JP2012051858A - Degerming agent composition and degerming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a degerming agent composition and a degerming method that permit effective degermination of a Gram-negative bacterium adhering to a textile product, particularly a cotton product.SOLUTION: The degerming agent composition comprises the following components (A)-(D). Component (A) is a zinc compound. Component (B) is at least one compound selected from the group consisting of polyethyleneimine, derivatives thereof, and a polymer having a constituting unit represented by general formula (II). Component (C) is hydrogen peroxide or a peroxide releasing hydrogen peroxide in water. Component (D) is an organic peroxide precursor that reacts with the component (C) to generate an organic peracid. In the formula, Aand Aare each independently a hydrogen atom, an alkyl group, a group represented by a general formula: -(CH)-COOX(wherein Xis a hydrogen atom or a salt-forming cation; and q is an integer of 0-2), or the like.

Description

  The present invention relates to a disinfectant composition and a disinfecting method.

Based on the recent increase in hygiene preference, a sterilization effect is strongly demanded also in the field of clothing washing. In general, detergents for clothing are mixed with a peroxide that releases hydrogen peroxide in water, such as sodium percarbonate, as a disinfecting component. However, sufficient disinfection may not be possible with hydrogen peroxide released from peroxide alone. In particular, sterilization tends to be insufficient at low temperatures.
In order to improve the sterilizing power, an organic peracid precursor typified by sodium 4-dodecanoyloxybenzenesulfonate is used in combination with such a problem. The organic peracid precursor exhibits a very excellent sterilizing effect against Gram-positive bacteria such as Staphylococcus aureus. However, on the other hand, there is a problem that sufficient effects cannot be obtained against gram-negative bacteria such as E. coli. In addition, since the organic peracid precursor is inactivated by forming a dimer when the concentration is increased, there is also a problem that the disinfection effect is not improved even if the blending amount is increased.
For such problems, in Patent Documents 1 to 3, a copper complex having a specific ligand promotes an oxidation reaction with hydrogen peroxide and exhibits an excellent bactericidal / sterilizing effect against gram-negative bacteria. It is described. Patent Document 4 describes an example in which an effect is expressed against both gram-negative and positive bacteria by using a copper complex having a specific ligand and an organic peracid precursor in combination. ing.

JP 2009-148682 A JP 2009-148683 A JP 2009-235058 A JP 2009-155292 A

The combined use of hydrogen peroxide and a copper complex having a specific ligand is an evaluation test for sterilization power by suspension method (used in an aqueous solution) as used in Patent Documents 1 to 4 for sterilization power evaluation. In a test in which a bacterium is dispersed and a sample (for example, a disinfectant composition) is added thereto, it is recognized that a very excellent sterilization effect is exhibited.
However, according to the study by the present inventors, when evaluated in an evaluation test that is more suitable for actual use than the suspension method, even when hydrogen peroxide and a copper complex having a specific ligand are used in combination, It was found that the sterilization effect against gram-negative bacteria was not sufficient. That is, when Gram-negative bacteria are attached to a textile product such as clothing, and hydrogen peroxide is allowed to act on the textile product in the presence of a copper complex having a specific ligand, when evaluated by a suspension method In comparison, the disinfection effect was greatly reduced. Such a problem is particularly remarkable when the fiber product is a cotton product.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a disinfectant composition and a disinfecting method that can effectively disinfect gram-negative bacteria attached to textile products, particularly cotton products. And

The present invention for solving the above problems has the following aspects.
[1] A disinfectant composition comprising the following components (A) to (D):
Component (A): Zinc compound.
Component (B): at least one selected from the group consisting of polyethyleneimine, a polymer having a structural unit represented by the following general formula (I), and a polymer having a structural unit represented by the following general formula (II) Compound.
Component (C): hydrogen peroxide or a peroxide that releases hydrogen peroxide in water.
Component (D): An organic peracid precursor that reacts with the component (C) to generate an organic peracid.

［式中、Ｙ^１〜Ｙ^４は、それぞれ独立に、水素原子、アルキル基、一般式−（ＣＨ_２）_ｍ−Ｘ^１｛式中、Ｘ^１は、１級アミノ基、２級アミノ基、３級アミノ基、アミド基または水酸基を表し、前記２級アミノ基、３級アミノ基、アミド基はそれぞれ置換基として−ＣＯＯＸ^１１（式中、Ｘ^１１は水素原子または塩形成カチオンを表す。）を有していてもよく、ｍは１または２を表す。｝で表される基、または一般式−（ＣＨ_２）_ｎ−ＣＯＯＸ^２｛式中、Ｘ^２は水素原子または塩形成カチオンを表し、ｎは１または２を表す。｝で表される基を表し、Ｙ^１〜Ｙ^４のうち少なくとも１つは、前記一般式−（ＣＨ_２）_ｍ−Ｘ^１で表され且つ該式中のＸ^１が置換基として−ＣＯＯＸ^１１を有する２級アミノ基、３級アミノ基もしくはアミド基である基、または前記一般式−（ＣＨ_２）_ｎ−ＣＯＯＸ^２で表される基である。］

[Wherein Y ^{1 to} Y ⁴ are each independently a hydrogen atom, an alkyl group, a general formula — (CH ₂ ) _m —X ¹ {wherein X ¹ is a primary amino group, a secondary amino group, A tertiary amino group, an amide group, or a hydroxyl group is represented, and the secondary amino group, the tertiary amino group, and the amide group each represent —COOX ¹¹ as a substituent (wherein X ¹¹ represents a hydrogen atom or a salt-forming cation). And m represents 1 or 2. } Or a general formula — (CH ₂ ) _n —COOX ² {wherein X ² represents a hydrogen atom or a salt-forming cation, and n represents 1 or 2. }, And at least one of Y ^{1 to} Y ⁴ is represented by the general formula — (CH ₂ ) _m —X ¹ , and X ¹ in the formula is —COOX ¹¹ as a substituent. Or a group represented by the general formula — (CH ₂ ) _n —COOX ² . ]

［式中、Ａ^１およびＡ^２は、それぞれ独立に、水素原子、アルキル基、一般式−（ＣＨ_２）_ｐ−Ｘ^３｛式中、Ｘ^３は、１級アミノ基、２級アミノ基、３級アミノ基、アミド基または水酸基を表し、前記２級アミノ基、３級アミノ基、アミド基はそれぞれ置換基として−ＣＯＯＸ^３１（式中、Ｘ^３１は水素原子または塩形成カチオンを表す。）を有していてもよく、ｐは０〜２の整数を表す。｝で表される基、または一般式−（ＣＨ_２）_ｑ−ＣＯＯＸ^４｛式中、Ｘ^４は水素原子または塩形成カチオンを表し、ｑは０〜２の整数を表す。｝で表される基を表し、Ａ^１およびＡ^２のうち少なくとも１つは、前記一般式−（ＣＨ_２）_ｐ−Ｘ^３で表され且つ該式中のＸ^３が置換基として−ＣＯＯＸ^３１を有する２級アミノ基、３級アミノ基もしくはアミド基である基、または前記一般式−（ＣＨ_２）_ｑ−ＣＯＯＸ^４で表される基である。］

[Wherein, A ¹ and A ² are each independently a hydrogen atom, an alkyl group, a general formula — (CH ₂ ) _p —X ³ {wherein X ³ is a primary amino group, a secondary amino group, A tertiary amino group, an amide group or a hydroxyl group is represented, and the secondary amino group, the tertiary amino group and the amide group each represent —COOX ³¹ as a substituent (wherein X ³¹ represents a hydrogen atom or a salt-forming cation). And p represents an integer of 0 to 2. } Or a general formula — (CH ₂ ) _q —COOX ⁴ {wherein X ⁴ represents a hydrogen atom or a salt-forming cation, and q represents an integer of 0 to 2. }, At least one of A ¹ and A ² is represented by the general formula — (CH ₂ ) _p —X ³ , and X ³ in the formula is —COOX ³¹ as a substituent. Or a group represented by the general formula — (CH ₂ ) _q —COOX ⁴ . ]

[2] The disinfectant composition according to [1], wherein a mass ratio of the component (B) to Zn derived from the component (A) is in a range of 0.5 to 12.
[3] The disinfectant composition according to [1] or [2], which is used by being contained in water so that the Zn concentration becomes 0.1 to 7 ppm.
[4] The disinfectant composition according to [1] or [2], further comprising the following component (E).
Component (E): Copper compound.
[5] The disinfectant composition according to [4], which is used by being contained in water so that the Zn concentration is 0.02 to 2.5 ppm and the Cu concentration is 0.002 to 0.15 ppm.
[6] The disinfectant composition according to any one of [1] to [5], wherein the component (D) is represented by the following general formula (d1).

［式中、Ｒ^１は炭素数７〜１８の直鎖状の脂肪族炭化水素基を表し、Ｘは水素原子、−ＣＯＯＭまたは−ＳＯ_３Ｍ（式中、Ｍは水素原子または塩形成カチオンを表す。）を表す。］

[Wherein R ¹ represents a linear aliphatic hydrocarbon group having 7 to 18 carbon atoms, X represents a hydrogen atom, —COOM or —SO ₃ M (wherein M represents a hydrogen atom or a salt-forming cation) Represents.) ]

  [7] A disinfecting method comprising contacting the disinfectant composition according to any one of [1] to [6] with a textile product in water.

  According to the present invention, it is possible to provide a disinfectant composition and a disinfecting method that can effectively disinfect gram-negative bacteria attached to textile products, particularly cotton products.

Hereinafter, the present invention will be described in detail.
The disinfectant composition of the present invention contains the following components (A) to (D), and as a preferred embodiment, contains the following component (E) in addition to the components (A) to (D). (Hereafter, it may be called 1st embodiment.), What contains component (A)-(D) and does not contain the following component (E) (henceforth 2nd embodiment). Can be mentioned.
Here, in the present specification and claims, “sterilization” means an action of removing bacteria adhering to the surface of an object to be sterilized (such as a textile product) from the surface.
“Disinfectant composition” means an assembly of the above 4 or 5 components that contribute to the disinfection effect.

<Component (A)>
Component (A) is a zinc compound.
The disinfectant composition is usually used by being poured into water. Therefore, the component (A) is preferably one that generates zinc ions in water.
Examples of zinc compounds that generate zinc ions in water include water-soluble salts of zinc. Examples of the water-soluble salt include nitrates, sulfates, chlorides, acetates, perchlorates, cyanides, ammonium chlorides, tartrates, and hydrates thereof.
As the component (A), zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, zinc chloride, zinc tartrate, zinc perchlorate, zinc glucone and the like are preferable, and easy to handle, Zinc sulfate, zinc sulfate monohydrate, and zinc sulfate heptahydrate are particularly preferable from the viewpoints of safety, price, and the like.

A component (A) may be used individually by 1 type, and may use 2 or more types together.
In the disinfectant composition, the content of the component (A) may be appropriately set in consideration of the balance with other components and the method of use. If an example is given, a component (A) will be a component which generate | occur | produces a zinc ion in water, and a zinc ion will form a complex with the component (B) mentioned later. This complex acts together with the components (C) and (D) described later to exert a sterilizing effect. Therefore, when the sterilizing composition is introduced into water for sterilization, the concentration of Zn in the water after the addition is within a range where a sufficient sterilizing effect can be obtained. It is preferable to set so that the amount of the disinfectant composition necessary to achieve a suitable amount for use. In particular, the component (E) to be described later is a component that generates copper ions in water, and the copper ion forms a complex with the component (B) as in the case of zinc ions, and components (C) and (D) to be described later. ) And exerts a sterilizing effect. Therefore, the preferable range of the Zn concentration in the water after adding the disinfectant composition is set mainly depending on whether or not the component (E) is blended.
Hereinafter, the water in which the disinfectant composition is charged may be referred to as a treatment liquid.
The Zn concentration in the treatment liquid is not particularly limited, but in the first embodiment containing the component (E), it varies depending on the Cu concentration, but is preferably 0.02 to 2.5 ppm. 06-1.2 ppm is more preferable, and 0.1-0.7 ppm is still more preferable. If it exceeds 2.5 ppm, the disinfection effect may be reduced, and if it is less than 0.02 ppm, a sufficient disinfection effect may not be obtained.
In 2nd embodiment which does not contain a component (E), 0.1-7 ppm is preferable, 0.2-4.5 ppm is more preferable, 0.45-1.2 ppm is further more preferable. If it exceeds 7 ppm, the disinfection effect may be reduced, and if it is less than 0.1 ppm, a sufficient disinfection effect may not be obtained.
In the present specification and claims, the concentration (ppm) means the mass (mg) of the component contained in 1000 g of the treatment liquid.

<Component (B)>
Component (B) is composed of polyethyleneimine, a polymer having a structural unit represented by a specific general formula (I) (hereinafter referred to as polymer (B2)), and a specific general formula (II). It is at least one compound selected from the group consisting of a polymer having a unit (hereinafter referred to as polymer (B3)).
Here, the “structural unit” indicates a repeating unit constituting the polymer.
Component (B) is a polymer having a plurality of carboxy groups that may form an amino group and / or a salt in the structure. By having these groups, component (B) is converted into water. When dissolved, it forms a complex with zinc ions released from component (A) or copper ions released from component (E). This is considered to contribute to the improvement of the sterilization effect.

Polyethyleneimine is a polymer obtained by polymerizing ethyleneimine, and usually a part of the nitrogen atom contained in the main chain forms a branching point or a branched or network structure. Contains primary to tertiary amino groups.
Polyethyleneimine may be synthesized by a known method or may be a commercially available product. As an example of a commercial item, the Lupasol series made from BASF, the Epomin series made from Nippon Shokubai Co., Ltd., etc. are mentioned, for example.

  The polymer (B2) has a structural unit represented by the following general formula (I) (hereinafter referred to as structural unit (I)).

［式中、Ｙ^１〜Ｙ^４は、それぞれ独立に、水素原子、アルキル基、一般式−（ＣＨ_２）_ｍ−Ｘ^１｛式中、Ｘ^１は、１級アミノ基、２級アミノ基、３級アミノ基、アミド基または水酸基を表し、前記２級アミノ基、３級アミノ基、アミド基はそれぞれ置換基として−ＣＯＯＸ^１１（式中、Ｘ^１１は水素原子または塩形成カチオンを表す。）を有していてもよく、ｍは１または２を表す。｝で表される基、または一般式−（ＣＨ_２）_ｎ−ＣＯＯＸ^２｛式中、Ｘ^２は水素原子または塩形成カチオンを表し、ｎは１または２を表す。｝で表される基を表し、Ｙ^１〜Ｙ^４のうち少なくとも１つは、前記一般式−（ＣＨ_２）_ｍ−Ｘ^１で表され且つ該式中のＸ^１が置換基として−ＣＯＯＸ^１１を有する２級アミノ基、３級アミノ基もしくはアミド基である基、または前記一般式−（ＣＨ_２）_ｎ−ＣＯＯＸ^２で表される基である。］

[Wherein Y ^{1 to} Y ⁴ are each independently a hydrogen atom, an alkyl group, a general formula — (CH ₂ ) _m —X ¹ {wherein X ¹ is a primary amino group, a secondary amino group, A tertiary amino group, an amide group, or a hydroxyl group is represented, and the secondary amino group, the tertiary amino group, and the amide group each represent —COOX ¹¹ as a substituent (wherein X ¹¹ represents a hydrogen atom or a salt-forming cation). And m represents 1 or 2. } Or a general formula — (CH ₂ ) _n —COOX ² {wherein X ² represents a hydrogen atom or a salt-forming cation, and n represents 1 or 2. }, And at least one of Y ^{1 to} Y ⁴ is represented by the general formula — (CH ₂ ) _m —X ¹ , and X ¹ in the formula is —COOX ¹¹ as a substituent. Or a group represented by the general formula — (CH ₂ ) _n —COOX ² . ]

In the formula (I), the alkyl group in Y ^{1 to} Y ⁴ may be either linear or branched, and the carbon number thereof is preferably 1 to 24, and more preferably 1 to 16.
Formula ^{_{- (CH 2) m -X X}} 1 in ^1, primary amino group _(-NH 2), 2 amino groups, tertiary amino group, an amido group, may be any of a hydroxyl group.
The secondary amino group, tertiary amino group, and amide group may each have —COOX ¹¹ (wherein X ¹¹ represents a hydrogen atom or a salt-forming cation) as a substituent. Examples of the salt-forming cation in X ¹¹ include the same salt-forming cations as mentioned in the description of X ² described later.
Each of the secondary amino group, the tertiary amino group, and the amide group may have a substituent other than —COOX ¹¹ . Examples of the other substituent include a primary to tertiary amino group, a hydroxyl group, and —SO ₃ X ¹² (wherein X ¹² represents a hydrogen atom or a salt-forming cation). Examples of the secondary to tertiary amino group as the substituent include the same as the secondary to tertiary amino groups in Y ^{1 to} Y ⁴ . Salts formed cation in X ^12, those similar to the salt-forming cations include in the description of X ² to be described later.

Among these, X ¹ is preferably a ^primary to tertiary amino group or an amide group, more preferably a ^primary to tertiary amino group, and still more preferably a secondary to tertiary amino group.
More specifically, examples of the secondary amino group include -NHR ¹¹ (R ¹¹ is a monovalent hydrocarbon group or alkoxy group which may have a substituent).
More specifically, as the tertiary amino group, for example, —NR ¹² R ¹³ (R ^{12 to} R ¹³ are each independently a monovalent hydrocarbon group or an alkoxy group which may have a substituent. .).
Examples of the monovalent hydrocarbon group for R ^{11 to} R ¹³ include an alkyl group and an alkenyl group, and an alkyl group is preferable. The alkyl group may be linear or branched, and the number of carbon atoms is preferably 1 to 24, more preferably 1 to 16.
The alkoxy group in R ^{11 to} R ¹³ may be either linear or branched, and the carbon number thereof is preferably 1 to 24, and more preferably 1 to 16.
Each of the monovalent hydrocarbon group and alkoxy group may have a substituent. Examples of the substituent include -COOX ¹¹ , a primary to tertiary amino group, a hydroxyl group, -SO ₃ X ^{5 and the} like described above.
More specifically, as the amide group, for example, —CO—NH ₂ , —CO—NHR ¹¹ , —CO—NR ¹² R ¹³ , a part or all of the hydrogen atoms of the primary amino group or the secondary amino group may be used. And a group substituted with an acyl group. R ^{11 to} R ¹³ in these amide groups are the same as described above. Examples of the acyl group include —C (═O) —R ¹⁴ (R ¹⁴ is a monovalent hydrocarbon group which may have a substituent). Examples of R ¹⁴ include the same as R ^{11 to} R ¹³ .

M in the formula — (CH ₂ ) _m —X ¹ is 1 or 2, and 2 is particularly preferable.
Preferable specific examples of the group represented by the formula — (CH ₂ ) _m —X ¹ include, for example, — (CH ₂ ) ₂ NH ₂ , — (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH ₂ , — ( _{CH 2) 2 N [(CH} 2) 2 NH 2] 2, - (CH 2) 2 OH, - (CH 2) 2 CONH 2, - (CH 2) 2 N [CH 2 COONa] 2 , and the like .
Examples of the salt-forming cation at X ² in the formula — (CH ₂ ) _n —COOX ² include alkali metals, alkaline earth metals, and cationic ammonium.
Examples of the alkali metal include sodium and potassium.
Examples of the alkaline earth metal include calcium and magnesium. Incidentally, when X ² is an alkaline earth metal equivalent to ½ atomic. For example when ^{X 2} is calcium, -COOX ² is ^"- 1/2 (Ca) ^- COO".
Examples of the cationic ammonium include alkanolamines such as monoethanolamine and diethanolamine, and specifically, those in which 1 to 3 hydrogen atoms of ammonium are substituted with alkanol groups. As for carbon number of an alkanol group, 1-3 are preferable.
X ² is preferably a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium, and more preferably a hydrogen atom or an alkali metal.
_{N in the} formula — (CH ₂ ) _n —COOX ² is 1 or 2.

In formula (I), at least one of Y ^{1 to} Y ⁴ is represented by the formula — (CH ₂ ) _m —X ¹ , and X ¹ in the formula has 2 —COOX ¹¹ as a substituent. A group that is a tertiary amino group, a tertiary amino group or an amide group, or a group represented by the general formula — (CH ₂ ) _n —COOX ² (hereinafter, these may be collectively referred to as a carboxy group-containing group). It is. Thereby, the outstanding disinfection effect is acquired.
Secondary amino group in which X ¹ has the -COOX ¹¹ as a substituent, tertiary amino group, the amide group, ^{R 11} for example in the -NHR ¹¹ or ^{-CO-NHR 11,} 1 valent having -COOX ¹¹ is a hydrocarbon group or an alkoxy group group, one or both of ^R 12 ^{to R 13} in the ^-NR 12 ^{R 13} or ^-NR 12 ^{R 13} is is a monovalent hydrocarbon group or an alkoxy group having -COOX ¹¹ Group, and the like. The monovalent hydrocarbon group having —COOX ¹¹ is preferably — (CH ₂ ) _k COOX ¹¹ . In the formula, k represents 1 or 2.
Among Y ^{1 to} Y ⁴ , 1 to 4 are preferable, and 3 to 4 are more preferable as the carboxy group-containing group.

The structural unit (I) contained in the polymer (B2) may be one type or two or more types.
The polymer (B2) may be composed of only the structural unit (I), or may be composed of the structural unit (I) and other structural units other than the structural unit (I). However, in consideration of the effect of the present invention, the ability to form a complex with the component (A) or the component (E), the proportion of the structural unit (I) in the polymer (B2) is the total amount of the polymer (B2). 40 mol% or more is preferable with respect to the total of structural units, and 80 mol% or more is more preferable. The upper limit of this ratio is not specifically limited, 100 mol% may be sufficient.
Examples of the structural unit other than the structural unit (I) that the polymer (B2) may have include, for example, Y ¹ to Y ⁴ in the general formula (I) are each independently a hydrogen atom or alkyl. A group represented by the general formula — (CH ₂ ) _m —X ¹ , and wherein X ¹ does not include —COOX ¹¹ (as a substituent among a secondary amino group, a tertiary amino group, and an amide group) A structural unit that does not have —COOX ¹¹ , a primary amino group, and a hydroxyl group).

Specific examples of the polymer (B2) include, for example, — (CH ₂ ) _n —COOX ² and / or — (CH ₂ ) _m —N () as a substituent on a nitrogen atom constituting the main chain of polyethyleneimine. Examples thereof include a polymer into which (CH ₂ ) _k COOX ¹¹ ) ₂ is introduced (hereinafter referred to as an aminopolycarboxylic acid polymer). In the formula, n, X ² , m, k, and X ¹¹ are the same as described above.
As the polymer (B2), one synthesized by a known method may be used, or a commercially available product may be used. For example, an example of a commercial product of the aminopolycarboxylic acid polymer is Trilon P manufactured by BASF.

  The polymer (B3) has a structural unit represented by the following general formula (II) (hereinafter referred to as structural unit (II)).

［式中、Ａ^１およびＡ^２は、それぞれ独立に、水素原子、アルキル基、一般式−（ＣＨ_２）_ｐ−Ｘ^３｛式中、Ｘ^３は、１級アミノ基、２級アミノ基、３級アミノ基、アミド基または水酸基を表し、前記２級アミノ基、３級アミノ基、アミド基はそれぞれ置換基として−ＣＯＯＸ^３１（式中、Ｘ^３１は水素原子または塩形成カチオンを表す。）を有していてもよく、ｐは０〜２の整数を表す。｝で表される基、または一般式−（ＣＨ_２）_ｑ−ＣＯＯＸ^４｛式中、Ｘ^４は水素原子または塩形成カチオンを表し、ｑは０〜２の整数を表す。｝で表される基を表し、Ａ^１およびＡ^２のうち少なくとも１つは、前記一般式−（ＣＨ_２）_ｐ−Ｘ^３で表され且つ該式中のＸ^３が置換基として−ＣＯＯＸ^３１を有する２級アミノ基、３級アミノ基もしくはアミド基である基、または前記一般式−（ＣＨ_２）_ｑ−ＣＯＯＸ^４で表される基である。］

[Wherein, A ¹ and A ² are each independently a hydrogen atom, an alkyl group, a general formula — (CH ₂ ) _p —X ³ {wherein X ³ is a primary amino group, a secondary amino group, A tertiary amino group, an amide group or a hydroxyl group is represented, and the secondary amino group, the tertiary amino group and the amide group each represent —COOX ³¹ as a substituent (wherein X ³¹ represents a hydrogen atom or a salt-forming cation). And p represents an integer of 0 to 2. } Or a general formula — (CH ₂ ) _q —COOX ⁴ {wherein X ⁴ represents a hydrogen atom or a salt-forming cation, and q represents an integer of 0 to 2. }, At least one of A ¹ and A ² is represented by the general formula — (CH ₂ ) _p —X ³ , and X ³ in the formula is —COOX ³¹ as a substituent. Or a group represented by the general formula — (CH ₂ ) _q —COOX ⁴ . ]

In the formula (II), the alkyl group in A ¹ and A ² may be either linear or branched, and the carbon number thereof is preferably 1 to 24, and more preferably 1 to 16.
Formula - _{(CH 2)} ^{X 3} in p -X ³ is a primary amino group, secondary amino group, tertiary amino group, an amido group, may be any of a hydroxyl group.
The secondary amino group, tertiary amino group, and amide group may each have —COOX ³¹ (wherein X ³¹ represents a hydrogen atom or a salt-forming cation) as a substituent. X ³¹ may be the same as X ¹¹ described above.
Each of the secondary amino group, the tertiary amino group, and the amide group may have a substituent other than —COOX ³¹ . Examples of the other substituent include a primary to tertiary amino group, a hydroxyl group, and —SO ₃ X ³² (wherein X ³² represents a hydrogen atom or a salt-forming cation). Examples of the secondary to tertiary amino group as the substituent include the same as the secondary to tertiary amino groups in Y ^{1 to} Y ⁴ . The X ^32, are the same as those for ^{X 12} in the _-SO 3 ^{X 12.}
Among these, X ³ is preferably a primary to tertiary amino group or an amide group, and more preferably a primary to tertiary amino group. These embodiments include the same ones as exemplified in the description of the X ^1.
- _{(CH 2)} p in p -X ³ is an integer of 0 to 2, 1 to 2 is more preferred.
Preferable specific examples of — (CH ₂ ) _p —X ³ include —NH ₂ , —NH (CH ₃ ) _{2 and the} like.
- in _(CH ^{2) X} 2 in ^{_{n -COOX 2 - (CH 2)}} q Salts formed cation in ^{X 4} in -COOX ^4, wherein the formula mentioned in the description of ^Y 1 to Y ⁴ in (I) The thing similar to a salt formation cation is mentioned.
_{Q in} — (CH ₂ ) _q —COOX ⁴ is an integer of 0 to 2, preferably 0 to 1, and particularly preferably 0.

In formula (II), at least one of A ¹ and A ² is represented by the formula — (CH ₂ ) _p —X ³ , and X ³ in the formula has 2 —COOX ³¹ as a substituent. It is a group that is a tertiary amino group, a tertiary amino group, an amide group, or a group represented by the general formula — (CH ₂ ) _q —COOX ⁴ . Thereby, the outstanding disinfection effect is acquired.
Secondary amino groups X ³ has -COOX ³¹ as a substituent, tertiary amino group, the amide group, ^{R 11} for example in the -NHR ¹¹ or ^{-CO-NHR 11,} 1 valent having -COOX ¹¹ is a hydrocarbon group or an alkoxy group group, one or both of ^R 12 ^{to R 13} in the ^-NR 12 ^{R 13} or ^-NR 12 ^{R 13} is is a monovalent hydrocarbon group or an alkoxy group having -COOX ¹¹ Group, and the like.

The structural unit (II) possessed by the polymer (B3) may be one type or two or more types.
The polymer (B3) may be composed of only the structural unit (II), or may be composed of the structural unit (II) and other structural units other than the structural unit (II). However, in consideration of the effect of the present invention, the ability to form a complex with the component (A) or the component (E), the proportion of the structural unit (II) in the polymer (B3) is the total amount of the polymer (B3). 40 mol% or more is preferable with respect to the total of structural units, and 80 mol% or more is more preferable. The upper limit of this ratio is not specifically limited, 100 mol% may be sufficient.
Examples of other structural units other than the structural unit (II) that the polymer (B3) may have include, for example, A ¹ and A ² in the general formula (II) are each independently a hydrogen atom or an alkyl group. A group or a group represented by the general formula — (CH ₂ ) _p —X ³ and wherein X ³ does not contain —COOX ³¹ (as a substituent among a secondary amino group, a tertiary amino group, and an amide group) A structural unit that does not have —COOX ³¹ , a primary amino group, and a hydroxyl group).

Specific examples of the polymer (B3) include, for example, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyhydroxyacrylic acid, polyfumaric acid, acrylic acid / maleic acid copolymer, acrylic acid / acrylamide copolymer, and the like. Can be mentioned. Among these, an acrylic acid / maleic acid copolymer is preferable in terms of complex forming ability with the component (A) and the component (E), ease of production, and cost.
As the polymer (B3), one synthesized by a known method may be used, or a commercially available product may be used. For example, examples of commercial products of acrylic acid / maleic acid copolymers include Socaran CP5 and Socaran CP7 manufactured by BASF, and Aquaric TL series manufactured by Nippon Shokubai Co., Ltd.

  Among the above components, component (B) is preferably polyethyleneimine, aminopolycarboxylic acid polymer, acrylic acid / maleic acid copolymer, more preferably polyethyleneimine or aminopolycarboxylic acid polymer, and polyethyleneimine. Particularly preferred.

The molecular weight of the component (B) is preferably in the range of 2000 to 200000, more preferably in the range of 5000 to 100,000, and still more preferably in the range of 10,000 to 50000 as the weight average molecular weight. If the weight average molecular weight is less than 2000, the effects of the present invention may not be sufficiently obtained. This is presumably because decomposition of hydrogen peroxide (derived from component (C)) in water is promoted. On the other hand, if the weight average molecular weight exceeds 200,000, handling becomes difficult as the viscosity increases.
The weight average molecular weight of the component (B) is determined by a gel permeation chromatography (GPC) method using pullulan having a known molecular weight as a standard substance.

The component (B) contained in the disinfectant composition may be one type or two or more types.
In the disinfectant composition, the content of the component (B) is set in consideration of the content of the component (A). The content of component (B) is such that the mass ratio of component (B) to Zn derived from component (A) (hereinafter referred to as “B / A (Zn)”) is in the range of 0.5 to 12. An amount that is within is preferred. B / A (Zn) is more preferably 0.8 to 7, and further preferably 1.5 to 5.5. If B / A (Zn) is less than 0.5 or more than 12, the effect of blending component (A) and component (B) may not be sufficiently obtained.

<Ingredient (C)>
Component (C) is hydrogen peroxide or a peroxide that releases hydrogen peroxide in water.
Specific examples of component (C) include sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate and the like. Among these, sodium percarbonate is preferable from the viewpoint of solubility during use and stability during storage.
When the disinfectant composition is solid (powder, granule, tablet, briquette, sheet, bar, etc.), a peroxide is used as the component (C). At this time, the disinfectant composition may contain the peroxide as it is, and the coated particles in which the peroxide particles are coated with a coating for improving stability during storage (for example, coated coating particles). Sodium carbonate particles) may be blended.
When the disinfectant composition is a liquid, as the component (C), either hydrogen peroxide or peroxide may be used.

As the coated particles, known particles can be used. For example, as coated sodium percarbonate particles, those coated with silicic acid and / or silicate and boric acid and / or borate, or a combination of a surfactant such as LAS and an inorganic compound were coated. Those are preferred. Specifically, as described in Japanese Patent No. 2,189,991 and the like, it is coated by spraying silicic acid and / or alkali metal silicate aqueous solution and boric acid and / or alkali metal borate aqueous solution. And those coated with an aromatic hydrocarbon sulfonic acid such as Japanese Patent No. 2871298 and / or an alkali silicate alkali salt, carbonate, bicarbonate and sulfate having an average particle size of 10 to 500 μm, paraffin, wax, etc. Examples thereof include those coated with a water-insoluble organic compound. For non-hazardous material, it may be used by powder blending with various inorganic materials such as sodium carbonate and sodium hydrogen carbonate.
Furthermore, when the disinfectant composition is a composition containing a large amount of water due to the incorporation of a surfactant, etc., a coating peroxide or aromatic coated with sodium percarbonate and silicic acid and sodium borate It is more preferable to use one coated with hydrocarbon sulfonic acid and alkali silicate, carbonate, bicarbonate and sulfate.
In addition, when the disinfectant composition is solid, the water content in the disinfectant composition is preferably 2% by mass or less in consideration of the stability of the component (C).
As coated sodium percarbonate particles, JP-A 59-196399, USP 4526698 (both sodium percarbonate coated with borate), JP-A-4-31498, JP-A-6-40709 Examples thereof include those produced by the methods described in JP-A Nos. 7-11803 and 2871298.

When the component (C) is blended in the disinfectant composition as particles (peroxide particles or coated particles), the average particle diameter of the particles is preferably 200 to 1000 μm, more preferably 500 to 1000 μm. In order to improve solubility and stability, the particle size of less than 125 μm and the particle size of more than 1400 μm are preferably 10% by mass or less in the component (C).
In the present specification, the “average particle diameter” is a value obtained by the following measurement method.
"Measurement method of average particle size"
First, the measuring object (sample) is classified using a 9-stage sieve and a saucer having openings of 1,680 μm, 1,410 μm, 1,190 μm, 1,000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm. Do. In the classification operation, first, the 9-stage sieve is stacked above the pan so that the openings gradually increase, and a sample of 100 g / time is placed on the top of the sieve having the top opening of 1,680 μm. . Next, it was covered and attached to a low-tap type sieve shaker (manufactured by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), and after shaking for 10 minutes, it remained on each sieve and saucer. Samples are collected for each mesh and the sample mass is measured.
The mass frequency of the tray and each sieve is integrated, the initial sieve opening with an integrated mass frequency of 50% or more is set to a μm, the opening of the sieve that is one step larger than a μm is set to b μm, The average particle diameter (mass 50%) is obtained by the following formula (1), where c% is the integration of the mass frequency up to the a μm sieve and d% is the mass frequency on the a μm sieve.

A component (C) may be used individually by 1 type, and may use 2 or more types together.
In the disinfectant composition, the content of the component (C) may be appropriately set in consideration of the balance with other components and the method of use. For example, when sterilization is performed by introducing the disinfectant composition into water, the concentration of the component (C) in the treatment liquid after the addition is set to a preferable range. Therefore, it is preferable to set so that the amount of the disinfectant composition necessary for this is an amount suitable for use.
Although the density | concentration of the component (C) in a process liquid is not restrict | limited in particular, as hydrogen peroxide conversion density | concentration, 1.6-1300 ppm is preferable, 1.6-650 ppm is more preferable, 3.2-50 ppm Is more preferable. Even if it exceeds 1300 ppm, the sterilizing effect may not be enhanced, or conversely, the sterilizing effect may be reduced. If it is less than 1.6 ppm, a sufficient sterilizing effect may not be obtained.
The hydrogen peroxide equivalent concentration is the concentration when the component (C) is hydrogen peroxide, and the hydrogen peroxide that can be generated from the peroxide when the component (C) is the peroxide. Concentration.

<Component (D)>
Component (D) is an organic peracid precursor that reacts with component (C) to generate an organic peracid. The component (D) usually reacts with the component (C) in water or a treatment liquid.
As the component (D), a bleach activator conventionally blended in a hydrogen peroxide-based bleach composition or the like can be used. Specifically, for example, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, octanoyloxy Benzoic acid, Nonanoyloxybenzoic acid, Decanoyloxybenzoic acid, Undecanoyloxybenzoic acid, Dodecanoyloxybenzoic acid, Octanoyloxybenzene, Nonanoyloxybenzene, Decanoyloxybenzene, Undecanoyloxybenzene, Dodecanoyloxy Benzene, tetraacetylethylenediamine, pentaacetylglucose, triacetin, diacetin, monoacetin, terephthalic acid monocholine ester, Phthalic acid di choline esters.

  As the component (D), a compound represented by the following general formula (d1) is particularly preferable.

［式中、Ｒ^１は炭素数７〜１８の直鎖状の脂肪族炭化水素基を表し、Ｘは水素原子、−ＣＯＯＭまたは−ＳＯ_３Ｍ（Ｍは水素原子または塩形成カチオンを表す。）を表す。］

[Wherein, R ¹ represents a linear aliphatic hydrocarbon group having 7 to 18 carbon atoms, X represents a hydrogen atom, —COOM or —SO ₃ M (M represents a hydrogen atom or a salt-forming cation)] Represents. ]

In the formula (d1), the aliphatic hydrocarbon group in R ¹ may be a saturated aliphatic hydrocarbon group (alkyl group) or an aliphatic hydrocarbon group having an unsaturated bond. As for carbon number of this aliphatic hydrocarbon group, 8-11 are preferable from the point which is excellent in the disinfection effect.
Examples of the salt-forming cation of M in —COOM or —SO ₃ M include alkali metals, alkaline earth metals, and cationic ammonium.
Examples of the alkali metal include sodium and potassium.
Examples of the alkaline earth metal include calcium and magnesium. In addition, when M is an alkaline earth metal, it corresponds to 1/2 atom. For example, when M is calcium, -COOM becomes "-COO ^- 1 / 2 (Ca)".
Examples of the cationic ammonium include alkanolamines such as monoethanolamine and diethanolamine, and specifically, those in which 1 to 3 hydrogen atoms of ammonium are substituted with alkanol groups. As for carbon number of an alkanol group, 1-3 are preferable.
As M, a hydrogen atom, an alkali metal, an alkaline earth metal or cationic ammonium is preferable, and a hydrogen atom or an alkali metal is more preferable.
In the formula (d1), the bonding position of X in the benzene ring is not particularly limited. From the viewpoint of production yield and organic peracid production efficiency, the para position (4th position) of the bonding position of R ¹ C (═O) O— is preferred.
Specific examples of the compound represented by the formula (d1) include, for example, decanoyloxybenzoic acid, sodium dodecanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, and the like. Therefore, decanoyloxybenzoic acid and sodium dodecanoyloxybenzenesulfonate are preferable. Among these, 4-decanoyloxybenzoic acid and sodium 4-dodecanoyloxybenzenesulfonate are preferable.

The component (D) is preferably blended as a granulated product or molded product, and more preferably blended as a granulated product, from the viewpoint of storage stability during storage.
In the granulated product or molded product, the content of the component (D) is preferably 30 to 95% by mass, and more preferably 50 to 90% by mass. If the content is less than 30% by mass or more than 95% by mass, the effect of granulation may not be sufficiently obtained.

Component (D) is preferably granulated or molded using a binder compound.
A well-known thing can be utilized as a binder compound. Preferable binder compounds include polyethylene glycol, saturated fatty acids having 12 to 20 carbon atoms, polyacrylic acid having a weight average molecular weight of 1,000 to 1,000,000 and salts thereof.
As the polyethylene glycol, polyethylene glycol having an average molecular weight of 500 to 25000 is preferable. The average molecular weight is more preferably 1000 to 20000, further preferably 2600 to 9300, and particularly preferably 7300 to 9300.
As a saturated fatty acid having 12 to 20 carbon atoms, a saturated fatty acid having 14 to 20 carbon atoms is preferable, and a saturated fatty acid having 14 to 18 carbon atoms is more preferable.
In addition, in this specification, the average molecular weight of polyethyleneglycol shows the average molecular weight described in cosmetic raw material standards (2nd edition comment). The weight average molecular weight of polyacrylic acid and its salt is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance.
In the granulated product or molded product, the content of the binder compound is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 5 to 20% by mass.

The granulated product or molded product may further contain a surfactant for improving the solubility of the granulated product or molded product in the treatment liquid.
Known surfactants can be used as the surfactant. Preferred surfactants include polyoxyalkylene alkyl ethers, olefin sulfonates, alkylbenzene sulfonates, alkyl sulfate esters, polyoxyethylene alkyl ether sulfates, mixtures of any two or more thereof, and the like.
The polyoxyalkylene alkyl ether preferably has 10 to 15 carbon atoms in the alkyl group, and the alkylene oxide is added with ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO). Is particularly preferred. The average number of added moles of alkylene oxide in the polyoxyalkylene alkyl ether is preferably 4 to 30 in total, and 5 to 15 in any case of EO, PO, or a mixture of EO and PO. More preferred. The molar ratio of EO / PO is preferably 5/0 to 1/5, and more preferably 5/0 to 1/2.
As the olefin sulfonate, a sodium salt or potassium salt of an α-olefin sulfonic acid having an alkyl group with 14 to 18 carbon atoms is preferable.
As the alkylbenzene sulfonate, a sodium salt or potassium salt of a linear alkylbenzene sulfonic acid having an alkyl group having 10 to 14 carbon atoms is preferable.
The alkyl sulfate ester salt is preferably an alkyl sulfate ester salt having an alkyl group having 10 to 18 carbon atoms, more preferably an alkali metal salt such as a sodium salt, more preferably sodium lauryl sulfate or sodium myristyl sulfate.
As a polyoxyethylene alkyl ether sulfate ester salt, the polyoxyethylene alkyl ether sulfate ester salt which has a C10-C18 alkyl group is preferable, and a sodium salt is more preferable. 1-10 are preferable and, as for the average polymerization degree (henceforth, average polymerization degree is described as POE) of the oxyethylene group in polyoxyethylene alkyl ether sulfate ester salt, 1-5 are more preferable. As the polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene lauryl ether sulfate sodium salt (POE = 2 to 5) and polyoxyethylene myristyl ether sulfate sodium salt (POE = 2 to 5) are particularly preferable.
In the granulated product or molded product, the content of the surfactant is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, and further preferably 5 to 30% by mass.

  The granulated product or molded product may further contain a film-forming polymer, zeolite, or the like. When the disinfectant composition contains an alkaline component and water, the presence of these components may cause hydrolysis of the component (D) during storage, which may impair the effect. And the occurrence of the decomposition can be suppressed.

The granulated product or molded product can be produced by a known granulation or molding method.
During granulation or molding, it is possible to melt the binder compound in advance and add it to component (D) (and surfactant, etc., if necessary) to maintain the strength, manufacturability, and storage stability of the granulated product or molded product. It is preferable because more favorable results can be obtained in improving the property. At this time, the temperature for melting the binder compound is preferably 40 to 100 ° C, more preferably 50 to 100 ° C, and still more preferably 50 to 90 ° C.
After stirring and mixing these components until uniform, a granulated product or molded product is obtained by granulating or molding.
As a preferable granulation method in the case of a granulated product, extrusion granulation can be exemplified. In this case, the average particle diameter of the granulated product is preferably 500 to 5000 μm, and more preferably 500 to 3000 μm.
Moreover, as a preferable shaping | molding method in the case of setting it as a molding, the method etc. which are made into a tablet shape with a briquette machine etc. are mentioned, for example.

A component (D) may be used individually by 1 type, and may use 2 or more types together.
In the disinfectant composition, the content of the component (D) may be appropriately set in consideration of the balance with other components and the method of use. For example, when the sterilizing composition is introduced into water to perform sterilization, the concentration of the component (D) in the treatment liquid after the addition is within a preferable range, and the concentration is set. Therefore, it is preferable to set so that the amount of the disinfectant composition necessary for the purpose is an amount suitable for use.
The concentration of the component (D) in the treatment liquid is not particularly limited, but is preferably 1.5 to 75 ppm, more preferably 1.5 to 45 ppm, and further preferably 1.5 to 30 ppm. If the concentration exceeds 75 ppm, the sterilization effect may not be enhanced, or conversely, the sterilization effect may be reduced. At the same time, damage to textiles such as clothing may occur. May not be obtained.

<Ingredient (E)>
Component (E) is a copper compound.
As described above, since the disinfectant composition is usually used by being poured into water, the component (E) is preferably one that generates copper ions in water.
Examples of copper compounds that generate copper ions in water include water-soluble copper salts. Examples of the water-soluble salt include nitrates, sulfates, chlorides, acetates, perchlorates, cyanides, ammonium chlorides, tartrates, and hydrates thereof.
As the component (E), copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, copper chloride, copper tartrate, copper perchlorate, copper gluconate, etc. are preferable and easy to handle. In view of safety, price, etc., copper sulfate pentahydrate is particularly preferable.

A component (E) may be used individually by 1 type, and may use 2 or more types together.
In the disinfectant composition, the content of the component (E) may be appropriately set in consideration of the balance with other components and the method of use. As an example, the component (E) is a component that generates copper ions in water, as described above, and the copper ion is the same as the component (B) as well as the zinc ions derived from the component (A). And forms a complex with the components (C) and (D) to exert a sterilizing effect. Therefore, when performing the sterilization by introducing the disinfectant composition into the treatment liquid, it is necessary for the concentration of Cu in the treatment liquid after the addition to be within a preferable range and for the concentration. It is preferable to set so that the amount of the disinfectant composition is an amount suitable for use.
The Cu concentration in the treatment liquid is not particularly limited and varies depending on the Zn concentration, but is preferably 0.002 to 0.15 ppm, more preferably 0.003 to 0.07 ppm, and 0.01 to 0.00. More preferred is 07 ppm. If it exceeds 0.15 ppm, the disinfection effect may be reduced, and if it is less than 0.002 ppm, a sufficient disinfection effect may not be obtained.
Further, the total concentration of Zn and Cu in the treatment liquid is not particularly limited, but is preferably 0.022 to 2.65 ppm, more preferably 0.063 to 1.27 ppm, More preferred is 0.77 ppm.

The component (A) and the component (E) are components that generate metal ions (zinc ions or copper ions) in water, as described above, and each metal ion forms a complex with the component (B). Can be formed. These complexes are considered to act together with the components (C) and (D) to exert a sterilizing effect.
In the disinfectant composition of the present invention, component (A) and component (E) are each complexed with component (B) (form a complex with component (B) with respect to zinc or copper contained in each component). You may mix | blend after letting it, and you may mix | blend without complexing.
Complexation may be performed for only one of component (A) and component (E), or may be performed for both components.
The complexation of component (E) can be carried out by the methods described in JP 2009-148682 A, JP 2009-148683 A, JP 2009-155292 A, and the like. The complexation of component (A) can be carried out by the same method as the complexation of component (E), except that component (A) is used instead of component (E).
In consideration of the beauty of the disinfectant composition, ease of production, and the like, it is preferable that the component (A) and the component (E) are not complexed and are individually added to the disinfectant composition.

The form of the disinfectant composition of the present invention may be a solid such as powder, granule, tablet, briquette, sheet or bar, or may be a liquid. A solid is preferable, and a powder is more preferable.
The method for preparing the disinfectant composition of the present invention is not particularly limited. For example, as described above, each part of the above-described components except that a part of the above components is appropriately complexed, granulated, or molded as necessary. It can be prepared according to a conventional method.

The disinfectant composition of the present invention is preferably used in combination with a detergent composition.
In this case, the disinfectant composition of the present invention may be used as a disinfectant separately from the detergent composition, and is blended in the detergent composition as a part of the components of the detergent composition. May be used.
The composition of the cleaning composition is not particularly limited, and conventionally known components can be used in appropriate combination as components to be blended in the cleaning composition. Examples of such components include components (I) to (XI) shown below.

[Component (I): Surfactant]
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Any one of these may be used alone, or two or more thereof may be appropriately combined. May be used.

The anionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various anionic surfactants can be used.
As an anionic surfactant, the following are mentioned, for example.
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(6) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(8) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(9) C8-20 saturated or unsaturated α-sulfo fatty acid salt or methyl, ethyl or propyl ester thereof. Among these, α-sulfo fatty acid salts or methyl esters thereof (α-SF or MES) are preferable.
(10) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(12) A higher fatty acid salt (soap) having 10 to 20 carbon atoms.
These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. Moreover, these anionic surfactants may mix any 2 or more types, and may use them as a mixture.

  Examples of the anionic surfactant include alkali metal salts of linear alkylbenzene sulfonic acid (LAS) (for example, sodium or potassium salt) and alkali metal salts of AOS, MES, AS, AES (for example, sodium or potassium salt). Further, alkali metal salts of higher fatty acids (for example, sodium or potassium salts) and the like can be mentioned as suitable ones, and it is particularly preferable to contain MES having a carbon chain length of 14 to 18.

The nonionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various nonionic surfactants can be used.
Examples of nonionic surfactants include the following.
(1) An average of 3 to 30 moles, preferably 4 to 20 moles, more preferably 5 to 17 moles of an alkylene oxide having 2 to 4 carbon atoms was added to an aliphatic alcohol having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.
(9) Fatty acid alkanolamide.
(10) Polyoxyethylene alkylamine.
(11) Alkyl glycoside.
(12) Alkylamine oxide.

Examples of the fatty acid alkyl ester alkoxylate (3) include those represented by the following general formula (31).
R ⁹ CO (OA) _n OR ¹⁰ (31)
In formula (31), R ⁹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms.
OA represents an addition unit of alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, and ethylene oxide, propylene oxide and the like are preferable.
n shows the average addition mole number of alkylene oxide, and is generally 3-30, Preferably it is 5-20.
R ¹⁰ represents an alkyl group having 1 to 3 carbon atoms which may have a substituent.

Among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ether having a melting point of 40 ° C. or less and an HLB value of 9 to 16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, fatty acid methyl ester and ethylene A fatty acid methyl ester ethoxylate to which an oxide is added, a fatty acid methyl ester ethoxypropoxylate in which ethylene oxide and propylene oxide are added to a fatty acid methyl ester, and the like are preferably used.
The HLB of the nonionic surfactant in the present invention is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991). , Page 234).
The melting point in the present invention is a value measured by a freezing point measurement method described in JIS K8001 “General rules for reagent test methods”.
Any one of these nonionic surfactants may be used alone, or two or more thereof may be used in appropriate combination.

The cationic surfactant is not particularly limited as long as it is conventionally used in detergents, and various cationic surfactants can be used.
Examples of the cationic surfactant include the following.
(1) Dilong chain alkyl dishort chain alkyl type quaternary ammonium salt.
(2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt.
(3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt.
The “long chain alkyl” in the above (1) to (3) represents an alkyl group having 12 to 26 carbon atoms. The alkyl group preferably has 14 to 18 carbon atoms.
“Short-chain alkyl” refers to an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkyl group preferably has 1 or 2 carbon atoms. Examples of the substituent that the alkyl group may have include a phenyl group, a benzyl group, a hydroxyl group, a hydroxyalkyl group, and a polyoxyalkylene group. 2-4 are preferable and, as for carbon number of a hydroxyalkyl group, 2 or 3 is more preferable. 2-4 are preferable and, as for carbon number of the alkylene group in a polyoxyalkylene group, 2 or 3 is more preferable.

  The amphoteric surfactant is not particularly limited as long as it is conventionally used in detergents, and various amphoteric surfactants can be used.

  In addition, this invention is not limited to the said surfactant, In addition, a well-known surfactant can be used suitably, Any 1 type of these may be used independently and 2 or more types are combined suitably. It may be used.

Component (I) is preferably blended into the detergent composition as surfactant-containing particles.
Suitable surfactant-containing particles include surfactant-containing particles having an anionic surfactant as a main surfactant and surfactant-containing particles having a nonionic surfactant as a main surfactant. Any one of these surfactant-containing particles may be used, or they may be used in combination.

[Surfactant-containing particles containing an anionic surfactant as the main surfactant]
Surfactant-containing particles having an anionic surfactant as a main surfactant (hereinafter referred to as anionic surfactant-containing particles) are those containing an anionic surfactant as an essential component and blended in the anionic surfactant-containing particles. It means the particles having the highest content of anionic surfactant among the active surfactants.
The anionic surfactant blended in the anionic surfactant-containing particles is not particularly limited, and the above-described various anionic surfactants can be used. The anionic surfactant blended in the anionic surfactant-containing particles may be one type or two or more types.
The anionic surfactant-containing particles can contain other surfactants (nonionic surfactants, cationic surfactants, amphoteric surfactants, etc.) other than anionic surfactants, although their contents are limited. is there.

The content of all the surfactants in the anionic surfactant-containing particles can be determined in consideration of the cleaning performance desired for the cleaning composition, for example, preferably 10 to 90% by mass, more preferably It is 15-70 mass%, More preferably, it is 15-50 mass%. If it is 10-90 mass%, sufficient washing | cleaning effect can be exhibited.
Further, in the anionic surfactant-containing particles, the mass ratio of the anionic surfactant / other surfactant is preferably 100/0 to 50/50, more preferably 100/0 to 55/45, and 95/5 to 70. / 30 is more preferable.

The anion-containing surfactant particles may contain components other than the surfactant.
Examples of other components that may be contained in the anionic surfactant-containing particles include components (II) to (XI) described later. Among these, an inorganic or organic detergency builder is preferable, and an inorganic builder is particularly preferable.
As the inorganic builder, potassium salts such as potassium carbonate and potassium sulfate, and alkali metal chlorides such as potassium chloride and sodium chloride are preferable because they have the effect of improving solubility. Among them, potassium carbonate, alkali metal chlorides such as potassium chloride and sodium chloride are preferable from the viewpoint of the balance between the effect of improving solubility and cost.
When potassium carbonate is blended, the content thereof is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and further preferably 3 to 3% in the anionic surfactant-containing particles from the viewpoint of improving the solubility. 10% by mass.
When blending an alkali metal chloride, the content is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, more preferably 2% by mass in the anion-containing surfactant-containing particles from the viewpoint of improving the solubility. It is 3-7 mass%.

Although the physical property value of the anionic surfactant-containing particles is not particularly limited, for example, the bulk density is usually preferably 0.3 g / mL or more, and preferably 0.5 to 1.2 g / mL. Is more preferable, and it is further more preferable that it is 0.6-1.1 g / mL.
The bulk density is a value measured according to JIS-K3362 (the same applies hereinafter).
Moreover, an average particle diameter (mass 50%) becomes like this. Preferably it is 200-1500 micrometers, More preferably, it is 300-1000 micrometers. If the average particle size (mass 50%) is less than 200 μm, dust may be easily generated, while if it exceeds 1500 μm, the solubility may be insufficient.
Furthermore, the fluidity of the anion-containing surfactant-containing particles is preferably 60 ° or less, particularly 50 ° or less as an angle of repose. If the angle of repose exceeds 60 °, the handleability of the particles may deteriorate.
The angle of repose can be measured by a so-called angle-of-rest angle of repose measuring method that measures the angle formed by the horizontal surface of the slip surface formed when particles filled in the container flow out (the same applies hereinafter).

Surfactant-containing particles having an anionic surfactant as a main surfactant can be obtained by a known method, for example, by the following method (1) or (2).
Method (1): A method of granulating a neutralized salt type anionic surfactant.
Method (2): A method in which an acid precursor of an anionic surfactant is dry neutralized and granulated.

Examples of the granulation method used in method (1) include the following methods (1-1) to (1-5).
(1-1) An extrusion granulation method in which a raw material powder of a detergent component and a binder compound (surfactant, water, liquid polymer component, etc.) are kneaded and kneaded, and then extruded and granulated.
(1-2) A kneading and crushing granulation method in which after kneading and kneading, the obtained solid detergent is crushed and granulated.
(1-3) An agitation granulation method in which a binder compound is added to a raw material powder and agitation is performed with an agitation blade to granulate.
(1-4) A rolling granulation method in which a raw material powder is rolled and sprayed with a binder compound for granulation.
(1-5) Fluidized bed granulation method in which a liquid binder is sprayed and granulated while fluidizing the raw material powder.

In the method (2), the acid precursor of the anionic surfactant and the alkaline inorganic powder are neutralized while being contacted and mixed, and granulated. As the granulation method at this time, basically, a granulation method similar to the granulation method mentioned in the method (1) can be used.
As the acid precursor of the anionic surfactant, any acid precursor can be suitably used as long as it is the acid precursor of the anionic surfactant described above.
Moreover, it is although it does not specifically limit as alkaline inorganic powder as a neutralizing agent, Alkali metal carbonate, alkali metal silicate, alkali metal phosphate, etc. are mentioned.
Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate / potassium carbonate and the like. Examples of the alkali metal silicate include sodium silicate and layered sodium silicate. Examples of the alkali metal phosphate include sodium tripolyphosphate and sodium pyrophosphate.
Among these, alkali metal carbonates are preferable, and sodium carbonate, potassium carbonate, and sodium carbonate / potassium are particularly preferable.
These can use 1 type (s) or 2 or more types.

  The anion-containing surfactant particles granulated by the above-described method can be classified as necessary, and only the anion-containing surfactant-containing particles having a desired particle size can be used in the product.

[Surfactant-containing particles containing nonionic surfactant as main surfactant]
Surfactant-containing particles containing a nonionic surfactant as a main surfactant (hereinafter referred to as nonionic surfactant particles) are nonionic surfactants that are essential components and are incorporated into nonionic surfactant particles. It means the particles having the highest content of nonionic surfactant among the active surfactants.
The nonionic surfactant blended in the nonionic surfactant-containing particles is not particularly limited, and the above-described various nonionic surfactants can be used. The nonionic surfactant blended in the nonionic surfactant-containing particles may be one type or two or more types.
Nonionic surfactant particles can contain other surfactants (anionic surfactants, cationic surfactants, amphoteric surfactants, etc.) other than nonionic surfactants, although their content is limited. is there.

The content of all the surfactants in the nonionic surfactant-containing particles can be determined in consideration of the cleaning performance desired for the cleaning composition, for example, preferably 5 to 85% by mass, more preferably It is 10-60 mass%. If it is 5-85 mass%, sufficient washing | cleaning effect can be exhibited.
Further, in the nonionic surfactant particles, the mass ratio of the anionic surfactant / other surfactant is preferably 100/0 to 50/50, more preferably 100/0 to 60/40, and 95/5 to 70. / 30 is more preferable.

The anion-containing surfactant particles may contain components other than the surfactant. The other components are not particularly limited, and for example, those mentioned as other components other than the surfactant in the description of the anionic surfactant-containing surfactant particles can be appropriately blended.
Among them, an inorganic or organic cleaning builder can be mentioned as a component that is suitably blended in the nonionic surfactant particles. As the cleaning builder, a cleaning builder that can be blended with the anionic surfactant-containing particles described above can be similarly used. The same applies to the content of suitable cleaning builder and cleaning builder.

Moreover, it is preferable to mix | blend the oil-absorbing support | carrier for carry | supporting a nonionic surfactant in nonionic surfactant particle | grains.
As the oil-absorbing carrier, an oil-absorbing substance having an oil absorption amount represented by the JIS-K5101 test method of preferably 80 mL / 100 g or more, more preferably 150 to 600 mL / 100 g is suitably used. Examples of such an oil-absorbing carrier include components described in JP-A-5-125400 and JP-A-5-209200. These oil-absorbing carriers can be used alone or in combination of two or more.
The oil-absorbing carrier is preferably contained in the nonionic surfactant particles in an amount of 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 15% by mass.

Moreover, it is preferable to mix | blend the clay mineral etc. as a granulation adjuvant in nonionic surfactant particle | grains.
As the clay mineral, those belonging to the smectite group and having a crystal structure of a dioctahedral three-layer structure or a trioctahedral three-layer structure are particularly preferable. The clay mineral that can be used as the detergent component preferably has an oil absorption of less than 80 mL / 100 g, more preferably 30 to 70 mL / 100 g, and a bulk density of preferably 0.1 g / mL or more, more preferably 0.2 to 1. 5 g / mL. Specific examples of such clay minerals include components described in JP-A-9-87691.
The clay mineral is preferably contained in the nonionic surfactant particles in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass.

The physical property value of the nonionic surfactant-containing particles is not particularly limited. For example, the bulk density is usually preferably 0.3 g / mL or more, and preferably 0.5 to 1.2 g / mL. Is more preferable, and it is further more preferable that it is 0.6-1.1 g / mL.
The average particle diameter is preferably 200 to 1500 μm, more preferably 300 to 1000 μm. When the average particle size is less than 200 μm, dust may be easily generated, while when it exceeds 1500 μm, the solubility may be insufficient.
Further, the fluidity of the nonionic surfactant-containing particles is preferably 60 ° or less, particularly 50 ° or less as an angle of repose. If it exceeds 60 °, the handleability of the particles may deteriorate.

The nonionic surfactant-containing particles can be obtained by the same granulation method as that for the anionic surfactant-containing particles.
The obtained nonionic surfactant particles can be classified as necessary, and only the nonionic surfactant-containing particles having a desired particle size can be used in products.

As the component (I), one type may be used alone, or two or more types may be used in combination.
The content of component (I) in the cleaning composition can be determined in consideration of the use of the cleaning composition.

[Component (II): Detergency Builder]
Detergency builders are roughly classified into inorganic builders and organic builders.
Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate, alkali metal sulfites such as sodium sulfite and potassium sulfite, and crystalline layered sodium silicate (for example, manufactured by Clariant Japan Co., Ltd.). Of crystalline alkali metal silicates such as [Na-SKS-6] (δ-Na ₂ O · 2SiO ₂ )), amorphous alkali metal silicates, sulfates such as sodium sulfate and potassium sulfate, sodium chloride And alkali metal chlorides such as potassium chloride, crystalline aluminosilicate, amorphous aluminosilicate, and the like. Among these, sodium carbonate, potassium carbonate, sodium silicate, and aluminosilicate are preferable.
As the aluminosilicate, either crystalline or amorphous (amorphous) can be used. From the viewpoint of cation exchange ability, crystalline aluminosilicate is preferred.
As the crystalline aluminosilicate, zeolite can be suitably blended, and any of A type, X type, Y type, and P type can be used as the zeolite.
The average primary particle size of the crystalline aluminosilicate is preferably 0.1 to 10 μm.

  When blending an inorganic builder as a cleaning composition in a disinfectant composition, the content of the inorganic builder in the cleaning composition may be appropriately set according to the type of inorganic builder used. For example, when crystalline aluminosilicate is blended as an inorganic builder, the content is 0.5 to 40 mass with respect to the total solid content of the cleaning composition in terms of powder properties such as detergency and fluidity. % Is preferable, 1 to 25% by mass is more preferable, 3 to 20% by mass is further preferable, and 5 to 15% by mass is particularly preferable.

Examples of the organic builder include polysaccharide oxides such as starch, cellulose, amylose and pectin, and polysaccharide derivatives such as carboxymethylcellulose.
The content of the organic builder is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, and further preferably 2 to 5% by mass with respect to the total solid content of the cleaning composition.

As a component (II), 1 type can be used individually or in combination of 2 or more types as appropriate. For the purpose of improving detergency and soil dispersibility in the washing liquid, it is preferable to use an organic builder and an inorganic builder such as zeolite in combination.
In order to provide sufficient detergency, the content of component (II) is preferably 10 to 80% by mass, and more preferably 20 to 75% by mass, based on the total solid content of the cleaning composition.

[Component (III): Fragrance]
The fragrance is not particularly limited, and for example, fragrance components and fragrance compositions described in JP-A Nos. 2002-146399 and 2003-89800 can be used.
In addition, a fragrance | flavor composition is a mixture which consists of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc.
When mix | blending the said fragrance | flavor composition in a cleaning composition, 0.001-20 mass% is preferable with respect to the total solid of a cleaning composition, and 0.01-10 mass% is more preferable. .
As a component (III), 1 type can be used individually or in combination of 2 or more types as appropriate.

[Component (IV): Dye]
Various dyes can be blended in order to improve the appearance of the composition.
As the pigment, either a dye or a pigment can be used. From the viewpoint of storage stability, a pigment is preferable, and a compound having oxidation resistance such as an oxide is particularly preferable. Examples of such compounds include titanium oxide, iron oxide, cobalt phthalocyanine, ultramarine blue, bitumen, cyanine blue, and cyanine green.
As a component (IV), 1 type can be used individually or in combination of 2 or more types as appropriate.

[Component (V): Optical brightener]
Examples of the optical brightener include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, and 2- (styryl). Examples thereof include fluorescent whitening agents such as phenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, and bis- (triazinylaminostilbene) disulfonic acid derivatives.
Examples of commercially available fluorescent whitening agents include Whiteex SA, Whitetex SKC (above, trade name; manufactured by Sumitomo Chemical Co., Ltd.), Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS-X (above, trade name; Ciba Specialty Chemicals), Lemonite CBUS-3B (above, trade name: manufactured by Khyati Chemicals), and the like. Of these, Tinopearl CBS-X and Tinopearl AMS-GX are preferred.
As a component (V), 1 type can be used individually or in combination of 2 or more types as appropriate.
As for content of a component (V), 0.001-1 mass% is preferable with respect to the total solid of a cleaning composition.

[Component (VI): Enzyme]
Enzymes (enzymes that inherently perform enzyme action during the washing step) are classified according to the reactivity of the enzymes, and include hydrolases, oxidoreductases, lyases, transferases, isomerases, etc. Either can be applied.
Particularly preferred are protease, esterase, lipase, nuclease, cellulase, amylase and pectinase.
Specific examples of protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promeline, carboxypeptidase A and B, aminopeptidase, aspergillopeptidase A and B, etc. As commercially available products, sabinase, alcalase, everase, cannase (manufactured by Novozymes), API21 (manufactured by Showa Denko KK), Maxacar, Maxapem (manufactured by Genencor), and protease K described in JP-A-5-25492 -14 or K-16.
Specific examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase and phosphotase.
Specific examples of the lipase include commercially available lipases such as lipolase, Lipex (trade name; manufactured by Novozymes), and liposome (manufactured by Showa Denko KK).
Specific examples of cellulase include commercially available cellzyme (trade name; manufactured by Novozymes), cellulase described in claim 4 of JP-A 63-264699, and the like.
Specific examples of amylase include commercially available stainzymes, termamyls, duramils (above, trade names; manufactured by Novozymes) and the like.
In addition, it is preferable that the enzyme is granulated as separately stable particles and used in a state of being dry blended with the detergent dough (particles).
As a component (VI), 1 type can be used individually or in combination of 2 or more types as appropriate.
As for content of component (VI), 0.3-2 mass% is preferable with respect to the total solid of a cleaning composition.

[Component (VII): Enzyme Stabilizer]
As the enzyme stabilizer, for example, calcium salt, magnesium salt, polyol, formic acid, boron compound and the like can be blended. Of these, sodium tetraborate and calcium chloride are more preferred.
As the component (VII), one type can be used alone, or two or more types can be used in appropriate combination.
As for content of a component (VII), 0.05-2 mass% is preferable with respect to the total solid of a cleaning composition.

[Component (VIII): Other polymers]
In order to impart a re-contamination preventing effect on hydrophobic fine particles as a binder and powder physical agent in the case of increasing the density, polyethylene glycol having an average molecular weight of 200 to 200,000, and cellulose derivatives such as polyvinyl alcohol and carboxymethyl cellulose Etc. can be blended.
Moreover, as a soil release agent, a copolymer or terpolymer of terephthalic acid and ethylene glycol and / or propylene glycol units can be blended.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer.
Among the above, polyethylene glycol having an average molecular weight of 1500 to 7000 is preferable.
As a component (VIII), 1 type can be used individually or in combination of 2 or more types as appropriate.
As for content of a component (VIII), 0.05-5 mass% is preferable with respect to the total solid of a cleaning composition.

[Component (IX): Anti-caking agent]
Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like.
As the component (IX), one type can be used alone, or two or more types can be used in appropriate combination.

[Component (X): Antifoaming agent]
Examples of the antifoaming agent include conventionally known antifoaming agents such as silicone / silica.
The antifoaming agent may be a defoaming agent granulated product produced using the method described in JP-A-3-186307, page 4, lower left column. Specifically, first, 20 g of Dow Corning silicone (compound type, PS antifoam) is added as a defoaming component to 100 g of maltodextrin (enzyme-modified dextrin) manufactured by Nissho Chemical Co., Ltd., and mixed to obtain a homogeneous mixture. . Next, 50% by mass of the obtained homogeneous mixture, 25% by mass of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25% by mass of neutral anhydrous sodium sulfate were mixed at 70 to 80 ° C., and then extruded by Fuji Powder Co., Ltd. Granulate with a granulator (model EXKS-1) to obtain a granulated product.
As a component (X), 1 type can be used individually or in combination of 2 or more types as appropriate.

[Component (XI): Reducing agent]
Examples of the reducing agent include sodium sulfite and potassium sulfite.

Furthermore, as long as the effect of the present invention is not hindered, components other than those described above, which are generally blended in clothing detergents and bleaching agents, can be blended.
The cleaning composition can be prepared by a known method.

The disinfectant composition of the present invention contains components (A) to (D), has a high disinfecting power, and is very difficult for conventional textile products such as clothing (especially cotton products). The attached gram-negative bacteria can be effectively removed. The disinfecting composition of the present invention has a high disinfecting power not only against Gram-negative bacteria but also against Gram-positive bacteria.
On the other hand, when any of the components (A) to (D) is missing, sufficient sterilizing power cannot be obtained.
For example, when the component (B) is not included among the components (A) to (D), the sterilizing power includes only the components (C) and (D) (not including the components (A) and (B)). It is equivalent to or lower than the case. The reason is that zinc ions generated from the component (A) degrade the overall sterilization effect by decomposing the hydrogen peroxide of the component (C) and the organic peracid generated from the component (D). It is done. The same applies to the component (E), and the copper ions generated from the component (E) decompose the hydrogen peroxide of the component (C) and the organic peracid generated from the component (D), thereby reducing the overall sterilization effect. It is thought to decrease. On the other hand, in this invention, it is estimated that a zinc ion and copper ion form a complex with a component (B), and exhibit a favorable microbe elimination effect, suppressing decomposition | disassembly of hydrogen peroxide etc.
Further, in the first embodiment of the present invention, the component (A) and the component (E) each exhibit a sterilization effect with different mechanism of action against Gram-negative bacteria, thereby synergistically eliminating the sterilization effect. Seems to be increasing. As the mechanism of action, the component (E) and the component (C) act on the cell wall of the gram-negative bacterium, the component (A) easily enters the gram-negative bacterium, and the component (A) is gram-negative. It is presumed that the enzyme possessed by the fungus is inhibited.

Therefore, the disinfectant composition of the present invention is suitable for disinfecting textile products, particularly cotton products. Examples of the textile products include textile products that are generally targeted for washing by washing (objects to be washed), and specifically include clothing, cloths, sheets, curtains, and the like.
However, the present invention is not limited to this, and can be applied to the sterilization of hard surfaces such as tableware, pottery, glass, plastic, and dentures.

Examples of the method for sterilizing a textile product using the sterilizing agent composition of the present invention include a method of bringing the sterilizing agent composition into contact with a textile product in water.
As the fiber product, a cotton product is particularly preferable because the effectiveness of the disinfectant composition of the present invention is high.
The contact between the disinfectant composition and the textile product is preferably performed under alkaline conditions of pH 10 or higher. If the pH is less than 10, sufficient sterilization effect may not be obtained. The pH here is a pH at 25 ° C.

The method for bringing the disinfectant composition into contact with the textile product is not particularly limited. For example, when the textile product is washed in a washing machine, the disinfectant composition is put into water, and the disinfectant composition is used. A method of immersing the fiber product in the added water is suitable.
The amount of the disinfectant composition used at this time is the Zn concentration in water, the concentration of component (C) (in terms of hydrogen peroxide), the concentration of component (D), and the Cu concentration in the description of each component. The concentration may be appropriately adjusted so as to be within the range mentioned as the preferred concentration in the treatment liquid. At this time, it is preferable that B / A (Zn) is within the preferable range mentioned in the description of the component (B).

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.
In the following examples, the raw materials used for the cleaning composition and the disinfecting composition are shown below.

(Raw material used for cleaning composition)
MES: Sodium salt of fatty acid methyl ester sulfonate having 16 carbon atoms / 18 carbon atoms = 80/20 (mass ratio) (manufactured by Lion Corporation; AI = 70%, the balance being unreacted fatty acid methyl ester, sodium sulfate, Methyl sulfate, hydrogen peroxide, water, etc.).
LAS-K: linear alkyl (10 to 14 carbon atoms) benzene sulfonic acid [Lypon LH-200 (LAS-H pure content 96%) manufactured by Lion Co., Ltd., 48% potassium hydroxide aqueous solution during preparation of surfactant composition Neutralized). The compounding amount in Table 1 indicates mass% as LAS-K converted to a pure component.
LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid [Lypon LH-200 (LAS-H pure content 96%) manufactured by Lion Co., Ltd., 48% sodium hydroxide aqueous solution when preparing the surfactant composition] Neutralized). The compounding amount in Table 1 indicates mass% as LAS-Na in terms of pure content.
Soap: fatty acid sodium having 12 to 18 carbon atoms [manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: C12: 11.7%, C14: 0.4%, C16: 29 2%, C18F0 (stearic acid): 0.7%, C18F1 (oleic acid): 56.8%, C18F2 (linoleic acid): 1.2%, molecular weight: 289].
Nonionic surfactant: Leox CC-150-90 (manufactured by Lion Chemical Co., Ltd., an average of 15 mol of ethylene oxide adduct of alcohol having an alkyl group having 12 to 14 carbon atoms).
A type zeolite: A type zeolite (manufactured by Mizusawa Chemical Co., Ltd.).
Potassium carbonate: Potassium carbonate (Asahi Glass Co., Ltd.).
-Anhydrous sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Shikoku Kasei Kogyo Co., Ltd.).
Enzyme: Mixture of Evalase 8T (Novozymes) / LIPEX50T (Novozymes) / Termamyl 60T (Novozymes) / Celzyme 0.7T (Novozymes) = 5/2/1/2 (mass ratio).
CMC: carboxymethylcellulose sodium (manufactured by Daicel Chemical Industries, CMC Daicel 1170).
-Sodium carbonate: Heavy sodium carbonate (Asahi Glass Co., Ltd., soda ash).

(Raw material used for disinfectant composition)
[Component (A)]
ZnSO ₄ · 7H ₂ O: Zinc (II) sulfate heptahydrate (manufactured by Kanto Chemical Co., Inc.).
ZnSO ₄ .H ₂ O: Zinc (II) sulfate monohydrate (manufactured by Shinyo Co., Ltd.).
ZnCl ₂ : Zinc (II) chloride (manufactured by Kanto Chemical Co., Inc.).
Zn (NO ₃ ) ₂ · 7H ₂ O: Zinc (II) sulfate heptahydrate (manufactured by Kanto Chemical Co., Inc.).

[Component (B)]
Polymer 1: Polyethyleneimine (manufactured by BASF, trade name Lupasol HF, weight average molecular weight: about 25000).
Polymer 2: An aminopolycarboxylic acid polymer (BASF) in which Y ^{1 to} Y ³ are —CH ₂ —COONa and Y ⁴ is — (CH ₂ ) ₂ N (CH ₂ COONa) ₂ in the general formula (I) Manufactured, trade name: Trilon P, weight average molecular weight: about 50000).
Polymer 3: A copolymer of acrylic acid and maleic acid represented by the general formula (II) (manufactured by Nippon Shokubai, trade name: Aqualic TL-400 (40% product), weight average molecular weight: about 50000).
The weight average molecular weight of the component (B) was determined by a gel permeation chromatography (GPC) method using pullulan having a known molecular weight (Shodex Standard P-82 manufactured by Showa Denko) as a standard substance.

[Component (C)]
Sodium percarbonate: Zhejiang JINKE CHEMICALS, Inc. Product name: SPCC, effective oxygen amount 13.8%, average particle size 870 μm.

[Component (D)]
OBS12: Sodium 4-dodecanoyloxybenzenesulfonate (synthetic product).
OBC10: 4-decanoyloxybenzoic acid (made by Mitsui Chemicals, Inc.).
TAED: Tetraacetylethylenediamine (manufactured by Clariant, trade name: Selective AN).

[Component (E)]
CuSO ₄ · _5H 2 O: copper (II) sulfate pentahydrate (manufactured by Kanto Chemical Co., Inc.).
CuCl ₂ · 2H ₂ O: Copper (II) chloride dihydrate (manufactured by Kanto Chemical Co., Inc.).
Cu (NO ₃ ) ₂ .3H ₂ O: Copper nitrate (II) trihydrate (manufactured by Kanto Chemical Co., Inc.).

The OBS 12 is synthesized by the following procedure.
Sodium p-phenolsulfonate (reagent manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide (reagent manufactured by Kanto Chemical Co., Ltd.), lauric acid chloride (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), acetone (Kanto Chemical Co., Ltd.) Synthesis was carried out by the following method using a reagent manufactured by the company. 100 g (0.46 mol) of sodium p-phenolsulfonate dehydrated in advance was dispersed in 300 g of dimethylformamide, and lauric acid chloride was added dropwise at 50 ° C. over 30 minutes while stirring with a magnetic stirrer. After completion of the dropwise addition, the reaction was carried out for 3 hours. Dimethylformamide was distilled off at 100 ° C. under reduced pressure (0.5 to 1 mmHg), washed with acetone, and then recrystallized in a water / acetone (= 1/1 mol) solvent. . The yield was 90%.

<Production Example 1: Preparation of detergent composition particles>
The detergent composition particles having the composition shown in Table 1 were prepared by a series of steps shown below.

[Spray drying process]
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. To this, a surfactant excluding MES and nonionic surfactant was added, and after stirring for 10 minutes, a part of the A-type zeolite (1.0% by mass for addition at the time of kneading from the addition amount described in Table 1) , 5.0 mass% for grinding aid, 1.5 mass% for surface modification excluding A-type zeolite), sodium carbonate, potassium carbonate, and anhydrous sodium sulfate were added. After further stirring for 20 minutes to prepare a slurry for spray drying having a moisture content of 38% by mass, the slurry is spray-dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size (mass 50%) of 320 μm, Spray-dried particles having a bulk density of 0.30 g / cm ³ and a water content of 5% were obtained.

[Kazuwa kneading process]
On the other hand, an aqueous slurry of MES-Na (prepared to a water concentration of 25% by mass) obtained by sulfonating and neutralizing the fatty acid ester of the raw material, a part of the nonionic surfactant (based on MES-Na). 25% by mass) and concentrated under reduced pressure with a thin-film dryer until the water concentration became 11% by mass to obtain a mixed concentrate of MES-Na and nonionic surfactant.
The spray-dried particles obtained in the above [spray-drying step], the above-described mixed concentrate, 1.0% by mass of A-type zeolite, the nonionic surfactant to be spray-added in the surface coating step described later, and the nonion in the mixed concentrate The remaining nonionic surfactant, excluding the surfactant, and water were put into a continuous kneader (KRC-S4 type, manufactured by Kurimoto Seiko Co., Ltd.), and kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. A surfactant-containing kneaded product having a water content of 6% by mass and containing a surfactant was obtained. The surfactant-containing kneaded material is cut with a cutter while extruding the pellet using a pelleter double (Fuji Powder Co., Ltd., EXBFJS-100 type) equipped with a die with a hole diameter of 10 mm (cutter peripheral speed is 5 m / m). s) to obtain a pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm.

[Crushing process]
Next, an amount corresponding to 5.0% by mass of particulate A-type zeolite (average particle diameter 180 μm) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and cold air (10 ° C., 15 m / s) was added. ) Grinding using a Fitzmill (Doka-3, manufactured by Hosokawa Micron Corporation) arranged in three stages in series under the coexistence (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm) The number of rotations: 1st stage / 2nd stage / 3rd stage is 4700 rpm) to obtain a pulverized product.

[Surface coating process]
Thereafter, the pulverized surfactant-containing particles and CMC were mixed into a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, clearance 13 mm between the inner wall surface of the drum and the inner wall surface of the container 131.7 L, height 45 mm). 1 type zeolite for surface modification under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm and 25 ° C., and 0.5% by mass Rolling for 1 minute while spraying the nonionic surfactant, surface-modified surfactant-containing particles were obtained.

[Powder mixing process]
While the obtained surfactant-containing particles were transferred at a speed of 0.5 m / s by a belt conveyor (surfactant-containing particle layer height 30 mm, layer width 300 mm on the belt conveyor), 1.0% by mass A considerable amount of enzyme was fed quantitatively to obtain the desired detergent composition particles.

<Test Example 1>
The sterilization test for evaluating the sterilization power against E. coli adhering to the cotton cloth is based on the assumption that the actual laundry is performed, and is described in Journal of the Association of Official Analytical Chemist 52; 836-842. N. This was performed according to the method of Petroci et al. The specific procedure is shown below.

(Pretreatment of cotton cloth)
Kanakin No. 3 (conforms to JIS L0803) was used as a cotton cloth to be subjected to a sterilization test, and pretreatment was performed by the method shown below before the test.
Polysorbate 80 and sodium carbonate were dissolved in 5 g of water each and diluted to 1000 ml as a wetting agent. A 5 L cleaning solution was prepared by dissolving 2.5 g of a wetting agent and 2.5 g of sodium carbonate in water. A cotton cloth was put therein and boiled for about 1 hour, and then boiled for about 5 minutes instead of distilled water. Further, the mixture was stirred with 5 L of cold distilled water for about 5 minutes and air-dried.

(Cutting of test cloth)
The pre-treated cotton cloth was cut to prepare a 2.5 cm × 3.75 cm cotton cloth and a 5.3 cm × 275 cm cotton cloth.
A cotton cloth of 5.3 cm × 275 cm was wound around a stainless steel spindle described in Journal of the Association of Official Analytical Chemist 52; 837, and used as a load cloth for bringing the quantity ratio of the test liquid and the cotton cloth closer to actual washing.
A 2.5 cm × 3.75 cm cotton cloth was used as a test cloth by adding a bacterial solution by the following method.
In addition, all subsequent operations were performed using cloth, water, instruments, etc. that had been sterilized at 121 ° C. for 10 minutes.

(Addition of E. coli solution)
After the test cloth was dried by holding at 110 ° C. for 1 hour in a dry heat sterilizer, 10 μL of physiological saline was added onto the test cloth. Subsequently, a mixed solution of 1.9 mL of E. coli solution adjusted so that the viable cell count is 5.0 × 10 ⁸ to 5.0 × 10 ⁹ cfu / mL and 0.1 mL of horse serum (manufactured by Invitrogen) And 20 μL of the mixture was added onto the test cloth.
Three test cloths were put in a petri dish with filter paper and held in a desiccator containing silica gel in a 37 ° C. constant temperature bath for 40 minutes, and then three test cloths to which a bacterial solution was added were wrapped around a spindle. Inserted between.

(Preparation of disinfectant composition aqueous solution (treatment solution))
In the glass container, the detergent composition particles and the respective components shown in Tables 2 to 8 are added, and water is added so that the total amount becomes 250 g. Excluding Examples 1 to 78 and Comparative Examples 1 to 14 A fungus composition aqueous solution was prepared.
In Tables 2-8, the compounding quantity (ppm) in each disinfectant composition aqueous solution was shown. The compounding amount of each component in the table indicates a value converted into a pure component. The blending amount is the mass (mg) of each component contained in 1000 g of the disinfectant composition aqueous solution.
In any example, the detergent composition particles were added so that the blending amount in the aqueous solution of the disinfectant composition was 620 ppm.

(Bacteria elimination test)
The load cloth into which the test cloth is inserted is immersed in the glass container containing the prepared disinfectant composition aqueous solution, and the glass container is covered and attached to a rotating device (manufactured by Matsushita Kogyo Co., Ltd.) at 60 rpm. Rotated at speed for 10 minutes.
After completion of the test, three test cloths were taken out with tweezers, placed in a sterilized plastic bag, 30 mL of SCDLP medium (Nippon Pharmaceutical's Soybean-Casein Broth with Lectin & Polysorbate 80) was added, and the test bacteria inoculated on the test cloth with an extractor Was washed out for 1 minute. 1.0 mL of the extract was collected and added to 9.0 mL of physiological saline to obtain a 10-fold diluted solution. The same method was repeated to obtain each diluted solution.
Collect 100 μL from each diluted solution, add to standard agar medium (manufactured by Actect Co., Ltd.), apply evenly with a congeal rod and incubate in a 37 ° C. thermostat for 1-2 days, then count the number of colonies The number of viable bacteria was determined by

(Sterilization power evaluation)
The number of viable bacteria was determined in the same manner as in the sterilization test except that a 500 ppm aqueous solution of polysorbate 80 was used as a control sample instead of the sterilizing agent aqueous solution.
From these results, the logarithm of the viable cell count when using each aqueous solution of the disinfectant composition and the viable cell count when using the control sample according to the following mathematical formula (2) as an index indicating the sterilization power The difference was calculated. The results are shown in Tables 2-8. The larger the logarithmic difference was, the higher the sterilizing power was, and a logarithmic difference of 1.8 or more was determined to have a sterilizing effect.
Logarithmic difference = log ₁₀ (viable cell count when using a control sample) −log ₁₀ (viable cell count when using a disinfectant composition aqueous solution) (2)

  In Tables 2 to 8, Mw means molecular weight.

Claims (7)

A disinfectant composition comprising the following components (A) to (D):
Component (A): Zinc compound.
Component (B): at least one selected from the group consisting of polyethyleneimine, a polymer having a structural unit represented by the following general formula (I), and a polymer having a structural unit represented by the following general formula (II) Compound.
Component (C): hydrogen peroxide or a peroxide that releases hydrogen peroxide in water.
Component (D): An organic peracid precursor that reacts with the component (C) to generate an organic peracid.

[Wherein Y ^{1 to} Y ⁴ are each independently a hydrogen atom, an alkyl group, a general formula — (CH ₂ ) _m —X ¹ {wherein X ¹ is a primary amino group, a secondary amino group, A tertiary amino group, an amide group, or a hydroxyl group is represented, and the secondary amino group, the tertiary amino group, and the amide group each represent —COOX ¹¹ as a substituent (wherein X ¹¹ represents a hydrogen atom or a salt-forming cation). And m represents 1 or 2. } Or a general formula — (CH ₂ ) _n —COOX ² {wherein X ² represents a hydrogen atom or a salt-forming cation, and n represents 1 or 2. }, And at least one of Y ^{1 to} Y ⁴ is represented by the general formula — (CH ₂ ) _m —X ¹ , and X ¹ in the formula is —COOX ¹¹ as a substituent. Or a group represented by the general formula — (CH ₂ ) _n —COOX ² . ]

[Wherein, A ¹ and A ² are each independently a hydrogen atom, an alkyl group, a general formula — (CH ₂ ) _p —X ³ {wherein X ³ is a primary amino group, a secondary amino group, A tertiary amino group, an amide group or a hydroxyl group is represented, and the secondary amino group, the tertiary amino group and the amide group each represent —COOX ³¹ as a substituent (wherein X ³¹ represents a hydrogen atom or a salt-forming cation). And p represents an integer of 0 to 2. } Or a general formula — (CH ₂ ) _q —COOX ⁴ {wherein X ⁴ represents a hydrogen atom or a salt-forming cation, and q represents an integer of 0 to 2. }, At least one of A ¹ and A ² is represented by the general formula — (CH ₂ ) _p —X ³ , and X ³ in the formula is —COOX ³¹ as a substituent. Or a group represented by the general formula — (CH ₂ ) _q —COOX ⁴ . ]   The disinfectant composition according to claim 1, wherein a mass ratio of the component (B) to Zn derived from the component (A) is in the range of 0.5 to 12.   The disinfectant composition according to claim 1 or 2, which is used by being contained in water so that the Zn concentration becomes 0.1 to 7 ppm. Furthermore, the disinfectant composition of Claim 1 or 2 containing the following component (E).
Component (E): Copper compound.   The disinfectant composition according to claim 4, which is used by being contained in water so that the Zn concentration is 0.02 to 2.5 ppm and the Cu concentration is 0.002 to 0.15 ppm. The disinfectant composition according to any one of claims 1 to 5, wherein the component (D) is represented by the following general formula (d1).

[Wherein R ¹ represents a linear aliphatic hydrocarbon group having 7 to 18 carbon atoms, X represents a hydrogen atom, —COOM or —SO ₃ M (wherein M represents a hydrogen atom or a salt-forming cation) Represents.) ]   A disinfecting method comprising contacting the disinfectant composition according to any one of claims 1 to 6 with a textile product in water.