The imino diacetic acid (the Tokyo Chemical Industries, Ltd. express) represented by Formula (7) was used.

(B1-13 (comparative product)): Laurolysin (Ajinomoto Co., Amihof) represented by Formula (8) (carbon number of acyl group: 12) was used.

(B1-14 (comparative product)): Lauroyl aspartic acid (Asahi Kasei Chemical Co., Ltd., aminoformer) (carbon number of acyl group: 12) represented by Formula (9) was used.

(B1-15 (comparative product)): Lauroyl sarcosine (Natural Fine Chemicals Co., Ltd., Soy phon) represented by Formula (10) was used (carbon number of acyl group: 12).

As a pH adjuster, the reagent shown below was used.

Sodium carbonate: manufactured by Kanto Chemical, Limited.

[Test 1: Preparation of Disinfectant Composition (1)]

<Examples 1-37, Comparative Examples 1-18>

(A1) component and (B1) component of the kind shown to Tables 1-3 are added to water so that it may become the density | concentration shown in Tables 1-3, and sodium carbonate so that concentration may become 0.106 mass% (10 mmol / L). Added. Subsequently, the fungicide composition (1) was obtained by adjusting aqueous solution to pH10.

Evaluation test of bactericidal effect:

The bactericidal power was evaluated by bacterial suspension using Staphylococcus aureus and Escherichia coli, respectively.

(Yellow staphylococcus)

In 9.9 ml of the above-mentioned disinfectant composition (1), yellow staphylococcus mother liquor (NBRC12732, which was prepared so that the number of bacteria was 107 / ml) (organization name: Instrument and Biogenetic Resources Division based on product evaluation technology) 0.1 ml each was added, it stirred uniformly, and the test liquid was obtained.

After the test solution was allowed to stand for 10 minutes, 1.0 mL of the test solution was collected and added to 9.0 mL of SCDLP medium (Hwagwang Pure Chemical Industries Co., Ltd., Soybean-Casein Digest Broth with Lectin & Polysorbate 80) to prepare a 10-fold dilution solution. The procedure of diluting the obtained dilution liquid 10 times again was repeated 4 times and 10 to 100000 times dilution liquid was obtained.

100 μl of each of these dilutions was collected, loaded onto a standard agar medium (manufactured by Atekuto Co., Ltd.), and then uniformly coated with Konradibong for 1 to 2 days in a constant temperature bath at 37 ° C. Choose one that can count the number of colonies, count the number of colonies to determine the number of live bacteria, survive the logarithm of the number of super bacteria (10 ⁷ / ml), and survive after the test. The difference with the logarithmic value of a bacteria number was made into the number of bacteria, and it evaluated by the following evaluation criteria. The results are shown in Tables 1-3.

Compared with the first germ count

X: Less than 1.0 paragraph of sterilization number

△: 1.0 or more to less than 1.5

(Circle): The number of germicidal cells 1.5 or more, but does not reach annihilation

◎: 0 remaining bacteria

(E. coli)

Instead of Staphylococcus aureus, Escherichia coli bacteria were obtained in the same manner as the above method of obtaining the number of bacteria of Staphylococcus aureus except for using Escherichia coli mother liquor (NBRC3972). Was evaluated and evaluated according to the same evaluation criteria. The results are shown in Tables 1-3.

TABLE 1

TABLE 2

[Table 3]

As shown in Tables 1-3, the bactericidal composition (1) obtained in Examples 1-37 has shown the favorable bactericidal effect not only to Escherichia coli which is a gram negative bacterium but also to Staphylococcus aureus which is a gram positive bacterium.

Among them, Examples 2 to 5 and 13 to (B1), in which the compound (B1-2) to compound (B1-5) having 12 to 18 carbon atoms in the alkyl group (R) in the formula (1), are used as the component (B1). In 16 and 26-29, the disinfection effect is high. This is considered to be because the balance of the hydrophobicity of the disinfectant composition 1 and the solubility in water is good. In addition, when the long-chain alkylamine represented by Formula (1) is used as a component (B1) (Example 7, 18, 31), and when the long-chain alkylamine represented by Formula (II) is used (Examples 8-8). Comparing 11, 19-22, 32-35), when the long-chain alkylamine represented by Formula (II) is used, there exists a tendency for a higher disinfection effect to be obtained. This is considered to be because the complex is stable because there are a plurality of nitrogen atoms coordinated to the metal, and the charge is neutral or higher as a whole, so that it is easy to adsorb to the bacteria and a higher bactericidal effect is obtained.

The comparative examples 1 and 7 which did not mix | blend the (B1) component have acquired the bactericidal effect to E. coli, but the bactericidal effect to Staphylococcus aureus was low. In addition, in Comparative Example 13, the antibacterial effect was not obtained together with Staphylococcus aureus and Escherichia coli.

In Comparative Examples 2, 8, and 14, in which the component (A1) was not added, the bactericidal effect was not obtained, and the bactericidal effect was not obtained together with Staphylococcus aureus and Escherichia coli.

In Comparative Examples 3, 9 and 15, since the imino diacetic acid which does not have an alkyl group at the terminal was used as compound (B1), the bactericidal effect to Staphylococcus aureus was not obtained. In particular, in Example 15, the bactericidal effect against Escherichia coli was not obtained.

In Comparative Examples 4, 10, and 16, laurolysine that did not conform to the formulas (I) and (II) was used as the compound (B1), so that the bactericidal effect against Staphylococcus aureus was not obtained. In particular, in Comparative Example 16, the bactericidal effect against Escherichia coli was not obtained.

In Comparative Examples 5, 11 and 17, since the lauroyl aspartic acid which does not correspond to Formula (I) and (II) was used as compound (B1), the bactericidal effect to Staphylococcus aureus was low. In particular, in Comparative Example 17, the bactericidal effect against Escherichia coli was not obtained.

In Comparative Examples 6, 12 and 18, since the lauroyl sarcosine which does not match Formula (I) and (II) was used as compound (B1), the bactericidal effect to Staphylococcus aureus was low. In particular, in Comparative Example 18, no bactericidal effect to E. coli was obtained.

In addition, when comparing the long-chain acyl group alkaline amino acids of Comparative Examples 4 to 6, 10 to 12, 16 to 18 and Examples 9, 20 and 33, the comparative example had an amide structure, and compared to amine, I think the power is weak. In addition, even if it considers from an electric charge etc., it is thought that the adsorption effect of the metal to microorganisms is weak. On the other hand, in the case of the Example, although it has a amide structure similarly, since there exists an amine structure in the comparatively close distance to it, it is guessed that a complex may be stable by a chirate effect.

[Test 2: Preparation of Disinfectant Composition (2)]

<Examples 38-50, Comparative Examples 19-24>

Hydrogen peroxide was added to the water (A1) component and the component (B1) of the kind shown in Table 4 to the density | concentration shown in Table 4, and sodium carbonate so that concentration might be 0.130 mass% (12.3 mmol / L). Each was added so that a concentration might be 0.0065 mass% (1.91 mmol / L). Subsequently, the disinfectant composition (2) was obtained by adjusting aqueous solution to pH10.

About the obtained disinfectant composition (2), the evaluation test of the disinfecting effect was done similarly to the disinfectant composition (1). The results are shown in Table 4.

[Table 4]

As shown in Table 4, the bactericidal composition (2) obtained in Examples 38 to 50 exhibits a good bactericidal effect not only against E. coli, which is a gram negative bacterium, but also Staphylococcus aureus, which is a gram positive bacterium.

In Comparative Example 19, in which the component (B1) was not added, the bactericidal effect to E. coli was obtained, but the bactericidal effect to Staphylococcus aureus was not obtained.

In Comparative Example 20 in which the component (A1) was not added, the bactericidal effect was not obtained, and the bactericidal effect was not obtained together with Staphylococcus aureus and Escherichia coli.

In the comparative example 21, since the imino diacetic acid which does not have an alkyl group at the terminal was used as compound (B1), the bactericidal effect to E. coli was obtained, but the bactericidal effect to Staphylococcus aureus was not obtained.

In the comparative example 22, since the laurolysine which does not match Formula (I) and (II) was used as compound (B1), the bactericidal effect to E. coli was obtained, but the bactericidal effect to Staphylococcus aureus was not obtained. .

In the comparative example 23, since the lauroyl aspartic acid which does not match Formula (I) and (II) was used as compound (B1), the bactericidal effect to E. coli was obtained, but the bactericidal effect to Staphylococcus aureus was low.

In the comparative example 24, since the lauroyl sarcosine which does not match Formula (I) and (II) was used as compound (B1), the bactericidal effect to E. coli was obtained, but the bactericidal effect to Staphylococcus aureus was low.

[Test 3: Preparation of Antimicrobial Composition]

<Examples 51 to 93, Comparative Examples 25 to 42>

(A1) component and (B1) component of the kind shown to Tables 5-7 are added to water so that it may become the density | concentration shown in Tables 5-7, and a nonionic surfactant (LMAO-90 made from Lion Chemical Co., Ltd.) Was added so that it became 0.0208 mass%. Subsequently, the antimicrobial composition was obtained by adjusting aqueous solution to pH7.

In addition, the antimicrobial composition for evaluation comparison was prepared like Example 51-93 and Comparative Examples 25-42 except not having mix | blended (A1) component and (B1) component.

Evaluation test of antibacterial effect:

In the evaluation of the antibacterial activity, the same yellow staphylococcus and E. coli as used in the evaluation of the antibacterial activity were used.

In addition, the instrument, water, etc. which are used for a test were sterilized previously by an autoclave, and used.

The cotton cloth which wash | cleaned, rinsed, dewatered, and dried by the normal washing process with the said antimicrobial composition was used as a test cloth. In addition, the cotton cloth which the washing process did not process was used as an untreated cloth.

(Yellow staphylococcus)

Using Staphylococcus aureus cultured according to JIS L1902, a Staphylococcus aureus mother liquor was prepared so that the nutrient medium was diluted 20-fold and the number of bacteria became 1 ± 0.3 × 10 ⁵ cells / ml.

0.1 ml of Staphylococcus aureus stock solution was inoculated in four places with respect to the test cloth (5 cm square), and it culture | cultivated for 18 hours in the 37 degreeC thermostat, and proliferated or bacteriostatic on the test cloth. Thereafter, bacteria were extracted from the test cloth using physiological saline for washing described in JIS L1902, and the extract was diluted 10-fold with physiological saline. The procedure of diluting the obtained dilution liquid 10 times again was repeated 4 times and 10 to 100000 times dilution liquid was obtained. In addition, with physiological saline for washing | cleaning, 8.5 g of sodium chlorides are extract | collected with 1000 ml of purified water, these are put into a fresco, and it fully melt | dissolves, and also polyoxyethylene sorbitan monooleate (Kanto) as a nonionic surfactant 2 g of "Polysolbeto 80, Tween 80" manufactured by a chemical company is added and dissolved, followed by high pressure steam sterilization (autoclave treatment).

100 μl was collected from each of these dilutions, loaded onto a standard agar medium (manufactured by Atekuto Co., Ltd.), and then uniformly coated with Conrad bar for 1 to 2 days in a constant temperature bath at 37 ° C., followed by colony water. By counting, the number of viable cells was obtained.

The untreated fabric was subjected to the same operation as the test fabric to measure the number of viable cells, and from these measured values, the antimicrobial activity value (A) was calculated by the following formula (i).

Antibacterial activity value = log (the number of living cells of untreated fabric / number of living cells of test cloth)... (i)

Subsequently, except for using the antimicrobial composition for evaluation comparison instead of the antimicrobial composition, the viable cell count was measured for the test cloth and the untreated cloth in the same manner as described above, and the antibacterial activity value (B) was calculated.

From the calculated antibacterial activity value (A) and antibacterial activity value (B), the difference (antibacterial activity value (A)-antibacterial activity value (B)) of antibacterial activity value was calculated | required, and the following evaluation criteria evaluated. The results are shown in Tables 5-7.

X: The difference of antibacterial activity value is less than 0.5 paragraph.

(Triangle | delta): The difference of antimicrobial activity value is 0.5 or more-less than 1.0 item.

(Circle): The difference of antibacterial activity value is 1.0 or more-less than 2.2.

(Double-circle): The difference of antibacterial activity value is 2.2 or more.

(E. coli)

Instead of Staphylococcus aureus, Escherichia coli cultured according to JIS L1902 was used, and the Escherichia coli mother liquor was prepared so that the nutrient medium was diluted 20-fold and the number of bacteria became 1 ± 0.3x10 ⁵ / ml.

The difference of the antibacterial activity value was calculated | required similarly to evaluation of the antimicrobial effect with respect to the above-mentioned Staphylococcus aureus, except that E. coli mother liquid was used instead of the staphylococcal mother liquid, and it evaluated by the same evaluation criteria. The results are shown in Tables 5-7.

TABLE 5

TABLE 6

TABLE 7

As shown in Tables 5-7, the antimicrobial composition obtained in Examples 51-93 has shown favorable antimicrobial effect not only to E. coli which is a gram negative bacterium, but also to Staphylococcus aureus which is a gram positive bacterium.

Particularly, Examples using the compounds (B1-2) to (B1-5) having 12 to 18 carbon atoms of the alkyl group (R) in the formula (1) as the component (B1) (Examples 52 to 55 and 65) -68, 80-83) or Example (Examples 58-62, 71-77, 86-92) using the long-chain alkylamine represented by Formula (II) as a component (B1) has high antibacterial effect. It is.

In addition, compared with the results of Examples 61 to 64, 74, 77, 78, 89, 92, and 93, the concentration of the component (A1) and the component (B1) in the antimicrobial composition contributes to the antibacterial effect against Staphylococcus aureus. okay.

The comparative examples 25, 31, 37 which did not mix | blend (B1) component were obtained the antibacterial effect to E. coli, but the antimicrobial effect to Staphylococcus aureus was low.

In Comparative Examples 26, 32, and 38, which did not contain the component (A1), antibacterial effects were not obtained, and antibacterial effects were not obtained together with Staphylococcus aureus and Escherichia coli.

In Comparative Examples 27, 33 and 39, since the imino diacetic acid which does not have an alkyl group at the terminal was used as compound (B1), the antibacterial effect to Staphylococcus aureus was low.

In Comparative Examples 28, 34 and 40, since the laurolysine which does not match Formula (I) and (II) was used as compound (B1), the antibacterial effect to Staphylococcus aureus was low.

In Comparative Examples 29, 35 and 41, since the lauroyl aspartic acid which does not correspond to Formula (I) and (II) was used as compound (B1), the antibacterial effect to Staphylococcus aureus was low.

In Comparative Examples 30, 36 and 42, since the lauroyl sarcosine which does not correspond to Formula (I) and (II) was used as compound (B1), the antibacterial effect to Staphylococcus aureus was low.

LIQUID CLEANER COMPOSITION

[Used raw materials]

As the starting materials, the reagents and compounds shown below were used.

As a component (A2), the reagent shown below was used.

(A2-1): silver sulfate; Huakwang Pure Pharmaceutical Co., Ltd .; Express

(A2-2): copper sulfate pentahydrate; Kanto Chemical Company; Express

(A2-3): zinc sulfate heptahydrate; Pure Chemistry, Limited

As the component (B2), the reagents and compounds shown below were used.

(B2-1): Polyethylenimine ("Epomin P-1000", the molecular weight 70,000 by the Japan Catalyst Corporation).

(B2-2): Alkyldiaminoethylglycine represented by Formula (6) (made by Sungwang Pure Chemical Co., Ltd., antibacterial antifungal research, 30 mass% solution) (Alkyl group (R) in Formula (6) is a C12 and 14 things center).

(B2-3): 2.5 g (19.5 mmol) of octylamine (made by Hwagwang Pure Chemical Co., Ltd.) which is an alkyl amine, 5.0 g (52.9 mmol) of monochloroacetic acid (made by Hwagwang Pure Chemical Co., Limited), 5 ml of water, ethanol (Kanto Chemical Co., Limited.) It was added to 32 ml of a mixed solution and stirred under reflux for 6 hours. During this reflux stirring, 7.8 ml of an aqueous sodium hydroxide solution (5.0 mol / L) prepared with sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to adjust the pH. The solution was then cooled to 4 ° C. and a precipitate formed. The resulting precipitate was washed with ethanol, filtered, dried under reduced pressure to recover a solid, and sodium octyliminodiacetic acid (carbon number of alkyl group (R): 8 in formula (1)) was obtained.

(B2-4): Except using 3.6 g (19.5 mmol) of lauryl amines (manufactured by Hwagwang Pure Chemical Co., Ltd., the highest grade) as an alkylamine, it operates by the same compounding as compound (B2-3), and shows the lauryl imide shown below. Sodium nodiacetic acid (C12 of alkyl group (R) in Formula (1)) was obtained.

(B2-5): Except using 4.2 g (19.5 mmol) of myristylamine (made by Tokyo Chemical Industry Co., Ltd.) as alkylamine, operation is carried out by the same compound as compound (B2-3), and the myristylim shown below. Sodium nodiacetic acid (carbon number of the alkyl group (R) in Formula (1): 14) was obtained.

(B2-6): Palmityl amine diacetic acid shown below is operated by operation similar to compound (B2-3), except that 4.7 g (19.5 mmol) of palmitylamine (made by Tokyo Chemical Industries, Ltd.) is used as an alkylamine. Sodium (C16 number of alkyl group (R) in formula (1)) was obtained.

(B2-7): Except using 5.3 g (19.5 mmol) of stearylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as the alkylamine, the procedure was carried out by the same formulation as that of the compound (B2-3) to show stearyliminodiacetic acid shown below. Sodium (carbon number of the alkyl group (R): 18) in Formula (1) was obtained.

(B2-8): According to eicosylamine (synthesis; Langmuir, 1994, No. 10, p. 1226) as an alkylamine, arachidic acid is reacted with thionyl chloride to give carboxylic acid chloride, which is ammonia. Was added to obtain eicosanamide, and this was reduced to lithium aluminum hydride to synthesize eicosylamine, except that 5.8 g (19.5 mmol) of Eicosylamine was used, and was operated in the same formulation as Compound (B2-3). Sodium silimino diacetate (carbon number of the alkyl group (R) in Formula (1): 20) was obtained.

(B2-9): 40.4 g (0.33 mol) of sodium monochloroacetate dissolved in 5 ml of lauryl amine (manufactured by Hwagwang Pure Chemical Co., Ltd., the highest grade), which is an alkyl amine, in 100 ml of ethanol and 50 ml of water therein. Was added to prepare a mixed liquid. After heating this mixed liquid to 60 degreeC, the sodium hydroxide aqueous solution (12.5 mol / L) was dripped, adjusting so that pH might not be 9 or less. After dropping, the mixture was allowed to react for 5 hours, and the precipitated salt was filtered off, washed, and the obtained liquid was removed under reduced pressure to obtain sodium laurylaminoacetate (carbon number of alkyl group: 12) represented by the formula (2).

(B2-10): Cocoalkyl propylene diamine (Lion arc irradiation agent, duomin) represented by Formula (3) (The alkyl group (R) in Formula (3) has a C12 and 14 thing centered.) Was used. .

(B2-11): 224 g (1.1 mol) of lauric acid (made by Tokyo Chemical Industry Co., Ltd., Limited) was added to four-necked Frasco, and nitrogen substitution was performed twice at 80 degreeC. Thereafter, 173 g (1.7 mol) of dimethylaminopropylamine (manufactured by Kanto Chemical Co., Ltd., rust express) was added dropwise to the mixture while heating up at 170 ° C and removing water to be replicated. Furthermore, it maintained at 170 degreeC-180 degreeC, and aged for 7 hours.

After aging, the reaction mixture was dried under reduced pressure to remove unreacted amine and water, thereby obtaining lauric acid dimethylaminopropylamide (acyl group having 12 carbon atoms) represented by formula (4).

(B2-12): 10.3 g (100 mmol) of diethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.0 g (10 mmol) of 1-yodododecane (manufactured by Hwagwang Pure Chemical Co., Ltd.) were stirred at 40 ° C for 5 hours. Then, 2.4 ml of sodium hydroxide aqueous solution (5.0 mol / L) was added, and also it stirred for a while. After allowing to cool, the extraction operation was performed five times with diethyl ether / water using a separating lot, and the organic layer was removed under reduced pressure. The obtained organic layer was subjected to a column (manufactured by Nakarai Tetsu Co., silica gel 60, spherical, neutral), eluent: chloroform (manufactured by Kanto Chemical Co., Ltd.) / Methanol (manufactured by Kanto Chemical Co., Limited) After the purification, the mixture was dried under a reduced pressure to recover a solid, thereby obtaining lauryl diethylenetriamine (carbon number of alkyl group: 12) represented by Formula (5).

(B2-13 (comparative product)): The imino diacetic acid (the Tokyo Chemical Industries, Ltd. express) represented by Formula (7) was used.

(B2-14 (comparative product)): Lauroyl lysine (Amihof Co., Ltd., Amihof) represented by Formula (8) was used (carbon number of acyl group: 12).

(B2-15 (comparative product)): Lauroyl aspartic acid (Asahi Kasei Chemical Co., Ltd., aminoformer) (carbon number of acyl group: 12) represented by Formula (9) was used.

(B2-16 (comparative product)): Lauroyl sarcosine (Soypon) made from natural fine chemicals, represented by formula (10) (carbon number of acyl group: 12) was used.

As the component (C), the reagents shown below were used.

<C-I: nonionic surfactant>

(C-1): 15 mol of ethylene oxide added to the natural alcohol CO-1214 by P & G.

(C-2): 15 mol of ethylene oxide added to the natural alcohol CO-1270 made by P & G.

(C-3): 12 mol of ethylene oxide added to the natural alcohol CO-1214 by P & G.

(C-4): 12 mol of ethylene oxide added to the natural alcohol CO-1270 made by P & G.

(C-5): 15 mol of ethylene oxide was added to Safol 23 alcohol manufactured by Sasol.

(C-6): 12 mol of ethylene oxide was added to Safol 23 alcohol manufactured by Sasol.

(C-7): Soaptanol 150, manufactured by Nippon Catalyst Co., Ltd.

(C-8): Soaptanol 90, manufactured by Nippon Catalyst Co., Ltd.

(C-9): 15 mol of ethylene oxide is added to the palm fatty acid methyl (lauric acid / myristic acid = 8/2) using the alkoxylation catalyst, a synthetic product.

(C-10): "Lutensol TO7" by BASF Corporation.

(C-11): "Lutensol XL70" by BASF Corporation.

(C-12): "Lutensol XA60" by BASF Corporation.

<C-II: Anionic Surfactant>

(C-13): Sodium linear alkylbenzenesulfonate (LAS) (made by Lion Corporation, alkyl group carbon chain length 10-14).

(C-14): Sodium secondary alkanesulfonate (SAS) (the "HOSTAPUR SAS30A" made by Cryogenic Japan Corporation).

(C-15): C12-13 alkyl ethoxy sulfate ester sodium (AES) [average EO chain length 2 mol, raw alcohol: Saporu 23 (manufactured by Sasol, C12 / C13 = 55% / 45%, linear rate 50%) )].

(C-16): C14-18 sodium alpha olefin sulfonate (AOS) (manufactured by Lion Co., Ltd., Liporan LB-840).

As another component, the reagent shown below was used.

Sodium benzoate: "Sodium benzoate" manufactured by Toa Synthetic Co., Ltd.

Trisodium citrate: manufactured by Miles Corporation (USA), `` Sodium Citrate.

95% ethanol: The product made by Nippon Alcohol Sales Co., Ltd., 95 degree of specific alcohol synthesis.

Paratoluenesulfonic acid: PTS acid, manufactured by Co., Ltd. fermentation industry.

Polyethylene glycol: A Lion company make "PEG # 1000".

Isothiazolone liquid: "Kayson CG (5-chloro-2-methyl-4- isothiazolin-3-one / 2-methyl-4- isothiazolin-3-one /" by the Rohm and House company Magnesium salt / water mixture).

Pharmaceutical: The pharmaceutical composition A of Table 11-18 of Unexamined-Japanese-Patent No. 2002-146399.

-Color: Gisa Kahwa Co., Ltd., "Green No. 3".

Sodium hydroxide: product made by academic procurement company.

Sulfuric acid: Made by Oriental Yeonsa Co., Ltd.

[Examples 1 to 52, Comparative Examples 1 to 4]

<Preparation of liquid detergent composition>

(C) component of the kind and compounding quantity (mass%) which show 6.0 mass% of 95% ethanol, 4.0 mass% of polyethyleneglycol, 2.0 mass% of paratoluenesulfonic acid, and Table 8-14 to a 500 ml beaker Was added and stirred sufficiently with a magnet steerer (MITAMURA KOGYO INC.).

Subsequently, a balance amount of water heated at 40 ° C. is added, and 0.5 mass% of sodium benzoate, 0.2 mass% of citric acid, 0.01 mass% of isothiazolone solution, 0.2 mass% of paint, and pigment 0.0001 mass% was added and stirred, and after dissolving these components, the component and the compounding quantity (mass%) of the components shown in Tables 8-14 were added, and it stirred again.

Then, the compounding quantity (solid amount: mass%) of (A2) component in a liquid detergent composition is the aqueous solution which melt | dissolved the water (A2) component of the kind shown in Tables 8-14 so that a density | concentration may be 10 mass%. After adding so that it may become the value shown to 8-14, it adjusted using sodium hydroxide and sulfuric acid as a pH adjuster so that pH of a solution might be 7, and the liquid detergent composition was obtained.

In addition, the balance amount of water is water which adjusted the compounding quantity so that the total amount of the liquid detergent composition which is a final product may be 100 mass%.

<Preparation of the liquid detergent composition for evaluation comparison>

A liquid detergent composition for evaluation comparison was prepared in the same manner as in Example 1 of the liquid detergent composition, except that the component (A2) and the component (B2) were not blended.

<Evaluation>

(Evaluation of Preservation Stability)

100 ml of the obtained liquid detergent composition was added to the transparent glass bottle (photosphere bottle PS-NO.11), and the lid was closed and sealed. After storing for 1 month in a thermostat bath at -5 ° C in this state, the appearance of the liquid was visually observed and evaluated according to the following criteria. The results are shown in Tables 8-14.

(Circle): A precipitate material is not recognized in the bottom of a bottle.

(Triangle | delta): Although the precipitate was recognized by the bottom of a bottle, precipitation was lost (dissolved) by heating to 40 degreeC.

X: Precipitate was recognized in the bottom of a bottle, and even if it heated to 40 degreeC, precipitation did not disappear.

(Evaluation of antibacterial effect)

In a fully automatic electric washing machine (JW-Z23A made in Haier company), approximately 100 g of cotton Mary Yasupo (made in Japan-made spinning company, "CK43202", a grain head shop) and cotton undershirt (BVD) Co., Ltd.) was adjusted so that the total of the total blood cell mass was about 800 g (injection ratio (washing water / the total blood cell mass: 15 times)). .

Next, 10 ml of a liquid detergent composition was added, and the washing | cleaning operation which performs washing | cleaning, rinsing, and dehydration is performed in a standard course sequentially. Regarding washing time, rinsing, dehydration, and the amount of water (set at low water level, about 12 L of water), the standard course setting of the washing machine was used without any adjustment.

After washing was finished, the extracted cotton maryyaspo was left to stand in a constant temperature and humidity chamber at 25 ° C and a humidity of 65% RH, and dried. After drying, it was cut into 5 × 5 cm, and this was used as a test cloth for evaluation of the antibacterial effect.

In addition, cotton maryaspo was used as an untreated cloth which did not process the washing operation.

(Evaluation method of antibacterial effect; Evaluation of antibacterial effect against Staphylococcus aureus)

The apparatus, water, etc. used for this evaluation were used after previously sterilizing by autoclave.

In this evaluation, Staphylococcus aureus was used as a bacterium.

Using Staphylococcus aureus cultured according to JIS L1902, a Staphylococcus aureus mother liquor was prepared so that the nutrient medium was diluted 20-fold and the number of bacteria became 1 ± 0.3 × 10 ⁵ cells / ml.

0.1 ml of the Staphylococcus aureus stock solution was inoculated in 4 places with respect to the test cloth (5x5 cm), and it culture | cultivated for 18 hours in the 37 degreeC thermostat, and proliferated or bacteriostatic on the test cloth. Thereafter, bacteria were extracted from the test cloth with an extract (physiological saline for washing described in JIS L1902), and the extract was diluted 10-fold with physiological saline. The procedure of diluting the obtained dilution liquid 10 times again was repeated 4 times, and 100000 times dilution liquid was obtained. In addition, with physiological saline solution for washing | cleaning, 8.5 g of sodium chlorides are extract | collected with 1000 ml of purified water, these are put into a fresco, and it fully melt | dissolves, and also polyoxyethylene sorbitan monooleate as a nonionic surfactant (Kanto 2 g of "Polysolbeto 80, Tween 80" manufactured by a chemical company is added and dissolved, followed by high pressure steam sterilization (autoclave treatment).

100 µl was collected from the obtained dilution liquid, placed on a standard agar medium (manufactured by Atekuto Co., Ltd.), and then uniformly coated with Conrad bar for 1 to 2 days in a constant temperature bath at 37 ° C. , Viable counts were obtained.

The untreated fabric was subjected to the same operation as that of the test fabric to measure the number of viable cells, and from these measured values, the antibacterial activity value (A) was calculated by the following formula (i).

Antibacterial activity value = log (the number of living cells of untreated fabric / number of living cells of test cloth)... (i)

Subsequently, except for using the liquid detergent composition for evaluation comparison instead of the liquid detergent composition, the viable cell count was measured for the test cloth and the untreated cloth, and the antibacterial activity value (B) was calculated.

From the calculated antibacterial activity value (A) and antibacterial activity value (B), the difference (antibacterial activity value (A)-antibacterial activity value (B)) of antibacterial activity value was calculated | required, and the following reference | standard evaluated. The results are shown in Tables 8-14.

(Double-circle): The difference of antibacterial activity value is 2.2 or more.

(Circle): The difference of antibacterial activity value is 1.0 or more-less than 2.2.

(Triangle | delta): The difference of antimicrobial activity value is 0.5 or more-less than 1.0 item.

X: The difference of antibacterial activity value is less than 0.5 term.

(Evaluation method of antibacterial effect; Evaluation of antibacterial effect on Escherichia coli)

E. coli (Escherichia coli) cultured according to JIS L1902 was used instead of Staphylococcus aureus, and E. coli mother liquor was prepared so that the nutrient medium was diluted 20-fold and the number of bacteria was 1 ± 0.3 × 10 ⁵ / ml. .

The difference of the antibacterial activity value was calculated | required similarly to evaluation of the antimicrobial effect with respect to the above-mentioned Staphylococcus aureus, except that E. coli mother liquid was used instead of the staphylococcal mother liquid, and it evaluated by the same evaluation criteria. The results are shown in Tables 8-14.

[Table 8]

TABLE 9

TABLE 10

TABLE 11

TABLE 12

TABLE 13

[Table 14]

As is apparent from Tables 8 to 14, the liquid detergent composition obtained in each Example was good in storage stability. In particular, the mass ratio {(B2) / (A2)} of (A2) component and (B2) component exists in the range of 1.75-10, and the mass ratio of (B2) component and (C-II) component {(C-II) Examples (1-48) of the liquid detergent composition whose / (B2)} is 1.05 or more were remarkably excellent in storage stability.

Moreover, the liquid detergent composition obtained by each Example has the outstanding antibacterial effect. Moreover, it also suggests that the liquid detergent composition obtained by each Example has the outstanding bactericidal effect.

On the other hand, since the imino diacetic acid which does not have an alkyl group at the terminal was used for the liquid detergent composition obtained by the comparative example 1, the antimicrobial effect to Staphylococcus aureus was not acquired especially. Moreover, the antimicrobial effect to Escherichia coli was also low compared with each Example.

In the liquid detergent composition obtained in the comparative example 2, since the laurolysine which does not match Formula (I) and (II) was used as (B2) component, the antibacterial effect to Staphylococcus aureus was not acquired especially. Moreover, the antimicrobial effect to Escherichia coli was also low compared with each Example.

Since the lauroyl aspartic acid which does not correspond with Formula (I) and (II) was used for the liquid detergent composition obtained by the comparative example 3 as a (B2) component, the antimicrobial effect to Staphylococcus aureus was not acquired especially. Moreover, the antimicrobial effect to Escherichia coli was also low compared with each Example.

In the liquid detergent composition obtained in the comparative example 4, since the lauroyl sarcosine which does not match Formula (I) and (II) was used as (B2) component, the antibacterial effect to Staphylococcus aureus was not acquired especially. Moreover, the antimicrobial effect to Escherichia coli was also low compared with each Example.

[Treatment Composition for Textile Products]

[Used raw materials]

As the starting materials, the reagents and compounds shown below were used.

As a component (A3), the reagent shown below was used.

(A3-1): silver sulfate; Hwagwang Pure Pharmaceuticals

(A3-2): copper sulfate pentahydrate; Kanto Chemical

(A3-3): zinc sulfate heptahydrate; Hwagwang Pure Pharmaceuticals

(A3-4): copper gluconate; Tokyo Hwaseong priest

(A3-5): copper chloride dihydrate; Kanto Chemical

(A3-6): zinc chloride; Kanto Chemical

(A3-7): zinc gluconate; Hwagwang Pure Pharmaceuticals

As the component (B3), reagents and compounds shown below were used.

(B3-1): Cocoalkyl propylene diamine (Lion arc irradiation agent, duomin) represented by Formula (3) (The alkyl group (R) in Formula (3) has a C12 and 14 thing centered.) Was used. .

Synthesis of (B3-2):

224 g (1.1 mol) of lauric acid (made by Tokyo Chemical Industry Co., Ltd.) was added to four-necked Frasco, and nitrogen substitution was performed twice at 80 degreeC. Thereafter, 173 g (1.7 mol) of dimethylaminopropylamine (manufactured by Kanto Chemical Co., Ltd., rust express) was added dropwise to the mixture while heating up at 170 ° C and removing water to be replicated. Furthermore, it maintained at 170 degreeC-180 degreeC, and aged for 7 hours.

After aging, the reaction mixture was dried under reduced pressure to remove unreacted amine and water, thereby obtaining lauric acid dimethylaminopropylamide (acyl group having 12 carbon atoms) represented by formula (4).

Synthesis of (B3-3):

10.3 g (100 mmol) of diethylene triamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.0 g (10 mmol) of 1-dododecane (manufactured by Hwagwang Pure Chemical Co., Ltd.) were stirred at 40 ° C for 5 hours. Then, 2.4 ml of sodium hydroxide aqueous solution (5.0 mol / L) was added, and also it stirred for a while. After allowing to cool, the extraction operation was performed five times with diethyl ether / water using a separating lot, and the organic layer was removed under reduced pressure. The obtained organic layer was subjected to a column (manufactured by Nakarai Tetsu Co., silica gel 60, spherical, neutral), eluent: chloroform (manufactured by Kanto Chemical Co., Ltd.) / Methanol (manufactured by Kanto Chemical Co., Limited) After the purification, the mixture was dried under a reduced pressure to recover a solid, thereby obtaining lauryl diethylenetriamine (carbon number of alkyl group: 12) represented by Formula (5).

(B3-4):

Alkyldiaminoethylglycine represented by Formula (6) (30% by mass solution for the antibacterial and antibacterial antifungal research), the alkyl group (R) in the formula (6) is 12 and 14 carbon atoms ).

Synthesis of (B3-5):

3.6g (19.5mmol) of laurylamine (the highest grade made by Hwagwang Pure Chemical Co., Ltd.) which is an alkylamine, 5.0g (52.9mmol) of monochloroacetic acid (made by Hwagwang Pure Chemical Co., Ltd., premium), 5 ml of water, ethanol (made by Kanto Chemical, To 32 ml of a mixed solution and stirred under reflux for 6 hours. During the reflux stirring, 7.8 ml of an aqueous sodium hydroxide solution (5.0 mol / L) prepared with sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to adjust the pH. The solution was then cooled to 4 ° C. and a precipitate formed. The resulting precipitate was washed with ethanol, filtered, dried under reduced pressure to recover a solid, and sodium lauryl imino diacetate (C12 of alkyl group (R): 12 in formula (11)) was obtained.

Synthesis of (B3-6):

As the alkyl amine, 4.2 g (19.5 mmol) of myristylamine (manufactured by Tokyo Chemical Industries, Ltd.) was used, and operation was carried out in the same formulation as Compound (B3-5) to give sodium myristyliminodiacetate (formula (11)). Carbon number of the alkyl group (R): 14) was obtained.

Synthesis of (B3-7):

Other than using 4.7 g (19.5 mmol) of palmitylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as the alkylamine, operation was carried out in the same manner as in compound (B3-5), and sodium palmityliminodiacetic acid (formula (11) was used as the alkyl group ( Carbon number of R) was obtained 16).

Synthesis of (B3-8):

Except for using 5.3 g (19.5 mmol) of stearylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as the alkylamine, the compound was operated in the same formulation as in Compound (B3-5), and sodium stearyliminodiacetic acid (In formula (11), the alkyl group ( Carbon number of R) was obtained 18).

Synthesis of (B3-9):

Other than using 2.5 g (19.5 mmol) of octyl amine (manufactured by Hwagwang Pure Chemical Co., Ltd.) as the alkylamine, the compound was operated in the same manner as in compound (B3-5), and sodium octyliminodiacetic acid (alkyl (Formula 11) Carbon number of R): 8) was obtained.

Synthesis of (B3-10):

According to eicosylamine (synthetic product; LDngmuir, 1994, 10, p. 1226) as an alkylamine, arachidic acid is reacted with thionyl chloride to make carboxylic acid chloride, and ammonia is added to eicosanamide. After obtaining, the resultant was reduced to lithium aluminum hydride to synthesize eicosylamine, and the resultant was operated in the same formulation as Compound (B3-5), except for using 5.8 g (19.5 mmol) of sodium eicosyliminodiacetic acid (Formula 11). ) And carbon number of the alkyl group (R): 20).

Synthesis of (B3-11):

55.5 g (0.3 mol) of laurylamine (manufactured by Hwagwang Pure Chemical Co., Ltd., an alkylamine), which is an alkylamine, was dissolved in 100 ml of ethanol, and 40.4 g (0.33 mol) of sodium monochloroacetate dissolved in 50 ml of water was added thereto to obtain a mixed solution. After heating this mixed liquid to 60 degreeC, the sodium hydroxide aqueous solution (12.5 mol / L) was dripped, adjusting so that pH might not be 9 or less. After dropping, the mixture was allowed to react for 5 hours, and the precipitated salt was filtered off, washed, and the obtained liquid was removed under reduced pressure to obtain sodium laurylaminoacetate (carbon number of alkyl group: 12) represented by the formula (2).

(B3-12 (comparative)):

Lauroyl aspartic acid (Asahi Kasei Chemical Co., Ltd., aminoformer) (carbon number of acyl group: 12) represented by Formula (9) was used.

(B3-13 (comparative)):

Lauroyl sarcosine (Natural Fine Chemicals Co., Ltd., Soyphon) represented by Formula (10) was used (C12 of acyl group).

(B3-14 (comparative)):

The imino diacetic acid (Tokyo Chemical Co., Ltd., express) represented by Formula (7) was used.

(B3-15 (comparative)):

Laurolysine (Ajinomoto Co., Amihof) represented by Formula (8) was used (C12 of acyl group).

As the component (D), the compounds and reagents shown below were used. In addition, (D-1)-(D-3) is corresponded to the mixture of the quaternized substance of the amine compound represented by said Formula (IV-4)-(IV-6), (D-4) is It corresponds to the mixture of the quaternized substance of the amine compound represented by said formula (IV-1).

(D-1): Long-chain hydrocarbon group containing quaternary ammonium methyl sulfate interrupted by ester group [monoester: diester: triester = 12: 54: 34]; synthetic.

(D-2): Mono / di / tri long-chain ester type quaternary ammonium methyl sulfate [monoester: diester: triester = 25: 55:20], carbon of the fatty acid residue which comprises a long chain ester group. Long chain mass ratio: C18 / C18F1 / C16 = 40/40/20]; Lion SoftEQ; Lion Arc Research.

(D-3): mono / di / tri long-chain ester type quaternary ammonium methyl sulfate; ARMOSOFT TEQ-E; AKZO NOBEL company.

(D-4): distearyl dimethylammonium chloride; Akado 2HT-75; Lion Arc Investigation.

(D-5): polymer of dimethylammonium chloride; Daidoru EC-004; Daedong Hwaseong Industrial Co., Ltd.

Synthesis of (D-1): Synthesis of methyl ester;

2.5 kg of palm fatty acid methyl (Lion, pastel M182, molecular weight 296) consisting of 75% by mass of methyl oleate, 16% by mass of methyl linoleate and 9% by mass of methyl stearate, and 0.9 g of commercially available stabilized nickel catalyst (0.1% by mass / fatty acid methyl) ) Was put into a 4L autoclave and nitrogen gas substitution was performed three times. Then, the rotation speed was adjusted to 800 rpm, and about 54 L of hydrogen gas was introduce | transduced at the temperature of 185 degreeC. After the introduced hydrogen was completely consumed, it was cooled, and hydrogenated methyl palm fatty acid was obtained except for the catalyst using a filtration aid.

The molecular weight of hydrogenated palm fatty acid methyl calculated | required by saponification was 297. In addition, the composition of the hydrogenated fatty acid methyl calculated | required by gas chromatography (GC) is 11 mass% of methyl stearate, 23 mass% of methyl ellidate (trans), 65 mass% of methyl oleate (cis), Methanol linoleate was 0 mass%, and the trans / cis ratio of unsaturated fatty acid methyl ester was 25/75 (mass ratio). In addition, the unsaturated alkyl group was measured by GB with the model and temperature conditions shown below.

A model: Hitachi FID gas black G-3000 (the column uses "TB-70" (0.25mm in internal diameter, length 30mm) made from GL Science).

Temperature conditions: The temperature of the temperature was raised from 150 ° C to 230 ° C at an elevated temperature of 10 ° C / min. The injector and the detector were set at 240 ° C. and the column pressure was 1.0 kgf / cm 2.

Synthesis | combination of an alkanolamine ester and its khakione;

489 g (1.65 mol) of hydrogenated palm fatty acid obtained above, 98 g (0.66 mol) of triethanolamine, 0.29 g of magnesium oxide, and 2.1 g of 14% sodium hydroxide aqueous solution were prepared using 2L of 4L with a stirrer, a cooler, a thermometer, and a nitrogen inlet tube. The mixture was placed in an old Frasco and subjected to nitrogen substitution, followed by continued flow of nitrogen at a flow rate of 0.52 L / min. It heated up to 190 degreeC by the speed | rate of 1.5 degreeC / min, and made it react for 6 hours. After confirming that unreacted methyl ester is 1 mass% or less, reaction was stopped. The fatty acid salt derived from a catalyst was filtered out from the obtained product, and the alkanolamine ester of the intermediate was obtained.

300 g of the obtained alkanolamine ester was placed in a four-necked fresco equipped with a thermometer, a dropping lot, and a cooler, and replaced with nitrogen. Subsequently, it heated at 85 degreeC and dripped 0.98 times mole of dimethyl sulfuric acid over 1 hour with respect to the alkanolamine ester. After completion of dropping, the temperature was maintained at 90 ° C and stirred for 1 hour. After the reaction was completed, the mixture was cooled while dropping ethanol to prepare an ethanol solution having a solid content of 85% by mass, and finally, peroxox CY-115 (manufactured by Lion Co., Ltd.) and dibutylhydroxytoluene (manufactured by Chuo Chemical Co., Ltd.) It added so that it might be set to a concentration of 100 ppm each, and obtained the compound (D-1).

Monoester ammonium salt: diester ammonium salt: triester ammonium salt is contained in the obtained compound (D-1) in 12:54:34 (mass ratio).

As optional components (F-1) to (F-4), the reagents shown in Tables 15 and 16 were used. In addition, the compounding quantity shown in Table 15, 16 is the quantity (mass%) in 100 mass% of treatment agent compositions.

TABLE 15

TABLE 16

Here, each chemical component which comprises the pharmaceutical composition (A) and pharmaceutical composition (B) of Tables 15 and 16 is shown in Table 17. In addition, the numerical value shown in Table 17 is the quantity (mass%) of each pharmaceutical component in 100 mass% of pharmaceutical composition (A) or pharmaceutical composition (B).

TABLE 17

[Examples 1 to 64, Comparative Examples 1 to 21]

<Preparation of treatment agent composition>

The treating agent composition was prepared by the following procedure using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (manufactured by Tojin Co., Ltd., Ajita SJ type).

First, the kind and compounding quantity (mass%) of (D) component shown in Tables 18-25, the ethanol in arbitrary components, and a pharmaceutical composition (A) or a pharmaceutical composition (B) are mixed and stirred, and it is oily. A mixture was obtained.

On the other hand, calcium chloride, ethylene glycol, and isothiazolone liquid in the arbitrary components of the kind shown in Tables 18-25 were dissolved in the balance purified water, and the water phase mixture was obtained. Here, the mass of the balance purified water corresponds to the remainder obtained by subtracting the total mass of the oily mixture, calcium chloride, and isothiazolone solution at 990 g.

Next, the oil-phase mixture heated to the melting point of the component (D) or higher was stored in a glass container and stirred, while the aqueous phase mixture heated to the melting point of the component (D) was added in two portions and stirred. Here, the split ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,000 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition.

In addition, the mixture which consists of (A3) component and (B3) component of the kind and compounding quantity (mass%, where (A3) component is a metal ion concentration (mass%) in the case of a component (A3) component) shown in Tables 18-25 is added, Adjust to pH2.5 with hydrochloric acid (reagent 1mol / L, Kanto Chemical Co., Ltd.) or sodium hydroxide (reagent 1mol / L, Kanto Chemical Co., Ltd.), if necessary, and add ion-exchanged water so that the total mass is 1,000 g. To obtain the desired treatment composition.

In addition, [B3] / [M3] in Tables 18-25 is the number-of-moles of [B3] of (B3) component, and [M3] of number-of-metals in (A3) component.

<Preparation of the treating agent composition for evaluation comparison>

Except not having mix | blended (A3) component and (B3) component, the processing agent composition for evaluation comparison was obtained by the procedure similar to Examples 1-64 and Comparative Examples 1-21. In addition, (F-1) was used as an arbitrary component.

<Evaluation>

(Evaluation of antibacterial effect 1: Staphylococcus aureus)

Diluent 10 [ml] / cotton dry matter No. 3 of the treating agent composition of an Example and a comparative example (for JIS dyeing firmness test based on JIS L0803) 1.5 [kg] was 20 [ml / kg] The treatment composition was diluted with ion exchanged water at 25 ° C. as far as possible. The cotton drier 3 was put into the dilution liquid of the obtained processing agent composition, and after stirring for 3 minutes, it dried in a sterile chamber and used as the test cloth. In addition, Cotton No. 3 that was not treated with the treatment agent composition was used as an untreated cloth.

After the test fabric was sterilized by the autoclave under the condition of a temperature of 121 ° C. and a pressure of 103 kPD, the test fabric was cut into about 18 mm square specimens, and 0.4 g (as test specimens of 10 to 10 sheets) were placed in a 30 ml vial bottle. The microfluidic solution was inoculated evenly in two places of the laminated | stacked cloth. As the bacterium, Staphylococcus aureus was used. In addition, adjustment of the bacterial liquid and the method of wash | cleaning a bacterium were based on the quantitative test method (uniform test method) of the antimicrobial test method (JIS L1902-2002) of a textile product.

After inoculating the bacterial solution, the cells were incubated at 37 ° C for 18 hours, and then grown or bacteriostatic on a test, and recovered, and the number of bacteria was measured.

The untreated cloth was subjected to the same operation as that of the test cloth, and the number of bacteria was measured, and bacteriostatic activity value (A) was calculated from the following formula (III) from these measured values.

Bacteriostatic activity value = Log (microbial count of untreated fabric / microbial count of test cloth) (Ⅲ)

Subsequently, except for using the treatment agent composition for evaluation comparison, the number of bacteria was measured for the test cloth and the untreated cloth except for the treatment agent composition for evaluation comparison, and the bacteriostatic activity value (A) was calculated.

From the calculated bacterium activity value (A) and bacteriostatic activity value (B), the difference between bacteriostatic activity values (difference of bacteriostatic activity value (A)-bacteriostatic activity value (B)}) was obtained, and evaluation of the antimicrobial effect against Staphylococcus aureus was performed by the following criteria. Was performed. The results are shown in Tables 18 to 25.

(Double-circle): The difference of bacteriostatic activity value is 1.5 or more.

(Circle): The difference of bacteriostatic activity value is 1.0 or more and less than 1.5.

(Triangle | delta): The difference of bacteriostatic activity value is 0.5 or more and less than 1.0.

X: The difference of bacteriostatic activity value is less than 0.5.

(Evaluation 2: Antibacterial Effect of Escherichia Coli)

Instead of Staphylococcus aureus, except for using Escherichia coli, the antimicrobial effect against Escherichia coli was evaluated in the same manner as in Evaluation 1 of the antimicrobial effect. The results are shown in Tables 18 to 25. In addition, evaluation criteria are the same as that of evaluation 1 of an antimicrobial effect.

(Evaluation of deodorization effect)

5 minutes of dehydration for commercial use men's undershirt (100% cotton) dehydration 15 minutes (cleaning agent use standard amount, bath ratio 30 times, 45 degrees Celsius) dehydration by commercial medical cleaner (product made by Lion company, top) using domestic two tank type washing machine After repeating the process of 2 cycles, the process of rinsing water 15 minutes-5 minutes of dehydration was repeated 5 times, and the naturally dried thing was made into the test cloth (test shirt for testing).

Another test undershirt for which the test undershirt obtained was half-cut and the semi-cut test undercut (A) uses any one treatment agent composition of an Example and a comparative example, and another semi-cut test undershirt (B) ), The treatment shown below was performed using the treatment composition for evaluation comparison.

In a household fully automatic washing machine (manufactured by Mitsubishi Electric Corporation, MAN-V8TP), 1.5 kg of semi-cut test undershirt (A) was added, and washed using 20 g of a commercial medical cleaner (Lion, Top) and 10 ml of the treatment composition. And finish treatment. Specifically, the home automatic washing machine is set to the standard course, the quantity of 28L, and the commercial detergent and the treatment composition are stored in the powder detergent inlet and the softener inlet respectively mounted in the washing machine, and are automatically added to the washing bath by the washing machine. Cleaning and finishing treatment were performed. Thereafter, the test undershirt A was taken out of the washing machine and dried for 20 hours under constant temperature and humidity conditions at 20 ° C and 45% RH.

The test undershirt B was also treated by the same method as the test undershirt A. FIG.

Subsequently, the test undershirt (A) and the test undershirt (B) after the treatment were sealed together to obtain an undershirt for evaluation of deodorization effect.

Thus, five pieces of evaluation undershirts obtained in this manner were worn by five men in their 20s and 30s for one day in August, and then five professional panelists each side of each undershirt for evaluation (test undershirt (A) A sensory pair comparison was performed about the smell of the side and the test shirt (B) side, and it scored by the following evaluation criteria. And the average value of the scoring was calculated | required and the deodorization effect was evaluated by the following criteria. The results are shown in Tables 18 to 25.

Evaluation standard ;

+2 point: Smell is surely good on the test undershirt (A) side compared with the test undershirt (B) side.

+1 point: Smell is slightly good on the test undershirt (A) side compared with the test undershirt (B) side.

0 points | pieces: The smell of test undershirt (A) side and test undershirt (B) side are about the same.

-1 point | piece: Smell is good on the test undershirt (B) side compared with the test undershirt (A) side.

-2 points | pieces: Smell is surely good on the test undershirt (B) side compared with the test undershirt (A) side.

Criteria ;

(Double-circle): An average score is 1.5 or more points.

(Circle): An average point is 1.0 or more and less than 1.5 points.

(Triangle | delta): An average point is 0.5 or more and less than 1.0 point.

X: An average point is less than 0.5 point.

TABLE 18

TABLE 19

TABLE 20

TABLE 21

Table 22

TABLE 23

TABLE 24

TABLE 25

As is apparent from Tables 18 to 25, the treatment agent composition obtained in each example was excellent in the antibacterial effect and the deodorizing effect. Moreover, it is also suggested that the treatment agent composition obtained in each Example has the outstanding bactericidal effect.

On the other hand, the treatment agent composition obtained by each comparative example is inferior to antibacterial effect (especially antimicrobial effect to Staphylococcus aureus) and deodorizing effect compared with each Example. Moreover, the comparative example 6, 7, 13, 14, 20, 21 which do not mix | blend the (D) component or (A3) component also has the antimicrobial effect with respect to E. coli compared with each Example.

(Industrial availability)

According to the bactericidal composition or the antimicrobial composition of the present invention, a bactericidal / antibacterial composition capable of exerting an excellent bactericidal / antibacterial effect against both gram positive bacteria and gram negative bacteria with a small amount of metal without the use of a peroxide is maintained. In addition, a liquid detergent composition capable of expressing an excellent bactericidal effect or an antibacterial effect, and a treatment agent composition for a textile product that can express an excellent bactericidal effect or an antibacterial effect and a deodorizing effect can be used.

Claims (5)

A mixture of the following (A1) component and (B1) component, or the complex formed from (A1) component and (B1) component is contained, The antibacterial and antimicrobial composition characterized by the above-mentioned.
(A1) Component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt.
(B1) component: The long-chain alkylamine compound selected from the group which consists of the following general formula (I) and (II), and / or an anion formed from this long-chain alkylamine compound.

[In formula (I), R <^1> represents a C8-C22 alkyl group. A ¹ represents a hydrogen atom or any of (CH ₂ ) _m -COOX ² . X ¹ and X ² may be the same or different and represent one kind selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]

[In formula (II), R <^2> represents either the C8-C22 alkyl group and the C8-C22 acyl group. Q is (NH- (CH ₂ ) _m ) and r represents 1 or 0. When r is 0, A <^2> , A <^3> may be same or different and is chosen from either a hydrogen atom or a methyl group. When r is 1, one of A ² and A ³ is a hydrogen atom, and the other is a hydrogen atom or any one of CH ₂ COOX ³ . X <^3> represents 1 type chosen from the group which consists of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.] The method of claim 1,
The R ¹ is an alkyl group having 12 to 18 carbon atoms. The method of claim 1,
R ² is either an alkyl group having 12 to 18 carbon atoms or an acyl group having 12 to 18 carbon atoms. The following (A2) component, (B2) component, and (C) component are contained, The liquid detergent composition characterized by the above-mentioned.
(A2) Component: Water-soluble zinc salt, water-soluble copper salt, or water-soluble silver salt.
(B2) Component: Polyethylenimine or an anion formed from the long-chain alkylamine compound and / or the said long-chain alkylamine compound (However, the said long-chain alkylamine compound is 1 from the group which consists of following General formula (I) and (II). More than one species).
(C) component: surfactant.

[In formula (I), R <^1> represents a C8-C22 alkyl group. A ¹ represents a hydrogen atom or any of (CH ₂ ) _m -COOX ² . X ¹ and X ² may be the same or different and represent one kind selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]

[In formula (II), R <^2> represents either the C8-C22 alkyl group and the C8-C22 acyl group. Q is (NH- (CH ₂ ) _m ) and r represents 1 or 0. When r is 0, A <^2> , A <^3> may be same or different and is chosen from either a hydrogen atom or a methyl group. When r is 1, one of A ² and A ³ is a hydrogen atom, and the other is a hydrogen atom or any one of CH ₂ COOX ³ . X <^3> represents 1 type chosen from the group which consists of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.] A mixture of the following (A3) component and (B3) component or the complex formed from (A3) component and (B3) component, and the following (D) component, The processing agent composition for textile products characterized by the above-mentioned.
(A3) Component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt.
(B3) Component: Polyethylenimine or an anion formed from a long chain alkylamine compound and / or the said long chain alkylamine compound (However, the said long chain alkylamine compound is 1 from the group which consists of following General formula (I) and (II). More than one species).
(D) component: A cationic surfactant or a cationic high molecular compound.

[In formula (I), R <^1> represents a C8-C22 alkyl group. A ¹ represents a hydrogen atom or any of (CH ₂ ) _m -COOX ² . X ¹ and X ² may be the same or different and represent one kind selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]

[In formula (II), R <^2> represents either the C8-C22 alkyl group and the C8-C22 acyl group. Q is (NH- (CH ₂ ) _m ) and r represents 1 or 0. When r is 0, A <^2> , A <^3> may be same or different and is chosen from either a hydrogen atom or a methyl group. When r is 1, one of A ² , is a hydrogen atom, and the other is a hydrogen atom, one of CH ₂ COOX ³ . X <^3> represents 1 type chosen from the group which consists of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1-3, and m represents either 1-3.]