JP2010184883A - Treating agent composition for fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating agent composition for a fiber product, exhibiting excellent disinfecting effects or antimicrobial effects, and deodorant effects. <P>SOLUTION: The treating agent composition for the fiber product contains the following component (A), and a mixture of the following components (B) and (C), or a complex formed out of the components (B) and (C); component (A): a cationic surfactant or a cationic polymer compound; component (B): a water-soluble silver salt, a water-soluble copper salt or a water-soluble zinc salt; and component (C): a polyethylene imine, or a long-chain alkyl amine compound and/or an anion produced from the long-chain alkylamine compound (with the proviso that the long-chain alkylamine compound is one or more kinds selected from the group consisting of general formula (I) and the like). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a treatment composition for textile products.

In recent years, due to the increase in cleanliness, as an effect when washing textile products, in addition to the detergency against dirt attached to the textile products, a deodorizing effect is required.
It is known that one of the causes of odor generation from a textile product after washing is that microorganisms decompose the remaining dirt such as sebum that is not completely removed by washing.

Therefore, a method of using a compound having antibacterial properties to cause it to act on bacteria such as microorganisms to obtain a deodorizing effect has been studied. For example, a softener composition containing an antibacterial compound has been proposed (for example, Patent Documents 1 and 2).
Antibacterial compounds include compounds containing metals such as silver, copper, and zinc that are excellent in sterilization and antibacterial properties, and inorganic metal compounds such as complexes of these metals with multidentate ligands (metal complexes) Often used.

JP 2001-192967 A Japanese Patent Laid-Open No. 2001-200473

  However, even if an antibacterial compound such as an inorganic metal compound is simply added, it is difficult to obtain a sufficient sterilizing effect or antibacterial effect or deodorizing effect, and further improvement of the sterilizing effect or antibacterial effect and deodorizing effect is required. ing.

  This invention is made | formed in view of the said situation, and it aims at providing the processing agent composition for textiles which can express the outstanding disinfection effect or antibacterial effect, and a deodorizing effect.

As a result of intensive studies, the present inventors have found that an inorganic metal compound is adsorbed on a textile after washing in order to obtain a deodorizing effect by utilizing the antibacterial effect of an antibacterial compound such as an inorganic metal compound by washing. Focused on the necessity. In order to adsorb the inorganic metal compound to the fiber product, it is effective to add the inorganic metal compound to a treatment agent such as a softening agent used at the time of rinsing. However, since most of the inorganic metal compounds in the treatment agent are easily washed away in the washing process, it is difficult for the inorganic metal compound to remain adsorbed on the textile after washing simply by adding the inorganic metal compound to the treatment agent. .
Therefore, as a result of examining the adsorption residual property of the inorganic metal compound, the present inventors have improved the adsorption residual property of the inorganic metal compound to the textile after washing by using a specific component together with the inorganic metal compound. The present inventors have found that this can be done and have completed the present invention.

That is, the textile composition treating agent composition of the present invention comprises the following component (A) and a mixture of the following component (B) and component (C) or a complex formed by component (B) and component (C): It is characterized by containing.
Component (A): a cationic surfactant or a cationic polymer compound.
(B) component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt.
Component (C): polyethyleneimine, or a long chain alkylamine compound and / or an anion generated from the long chain alkylamine compound (however, the long chain alkylamine compound is represented by the following general formulas (I) and (II)) One or more selected from the group consisting of:

In formula (I), R ¹ represents an alkyl group having 8 to 22 carbon atoms. A ¹ represents any ^one of a hydrogen atom and (CH ₂ ) _m —COOX ² . X ¹ and X ² may be the same or different and represent one 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 to 3, and m represents any of 1 to 3.

In formula (II), R ² represents either an alkyl group having 8 to 22 carbon atoms or an acyl group having 8 to 22 carbon atoms. Q is (NH— (CH ₂ ) _m ), and r represents 1 or 0. When r is 0, A ² and A ³ may be the same or different and are selected from a hydrogen atom and a methyl group. When r is 1, one of A ² and A ³ is a hydrogen atom, and the other is either a hydrogen atom or CH ₂ COOX ³ . X ³ represents one 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 to 3, and m represents any of 1 to 3.

  According to the treatment composition for textiles of the present invention, an excellent sterilizing effect or antibacterial effect and an odor preventing effect can be exhibited.

Hereinafter, the present invention will be described in detail.
The treatment composition for textiles of the present invention (hereinafter sometimes simply referred to as “treatment composition”) is a mixture of the following component (A) and the following component (B) and component (C): And a complex formed by the component (C).
Component (A): a cationic surfactant or a cationic polymer compound.
(B) component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt.
Component (C): polyethyleneimine, or a long-chain alkylamine compound and / or an anion generated from the long-chain alkylamine compound (provided that the long-chain alkylamine compound has the above general formulas (I) and (II)) One or more selected from the group consisting of:

[(A) component]
The component (A) is (A-1) a cationic surfactant or (A-2) a cationic polymer compound.
In order to improve the component (A) flexibility and antibacterial properties of the treating agent composition and the adsorption persistence of the component (B) on the textile product after washing (hereinafter sometimes referred to as “clothing”). Use.

(A-1) a 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 product thereof is preferable. The long-chain hydrocarbon group having 10 to 24 carbon atoms may be separated by an amide group, an ester group and / or an ether group (hereinafter referred to as “linking group”).

Examples of such cationic surfactants include amine compounds represented by the following general formulas (III-1) to (III-8), neutralized products of these amine compounds with organic acids or inorganic acids, and these amine compounds. And the quaternized product. Hereinafter, the amine compound represented by the following general formula (III-1) is referred to as compound (III-1). Other amine compounds are also described in the same manner.
These cationic surfactants can be used as one kind or a mixture of two or more kinds. When used as a mixture of two or more kinds, the treatment agent composition of the present invention is such that the mass ratio of the cationic surfactant having two or three long-chain hydrocarbon groups in 100% by mass of the mixture is 50% by mass or more. This is preferable because good flexibility can be imparted to the textile finished by using a product.
In addition, from the viewpoint of imparting biodegradability after being discarded into the natural environment after use, it contains an ester group in the middle of the long-chain hydrocarbon group (that is, the long-chain hydrocarbon group was divided by the ester group). ) Cationic surfactants are preferred, and for example, compounds (III-2) to (III-6) and compound (III-8) are preferred.
In addition, compound (III-2), compound (III-3), compound (III-7), and compound (III-8) have at least one long-chain hydrocarbon group of compound (III-1) as a linking group. A split amine compound.

In formula (III-1), R ³ and R ⁴ may be the same or different, and are a long-chain hydrocarbon group having 10 to 24 carbon atoms, preferably 12 to 20 carbon atoms. R ³ and R ⁴ may be saturated or unsaturated, and may be linear or branched.
R ³ and R ⁴ are preferably a linear alkyl group or an alkenyl group.

In formulas (III-2) to (III-8), R ^{5 to} R ⁷ may be the same or different and are residues obtained by removing a carboxyl group from a fatty acid having 10 to 20 carbon atoms and are saturated. Derived from any of fatty acids, unsaturated fatty acids, straight chain fatty acids and branched fatty acids. In the case of an unsaturated fatty acid, a cis isomer and a trans isomer exist, and the mass ratio is preferably cis isomer / trans isomer = 25/75 to 100/0, and more preferably 40/60 to 80/20.

  As fatty acids having 10 to 20 carbon atoms, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partially hydrogenated beef tallow fatty acid (iodine value) 10-60). Among these, stearic acid, palmitic acid, myristic acid, oleic acid and elaidic acid are combined in a predetermined amount, specifically, a saturated fatty acid / unsaturated fatty acid mass ratio of 95/5 to 50/50, cis / The mass ratio of the trans isomer is 40/60 to 80/20, the iodine value is 10 to 50, the ratio of the fatty acid having 18 carbon atoms is 80 mass% or more, the ratio of the fatty acid having 20 carbon atoms is 2 mass% or less, and the carbon number is 22 It is preferable to use a fatty acid composition adjusted so that the ratio of the fatty acid is 1% by mass or less.

The amine compound described above is preferably used as a neutralized product (amine salt) neutralized with an acid or a quaternized product quaternized with a quaternizing agent.
Examples of the acid used for neutralization include organic acids and inorganic acids, among which hydrochloric acid, sulfuric acid, and methyl sulfuric acid are preferable. In the neutralization step, a pre-neutralized tertiary amine compound may be dispersed in water, or the tertiary amine compound may be charged into an acid aqueous solution in liquid or solid form. Moreover, you may throw in a tertiary amine compound and an acid simultaneously.
Examples of the quaternizing agent used for quaternization include methyl chloride and dimethyl sulfate. A known method can be applied to the quaternization step.

Compound (III-2) and compound (III-3) can be synthesized, for example, by a condensation reaction between the above-described fatty acid composition or fatty acid methyl ester composition and methyldiethanolamine. At that time, from the viewpoint of improving the dispersion stability, the abundance ratio of the compound (III-2) to the compound (III-3) is 99 by mass ratio {compound (III-3) / compound (III-2)}. It is preferable to synthesize | combine so that it may become / 1-50 / 50.
Further, in order to obtain a quaternized product of the compound (III-2) or the compound (III-3), it is preferable to use methyl chloride because it has a low molecular weight and can be used in a small amount. At that time, from the viewpoint of improving the dispersion stability, the abundance ratio of the quaternized product of the compound (III-2) and the compound (III-3) is the mass ratio {the quaternized product of the compound (III-3) / compound. It is preferable to synthesize | combine so that it may become 99/1-50/50 with the quaternized material of (III-2).
In addition, when the compound (III-2) or the compound (III-3) is quaternized, generally an ester amine that is not quaternized remains. These mass ratios are preferably 99/1 to 70/30 in terms of mass ratio (quaternized / non-quaternized ester amine) from the viewpoint of hydrolytic stability of the ester group.

Compound (III-4) to Compound (III-6) can be synthesized, for example, by a condensation reaction between the above-described fatty acid composition or fatty acid methyl ester composition and triethanolamine. At that time, from the viewpoint of improving the dispersion stability, the abundance ratio of the compound (III-4) to the compound (III-6) is a mass ratio {[compound (III-5) + compound (III-6)] / Compound (III-4)} is preferably synthesized so as to be 99/1 to 50/50.
In order to obtain a quaternized product of compound (III-4) to compound (III-6), it is preferable to use dimethyl sulfate 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 product of the compound (III-4) to the compound (III-6) is the mass ratio {[quaternized product of the compound (III-5) + Compound (III-6) quaternized product] / Compound (III-4) quaternized product} is preferably synthesized so as to be 99/1 to 50/50.
In addition, when the compound (III-4) to the compound (III-6) are quaternized, esteramine that is generally not quaternized remains. These mass ratios are preferably 99/1 to 70/30 in terms of mass ratio (quaternized / non-quaternized ester amine) from the viewpoint of hydrolytic stability of the ester group.

Compound (III-7) and compound (III-8) can be synthesized by a condensation reaction between the above-described fatty acid composition and N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine. At that time, the abundance ratio of the compound (III-7) and the compound (III-8) is 99/1 to 50/50 in mass ratio {compound (III-8) / compound (III-7)}. It is preferable to synthesize. N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine is an adduct of N-methylethanolamine and acrylonitrile, “J. Org. Chem., VOL. 26 (1960) 3409”. It can be synthesized by a known method described in the above.
In order to obtain a quaternized compound (III-7) or compound (III-8), methyl chloride is preferably used. At that time, the abundance ratio of the quaternized product of the compound (III-7) and the compound (III-8) is the mass ratio {the quaternized product of the compound (III-8) / the quaternized product of the compound (III-7)}. It is preferable to synthesize | combine so that it may become 99/1-50/50.
In addition, when the compound (III-7) or the compound (III-8) is quaternized, generally an ester amine that is not quaternized remains. These mass ratios are preferably 99/1 to 70/30 in terms of mass ratio (quaternized / non-quaternized ester amine) from the viewpoint of hydrolytic stability of the ester group.

Among the above-mentioned amine compounds, the quaternized compound (III-4), the quaternized compound (III-5), and the quaternized compound (III-6) are particularly preferable as the cationic surfactant. . When synthesizing the compound (III-4) to the compound (III-6), from the viewpoint of imparting flexibility, the individual content ratio with respect to the total mass of the compound (III-4) is 5 to 98% by mass. The compound (III-5) is preferably synthesized in an amount of 1 to 60% by mass, and the compound (III-6) is preferably synthesized in an amount of 0.1 to 40% by mass. More preferably, the compound (III-4) is 10%. -55 mass%, compound (III-5) is 30-60 mass%, and compound (III-6) is 5-35 mass%.
Moreover, when synthesize | combining the quaternized compound of a compound (III-4)-a compound (III-6), from a viewpoint of providing a softness | flexibility, each content ratio with respect to these total mass is a compound (III-4). So that the quaternized product of compound (III-5) is 1 to 60% by mass, and the quaternized compound (III-6) is 0.1 to 40% by mass. It is preferable to synthesize, more preferably, the quaternized compound (III-4) is 10 to 55% by mass, the quaternized compound (III-5) is 30 to 60% by mass, and the compound (III-6). The quaternized product is 5 to 35% by mass.

  Commercially available cationic surfactants may be used. For example, “LION SOFTER EQ”, “ARCARD 2HT-75”, “ARCARD 210-85E”, “ARCARD T-800” manufactured by Lion Akzo; “ARMOSOF TEQ-E” manufactured by AKZO NOBEL may be used.

  1-40 mass% is preferable, as for the compounding quantity of the cationic surfactant in a processing agent composition, 3-25 mass% is preferable, and 8-20 mass% is especially preferable. When the blending amount of the cationic surfactant is 1% by mass or more, sufficient flexibility-imparting performance can be obtained, and antibacterial properties and adsorption persistence of the component (B) to be described later can be improved. On the other hand, if the amount of the cationic surfactant is 40% by mass or less, a composition having good stability can be obtained.

(A-2) a cationic polymer compound;
As the cationic polymer compound, those having a cationic property when dissolved in water can be used. For example, at least one cationic group selected from the group consisting of an amino group, an amine group, and a quaternary ammonium group is used. A water-soluble polymer compound having The cationic polymer compound can be used as one kind or a mixture of two or more kinds.
In the present invention, the cationic group refers to a monomer having a positively charged atom. The term “water-soluble” means that when 1 g of a target compound is added to 100 g of water at 25 ° C., the liquid is transparent without becoming cloudy.

The cationic polymer compound preferably has a degree of cationization of 0.1% or more, more preferably 0.1 to 35%, and particularly preferably 2.5 to 15%. If the degree of cationization is 0.1% or more, it is possible to further improve the adsorption residual property of the component (B) described later to clothing.
Here, the degree of cationization means that the polymer compound is a polymer of a cationic monomer, a copolymer of a cationic monomer and a nonionic monomer, or a part of a nonionic polymer modified or substituted with a cationic group. In the case of a thing (for example, cationized cellulose etc.), it is a value calculated by the following formula (i). Further, when the polymer 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, the value calculated by the following formula (ii) That is.
Cation degree (%) = S × T × 100 (i)
Cation degree (%) = S × (TU) × 100 (ii)
S: Atomic weight of a cationized atom (such as nitrogen) in the cationic group of the polymer compound.
T: The number of moles of the cationic group contained in 1 g of the polymer compound.
U: Number of moles of anionic group contained in 1 g of the polymer compound (an anionic group means a carboxyl group, a sulfonic acid group, etc. contained in the monomer unit in the polymer chain. Specifically, Such as carboxylic acid in acrylic acid, but does not include counter ion of cationic group.)

  The cationic polymer compound preferably has a mass average molecular weight of 1,000 to 5,000,000 as measured by gel permeation chromatography using polyethylene glycol as a standard substance, and 3,000 to 1 1,000,000 is more preferable, and 5,000 to 500,000 is particularly preferable. If a 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 becomes favorable.

  Commercially available products may be used as the cationic polymer compound. For example, “MERQUAT100” manufactured by NALCO, “ADEKA KACHIOACE PD-50” manufactured by ADEKA, “DAIDOL EC-004”, “DAIDOL HEC”, “DAIDOL EC” manufactured by Daido Kasei Kogyo Co., etc. A dimethyldiallylammonium chloride / acrylic acid copolymer such as “MERQUAT550 JL5” manufactured by NALCO; a dimethyldiallylammonium chloride / acrylic acid copolymer such as “MERQUAT280” manufactured by NALCO; Cationized cellulose such as “KGP”; imidazolinium chloride / vinylpyrrolidone copolymer such as “LUVIQUAT-FC905” manufactured by B.A.S.F; “LUGALVAN-G15000” manufactured by B.A.S.F. Polyethylene etc. Renimine; Cationized polyvinyl alcohol such as “Poval CM318” manufactured by Kuraray Co., Ltd .; Natural polymer derivative having amino group such as chitosan; Copolymerization with vinyl monomer having hydrophilic group to which diethylaminomethacrylate, ethylene oxide or the like is added Examples of the polymer compound include, but are not limited to, this example as long as the polymer compound is cationic when dissolved in water.

  Among these cationic polymer compounds, when the cationic polymer compound alone is adsorbed to clothing, the rigidity imparted to the clothing can be reduced, and dimethyl diallylammonium chloride is used from the viewpoint of suppressing the hindering of the texture such as flexibility. The polymer is preferred. A polymer of dimethyldiallylammonium chloride is obtained by polymerizing a methyldiallylammonium salt represented by the following general formula (IV).

In the formula (IV), Xa ⁻ represents an arbitrary negative ion such as a chloride ion or a bromide ion.
The structural unit of the polymer of dimethyldiallylammonium chloride is usually represented by the following general formula (V) or (VI). The polymer of dimethyldiallylammonium chloride may contain a structural unit represented by the following general formula (V) or a structural unit represented by the following general formula (VI) alone, or these structural units. Both units may be included.

In the formulas (V) and (VI), Xa ⁻ represents an arbitrary negative ion such as a chloride ion or a bromide ion. Moreover, a and b are average degree of polymerization, 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 polymer compound in a processing agent composition, 3-25 mass% is preferable, and 8-20 mass% is especially preferable. When the blending amount of the cationic polymer compound is 1% by mass or more, sufficient flexibility-imparting performance can be obtained, and antibacterial properties and adsorption persistence of the component (B) to be described later can be improved. On the other hand, if the amount of the cationic polymer compound is 40% by mass or less, a composition having good stability can be obtained.

[Component (B)]
The component (B) is (B-1) a water-soluble silver salt, (B-2) a water-soluble copper salt, or (B-3) a water-soluble zinc salt.
The component (B) is used for imparting a sterilizing effect or an antibacterial effect as well as a deodorizing effect to the treatment composition.
The sterilization effect indicates an effect of reducing the number of bacteria present in the cleaning liquid or on the surface of the object to be cleaned, and the antibacterial effect indicates an effect of suppressing the growth of bacteria attached to the surface of the object to be cleaned.

(B-1) Water-soluble silver salt;
The water-soluble silver salt is not particularly limited as long as it is soluble in water and releases silver ions at that time, but it is 0.5 g or more soluble in 100 mL of water at 20 ° C. Salts are preferred. Examples of such water-soluble silver salts include silver sulfate, silver nitrate, silver acetate, silver fluoride, and silver perchlorate. Silver sulfate is preferred from the standpoint of handleability and odor.
Although the compounding quantity of the water-soluble silver salt in a processing agent composition is not specifically limited, 0.03-10 mass% is preferable, 0.1-5 mass% is more preferable, 0.16-3 mass% is Particularly preferred. If the compounding amount of the water-soluble silver salt is 0.03% by mass or more, a sufficient sterilizing effect or antibacterial effect and deodorizing effect can be obtained. When the amount of the water-soluble silver salt is less than 0.03% by mass, the antibacterial effect on Escherichia coli tends to be reduced. On the other hand, if the amount of the water-soluble silver salt is 10% by mass or less, a composition having good stability can be obtained. Even if the blending amount of the water-soluble silver salt exceeds 10% by mass, it is difficult to obtain a sterilization and antibacterial improvement effect corresponding to the amount, and this is economically disadvantageous.

(B-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 it dissolves at least 0.5 g per 100 mL of water at 20 ° C. Salts are preferred. Examples of such water-soluble copper salts include copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, copper chloride ammonium, copper gluconate, copper tartrate, copper perchlorate and the like. However, copper sulfate, copper chloride, and copper gluconate are preferable in terms of handling property, cost, raw material supply property, etc., and copper sulfate is particularly preferable.
Although the compounding quantity of the water-soluble copper salt in a processing agent composition is not specifically limited, 0.07-10 mass% is preferable, 0.2-5 mass% is more preferable, 0.4-3 mass% is Particularly preferred. If the compounding amount of the water-soluble copper salt is 0.07% by mass or more, a sufficient sterilizing effect or antibacterial effect and deodorizing effect can be obtained. When the blending amount of the water-soluble copper salt is less than 0.07% by mass, the antibacterial effect particularly against E. coli tends to be lowered. On the other hand, if the amount of the water-soluble copper salt is 10% by mass or less, a composition having good stability can be obtained. Even if the blending amount of the water-soluble copper salt exceeds 10% by mass, it is difficult to obtain a sterilization and antibacterial improvement effect corresponding to the amount, which is economically disadvantageous.

(B-3) a 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 it dissolves 0.5 g or more in 100 mL of water at 20 ° C. Salts are preferred. Examples of such water-soluble zinc salts include zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, zinc chloride ammonium, zinc gluconate, zinc tartrate, zinc perchlorate and the like. However, zinc sulfate, zinc chloride, and zinc gluconate are preferable from the viewpoints of handleability, cost, raw material supply property, etc., and zinc sulfate is particularly preferable.
Although the compounding quantity of the water-soluble zinc salt in a processing agent composition is not specifically limited, 0.13-10 mass% is preferable, 0.4-5 mass% is more preferable, 0.6-3 mass% is Particularly preferred. If the blending amount of the water-soluble zinc salt is 0.13% by mass or more, a sufficient sterilizing effect or antibacterial effect and deodorizing effect can be obtained. When the blending amount of the water-soluble zinc salt is less than 0.13% by mass, the antibacterial effect particularly on E. coli tends to be lowered. On the other hand, if the amount of the water-soluble zinc salt is 10% by mass or less, a composition having good stability can be obtained. Even if the blending amount of the water-soluble zinc salt exceeds 10% by mass, it is difficult to obtain a sterilization and antibacterial improvement effect commensurate with it, which is economically disadvantageous.

[Component (C)]
The component (C) is (C-1) polyethyleneimine, or (C-2) a long-chain alkylamine compound and / or an anion generated from the long-chain alkylamine compound.
(C) component is used in order to improve the adsorption residual property of (B) component to the clothes after washing. By using together with the component (B) described above, a sterilizing effect or antibacterial effect on both S. aureus and E. coli can be obtained.

(C-1) polyethyleneimine;
As the polyethyleneimine, commercially available products can be used, and examples thereof include “Epomin (P-1000), molecular weight 70000” manufactured by Nippon Shokubai Co., Ltd.
0.1-20 mass% is preferable with respect to the total mass of a processing agent composition, as for the compounding quantity of a polyethyleneimine, More preferably, it is 0.2-17 mass%, Especially preferably, 0.4-14 mass %. If the blending amount of polyethyleneimine is 0.1% by mass or more, sterilization or antibacterial properties as well as deodorization can be imparted to the clothes after washing. When the amount of polyethyleneimine is less than 0.1% by mass, the antibacterial effect particularly against S. aureus tends to decrease. On the other hand, even if blending more than 20% by mass of polyethyleneimine, it is difficult to obtain an effect of improving sterilization and antibacterial properties, which is economically disadvantageous.

(C-2) a long-chain alkylamine compound and / or an anion generated from 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 the general formula (I), R ¹ is an alkyl group having 8 to 22 carbon atoms, and more preferably 12 to 18 carbon atoms. If the number of carbon atoms in the alkyl group is 8 or more, the alkyl group tends to be adsorbed to the bacteria, and the metal ions tend to come into contact with the bacteria. 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 sterilization ability and antibacterial ability are maintained. In particular, when R ¹ is an alkyl group having 12 to 18 carbon atoms, the balance between hydrophobicity (that is, adsorptivity to bacteria) and hydrophilicity (that is, solubility in water) becomes better, and therefore, more It can effectively exhibit sterilizing ability and antibacterial ability.
A ¹ is any ^one of a hydrogen atom and (CH ₂ ) _m —COOX ² .
X ¹ and X ² may be the same or different and are one 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, examples of the alkaline earth metal atom include magnesium and calcium, and examples of the cationic ammonium group include trimethylammonium and tetramethylammonium.
n is any one of 1 to 3, and if n is within this range, it is considered that the complex formed by the component (B) and the component (C) is stably present in the treatment agent composition. Further, m is any one of 1 to 3, and if m is within this range, it is considered that the complex is more stably present in the treatment agent composition.

  The general formula (I) can be represented by the following general formula (I-1) and general formula (I-2). The symbols in each formula are the same as those in the general formula (I).

Specific examples represented by the general formula (I-1) include sodium octyliminodiacetate, sodium lauryliminodiacetate, sodium myristyliminodiacetate, sodium palmitateiminodiacetate and the like, octyliminodiacetate Examples thereof include alkyliminodipropionates such as sodium propionate, sodium lauryliminodipropionate, sodium myristyliminodipropionate, sodium palmityliminodipropionate.
Specific examples represented by the general formula (I-2) include sodium laurylaminoacetate, sodium myristylaminoacetate, sodium palmitylaminoacetate, sodium laurylaminopropionate, sodium myristylaminopropionate, sodium palmitylaminopropionate and the like. Is mentioned.
Of these, alkyliminodiacetate is preferred in view of the stability of the complex.

In the general formula (II), R ² is any one of an alkyl group having 8 to 22 carbon atoms and an acyl group having 8 to 22 carbon atoms. In addition, in both an alkyl group and an acyl group, the number of carbon atoms is more preferably 12-18. If the alkyl group or acyl group has 8 or more carbon atoms, the alkyl group is adsorbed to the bacterium, and the metal ions tend to come into contact with the bacterium. On the other hand, when the number of carbon atoms in the alkyl group or acyl group is 22 or less, there is no problem of solubility in water, and sterilization ability and antibacterial ability are maintained. In particular, when R ² is any one of an alkyl group having 12 to 18 carbon atoms and an acyl group having 12 to 18 carbon atoms, it is hydrophobic (that is, adsorptive to bacteria) and hydrophilic (that is, dissolved in water). Therefore, the sterilization ability and 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 come into contact with bacteria.
When r is 0 (single bond), A ² and A ³ may be the same or different and are selected from a hydrogen atom and 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 either a hydrogen atom or CH ₂ COOX ³ . At this time, X ³ is one selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. Specific examples of the alkali metal atom, alkaline earth metal atom and cationic ammonium include the same as those in the general formula (I).
n is any one of 1 to 3, and if n is within this range, it is considered that the complex is stably present in the treatment agent composition.
m is any one of 1 to 3, and if m is within this range, the complex is considered to exist more stably in the treatment agent composition.

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

Specific examples of the general formula (II-1) include cocoalkylpropylenediamine, beef tallow alkylpropylenediamine, laurylethylenediamine, myristylethylenediamine, palmitylethylenediamine, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmiticin. And acid dimethylaminopropylamide.
Specific examples of the general formula (II-2) include lauryl diethylene triamine, myristyl diethylene triamine, palmityl diethylene triamine, lauryl dipropylene triamine, myristyl dipropylene triamine, palmityl dipropylene triamine, alkyldiaminoethyl glycine, and the like.
Of these, alkyldiaminoethylglycine is preferred in view of the stability of the complex.

The long-chain alkylamine compound represented by the general formula (II) and the long-chain alkylamine compound represented by the general formula (II) are more preferable than the long-chain alkylamine compound represented by the general formula (II). There is a tendency that the disinfection effect or the antibacterial effect is large. This is considered to be due to the following reason.
In the long-chain alkylamine compound represented by the general formula (I), the charge of the metal ion is reduced or canceled by the carboxyl group of the terminal group. On the other hand, the long-chain alkylamine compound represented by the general formula (II) maintains the charge of the metal ion as it is because the amino group interacts with the metal ion. It is thought to show.
Moreover, since the long-chain alkylamine compound represented by the general formula (II) has a long alkyl group or acyl group having 8 to 22 carbon atoms, it tends to be adsorbed particularly to Escherichia coli. As a result, the metal ion derived from the component (B) that forms a complex with the component (C) can be contacted with bacteria without distinction between Escherichia coli and Staphylococcus aureus. More excellent sterilization effect or antibacterial effect can be exhibited against both bacteria.

  The compounding amount of the long-chain alkylamine compound and / or the anion generated from the long-chain alkylamine compound (hereinafter sometimes referred to as “(C-2) component”) is the total mass of the treating agent composition. The content is preferably 0.1 to 20% by mass, more preferably 0.2 to 17% by mass, and particularly preferably 0.4 to 14% by mass. (C-2) If the compounding quantity of a component is 0.1 mass% or more, it can provide sterilization property or antibacterial property, and deodorizing property to the clothes after washing. When the blending amount of the component (C-2) is less than 0.1% by mass, the antibacterial effect particularly against S. aureus tends to decrease. On the other hand, even if it contains more than 20 mass% of (C-2) component, the improvement effect of disinfection and antibacterial property corresponding to it is difficult to be obtained, and it becomes economically disadvantageous.

  Moreover, the compounding quantity of (C) component in a processing agent composition is the molar ratio [C] of the number-of-moles [C] of (C) component, and the number-of-moles [M] of the metal ion in (B) component. / [M] is preferable. At this time, based on the number of moles [M] of metal ions in the component (B) to be blended, [C] / [M] is preferably 0.1 to 50, and preferably 0.15 to 45. More preferably, it is especially preferable in it being 0.2-40. If the blending amount of the component (C) based on the number of moles [M] of metal ions in the component (B) is within the above range, the sterilization performance or antibacterial performance is significantly improved, and the component (B) A complex stable with the component (A) can be formed in the treating agent composition. In addition, a composition having good stability can be obtained.

In the present invention, the component (B) and the component (C) described above may be individually mixed to prepare a treatment agent composition, or may be formed of the component (B) and the component (C). A treating agent composition may be prepared by blending in the form of a complex.
Moreover, although mentioned later in detail, when using the processing agent composition of this invention as a liquid composition, it is thought that (B) component and (C) component have formed the complex in processing agent composition. It is done.
In this way, if the component (B) and the component (C) are blended in the form of a complex, or if the component (B) and the component (C) form a complex in the treating agent composition, the component (C) Depending on the component, the adsorptivity of the metal ions derived from the component (B) to clothing and fungi can be improved. Therefore, a more excellent sterilizing effect or antibacterial effect as well as a deodorizing effect can be exhibited with a small amount of metal.

  As described above, the combined use of the component (B) and the component (C) provides a sterilization effect or antibacterial effect against both S. aureus and E. coli. Although it does not restrict | limit especially as a combination of (B) component and (C) component, In consideration of storage stability, such as discoloration of a processing agent composition, as a (B) component, zinc sulfate or zinc chloride, and (C) component A combination with alkyldiaminoethylglycidin is preferred.

[Other ingredients]
In the treatment agent composition of the present invention, components usually used in treatment agents such as a softening agent can be blended as necessary within a range not impairing the effects of the present invention.
Examples of other components include those shown below.

(Silicone compound)
The treatment agent composition of the present invention may contain a silicone compound for the purpose of improving slipperiness. The silicone compound is not particularly limited as long as it can provide smoothness when adsorbed on clothing. For example, dimethyl silicone, polyether-modified silicone, methylphenyl silicone, alkyl-modified silicone, higher fatty acid-modified silicone, methyl Examples include hydrogen silicone, fluorine-modified silicone, epoxy-modified silicone, carboxy-modified silicone, polyglycerol-modified silicone, carbinol-modified silicone, and amino-modified silicone. These silicone compounds can be used as one kind or a mixture of two or more kinds.
The molecular structure of the silicone compound may be linear, branched or cross-linked. The modified silicone compound may be modified with one kind of organic functional group, or may be modified with two or more kinds of organic functional groups.
Kinematic viscosity at 25 ° C. of the silicone compounds is preferably from 10~100,000,000mm ² / s, and more preferably 1,000~100,000mm ² / s. When the kinematic viscosity is in such a range, the ease of blending and the slipperiness of the garment treated with the treating agent composition of the present invention are improved.

The silicone compound can be used as an oil or as an emulsion dispersed by any emulsifier. Furthermore, it is preferable to be nonionic from the viewpoint of high effect of adsorbing on clothes and enhancing flexibility and smoothness. More preferable examples include dimethyl silicone, carbinol-modified silicone, polyglycerol-modified silicone, and epoxy-modified silicone. And polyether-modified silicone.
Among these, particularly preferable silicone compounds include polyether-modified silicone and dimethyl silicone from the viewpoint of imparting flexibility. These silicone compounds have less flexibility and better flexibility than low molecular weight dimethyl silicones that do not have a polyether group.
Preferred polyether-modified silicones include copolymers of alkyl (C1 to C3) siloxane and polyoxyalkylene (preferably having 2 to 5 carbon atoms of an alkylene group). Among these, a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, random or block copolymer of polyoxyethylene and polyoxypropylene, etc.) is preferable.

  Specific examples of the polyether-modified silicone oil include “SH3772M”, “SH3775M”, “SH3748”, “SH3749”, “SF8410”, “SF8416”, “SH8700”, “SH200C” manufactured by Toray Dow Corning. -5000CS "," 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-F1-0 9-01 "," 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 ”; Shin-Etsu Chemical “KF352A”, “KF6008”, “KF615A”, “KF6016”, “KF6017” manufactured by GE Toshiba Silicone, Inc., and “TSF4450”, “TSF4452”, and the like. These polyether-modified silicone oils can be used as one kind or a mixture of two or more kinds.

  The compounding amount of the silicone compound in the treatment agent composition is not particularly limited, but is preferably 0.05 to 20% by mass, more preferably 0.2 to 10% by mass, and 0.5 to 5% by mass. Is particularly preferred.

(water)
The treatment agent composition of the present invention is preferably an aqueous composition, and as water that can be used, any of tap water, ion-exchanged water, pure water, distilled water, etc. can be used. Water from which hardness components such as calcium and magnesium and heavy metals such as iron are removed is preferable, and ion-exchanged water is most preferable in consideration of cost.

(Water-soluble solvent)
The water-soluble solvent is 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 (VII) A solvent can be contained.
^{_{R 8 -O- (C 2 H 4}} O) c - (C 3 H 8 O) d -H ··· (VII)

In Formula (VII), R ⁸ is an alkyl group or alkenyl group having 1 to ⁸ carbon atoms. In addition, in an alkyl group and an alkenyl group, it is preferable in carbon number being 2-6.
c and d are average addition mole numbers, 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 the water-soluble solvent.
0.1-30 mass% is preferable and the compounding quantity of the water-soluble solvent in a processing agent composition has more preferable 2-20 mass%.

(Fragrance)
In this invention, a fragrance | flavor can be added for the fragrance of a processing agent composition. Although it does not specifically limit as a fragrance | flavor, The list | wrist of the fragrance | flavor raw material which can be used is various literature, for example, "Perfume and Flavor Chemicals", Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994), “Synthetic fragrance chemistry and product knowledge”, Motoichi Into, Chemical Industry Daily (1996), “Perfume and Flavor Materials of Natural Origin”, Stephen Arctander, Allred Pub. Co. (1994), "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989), "Performer Material Performance V.3.3", Bolens Aroma Chemical Information Service (1996), "Flower oils". , Danute Lajaujis Anonis, Allured Pub. Co. (1993).

(Antioxidant)
In the present invention, an antioxidant can be added to improve the aroma stability and color tone stability of the treatment composition. As the antioxidant, generally known natural antioxidants and synthetic antioxidants can be used. Specifically, a mixture of ascorbic acid, ascorbyl palmitate, propyl gallate, BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, hydroquinone, tertiary butylhydroquinone Natural tocopherol compounds, long chain esters of gallic acid (8 to 22 carbon atoms) such as dodecyl gallate, irganox compounds available from Ciba Specialty Chemicals, citric acid and / or isopropyl citrate, 4, 5-Dihydroxy-m-benzenesulfonic acid / sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoid, furans, amino acids and the like.
Among these, BHT (butylated hydroxytoluene), methoxyphenol, tocopherol compounds, and the like are preferable from the viewpoint of storage stability of the treatment agent composition.
As for the compounding quantity of antioxidant in a processing agent composition, 0.01-1 mass% is preferable.

(Preservative)
Preservatives are mainly used to maintain antiseptic properties during long-term storage. Examples of the inhibitor include isothiazolone organic sulfur compounds, benzisothiazolone 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, 2-benzyl-3-isothiazolone, 2-phenyl-3 -Isothiazolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazoline-3-one, and mixtures thereof. Among these, a water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one is preferable, and more preferably about 77% by mass of 5-chloro A water-soluble mixture of 2-methyl-4-isothiazolin-3-one and about 23% by weight 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 an analogous compound, and these can be used by arbitrary mixing ratios. Among these, 1,2-benzisothiazolin-3-one is particularly preferable.
Examples of benzoic acids include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate, and the like. it can.
As for the compounding quantity of the preservative in a processing agent composition, 0.0001-1 mass% is preferable.

(dye)
The addition of the dye is optional, and even if added, it is not particularly limited. In the case of adding a dye, a water-soluble dye is preferable from the viewpoint of ease of addition, and among these, one or more water-soluble dyes selected from an acid dye and a direct dye are preferable.
Specific examples of the dyes that can be added include, for example, the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, issued July 20, 1969, Maruzen Co., Ltd.), Dye Note 22nd Edition (Color Dye Co., Ltd.), Legal Dye Handbook (Edited by the Japan Cosmetic Industry Association, published on November 28, 1988, Yakuho Nippo Co., Ltd.).
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, it can prevent that the color colored by the processing agent composition becomes very thin, and while it can make the coloring effect sufficient, it is colored by the processing agent composition. Can prevent the color from becoming too dark.

(Antifoaming agent, other additives)
In the treatment agent composition of the present invention, antifoaming agents and other additives that are used in treatment agents such as ordinary household softeners can be used as long as the effects of the present invention are not hindered. . Examples of antifoaming agents and other additives include water-soluble salts such as sodium chloride, ammonium chloride, calcium chloride, magnesium chloride, potassium chloride, and sodium citrate, oils such as liquid paraffin and higher alcohol, urea, hydrocarbons, non- Examples thereof include an ionic cellulose derivative, an ultraviolet absorber, a fluorescent brightener, and a pH adjuster described later.

[Physical properties of treatment composition]
(PH of treatment agent composition)
The pH of the treatment agent composition of the present invention is not particularly limited, but the pH at 25 ° C. is 1 to 6 for the purpose of suppressing hydrolysis of the ester group contained in the molecule of the component (A) that accompanies storage days. It is preferable to adjust to a range, 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, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethane diphosphonic acid, phytic acid, ethylenediaminetetraacetic acid, PH adjustment of short chain amine compounds such as triethanolamine, diethanolamine, dimethylamine, N-methylethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, and alkali metal silicates An agent can be used.

(Viscosity of treatment composition)
The treating agent composition of the present invention preferably has a viscosity of 1000 mPa · s measured at 25 ° C. using a B-type viscometer (manufactured by TOKIMEC). Considering the increase in viscosity due to storage aging, the viscosity immediately after the blending of each component is more preferably less than 500 mPa · s, and particularly preferably less than 300 mPa · s. If the viscosity of the treating agent composition is within the above range, it is preferable because the usability such as the handling property at the time of loading into the washing machine is good.
In 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-toluenesulfonate, and the like can be used, among which calcium chloride and magnesium chloride are preferable. These water-soluble salts can be blended in the treating agent composition in an amount of about 0 to 1% by mass, and may be blended in any process for producing the treating agent composition.

(Form of treatment composition)
The dosage form of the treatment agent composition of the present invention is not particularly limited, and powder (A), component (B), component (C), and other components are mixed as necessary. And a granulated composition may be produced and used, or may be used as a liquid composition by dissolving or dispersing in a solvent such as water.
Alternatively, a complex formed by the component (B) and the component (C), the component (A), and other components as necessary may be blended to produce and use a powdered or granulated composition. Alternatively, it may be used as a liquid composition by dissolving or dispersing in a solvent such as water.
The liquid composition can be used as it is or after being diluted with a solvent and applied or sprayed.

Since the treating agent composition of the present invention described above contains the specific component (B) and component (C), the adsorption residue of the component (B) (inorganic metal compound) on the textile can be improved. In particular, when a complex formed by the component (B) and the component (C) is blended or when the treating agent composition is used as a liquid composition, the component (B) and the component (C) form a complex in water. Since it is easy to do, the adsorption | suction residual property of (B) component can be improved more. Furthermore, by containing a specific component (A), flexibility can be imparted to the treatment agent composition, and the adsorption residual property of the component (B) can be improved.
Therefore, the treatment agent composition of the present invention can exhibit an excellent sterilization effect or antibacterial effect. Since the sterilizing effect or antibacterial effect acts on microorganisms such as microorganisms, degradation by microorganisms can be suppressed even if dirt such as sebum remains on clothes after washing. Therefore, the treatment agent composition of the present invention can reduce the generation of odor and exhibit an excellent deodorizing effect.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[Raw materials]
As the component (A), the compounds and reagents shown in Table 1 were used. In addition, (a-1) to (a-3) described in Table 1 correspond to a mixture of quaternized amine compounds represented by the above formulas (III-4) to (III-6), a-4) corresponds to a mixture of quaternized amine compounds represented by the above formula (III-1).

Synthesis of (a-1):
Synthesis of methyl esters;
2.5 kg of palm fatty acid methyl (Lion, Pastel M182, molecular weight 296) consisting of 75% by weight of methyl oleate, 16% by weight of methyl linoleate and 9% by weight of methyl stearate, and 0.9 g of a commercially available stabilized nickel catalyst (0.1% by mass / methyl fatty acid) was charged into a 4 L autoclave, and nitrogen gas substitution was performed three times. Next, the rotational speed was adjusted to 800 rpm, and about 54 L of hydrogen gas was introduced at a temperature of 185 ° C. After the introduced hydrogen was completely consumed, it was cooled, the catalyst was removed using a filter aid, and hydrogenated palm fatty acid methyl was obtained.
The molecular weight of hydrogenated palm fatty acid methyl determined from the saponification value was 297. Moreover, the composition of the hydrogenated fatty acid methyl obtained by gas chromatography (GC) was 11 mass% methyl stearate, 23 mass% methyl elaidate (trans isomer), 65 mass% methyl oleate (cis isomer), The methyl linoleate was 0% by mass, and the trans / cis ratio of the unsaturated fatty acid methyl ester was 25/75 (mass ratio). The unsaturated alkyl group was measured by GC under the following model and temperature conditions.
Model: Hitachi FID Gaschrom G-3000 (column uses "TC-70" (inner diameter 0.25 mm, length 30 mm) manufactured by GL Sciences).
Temperature conditions: The column temperature was increased from 150 ° C. to 230 ° C. at a temperature increase temperature of 10 ° C./min. The injector and detector were set to 240 ° C., and the column pressure was set to 1.0 kgf / cm ² .

Synthesis of alkanolamine esters and their cations;
489 g (1.65 mol) of hydrogenated palm fatty acid obtained previously, 98 g (0.66 mol) of triethanolamine, 0.29 g of magnesium oxide, and 2.1 g of 14% aqueous sodium hydroxide solution were stirred, cooled, After putting in a 2 L four-necked flask equipped with a thermometer and a nitrogen introduction tube and performing nitrogen replacement, nitrogen was continuously supplied at a flow rate of 0.52 L / min. The temperature was raised to 190 ° C. at a rate of 1.5 ° C./min and the reaction was carried out for 6 hours. After confirming that the unreacted methyl ester was 1% by mass or less, the reaction was stopped. The fatty acid salt derived from the catalyst was removed by filtration from the obtained product to obtain an intermediate alkanolamine ester.
300 g of the obtained alkanolamine ester was placed in a four-necked flask equipped with a thermometer, a dropping funnel and a cooler, and the atmosphere was replaced with nitrogen. Subsequently, it heated at 85 degreeC and 0.98 times mole dimethyl sulfuric acid was dripped over 1 hour with respect to alkanolamine ester. After completion of dropping, the temperature was kept at 90 ° C. and stirred for 1 hour. After completion of the reaction, ethanol was added dropwise to cool the mixture to prepare an ethanol solution having a solid content of 85% by mass. Finally, Feriox CY-115 (manufactured by Lion) and dibutylhydroxytoluene (manufactured by Sumitomo Chemical) were each prepared. It added so that it might become a density | concentration of 100 ppm, and the compound (a-1) was obtained.
The obtained compound (a-1) contained monoester ammonium salt: diester ammonium salt: triester ammonium salt at 12:54:34 (mass ratio).

  As the component (B), the reagents shown in Table 2 were used.

  As the component (C), the compounds and reagents shown in Table 3 were used.

(C-1):
Cocoalkylpropylenediamine represented by the formula (1) (manufactured by Lion Akzo, Duomine) (the alkyl group (R) in the formula (1) mainly has 12 and 14 carbon atoms) was used.

Synthesis of (c-2):
In a four-necked flask, 224 g (1.1 mol) of lauric acid (manufactured by Tokyo Chemical Industry Co., Ltd., special grade) was charged, and nitrogen substitution was performed twice at 80 ° C. Thereafter, the temperature was raised to 170 ° C., and 173 g (1.7 mol) of dimethylaminopropylamine (manufactured by Kanto Chemical Co., Ltd., deer special grade) was added dropwise over 2 hours while distilling off the replicating water. Furthermore, it was kept at 170 ° C. to 180 ° C. and aged for 7 hours.
After aging, the pressure was reduced and unreacted amine and water were distilled off to obtain dimethylaminopropylamide laurate (carbon number of acyl group: 12) represented by the formula (2).

Synthesis of (c-3):
Diethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.3 g (100 mmol) and 1-iodododecane (manufactured by Wako Pure Chemical Industries, Ltd.) 3.0 g (10 mmol) were stirred at 40 ° C. for 5 hours. Thereafter, 2.4 mL of an aqueous sodium hydroxide solution (5.0 mol / L) was added, and the mixture was further stirred for a while. After allowing to cool, extraction operation was performed 5 times with diethyl ether / water using a separatory funnel, and the organic layer was distilled off under reduced pressure. The obtained organic layer is a column (manufactured by Nacalai Tesque, silica gel 60, spherical, neutral), eluent: chloroform (manufactured by Kanto Chemical Co., special grade) / methanol (manufactured by Kanto Chemical Co., special grade) = 1/1, or more After being purified by column chromatography under the conditions of (2), the solid was recovered by drying under reduced pressure to obtain lauryldiethylenetriamine (carbon number of alkyl group: 12) represented by the formula (3).

(C-4):
Alkyldiaminoethylglycine represented by formula (4) (manufactured by Wako Pure Chemical Industries, for sterilization and antibacterial and antifungal research, 30% by mass solution) (the alkyl group (R) in formula (4) has 12 and 14 carbon atoms) Stuff).

Synthesis of (c-5):
An alkylamine laurylamine (manufactured by Wako Pure Chemical Industries, Ltd., primary) 3.6 g (19.5 mmol), monochloroacetic acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade) 5.0 g (52.9 mmol), water 5 mL, The mixture was added to a mixed solution of 32 mL of ethanol (manufactured by Kanto Chemical Co., Ltd., special grade) and stirred at reflux for 6 hours. During this reflux stirring, 7.8 mL of an aqueous sodium hydroxide solution (5.0 mol / L) prepared from sodium hydroxide (manufactured by Kanto Chemical Co., Ltd., special grade) was added to adjust the pH. Thereafter, the solution was cooled to 4 ° C. to form a precipitate. The generated precipitate was washed with ethanol, filtered, and dried under reduced pressure to collect a solid, to obtain sodium lauryliminodiacetate (carbon number of alkyl group (R) in formula (5): 12). .

Synthesis of (c-6):
Except for using 4.2 g (19.5 mmol) of myristylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as the alkylamine, the same operation as in compound (c-5) was performed, and myristyliminodiacetate sodium (formula In (5), the carbon number of the alkyl group (R): 14) was obtained.

Synthesis of (c-7):
Except that 4.7 g (19.5 mmol) of palmitylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the alkylamine, the same operation as in compound (c-5) was carried out, and sodium palmiticyliminodiacetate (formula In (5), the carbon number of the alkyl group (R): 16) was obtained.

Synthesis of (c-8):
Except for using 5.3 g (19.5 mmol) of stearylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as the alkylamine, the same operation as in compound (c-5) was carried out, and sodium stearyliminodiacetate (formula (5 ), The number of carbon atoms of the alkyl group (R) was 18).

Synthesis of (c-9):
Except for using 2.5 g (19.5 mmol) of octylamine (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) as the alkylamine, the operation was performed in the same manner as compound (c-5), and sodium octyliminodiacetate ( In formula (5), carbon number of alkyl group (R): 8) was obtained.

Synthesis of (c-10):
Eicosylamine as an alkylamine (synthetic product; based on Langmuir, 1994, No. 10, page 1226, arachidic acid is reacted with thionyl chloride to give carboxylic acid chloride, and ammonia is added to obtain eicosanamide. After that, this is reduced with lithium aluminum hydride to synthesize eicosylamine. Except for using 5.8 g (19.5 mmol), the operation is carried out with the same composition as compound (c-5). Sodium iminodiacetate (carbon number of alkyl group (R): 20 in formula (5)) was obtained.

Synthesis of (c-11):
55.5 g (0.3 mol) of alkylamine laurylamine (manufactured by Wako Pure Chemical Industries, Ltd., first grade) was dissolved in 100 mL of ethanol, and 40.4 g (0.33 mol) of sodium monochloroacetate dissolved in 50 mL of water was dissolved therein. In addition, a mixed solution was obtained. The mixture was heated to 60 ° C., and an aqueous sodium hydroxide solution (12.5 mol / L) was added dropwise while adjusting the pH so as not to be 9 or less. After the dropwise addition, the mixture was reacted for 5 hours, the precipitated salt was filtered and removed by washing, and the obtained filtrate was distilled off under reduced pressure to obtain sodium laurylaminoacetate represented by the formula (6) (carbon number of alkyl group: 12 )

(C-12 (comparative product)):
Lauroyl aspartic acid represented by formula (7) (produced by Asahi Kasei Chemicals Corporation, amino former) (carbon number of acyl group: 12) was used.

(C-13 (comparative product)):
Lauroyl sarcosine represented by formula (8) (manufactured by Kawaken Fine Chemical Co., Soypon) (carbon number of acyl group: 12) was used.

(C-14 (comparative product)):
Iminodiacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd., special grade) represented by the formula (9) was used.

(C-15 (comparative product)):
Lauroyl lysine (Ajinomoto Co., Amihope) (carbon number of acyl group: 12) represented by the formula (10) was used.

  As optional components (d-1) to (d-4), the reagents shown in Tables 4 and 5 were used. In addition, the compounding quantity shown to Table 4, 5 is the quantity (mass%) in 100 mass% of processing agent compositions.

Here, each fragrance | flavor component which comprises the fragrance | flavor composition A and the fragrance | flavor composition B of Table 4, 5 is shown in Table 6. In addition, the numerical value shown in Table 6 is the quantity (mass%) of each fragrance | flavor component in fragrance | flavor composition A or fragrance | flavor composition B100 mass%.

[Examples 1 to 64, Comparative Examples 1 to 21]
<Preparation of treating 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 (Shimadzu Corporation, Agitator SJ type).
First, (A) component of the kind and the compounding quantity (mass%) shown in Tables 7-14, ethanol in arbitrary components, and perfume composition A or perfume composition B were mixed and stirred, and an oil phase mixture was obtained. It was.
On the other hand, calcium chloride, ethylene glycol and isothiazolone liquid in optional components of the types shown in Tables 7 to 14 were dissolved in purified water for balance to obtain an aqueous phase mixture. Here, the mass of the balance purified water corresponds to the balance obtained by subtracting the total mass of the oil phase mixture, calcium chloride, and isothiazolone liquid from 990 g.
Next, the oil phase mixture heated above the melting point of component (A) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of component (A) is added in two portions. And stirred. Here, the division 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. It was.
Furthermore, the mixture which consists of (B) component and (C) component of the kind and compounding quantity (mass%, but in the case of (B) component, it is metal ion concentration (mass%)) shown in Tables 7-14 is added. If necessary, the pH is adjusted to 2.5 with hydrochloric acid (reagent 1 mol / L, manufactured by Kanto Chemical Co.) or sodium hydroxide (reagent 1 mol / L, manufactured by Kanto Chemical Co., Ltd.), and the total mass is 1,000 g. Ion exchange water was added so that the desired treating agent composition was obtained.
In Tables 7 to 14, “[C] / [M]” is [C] is the number of moles of the component (C), and [M] is the number of moles of metal ions in the component (B).

<Preparation of treatment composition for evaluation comparison>
A treatment composition for evaluation and comparison was obtained by the same procedure as in Examples 1 to 64 and Comparative Examples 1 to 21, except that the component (B) and the component (C) were not blended. In addition, (d-1) was used as an arbitrary component.

<Evaluation>
(Evaluation of antibacterial effect 1: Staphylococcus aureus)
Diluent 10 [mL] of the treating agent composition of any of Examples and Comparative Examples / Cotton width 3 (for JIS dyeing fastness test, conforming to JIS L0803) 1.5 [kg] is 20 [mL / kg The treatment composition was diluted with ion exchange water at 25 ° C. A cotton wrench No. 3 was put into the diluted solution of the obtained treating agent composition, stirred for 3 minutes, and then dried in an aseptic room to obtain a test cloth. In addition, No. 3 was used as an untreated cloth that was not treated with the treating agent composition.
The test cloth is sterilized by autoclaving at a temperature of 121 ° C. and a pressure of 103 kPa, and then the test cloth is cut into approximately 18 mm square test pieces and 0.4 g (as 10 to 10 or more test pieces) in a 30 mL vial. Were stacked vertically and the bacterial solution was evenly inoculated at two places on the stacked cloth. As a bacterium, Staphylococcus aureus was used. Further, the preparation of the bacterial solution and the method of washing out the bacteria were in accordance with the quantitative test method (unified test method) of the antibacterial test method for textiles (JIS L1902-2002).
After inoculating the bacterial solution, the cells were cultured at 37 ° C. for 18 hours, grown or bacteriostatic on the test, collected, and the number of bacteria was measured.
For the untreated cloth, the number of bacteria was measured by the same operation as the test cloth, and the bacteriostatic activity value (A) was calculated from the following formula (iii) from these measured values.
Bacteriostatic activity value = Log (the number of bacteria in untreated cloth / the number of bacteria in test cloth) (iii)

Subsequently, the number of bacteria was measured for the test cloth and the untreated cloth in the same manner as described above except that the treatment composition for evaluation and comparison was used instead of the treatment composition, and the bacteriostatic activity value (B ) Was calculated.
From the calculated bacteriostatic activity value (A) and bacteriostatic activity value (B), a difference in bacteriostatic activity value {difference in bacteriostatic activity value (A)-bacteriostatic activity value (B)} is obtained, according to the following criteria The antibacterial effect against Staphylococcus aureus was evaluated. The results are shown in Tables 7-14.
A: The difference in bacteriostatic activity value is 1.5 or more.
A: The difference in bacteriostatic activity value is 1.0 or more and less than 1.5.
(Triangle | delta): The difference of bacteriostatic activity value is 0.5-1.0.
X: The difference in bacteriostatic activity value is less than 0.5.

(Evaluation of antibacterial effect 2: E. coli)
The antibacterial effect on E. coli was evaluated in the same manner as in the antibacterial effect evaluation 1 except that Escherichia coli was used instead of S. aureus. The results are shown in Tables 7-14. The evaluation criteria are the same as in the antibacterial effect evaluation 1.

(Evaluation of deodorizing effect)
A commercially available men's skin shirt (100% cotton) was washed with a commercial clothing detergent (Lion Corporation, Top) using a household two-tank washing machine for 15 minutes (detergent was used in standard amount, bath ratio 30 times, 45 ° C. tap water) → Dehydration 5 minutes was repeated 2 cycles, then rinsed with running water 15 minutes → dehydration 5 minutes was repeated 5 times, and then naturally dried to obtain a test cloth (skin shirt for testing).

The test skin shirt obtained previously was cut in half, and one test skin shirt (A) that was cut in half was the other test skin shirt that was cut in half using the treatment composition of either Example or Comparative Example. (B) performed the process shown below using the processing agent composition for evaluation comparison.
A full-automatic washing machine for home use (manufactured by Mitsubishi Electric Corporation, MAN-V8TP) is charged with 1.5 kg of a half-cut skin shirt for testing (A), 20 g of a commercial laundry detergent (manufactured by Lion Corporation, top), and a treatment agent. 10 mL of the composition was used for washing and finishing treatment. Specifically, a fully automatic washing machine for home use is set to a standard course and a water volume of 28 L, and a commercial detergent and a treating agent composition are respectively stored in a powder detergent inlet and a softener inlet installed in the washing machine. Washing and finishing treatments were performed by automatically adding to the washing bath by a washing machine. Thereafter, the test skin shirt (A) was taken out of the washing machine and dried under constant temperature and humidity conditions of 20 ° C. and 45% RH for 20 hours.
The test skin shirt (B) was also treated in the same manner as the test skin shirt (A).
Next, the test skin shirt (A) and the test skin shirt (B) after the treatment were stitched together to obtain a skin shirt for evaluation of the deodorizing effect.

After 5 skin shirts for evaluation obtained in this way were worn by 20 males in their 20s and 30s for one day each in August, both professional skinners on both sides of each skin shirt for evaluation ( The sensory shirt (A) side and the test skin shirt (B) side) were subjected to a sensory pair comparison and scored according to the following evaluation criteria. And the average value of scoring was calculated | required and the deodorizing effect was evaluated by the following criteria. The results are shown in Tables 7-14.
Evaluation criteria;
+2 points: The test skin shirt (A) side is clearly better in odor than the test skin shirt (B) side.
+1 point: The test skin shirt (A) side has a slightly better odor than the test skin shirt (B) side.
0 points: The odors on the test skin shirt (A) side and test skin shirt (B) side are almost the same.
-1 point: The test skin shirt (B) side has a slightly better odor than the test skin shirt (A) side.
-2 point: The test skin shirt (B) side is clearly better in odor than the test skin shirt (A) side.
Judgment criteria;
A: The average score is 1.5 or more.
A: The average score is 1.0 point or more and less than 1.5 point.
(Triangle | delta): An average score is 0.5 point or more and less than 1.0 point.
X: The average score is less than 0.5 points.

  As is clear from Tables 7 to 14, the treatment agent compositions obtained in each Example were excellent in antibacterial effect and deodorization effect. It is also suggested that the treatment composition obtained in each example has an excellent sterilizing effect.

  On the other hand, the treatment composition obtained in each comparative example was inferior in antibacterial effect (particularly, antibacterial effect against Staphylococcus aureus) and deodorizing effect as compared with each example. Moreover, the comparative examples 6, 7, 13, 14, 20, and 21 which do not mix | blend (A) component or (B) component were inferior to each Example also in the antimicrobial effect with respect to colon_bacillus | E._coli.

Claims (1)

A treating composition for a textile product comprising the following component (A) and a mixture of the following component (B) and component (C) or a complex formed by component (B) and component (C): object.
Component (A): a cationic surfactant or a cationic polymer compound.
(B) component: Water-soluble silver salt, water-soluble copper salt, or water-soluble zinc salt.
Component (C): polyethyleneimine, or a long chain alkylamine compound and / or an anion generated from the long chain alkylamine compound (however, the long chain alkylamine compound is represented by the following general formulas (I) and (II)) One or more selected from the group consisting of:

[In the formula (I), R ¹ represents an alkyl group having 8 to 22 carbon atoms. A ¹ represents any ^one of a hydrogen atom and (CH ₂ ) _m —COOX ² . X ¹ and X ² may be the same or different and represent one 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 to 3, and m represents any of 1 to 3. ]

[In Formula (II), R ² represents either an alkyl group having 8 to 22 carbon atoms or an acyl group having 8 to 22 carbon atoms. Q is (NH— (CH ₂ ) _m ), and r represents 1 or 0. When r is 0, A ² and A ³ may be the same or different and are selected from a hydrogen atom and a methyl group. When r is 1, one of A ² and A ³ is a hydrogen atom, and the other is either a hydrogen atom or CH ₂ COOX ³ . X ³ represents one 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 to 3, and m represents any of 1 to 3. ]