JP5557627B2 - Detergent composition, method for producing the same, and washing method - Google Patents

Description

The present invention relates to a detergent composition, a method for producing the same, and a washing method.

In commercial cleaning, commercial washing machines such as large drum washing machines and continuous washing machines are generally used. In addition, a detergent solution in which a detergent, a cleaning aid, and the like are dissolved and dispersed is prepared in advance, and the detergent solution is put into a commercial washing machine for washing.
At that time, for example, when an oxygen-based bleaching agent containing hydrogen peroxide or the like as a bleaching component is used in combination, an oxygen-based bleaching solution is prepared separately from the detergent solution and put into a commercial washing machine.

So far, in a washing method using an oxygen-based bleach, a method of adding a water-soluble salt containing manganese or iron and a multidentate ligand (chelating agent) as a means for enhancing the activity of a bleaching component has been disclosed. (For example, see Non-Patent Documents 1 and 2).
Moreover, the oxidation catalyst containing the copper compound and the specific chelating agent which has a disinfection effect with a bleaching effect is disclosed (for example, refer patent document 1).

Nature, VOL. 369 (1994) 637-639 J. et al. Am. Chem. Soc, VOL. 115 (1993) 1772-1773.

WO09 / 0748459 pamphlet

In commercial cleaning, not only a bleaching effect on stains such as stains but also oil stains are required to have a higher cleaning effect than ordinary washing at home. Moreover, with the recent increase in hygiene awareness, sanitization and sterilization effects are also required for commercial cleaning. For this reason, a detergent composition that can be used in combination with a bleaching agent to obtain a sterilizing and sterilizing effect and also exhibits a high cleaning effect against oil stains in addition to a bleaching effect against stains such as stains.
However, in conventional detergent compositions, for example, even when used in combination with an oxygen-based bleach, the detergent composition and the oxygen-based bleach exhibit a washing effect and a bleaching effect, respectively, or bleach components by the detergent composition Since the effect of increasing the activity of the oil was weak, there was nothing that could sufficiently clean the oil stains.
The present invention has been made in view of the above circumstances, and it is intended to provide a detergent composition and a washing method capable of sufficiently washing oil stains by using the oxygen-based bleach in combination with the activity of the bleaching component to be significantly improved. Let it be an issue. Furthermore, this invention makes it a subject to provide the detergent composition and washing | cleaning method which can obtain a high disinfection and bactericidal effect in combination with an oxygen type bleaching agent.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the detergent composition of the present invention comprises a granular water-soluble salt (A) containing a transition element, zinc or silver in the fourth period of the periodic table, an aminocarboxylic acid or a salt thereof (B), and an alkali agent ( C) and the water-soluble salt (A) is characterized in that particles having a particle size of 300 μm or less are 30% by mass or more.

In the detergent composition of the present invention, the aminocarboxylic acid or a salt thereof (B) is selected from the group consisting of methylglycine diacetate, iminodisuccinic acid, hydroxyiminodisuccinic acid, nitrilotriacetic acid, alkylaminodiacetic acid, and salts thereof. It is preferable to include at least one selected.
Moreover, it is preferable that the detergent composition of the present invention further comprises a polycarboxylic acid polymer compound (D).

  The washing method of the present invention is characterized in that the detergent composition of the present invention is used in combination with at least one selected from the group consisting of a compound that dissolves in water to generate hydrogen peroxide and hydrogen peroxide. And

According to the detergent composition of the present invention, the activity of the bleaching component can be remarkably enhanced when used in combination with an oxygen-based bleaching agent, so that oil stains can be sufficiently washed.
Further, according to the washing method of the present invention, the activity of the bleaching component is remarkably increased, and the oil stain can be sufficiently washed.
Furthermore, this invention can provide the detergent composition and washing | cleaning method which can obtain a high disinfection and bactericidal effect in combination with an oxygen bleach.

<Detergent composition>
The detergent composition of the present invention comprises a granular water-soluble salt (A) (hereinafter referred to as “component (A)”) containing a transition element, zinc or silver in the fourth period of the periodic table, an aminocarboxylic acid or its A salt (B) (hereinafter referred to as “component (B)”) and an alkali agent (C) (hereinafter referred to as “component (C)”) are blended.

Among the transition elements in the 4th period of the periodic table, zinc or silver, when used in combination with an oxygen-based bleach, the detergency and sterilization power of oil stains will increase, so copper, manganese, nickel , Cobalt, iron, zinc and silver are preferable, copper, manganese and zinc are more preferable, and copper is particularly preferable.
Examples of water-soluble salts include sulfates, chlorides, acetates, and citrates, and sulfates and chlorides are preferred because of their particularly good solubility in solvents such as water. More preferred.
Specific examples of the component (A) include sulfates such as copper sulfate, manganese sulfate, nickel sulfate, cobalt sulfate, iron sulfate, zinc sulfate, and silver sulfate; cupric chloride, manganese chloride, nickel chloride, cobalt chloride, and chloride. Examples include chlorides such as iron and zinc chloride. Among them, copper sulfate, manganese sulfate, and secondary chloride are good because they have good cleaning power and disinfection / sterilization power against oil stains and solubility in solvents. Copper and zinc sulfate are preferable, and copper sulfate, manganese sulfate, and zinc sulfate are more preferable.
As the component (A), a hydrate of the above compound can be used in addition to the above compound.

  The component (A) in the present invention is granular, and particles having a particle diameter of 300 μm or less are 30% by mass or more, preferably 45% by mass or more, more preferably 60% by mass or more, More preferably, it is 75 mass% or more, and may be 100 mass%. When the ratio of particles having a particle diameter of 300 μm or less is at least the lower limit value, oil stains can be sufficiently washed in combination with an oxygen bleach. In addition, the sterilization and bactericidal power is enhanced in combination with an oxygen bleach.

  In addition, the component (A) is preferably less than 20% by mass of particles having a particle diameter of 710 μm or more, more preferably less than 15% by mass, and more preferably less than 10% by mass. The content is more preferably less than mass%, particularly preferably less than 1 mass%, and most preferably not containing particles having a particle diameter of 710 μm or more. When the proportion of particles having a particle size of 710 μm or more is less than 20% by mass, the solubility of the component (A) is further improved, and oil stains can be sufficiently washed in combination with an oxygen bleach. In addition, the sterilization and bactericidal power is enhanced in combination with an oxygen bleach.

Here, the “ratio of particles having a particle size of 300 μm or less” means the mass value of all particles having a particle size of 300 μm or less with respect to the mass of the entire component (A).
The “ratio of particles having a particle diameter of 710 μm or more” means the value of the mass of all particles having a particle diameter of 710 μm or more with respect to the mass of the entire component (A).

In order to obtain the component (A) having a particle size of 300 μm or less or 710 μm or more, the following classification operation (a) is performed using a mortar or a pulverizer as necessary, and the following classification operation (a) is performed with an opening of 300 μm or 710 μm. What is necessary is just to perform suitably using a sieve.
Classification operation (a):
This is performed using a sieve having an opening of a desired size according to JIS Z8801-1 and a tray.
Specifically, 100 g of the component (A) is put on a sieve having an opening of 300 μm or 710 μm, covered with a low-tap type sieve shaker (manufactured by Iida Manufacturing Co., Ltd., tapping: 156 times / minute, rolling : 290 times / min), and after shaking for 10 minutes, the one remaining on the saucer is separated.

(A) A component should just contain a particle | grain with a particle diameter of 300 micrometers or less in a predetermined ratio as mentioned above.
The individual particles in component (A) preferably have a particle size of 300 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less. When the particle diameter is 300 μm or less, the solubility in water and the like is improved, the detergency against oil stains is further increased, and the sterilization / sterilization power is also increased.
The smaller the particle size of the component (A) is, the lower limit is not particularly limited, and the particle size is about 100 μm, and a sufficiently high cleaning effect against oil stains can be obtained. The effect is improved.

(A) As a method of mix | blending a component, the method of spraying the solution which melt | dissolved the (A) component in water or the organic solvent to the detergent raw material mixture which (A) component is not mix | blended is preferable. In particular, in view of the solubility of the component (A) itself and the cost of the solvent, it is most preferable to use an aqueous solution in which the component (A) is dissolved in water.
When spraying the aqueous solution, the temperature of the aqueous solution is preferably room temperature (25 ° C.) or more and less than 100 ° C., more preferably 30 ° C. or more and less than 90 ° C. Further, the concentration of the aqueous solution is preferably a concentration of 1/2 or more of the saturation concentration at room temperature (25 ° C.), and is a concentration of 3/4 or more of the saturation concentration at room temperature (25 ° C.). More preferably, it is particularly preferably a saturated concentration or more at room temperature. When the concentration of the aqueous solution is low, the amount of water in the aqueous solution increases, and the detergent composition tends to solidify. Therefore, it is preferable that the aqueous solution is heated to room temperature (25 ° C.) or higher, and sprayed with a solution having a saturated concentration or higher at room temperature. Thereby, the spraying quantity of this aqueous solution can be reduced, and spraying time can be shortened.

(A) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The proportion of the component (A) in the detergent composition of the present invention is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, and 0.1 to 0.5% by mass. More preferably. When the proportion of the component (A) is at least the lower limit value, when used in combination with an oxygen bleach, the cleaning power against oil stains is further increased, and the sterilization / sterilization power is increased. If it is below the upper limit, sufficient detergency, disinfection and sterilization power against oil stains can be obtained. It is also economically advantageous.

[Aminocarboxylic acid or salt thereof (B)]
(B) A component is not specifically limited, What is mix | blended with the powder detergent for clothing etc. can be used generally.
Among the components (B), suitable compounds are those represented by the following general formula (I), for example, the following general formula, since the detergency against oil stains is further improved when used in combination with an oxygen bleach. The compound represented by (II) is mentioned.

［式（Ｉ）中、ＡはＣＨ_３、ＣＨ_２ＯＨ、ＯＨ、Ｈ、又はＣＯＯＭを表し；ｍ及びｎは、それぞれ０〜２の整数である。式（ＩＩ）中、ＸはＯＨ又はＨを表す。Ｍは、それぞれＨ、アルカリ金属原子、又はカチオン性アンモニウムを表す。］

[In formula (I), A is _{CH 3, CH 2 OH, OH} , H, or an COOM; m and n are each an integer of 0 to 2. In formula (II), X represents OH or H. M represents H, an alkali metal atom, or cationic ammonium, respectively. ]

In the general formula (I), A represents CH ₃ , CH ₂ OH, OH, H, or COOM. A is preferably CH ₃ , OH, H or COOM, more preferably CH ₃ or H, and particularly preferably CH ₃ .
m and n are each an integer of 0-2. m is preferably 0 or 1. n is preferably 0 or 1.
When both m and n are 0, A is preferably CH ₃ or H.
M represents H, an alkali metal atom, or cationic ammonium, respectively. As an alkali metal atom, sodium and potassium are preferable. The cationic _{ammonium, NH 3 CH 2 CH 2 OH} , NH 2 (CH 2 CH 2 OH) 2, NH (CH 2 CH 2 OH) 3, NH 4, trimethylammonium, tetramethylammonium preferred. As M, an alkali metal atom is preferable, and sodium is particularly preferable. Further, the plurality of M may be the same or different.

  Among the compounds represented by the general formula (I), preferred are methylglycine diacetate (MGDA), aspartate diacetate (ASDA), isoserine diacetate (ISDA), β-alanine diacetate (ADAA), Examples include serine diacetate (SDA), glutamate diacetate (GLDA), nitrilotriacetic acid (NTA), or salts thereof, and methylglycine diacetate (MGDA), nitrilotriacetic acid (NTA), or salts thereof are more preferable. More preferred is methylglycine diacetic acid (MGDA) or a salt thereof.

In the general formula (II), X represents OH or H.
M is the same as M in the general formula (I), and the plurality of M may be the same or different.
Preferred examples of the compound represented by the general formula (II) include iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), and salts thereof, among which hydroxyiminodisuccinic acid. (HIDS) or a salt thereof is more preferable.

In addition, as a suitable component (B), when used in combination with an oxygen-based bleach, the detergency against oil stains is further enhanced, and a high sterilizing and bactericidal effect against both E. coli and S. aureus Can be easily obtained, and aminocarboxylic acids having a long chain (preferably having 8 or more carbon atoms) hydrocarbon group or salts thereof are also included.
The long chain (preferably having 8 or more carbon atoms) hydrocarbon group may be saturated or unsaturated, and the carbon number thereof is preferably 8 to 22, and more preferably 12 to 18.
Preferred examples of the aminocarboxylic acid having a long chain (preferably having 8 or more carbon atoms) hydrocarbon group or a salt thereof include compounds represented by the following general formula (III).

［式（ＩＩＩ）中、Ｒ^９は炭素数８〜２２の直鎖状もしくは分岐鎖状のアルキル基又はアルケニル基であり、Ａ^１はＨ、ＣＨ_３、又は（ＣＨ_２）ｒ−ＣＯＯＸ^２であり、Ｘ^１及びＸ^２はそれぞれＨ、アルカリ金属原子、アルカリ土類金属原子、又はカチオン性アンモニウムを表す。ｐ及びｒはそれぞれ１〜３の整数である。］

[In Formula (III), R ⁹ is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and A ¹ is H, CH ₃ , or (CH ₂ ) r-COOX ² X ¹ and X ² each represent H, an alkali metal atom, an alkaline earth metal atom, or cationic ammonium. p and r are integers of 1 to 3, respectively. ]

In the general formula (III), R ⁹ is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms.
The number of carbon atoms of R ⁹ is more preferably 12 to 18. Although the reason for this is not clear, if the alkyl group or alkenyl group has 8 or more carbon atoms, the alkyl group or alkenyl group is particularly likely to be adsorbed to bacteria, and the metal (in the fourth period) It is considered that transition elements, zinc, and silver) ions tend to come into contact with bacteria. On the other hand, when the number of carbon atoms in the alkyl group or alkenyl group is 22 or less, the solubility in water is increased, and the sterilization performance and bactericidal performance are maintained. Preferably, when R ⁹ is an alkyl group or alkenyl group having 12 to 18 carbon atoms, the balance between hydrophobicity (adsorbability to bacteria) and hydrophilicity (solubility in water) is improved, so that it is more effective. It is thought that sterilization performance and sterilization performance can be expressed.

A ¹ is H, CH ₃ , or (CH ₂ ) r—COOX ² , and particularly preferably (CH ₂ ) r—COOX ² .
r is an integer of 1 to 3. If r is within this range, it is considered that a metal complex (described later) formed by mixing the component (A) and the component (B) is more stably formed.
X ¹ and X ² each represent H, an alkali metal atom, an alkaline earth metal atom, or cationic ammonium.
Examples of the alkali metal atom include sodium and potassium. Examples of the alkaline earth metal atom include magnesium and calcium. Examples of the cationic ammonium include NH ₄ , trimethylammonium, tetramethylammonium, NH ₃ (CH ₂ CH ₂ OH), NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) _{3 and the} like. .
If A ¹ is ^{_{(CH 2) r-COOX 2}} , X 1 and ^{X 2} may be the same or different.

  p is an integer of 1 to 3. If p is in this range, it is considered that a metal complex (described later) formed by mixing the component (A) and the component (B) is more stably formed.

Specific examples of the compound represented by the general formula (III) include alkyl or alkenylamino acetates such as sodium octylaminoacetate, sodium laurylaminoacetate, sodium myristylaminoacetate, sodium palmitylaminoacetate, sodium oleylaminoacetate;
Alkyl or alkenylaminopropionates such as sodium octylaminopropionate, sodium decylaminopropionate, sodium laurylaminopropionate, sodium myristylaminopropionate, sodium palmitylaminopropionate, sodium oleylaminopropionate;
N-octyl-N-methylglycine sodium, N-decyl-N-methylglycine sodium, N-lauryl-N-methylglycine sodium, N-myristyl-N-methylglycine sodium, N-palmityl-N-methylglycine sodium, N-alkyl or alkenyl-N-methylglycine salts such as N-oleyl-N-methylglycine sodium;
N-octyl-N-methyl-β-alanine sodium, N-decyl-N-methyl-β-alanine sodium, N-dodecyl-N-methyl-β-alanine sodium, N-myristyl-N-methyl-β-alanine N-alkyl or alkenyl-N-methyl-β-alanine salts such as sodium, sodium N-palmityl-N-methyl-β-alanine, N-oleyl-N-methyl-β-alanine sodium;
Alkyl or alkenylamino diacetates such as sodium octylaminodiacetate, sodium decylaminodiacetate, sodium laurylaminodiacetate, sodium myristylaminodiacetate, sodium palmitylaminodiacetate, sodium oleylaminodiacetate;
Alkyl or alkenylamino dipropion such as sodium octylaminodipropionate, sodium decylaminodipropionate, sodium laurylaminodipropionate, sodium myristylaminodipropionate, sodium palmitylaminodipropionate, sodium oleylaminodipropionate Examples include acid salts.
Among the compounds represented by the general formula (III), alkyl or alkenylaminodiacetic acid or a salt thereof is preferable from the viewpoint of the stability of a metal complex (described later). Among them, decylaminodiacetic acid, laurylaminodiacetic acid, myristylamino are preferable. Diacetic acid, palmitylaminodiacetic acid or a salt thereof is preferred, and laurylaminodiacetic acid, myristylaminodiacetic acid, palmitylaminodiacetic acid or a salt thereof is particularly preferred.

Among these, the component (B) is used in combination with an oxygen-based bleaching agent, and has a particularly good detergency against oil stains, and also has improved sterilization and sterilization power. Therefore, methylglycine diacetic acid, iminodisuccinic acid, hydroxyiminodi It preferably contains at least one selected from the group consisting of succinic acid, nitrilotriacetic acid, alkylaminodiacetic acid and salts thereof, methylglycine diacetate, hydroxyiminodisuccinic acid, laurylaminodiacetic acid, myristylaminodiacetic acid, More preferably, it contains at least one selected from the group consisting of palmitylaminodiacetic acid and salts thereof.
Among these, methylglycine diacetic acid or a salt thereof is particularly preferable from the viewpoint that the detergency against oil stains is further increased. In addition, not only against Escherichia coli but also against staphylococcus aureus, a high sterilizing and bactericidal effect is easily obtained, and therefore alkylaminodiacetic acid or a salt thereof is preferable, laurylaminodiacetic acid, myristylaminodiacetic acid, Palmitylaminodiacetic acid or a salt thereof is particularly preferred.

(B) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The proportion of the component (B) in the detergent composition of the present invention is 0.1 to 40% by mass when the component (B) is a compound represented by the formula (I) or formula (II). Is more preferable, and it is more preferable that it is 2-20 mass%, and when (B) component is a compound represented by the said Formula (III), it is preferable that it is 0.1-20 mass%, 0.2 More preferably, it is 10 mass%.
(B) When the ratio of a component is more than a lower limit, when it uses together with an oxygen-type bleach, the cleaning power with respect to oil stains will increase more, and disinfection and disinfection power will also increase. If it is below the upper limit, sufficient detergency against oil stains can be obtained, and sufficient sterilization and sterilization power can be obtained. Further, it is possible to achieve a blending balance with other components, which is economically advantageous.

In the detergent composition of the present invention, the mixing ratio of the component (A) and the component (B) is a mass ratio when the component (B) is a compound represented by the formula (I) or the formula (II). (A) / (B) = 0.001 to 0.5, preferably 0.01 to 0.1, and the component (B) is represented by the formula (III). In the case of a compound, the mass ratio is preferably (A) / (B) = 0.001 to 2, and more preferably 0.01 to 1.
When the ratio of the component (A) to the component (B) is at least the lower limit, when used in combination with an oxygen bleach, the activity of the bleaching component is further improved, the detergency against oil stains is further increased, and sterilization and sterilization are performed. Power also increases. If it is below the upper limit, sufficient detergency against oil stains can be obtained, and sufficient sterilization and sterilization power can be obtained. It is also economically advantageous.

  As the component (B), the compounds represented by the above formula (I), formula (II), and formula (III) can be used in combination, but when used as a disinfecting / sterilizing detergent, It is preferable to use the compound represented by (III) alone.

[Alkaline agent (C)]
In the present specification and claims, the term “alkali agent” means a component having an effect of raising the pH of a detergent solution and a certain pH buffering action, and includes carbonates, silicates, and amines. .
As the component (C), carbonates, silicates, and amines generally blended in clothing powder detergents and the like can be used.

Specific examples of the carbonate include sodium carbonate, sodium sesquicarbonate, sodium bicarbonate, potassium carbonate and the like, and sodium carbonate is preferable.
In the present invention, the carbonate is, for example, a commercial product such as sodium carbonate (manufactured by Soda Ash Japan Co., Ltd., trade name: light ash), sodium carbonate (manufactured by Soda Ash Japan Co., Ltd., trade name: granular ash), and the like. Can be used.

Specific examples of silicates include sodium silicate, layered sodium silicate, sodium metasilicate, sodium orthosilicate, potassium metasilicate, potassium orthosilicate, and the like, and sodium metasilicate is preferred.
The molar ratio (SiO ₂ / M ″ ₂ O) between M ″ ₂ O and SiO ₂ in the silicate is not particularly limited, and the molar ratio (SiO ₂ / M ″ ₂ O) is 0.3 to 3.0. Preferably, it is 0.35-2.0, more preferably 0.4-1.5, particularly preferably 0.5-1.5, 0.7 Most preferably, it is ˜1.5, where M ″ represents an alkali metal atom such as sodium or potassium.
Among the silicates, more preferable are sodium metasilicate and potassium metasilicate having a molar ratio (SiO ₂ / M ″ ₂ O) of 1.0 and a molar ratio (SiO ₂ / M ″ ₂ O) of 0. No. 5 sodium orthosilicate, ortho orthosilicate potassium and the like, and sodium metasilicate having a molar ratio (SiO ₂ / M ″ ₂ O) of 1.0 is particularly preferable.
In the present invention, for example, sodium silicate (manufactured by Occidental Chemical Co., Ltd., trade name: anhydrous sodium metasilicate, molar ratio (SiO ₂ / Na ₂ O) = 1.0), sodium orthosilicate ( Commercial products such as Nippon Chemical Industry Co., Ltd., trade name: granular ortho, molar ratio (SiO ₂ / Na ₂ O) = 0.5) can be used.

  Specific examples of amines include monoethanolamine, diethanolamine, triethanolamine and the like.

(C) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.
Among these, as the component (C), carbonate and silicate are preferable because they have good cleaning power against oil stains and good sterilization / sterilization power.
The proportion of the component (C) in the detergent composition of the present invention is preferably 5 to 70% by mass, more preferably 20 to 60% by mass, and further preferably 30 to 50% by mass. (C) When the ratio of a component is more than a lower limit, when it uses together with an oxygen-type bleach, the cleaning power with respect to oil stains will increase more, and disinfection and disinfection power will also increase. If it is below an upper limit, the mixing | blending balance with another component can be taken. It is also economically advantageous.

[Polycarboxylic acid polymer compound (D)]
It is preferable that the detergent composition of the present invention further comprises a polycarboxylic acid polymer compound (D) (hereinafter referred to as “component (D)”).
In the present specification and claims, the “polycarboxylic acid polymer compound” means a polymer having a structural unit (repeating unit) containing a carboxy group, preferably having a mass average molecular weight of 1000 or more. This refers to a polymer.

(D) It is preferable that the mass mean molecular weight of a component is 1000 or more, the range of 1500-200000 is more preferable, and the range of 2000-60000 is further more preferable. When the weight average molecular weight of the component (D) is 1000 or more, particularly 1500 or more, the activity of the bleaching component is further improved when used in combination with an oxygen bleach, and when it is 200000 or less, the viscosity of the component (D) The increase is suppressed and the handleability is improved.
In the present specification, “mass average molecular weight” indicates a value obtained by analysis by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard substance.

(D) As what is suitable in a component, what introduce | transduced the side chain containing a carboxy group or a carboxy group into the principal chain which has a hydrocarbon group is mentioned.
For example, what has a structural unit represented by the following general formula (IV) is mentioned preferably.

［式（ＩＶ）中、Ｚは水素原子、直鎖状もしくは分岐鎖状のアルキル基、又は下記一般式（Ｖ）で表される基を表す。複数のＺは同一であってもよく、異なっていてもよい。ただし、複数のＺのうち、少なくとも一つは下記一般式（Ｖ）で表される基であって、ＹがＣＯＯＭ’である。］

[In formula (IV), Z represents a hydrogen atom, a linear or branched alkyl group, or a group represented by the following general formula (V). A plurality of Z may be the same or different. However, at least one of the plurality of Z is a group represented by the following general formula (V), and Y is COOM ′. ]

［式（Ｖ）中、Ｙはアミノ基又はＣＯＯＭ’（Ｍ’は水素原子、アルカリ金属原子、又はカチオン性アンモニウムである）を表す。ｑは０〜２の整数を表す。］

[In Formula (V), Y represents an amino group or COOM ′ (M ′ represents a hydrogen atom, an alkali metal atom, or cationic ammonium). q represents the integer of 0-2. ]

In said formula (IV), as an alkyl group in Z, it is preferable that it is C1-C4, and it is more preferable that it is C1-C3. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
In the formula (V), preferred examples of the amino group for Y include —NR ¹ R ² (wherein R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). It is done. M ′ may be the same as M described above.
q represents an integer of 0 to 2, and 0 is preferable.

The component (D) may be a polymer composed of repetitions of the same structural unit, or may be a copolymer composed of repetitions of plural types of structural units. In the case of a copolymer composed of repeating plural kinds of structural units, the copolymer may be a random copolymer or a block copolymer.
Specific examples of the component (D) include, for example, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyhydroxyacrylic acid, polyfumaric acid, polyacetal carboxylic acid, a copolymer of acrylic acid and maleic acid (acrylic acid-maleic acid) Copolymer), a copolymer of acrylic acid and acrylic acid amide (acrylic acid-acrylic acid amide copolymer), or a salt thereof.
Among these, as the component (D), those having a structural unit derived from an acrylic acid monomer are preferable because the detergency against oil stains is particularly good and the sterilization and bactericidal power is well maintained. An acid homopolymer, an acrylic acid copolymer, or a salt thereof is more preferable, and an acrylic acid-maleic acid copolymer or a salt thereof is particularly preferable.

(D) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The proportion of the component (D) in the detergent composition of the present invention is preferably 0.1 to 30% by mass, and more preferably 3 to 20% by mass. When the proportion of the component (D) is at least the lower limit, when used in combination with an oxygen bleach, the activity of the bleaching component is further improved, the detergency against oil stains is further increased, and the sterilization / sterilization power is also increased. If it is below an upper limit, the mixing | blending balance with another component can be taken. It is also economically advantageous.

  The total ratio of the component (B) and the component (D) in the detergent composition of the present invention is preferably 0.2 to 70% by mass, more preferably 5 to 40% by mass. It is especially preferable that it is -25 mass%. When the total ratio of the component (B) and the component (D) is not less than the lower limit, when used in combination with an oxygen bleach, the activity of the bleach component is further improved and the detergency against oil stains is further increased. Bacteria and bactericidal power also increases. If it is below an upper limit, the mixing | blending balance with another component can be taken. It is also economically advantageous.

In the detergent composition of the present invention, the mass ratio of the component (A) to the sum of the components (B) and (D) is (A) / {(B) + (D)} = 0.0001 to 1. It is preferable that it is, and it is more preferable that it is 0.001-0.1.
If the mass ratio is less than or equal to the upper limit of the mass ratio (the sum of the components (B) and (D) is greater than or equal to the lower limit), when used in combination with an oxygen-based bleach, the activity of the bleaching component is further improved and washing against oil stains Power increases, and sterilization and sterilization power also increases.
If it is more than the lower limit of the mass ratio (the sum of the components (B) and (D) is not more than the upper limit), the blending balance with other components can be achieved. It is also economically advantageous.

[Other ingredients]
In the detergent composition of this invention, you may use together other components other than said (A)-(D) component as needed.
Examples of other components include surfactants, inorganic salts, oil-absorbing powders, dissolution accelerators, swellable water-insoluble substances, enzymes, fluorescent whitening agents, anti-staining agents such as polyethylene glycol, and silicones. Examples include antifoaming agents, pigments, and fragrances.
Each of the other components may be used alone or in combination of two or more.

(Surfactant)
As the surfactant, for example, an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant can be used.

-Anionic surfactant An anionic surfactant is not specifically limited, What is generally mix | blended with the powder detergent for clothes etc. can be used. For example, the following can be used.
Α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
A linear or branched alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 18 carbon atoms.
Alkane sulfonate (SAS) having 10 to 20 carbon atoms.
An alkyl ether having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average addition mole number of 10 moles or less added ethylene oxide, propylene oxide, butylene oxide or a mixture thereof Sulfate (AES) or alkenyl ether sulfate.
An alkyl ether having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average addition mole number of 10 moles or less added ethylene oxide, propylene oxide, butylene oxide or a mixture thereof Carboxylate or alkenyl ether carboxylate.
Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms;
A higher fatty acid salt having 10 to 20 carbon atoms.
α-sulfo fatty acid salt or ester salt thereof. Preferably, it is a saturated or unsaturated α-sulfo fatty acid salt having 8 to 20 carbon atoms (preferably 12 to 18) or an ester salt thereof (preferably a methyl ester salt (MES), an ethyl ester salt or a propyl ester salt) ( α-SF).

-Cationic surfactant As the cationic surfactant, for example, a mono, di, or trialkyl cation having 1 to 3 long chain (preferably 8 or more carbon atoms) hydrocarbon groups can be used. In particular, a cationic surfactant containing 1 to 2 ester groups and 1 to 2 long-chain hydrocarbon groups in the molecule is preferable.
Specifically, a mono long-chain alkyltrimethylammonium chloride containing one long-chain alkyl group or alkenyl group having 8 to 22 carbon atoms, a di-long chain containing two long-chain alkyl groups or alkenyl groups having 8 to 22 carbon atoms Alkyldimethylammonium chloride, tri-long-chain alkylmethylammonium chloride containing 3 long-chain alkyl or alkenyl groups having 8 to 22 carbon atoms, N-acyloxy containing 1 long-chain alkyl or alkenyl group having 8 to 22 carbon atoms Ethyl-N, N-dimethyl-N-hydroxyethylammonium chloride, N, N-diacyloxyethyl-N, N-dimethylammonium chloride containing two long-chain alkyl or alkenyl groups having 8 to 22 carbon atoms, etc. are used. be able to.

-Amphoteric surfactant As the amphoteric surfactant, sulfobetaine or carboxybetaine having one or two long chain (preferably having 8 or more carbon atoms) hydrocarbon groups can be used.
The long chain hydrocarbon group may include an ester group, an amide group, or an ether group. Further, the long chain hydrocarbon group may be a single chain type or a two chain type. Further, the ratio of the saturated / unsaturated type in the long chain hydrocarbon group, the distribution of the carbon chain length, the ratio of the cis isomer / trans isomer of the unsaturated group, etc. are not particularly limited. Further, the long chain hydrocarbon group may be derived from a fatty acid or a fatty acid methyl ester which is a raw material for producing the above-mentioned cationic surfactant.
Specific examples of amphoteric surfactants include betaines such as N, N-diacyloxyethyl-N-methylammonioethyl sulfate and N, N-diacyloxyethyl-N-methylammonioethylcarboxylate; N-acyloxy Ethyl-N-hydroxyethyl-N-methylammoniobetaines, N-acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-N, N′-dimethyl-N′-β-hydroxy And propylammoniobetaine.
The amphoteric surfactant may contain an aminobetaine such as a compound whose nitrogen atom is not quaternized, a raw material alkanolamine, a neutralized product thereof, or a quaternized product thereof.

-Nonionic surfactant The thing shown below can be used for a nonionic surfactant, for example.
Polyoxyalkylene alkyl ether or polyoxyalkylene obtained by adding an average of 3 to 30 mol, preferably 5 to 20 mol, of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms Alkenyl ether (alcohol alkoxylate). Among these, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group of the aliphatic alcohol may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.

  Polyoxyethylene alkyl phenyl ether, polyoxyethylene alkenyl phenyl ether.

  A fatty acid alkyl ester alkoxylate represented by the following general formula (VI), for example, having an alkylene oxide added between ester bonds of a long-chain fatty acid alkyl ester.

_{^{R 3 CO- [OR 5] n}} '-OR 4 ··· (VI)
[In the formula (VI), R ³ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms; OR ⁵ represents an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms (for example, , Ethylene oxide, propylene oxide, etc.); n ′ represents the average number of moles of alkylene oxide added, and is generally 3-30, preferably 5-20. R ⁴ represents a lower alkyl group having 1 to 4 carbon atoms which may have a substituent having 1 to 3 carbon atoms. ]

  Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, glycerin fatty acid ester.

As a nonionic surfactant, it is preferable that melting | fusing point is 50 degrees C or less, More preferably, it is 40 degrees C or less, and it is preferable that HLB is 7-16, More preferably, it is 8-14. HLB is a value determined by the Griffin method (see Yoshida, Shindo, Ogaki, Yamanaka, edited by "New Edition Surfactant Handbook", Kogyoshosho Co., Ltd., 1991, page 234).
The melting point is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical product”.

Specific examples include polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene having a melting point of 50 ° C. or lower and an HLB of 7 to 16. Examples include alkenyl ether, fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to fatty acid methyl ester, and fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to fatty acid methyl ester.
Among them, particularly preferred is a polyoxy compound having ethylene oxide (EO) and propylene oxide (PO) added to alcohol (R ⁶ OH) having a melting point of 50 ° C. or lower and an HLB of 7 to 16, respectively. Ethylene polyoxypropylene alkyl ether (alcohol ethoxylate propoxylate), for example, a compound represented by the following general formula (VII).

R _< ⁶ _> -O- (EO) _{m "} -(PO) _n" -H ... (VII)
[In the formula (VII), R ⁶ represents a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms, EO represents an addition unit of ethylene oxide, and PO represents an addition unit of propylene oxide. M ″ represents the average number of moles of ethylene oxide added and is a number from 3 to 15; n ″ represents the average number of moles added of propylene oxide and is a number from 1 to 5; ]

In the formula (VII), R ⁶ is a linear or branched alkyl group having 10 to 18 carbon atoms, or a linear or branched alkenyl group having 10 to 18 carbon atoms. The alkyl group and the alkenyl group in R ⁶ have 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms. When the carbon number is 10 to 18, the detergency against oil stains is improved.
m ″ represents the average number of moles of ethylene oxide added and is a number of 3 to 15, preferably 4 to 10. n ″ represents the average number of moles of propylene oxide added and is a number of 1 to 5, preferably Is 1-3. When m ″ and n ″ are equal to or higher than the lower limit, solubility in water is improved, and when it is equal to or lower than the upper limit, occurrence of foaming during use can be suppressed.
In the general formula (VII), EO and PO may be random addition or block addition, and in the case of block addition, either EO or PO may be added to the terminal.

Furthermore, since it has excellent detergency against oil stains and good antifoaming properties during washing, it is a compound having 1 to 20% by mass of the compound represented by the formula (VII) and a higher fatty acid salt having 10 to 20 carbon atoms. It is preferable to use 1 to 10% by mass in combination, and it is more preferable to contain these in a total amount of 5 to 20% by mass.
In particular, a compound represented by the following formula (VII-1), a compound represented by the formula (VII-2), and a higher fatty acid salt having 10 to 20 carbon atoms are represented by a mass ratio of (VII-1). ) / (VII-2) = 1-8, and [(VII-1) + (VII-2)] / (C10-20 higher fatty acid salt) = 1-12. Is preferred.
^{_{R 7 -O- (EO) m1 "}} (PO) n1" -H ··· (VII-1)
[In Formula (VII-1), R ⁷ represents a primary or secondary alkyl group or alkenyl group having 10 to 18 carbon atoms. m1 ″ is a number from 5 to 9, and n1 ″ is a number from 1 to 3. ]
^{_{R 8 -O- (EO) m2 "}} (PO) n2" -H ··· (VII-2)
[In Formula (VII-2), R ⁸ represents a primary or secondary alkyl group or alkenyl group having 10 to 18 carbon atoms. m2 ″ is a number from 13 to 15, and n2 ″ is a number from 1 to 3. ]

(Inorganic salt)
Use inorganic salts such as sulfites such as sulfate and sodium sulfite, phosphates such as orthophosphate, metaphosphate, hexametaphosphate, and phytate, crystalline aluminosilicate, and amorphous aluminosilicate. Can do.

Examples of the crystalline aluminosilicate include the following.
_{x 1 (M "2 O)} · Al 2 O 3 · y 1 (SiO 2) · w 1 (H 2 O)
(Wherein M ″ represents an alkali metal atom such as sodium or potassium; x ₁ , y ₁ and w ₁ represent the number of moles of each component, respectively. In general, x ₁ is 0.7 to 1.5, y ₁ represents 0.8 to 6, and w ₁ represents an arbitrary positive number.)

Examples of the amorphous aluminosilicate include the following.
_{x 2 (M "2 O)} · Al 2 O 3 · y 2 (SiO 2) · w 2 (H 2 O)
(Wherein M ″ is an alkali metal atom such as sodium or potassium; x ₂ , y ₂ and w ₂ represent the number of moles of each component, respectively, generally x ₂ is 0.7 to 1.2, y ₂ represents 1.6 to 2.8, and w ₂ represents 0 or an arbitrary positive number.)
_{x 3 (M "2 O)} · Al 2 O 3 · y 3 (SiO 2) · z 3 (P 2 O 5) · w 3 (H 2 O)
(In the formula, M ″ represents an alkali metal atom such as sodium or potassium; x ₃ , y ₃ , z ₃ and w ₃ represent the number of moles of each component, respectively. In general, x ₃ is 0.2 to 1 .1, _{y 3} is 0.2 to 4.0, _{z 3} is 0.001 to 0.8, _{w 3} represents 0 or any positive number.)

(Oil-absorbing powder)
The oil-absorbing powder preferably has an oil absorption of 20 to 500 mL / 100 g, more preferably 100 to 400 mL / 100 g. The oil absorption is measured by a method according to JIS K5101.
Specific examples of the oil-absorbing powder include anhydrous silicic acid, hydrous silicic acid, hydrous silicic acid silicate, talc, barium sulfate, titanium oxide and zinc oxide. Of these, anhydrous silicic acid, hydrous silicic acid, hydrous silicic acid silicate, and talc are preferable, and anhydrous silicic acid and hydrous silicic acid are more preferable from the viewpoint of oil absorption capacity, difficulty in solidification, and ease of rinsing.

(Dissolution promoter)
Specific examples of the dissolution accelerator include inorganic ammonium salts such as ammonium chloride; benzenesulfonates having a short-chain alkyl group having 1 to 5 carbon atoms such as sodium p-toluenesulfonate, sodium xylenesulfonate, sodium cumenesulfonate, etc. Water-soluble substances such as sodium benzoate, sodium benzenesulfonate, sodium chloride, citric acid, D-glucose, urea and sucrose.

(Swellable water-insoluble substance)
Specific examples of the swellable water-insoluble substance include clay minerals such as powdered cellulose, crystalline cellulose, and bentonite.

(enzyme)
An enzyme is not specifically limited, What is generally mix | blended with the powder detergent for clothes etc. can be used.
Specific examples of enzymes include Esperase 4.0T, Sabinase 6.0T, Sabinase 12T, Sabinase 24T, Cannase 12T, Cannase 24T, Evalase 8T, Dezyme and other lipases, Lipase Ultra 50T, Lipex 100T and other lipases, stains Examples include amylases such as Zyme 12T and Termamyl 100T, cellulases such as Cellzyme 0.7T (noted by Novozymes); Maxacal 45G, Maxapem 30G, properase 1000E (notably provided by Dienencore), and the like. Of these, protease, amylase, and lipase are preferable.

(Fluorescent brightener)
Specific examples of the optical brightener include bis (triazinylaminostilbene) disulfonic acid derivative (trade name: Tinopal AMS-GX), bis (sulfostyryl) biphenyl salt (trade name: Tinopal CBS-X) and the like. It is done.

The manufacturing method of the detergent composition of the present invention is not particularly limited as long as it is a method of manufacturing using the component (A), the component (B), and the component (C). It can be produced by a conventionally known method for producing a detergent composition using the component (C) and other components as necessary.
For example, a method in which powdery detergent raw materials are mechanically mixed, a method in which a slurry is prepared and spray-dried; a method of kneading / extrusion, stirring granulation, rolling granulation, etc. A method of performing summation, granulation, compression molding and the like, and further pulverizing as necessary; it can be produced by a combination of these methods as appropriate.
In particular, in order to maintain the particle size of the component (A), the component (A) is added together with other powdery detergent raw materials and mechanically mixed to produce, or other powdered detergent It is preferable to add by spraying a solution in which component (A) is dissolved in water or an organic solvent to the raw material or a mixture thereof. That is, in the manufacturing process of the detergent composition, after adding the component (A), it is preferable that, for example, only the stirring and mixing is performed and the granulation process is not substantially included.

When the form of the detergent composition of the present invention is a powder, the particle size of the particles of the powder detergent composition is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, more preferably 300 to 300 μm. Most preferably, it is 700 μm. When the average particle size is equal to or greater than the lower limit, dusting is suppressed during use, and when the average particle size is equal to or less than the upper limit, the solubility in water is improved, and when used in combination with an oxygen-based bleach, the detergency against oil stains is improved. The sterilization and sterilization power will increase.
In addition, this average particle diameter shows the value calculated from the particle size distribution by the sieving shown below. That is, classification operation (b) is performed on the detergent composition using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm and 149 μm and a saucer.
In the classification operation (b), a small sieve sieve is stacked on a tray in the order of a large sieve sieve, 100 g / time of the detergent composition is placed on the top 1680 μm sieve, the lid is covered, and a low-tap type. Attached to a sieve shaker (manufactured by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute), and shaken for 10 minutes, the detergent composition remaining on each sieve and tray was sieved. Collect each eye and measure the mass of the sample.
When the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is set to “a μm”, and the opening of the sieve that is one step larger than “a μm” Is “b μm”, the integrated value of the mass frequency from the saucer to the “a μm” sieve is “c%”, and the mass frequency on the “a μm” sieve is “d%”. (Mass 50%) is determined and set as the average particle size of the detergent composition.

  When the form of the detergent composition of the present invention is a powder, the bulk density of the powder detergent composition is preferably 0.5 to 1.2 g / mL, and 0.7 to 1.0 g / mL. Is more preferable. When the bulk density is equal to or higher than the lower limit value, a space (storage location) required for storing the powder detergent composition may be narrower, which is advantageous in terms of cost. On the other hand, if it is not more than the upper limit value, the solubility of the powder detergent composition in water will be good even after long-term storage.

  As described above, the detergent composition of the present invention comprising the component (A), the component (B), and the component (C) with controlled particle size is used in combination with an oxygen-based bleach. Therefore, oil stains can be sufficiently washed, and a high sterilization and sterilization effect can be obtained.

<How to wash>
The washing method of the present invention comprises at least one selected from the group consisting of the detergent composition of the present invention, a compound that dissolves in water to generate hydrogen peroxide, and hydrogen peroxide (hereinafter referred to as “component (E)”). In combination).

[(E) component]
Examples of the component (E) include those contained in an oxygen-based bleach as a bleaching component.
The compound that dissolves in water and generates hydrogen peroxide may be any compound that generates hydrogen peroxide in an aqueous solution, and examples thereof include peroxides. Suitable examples of the peroxide include percarbonate, perboric acid, and salts thereof. Examples of the salt include alkali metal salts and ammonium salts.
Among the above, as the component (E), hydrogen peroxide and sodium percarbonate are preferable, and hydrogen peroxide is particularly preferable.
(E) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.
(E) It is preferable that it is 1-200 mass parts with respect to 100 mass parts of detergent composition of this invention, and, as for the usage-amount of a component, it is more preferable that it is 3-100 mass parts, and is 10-75 mass parts. It is particularly preferred. Within this range, the effects of the present invention can be obtained better.

As an example, the washing method of the present invention is a mixture of a washing composition and water in a washing tub of a washing machine, and a separately prepared detergent composition and an oxygen bleach containing component (E). Supply and do laundry.
The mixture of the detergent composition and the oxygen-based bleaching agent is preferably supplied to the washing tub within 30 minutes after mixing both because the decomposition of hydrogen peroxide is suppressed and the detergency is further improved. It is particularly preferred to supply the washing tub within minutes.
In addition, the washing machine and the washing tub are filled with the item to be washed and water, and the detergent composition prepared separately and the oxygen bleach containing the component (E) are separately supplied for washing. You can also. In this case, it is preferable to supply an oxygen-based bleach containing the component (E) after supplying the detergent composition.
In addition, the washing tub of the washing machine is filled with water to be washed and water, and a separately prepared detergent composition, an alkali assistant containing component (C), and an oxygen bleach containing component (E) Laundry can also be performed by supplying a mixture with the agent.
Furthermore, a washing machine and a washing tub are filled with water to be washed and water, and a separately prepared detergent composition, an alkali assistant containing component (C), and an oxygen bleach containing component (E) It is also possible to carry out washing by supplying the agent separately. In this case, the alkali assistant containing the component (C), the detergent composition, and the oxygen bleach containing the component (E) are supplied in this order, or the alkali assistant containing the detergent composition and the component (C). It is preferable to supply the agent and the oxygen bleach containing the component (E) in this order.

As described above, according to the detergent composition and the washing method of the present invention, the activity of the bleaching component is remarkably increased in combination with the oxygen-based bleaching agent, and the oil stain can be sufficiently washed. The reason why such an effect is obtained is not certain but is presumed as follows.
In the present invention, first, when the detergent composition is dissolved in water, a granular water-soluble salt containing a transition element, zinc or silver in the fourth period of the periodic table, stably in the presence of the alkaline agent (C) ( A metal complex of A) and aminocarboxylic acid or its salt (B) is formed. When the detergent composition is used in combination with an oxygen bleach, hydrogen peroxide generated from the oxygen bleach is activated by the metal complex. The metal complex formed from the component (A) and the component (B) is considered to have a much higher ability to activate hydrogen peroxide than a conventional metal complex.
Further, as the component (A), particles having a particle size of 300 μm or less are 30% by mass or more (preferably, particles having a particle size of 300 μm or less are 30% by mass or more, and particles having a particle size of 710 μm or more are less than 20% by mass. By using what is preferably less than 15% by mass, and more preferably less than 10% by mass, the solubility of the detergent composition in water or the like is improved. In particular, when a detergent composition is produced by spraying a solution in which the component (A) is dissolved in a solvent such as water onto a detergent raw material mixture, the particle size of the detergent composition becomes finer. It is considered that the solubility in the above is further improved.
By improving the solubility in water, etc., the (A) component is less likely to insolubilize or oxidize due to contact with the (C) component or hydrogen peroxide. It can be used sufficiently to form a metal complex without forming a product, and the catalytic action of the metal complex is exhibited well. Therefore, it is considered that the activity of hydrogen peroxide can be significantly increased. For these reasons, it is estimated that such an effect can be obtained.

According to the detergent composition of the present invention, since the generation of insoluble matter derived from the component (A) is suppressed, washing can be performed without remaining the insoluble matter in the article to be washed after washing.
Moreover, since the detergent composition of this invention can raise the activity of a bleaching component markedly, it is excellent also in the bleaching effect with respect to stain | pollution | contamination, such as a stain.

In general, oxygen-based bleaching agents containing hydrogen peroxide, percarbonate, or the like as bleaching components are generally less effective for cleaning or disinfecting / disinfecting than chlorine-based bleaching agents such as hypochlorous acid. Even when an oxygen-based bleach is used under high temperature and high pH conditions, the cleaning effect or the sterilizing / sterilizing effect has been insufficient.
According to the washing method of the present invention, the combined use of the detergent composition and the oxygen-based bleaching agent significantly increases the activity of the bleaching component and can sufficiently wash the oil stains. High sterilization and bactericidal effects can be obtained against cocci.
The detergent composition and laundry method of the present invention are suitable for commercial cleaning applications.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. However, Examples 1 to 10 and 13 are reference examples. “%” Means “% by mass” unless otherwise specified.

(Preparation of granular water-soluble salt)
Using a sieve having a predetermined opening according to JIS Z8801-1 and a saucer, 100 g of a water-soluble salt as a sample is placed on the sieve, covered with a low-tap sieve shaker ((Co., Ltd.) Attached to Iida Seisakusho, Tapping: 156 times / min, Rolling: 290 times / min) After vibrating for 10 minutes, the above-mentioned classification operation (a) for taking out what remains on the saucer is carried out, whereby predetermined particles are obtained. A granular water-soluble salt having a controlled diameter was obtained.

<Manufacture of detergent composition>
(Examples 1-10, Comparative Examples 1-5)
The detergent compositions in each example are shown in Tables 1 and 2 using a ribbon mixer (Model 1102-20, manufactured by Yoshida Seisakusho Co., Ltd.) as a stirring mixer, under the conditions of a filling rate of 50% by volume and a jacket temperature of 25 ° C. According to the composition shown in FIG.
First, Na carbonate and Na sulfate are added in advance to the ribbon mixer while the main shaft is stopped, and then the component (B) or (B ′) is added, and then the component (A) or component (A ′). , (D) component, fluorescent agent 1 and fluorescent agent 2 are sequentially added in this order, and the charged raw materials are mixed with the main shaft rotated at 30 rpm, and preheated to 60 ° C. Nonion 1 and Nonion 2 After spraying water at a pressure of 0.5 to 1.5 MPa using a spray nozzle, the remaining sodium silicate, soap, enzyme 1 and enzyme 2 are sequentially added to the ribbon mixer in this order and mixed. A detergent composition was prepared.
In this production method, a detergent composition was produced at a temperature of 25 to 35 ° C. for a mixing time of 30 minutes.

(Example 11, Example 13)
Using a ribbon mixer (model 1102-20, manufactured by Yoshida Seisakusho Co., Ltd.) as a stirring type mixer, under the conditions of a filling rate of 50 vol% and a jacket temperature of 25 ° C., according to the composition shown in Table 3, Manufactured.
First, to the ribbon mixer, with the main shaft stopped, sodium silicate, carbonate, and sodium sulfate were added in advance, and then component (D) was added, and then component (B), fluorescent agent 1, and fluorescent agent 2 were added. In this order, the charged raw materials are mixed by rotating the main shaft at 30 rpm and mixing the nonionic 1, nonionic 2, and moisture previously heated to 60 ° C. using a spray nozzle at a pressure of 0.5 to 1. After spraying at 5 MPa, the remaining soap, component (A), enzyme 1 and enzyme 2 were sequentially added to the ribbon mixer in this order, and mixed to prepare a detergent composition.
In this production method, a detergent composition was produced at a temperature of 25 to 35 ° C. for a mixing time of 30 minutes.

(Comparative Example 6)
In the production examples described in Examples 11 and 13, a detergent composition was produced without blending only the component (B).

(Example 12)
In advance, copper sulfate pentahydrate (fine copper sulfate-1) was added to ion-exchanged water so that the copper sulfate concentration was 20% by mass, heated to 50 ° C. and uniformly dissolved, and 20% by mass copper sulfate aqueous solution. Was prepared.
Next, with the main shaft stopped, the silica mixer, sodium carbonate, and sodium sulfate are added in advance to the ribbon mixer, and then the component (D), the fluorescent agent 1, and the fluorescent agent 2 are sequentially added in this order. While mixing the raw material rotated at 30 rpm, nonion 1, nonion 2, and water previously heated to 60 ° C. were sprayed at a pressure of 0.5 to 1.5 MPa using a spray nozzle. Subsequently, the 20 mass% copper sulfate aqueous solution previously heated to 50 ° C. is sprayed using a spray nozzle so that the spray amount of the copper sulfate aqueous solution is adjusted to 1.0 to 3.0 kg / min. did. Thereafter, soap, enzyme 1, enzyme 2, and component (B) were sequentially added to the ribbon mixer in this order and mixed to prepare a detergent composition.
In this production method, a detergent composition was produced at a temperature of 25 to 35 ° C. for a mixing time of 30 minutes.

In addition, the unit of the compounding quantity in a table | surface is the mass%, and all the compounding quantities of each component show the amount equivalent to a pure part. “Balance” in the table means the blending amount of sodium sulfate in the detergent composition adjusted so that the total amount of each component contained in the detergent composition is 100% by mass. “-” In the table indicates that the component is not blended.
Below, the component shown in the table | surface is demonstrated.

[Description of components shown in the table].
-Granular water-soluble salt (A) containing a transition element, zinc, or silver in the fourth period of the periodic table
Fine copper sulfate-1: Copper sulfate pentahydrate (trade name “Iupinogue”, manufactured by Nikko Metal Co., Ltd.). As a result of measuring the particle size distribution of the raw material itself, the particle size exceeding 300 μm was 53.8% by mass (of these, the particle size of 710 μm or more was 12.4% by mass), and the particle size of 150 μm to 300 μm was 46 0.02% by mass and particles having a particle diameter of less than 150 μm were 0.2% by mass. Average particle diameter (mass 50%) 320 μm determined by the classification operation (b).
Fine powdered copper sulfate-2: Copper sulfate pentahydrate (trade name “Iupinogue”, manufactured by Nikko Metal Co., Ltd.) is subjected to the above classification operation (a), thereby comprising only particles having a particle diameter of 300 μm or less. Prepared to. Average particle size (mass 50%) 200 μm.
Fine powdered copper sulfate-3: Copper sulfate pentahydrate (trade name “Iupinogue”, manufactured by Nikko Metal Co., Ltd.) is ground in a mortar and subjected to the same operation as the above classification operation (a), thereby obtaining a particle size. Prepared to consist only of particles of 150 μm or less. Average particle size (mass 50%) 130 μm.
Fine powdered copper sulfate-5: The above classification operation (a) is performed on copper sulfate pentahydrate (trade name “Iupinogue”, manufactured by Nikko Metal Co., Ltd.), and the ratio of particles having a particle diameter of 710 μm or more is 8.7. What prepared the ratio of the particle | grains whose particle diameter is 300 micrometers or less of the mass% to 32.6 mass%. Average particle diameter (mass 50%) 340 μm.
Fine powdered copper sulfate-6: The above classification operation (a) is performed on copper sulfate pentahydrate (trade name “Iupinogue”, manufactured by Nikko Metal Co., Ltd.), and the ratio of particles having a particle diameter of 710 μm or more is 18.7. What prepared the ratio of the particle | grains whose particle diameter is 300 micrometers or less of the mass% to 32.6 mass%. Average particle diameter (mass 50%) 430 μm.
Fine powdered manganese sulfate-1: Manganese sulfate monohydrate (trade name “C2 grade”, manufactured by Chuo Denki Kogyo; average particle size (mass 50%) approximately 200 μm), the same operation as the above classification operation (a) What was prepared to consist only of particles having a particle diameter of 150 μm or less. Average particle diameter (mass 50%) 140 μm.

-Component (A) comparative component [hereinafter referred to as "(A ') component". ]
Copper sulfate-4: Copper sulfate pentahydrate (trade name “Iupinogue”, manufactured by Nikko Metal Co., Ltd.) is subjected to the above classification operation (a) to remove particles having a particle diameter of 300 μm or less. What was prepared to consist only of particles having a particle diameter of more than 300 μm. Among these, the particle size of 710 μm or more was 25.2% by mass. Average particle diameter (mass 50%) 520 μm.
Copper sulfate-7: Copper sulfate pentahydrate (trade name “Iupinogue”, manufactured by Nikko Metal Co., Ltd.) is subjected to the above classification operation (a) to prepare only particles having a particle diameter of 710 μm or less. What prepared the ratio of the particle diameter of 300 micrometers or less to 23.1 mass%. Average particle diameter (mass 50%) 380 μm.

・ Aminocarboxylic acid or its salt (B)
MGDA: methyl glycine diacetate 3Na, trade name “Trilon M Powder”, manufactured by BASF Corporation.
HIDS: Hydroxyiminodisuccinic acid 3Na, HIDS (manufactured by Nippon Shokubai Co., Ltd.) dried to a moisture content of 5% and powdered.
IDS: Iminodisuccinic acid 4Na, IDS-4Na, manufactured by LANXESS.
NTA: nitrilotriacetic acid 3Na, trade name “Trilon A92R”, manufactured by BASF Japan Ltd .; pure content 92% by mass, moisture content 1% by mass.
C12-IDA: Laurylaminodiacetic acid, trade name “Nissan Anon Powder”, manufactured by NOF Corporation.

-Component (B) comparative component [hereinafter referred to as "(B ') component". ]
Tripolyphosphate Na: Trade name “Tripolyphosphate soda”, manufactured by Mitsui Chemicals, Inc.

・ Alkaline agent (C)
Na carbonate: sodium carbonate, trade name “light ash”, manufactured by Soda Ash Japan Co., Ltd.
Silicate Na: sodium metasilicate, trade name “anhydrous metasilicate soda” manufactured by Occidental Chemical Co., Ltd.

・ Polycarboxylic acid polymer compound (D)
Polymer (MA): Acrylic acid-maleic acid copolymer sodium salt, Aquaric TL-400 (trade name, manufactured by Nippon Shokubai Co., Ltd.) dried to a moisture content of 5% and powdered.

Other components Nonion 1: Alcohol alkoxylate, ECOROL26 (trade name, manufactured by ECOGREEN, an alcohol having an alkyl group having 12 to 16 carbon atoms) added with an average of 15 mol of ethylene oxide and an average of 3 mol of propylene oxide (Lion Co., Ltd.); 84% by mass pure.
Nonion 2: Alcohol alkoxylate, ECOROL26 (trade name, manufactured by ECOGREEN, an alcohol having an alkyl group having 12 to 16 carbon atoms) added with an average of 5 mol of ethylene oxide and an average of 2 mol of propylene oxide (Lion Corporation) ); Pure content 94% by mass.
Soap: higher fatty acid sodium, trade name “Kona Bulk 70B”, manufactured by Miyoshi Oil & Fats Co., Ltd.
Fluorescent agent 1: fluorescent brightener, trade name “Chinopearl CBS-X”, manufactured by Ciba Specialty Chemicals.
Fluorescent agent 2: fluorescent whitening agent, trade name “Chinopearl AMS-GX”, manufactured by Ciba Specialty Chemicals.
Enzyme 1: Protease, trade name “Sabinase 12T”, manufactured by Novozymes Japan.
Enzyme 2: Protease, trade name “Esperase 4.0T”, manufactured by Novozymes Japan.
Moisture Sulfate Na: Trade name “Neutral Anhydrous Glass”, manufactured by Shikoku Chemicals Co., Ltd.

<Evaluation of detergency against oil stains>
[Preparation of detergent solution]
200L (temperature 35 ° C) of tap water is stored in a 300L stainless steel stock tank (cylindrical shape with a diameter of 1.5m), and 10kg of detergent composition is added to it, and stirring blades (diameter 30cm, width 5cm) The detergent solution of each example was prepared by stirring for 20 minutes at a speed of 150 revolutions per minute.

[Preparation of washing object]
An evaluation cloth (trade name “EMPA101”, manufactured by EMPA TESTMATERIAL) cut into 5 cm × 5 cm and a white bath towel (70 cm × 140 cm) were prepared.
Then, 5 pieces of the white bath towels sewn so as not to overlap the 5 evaluation cloths and 15 pieces of the white bath towels together were used as washing objects in one wash.

[How to wash]
As a washing machine, a batch washer (product number “MOX-15”, manufactured by Tokyo Dyeing Machinery Co., Ltd.) was used.

10 kg of the object to be washed was put in the washing tub of the washing machine, and the operation of the following washing program was started.
In the cleaning step (1), the cleaning program was temporarily stopped when the water level reached 3 and the temperature reached 30 ° C. Then, 2 L of the detergent solution and 0.1 L of hydrogen peroxide (Mitsubishi Gas Chemical Co., Ltd., food additive; 35% (w / w)) as an oxygen bleach are mixed and put into the detergent solution supply tank. Both were mixed and the mixed solution was supplied to the washing tub within about 5 minutes. Immediately after the feed, the wash program was resumed.

(Cleaning program)
Washing is performed in the order of the washing step (1), the dehydration step (1), the rinsing step (1), the dehydration step (2), the rinsing step (2), and the dehydration step (3). Carried out.
Washing step (1): water level 3, temperature 30 ° C., time 10 minutes Dehydration step (1): time 1 minute Rinsing step (1): water level 5, temperature 25 ° C., time 3 minutes Dehydration step (2): time 1 minute Rinsing step (2): water level 5, temperature 25 ° C., time 3 minutes Dehydration step (3): time 3 minutes

[Measurement of cleaning rate]
After the washing program was completed, the objects to be washed were taken out from the batch washer washing tub. Next, the evaluation fabric was taken out from the article to be washed and dried.
After drying, the reflectance of the evaluation fabric surface was measured using a product name “Spectro Color Meter SE2000” (manufactured by Nippon Denshoku Industries Co., Ltd.). And the washing | cleaning rate (%) was calculated | required from the following formula, and the detergency with respect to oil dirt was evaluated according to the evaluation criteria of the following washing | cleaning rate. The results are shown in Tables 1-3.
In the following formula, “clean cloth” refers to an evaluation cloth (cotton cloth) itself to which no oil stain component is attached. A numerical value of “84” was used as the reflectance of the clean cloth.

  Washing rate (%) = [(reflectance of evaluation cloth after washing−reflectance of evaluation cloth before washing) / (reflectance of clean cloth) − (reflectance of evaluation cloth before washing)] × 100

(Evaluation criteria for cleaning rate)
A: Cleaning rate is 30% or more.
A: The cleaning rate is 27% or more and less than 30%.
○: The cleaning rate is 24% or more and less than 27%.
Δ: The cleaning rate is 21% or more and less than 24%.
X: The cleaning rate is 18% or more and less than 21%.
XX: Cleaning rate is less than 18%.

<Evaluation of persistence of insoluble matter in the object to be washed>
Washing was performed in the same manner as in the above [Laundry method], and when the washing step (1) and the dehydration step (1) were completed in the washing program, the washing program was temporarily stopped and five towels were taken out.
About the taken-out towel, the presence or absence of dark insoluble matter (undissolved residue) was visually evaluated according to the following undissolved evaluation criteria. The results are shown in Tables 1-3.
(Evaluation criteria for remaining melt)
(Double-circle): Insoluble matter (undissolved residue) was not recognized at all in all five towels.
A: Insoluble matter (undissolved residue) was slightly observed in 1 to 2 of the 5 towels.
(Triangle | delta): In 3 or more towels, insoluble matter (undissolved residue) was recognized, and the towel in which the insoluble matter (undissolved residue) was recognized clearly was 1 or less.
X: Insoluble matter (undissolved residue) was observed in 3 or more towels, and insoluble matter (residual residue) was clearly recognized in 2 or more towels.

From the results of Tables 1 and 2, it was confirmed that the detergent compositions of Examples 1 to 10 according to the present invention were able to sufficiently wash oil stains in combination with an oxygen bleach.
Further, from the comparison between Example 1 and Example 2, it was confirmed that when the polycarboxylic acid polymer compound (D) was further blended, the detergency against oil stains was further improved.
In addition, from the comparison between Example 1, Example 6 and Example 7, the use of the component (A) containing many particles having a small particle diameter improves the cleaning power against oil stains, and further allows washing. It can be seen that insoluble matter hardly remains in the product.
Further, from comparison between Example 9 and Example 10, it can be seen that the smaller the proportion of particles having a particle diameter of 710 μm or less, the less insoluble matter remains in the article to be washed.

Comparative Example 5 comprising a detergent composition of Comparative Example 1 containing only copper sulfate having a particle size of more than 300 μm and a copper sulfate having a particle size of 300 μm or less but containing less than 30% by mass of copper sulfate. It was confirmed that the detergent composition of No. 1 had lower detergency against oil stains than the detergent compositions of Examples 1-10.
The detergent compositions of Comparative Examples 1 and 3 lacking the component (A) of the constitution of the present invention, or the detergent compositions of Comparative Examples 2 and 4 lacking the component (B), all have poor detergency against oil stains. It could be confirmed.

  From the above, it can be seen that according to the detergent composition and the washing method of the present invention, the activity of the bleaching component is remarkably increased in combination with the oxygen bleaching agent, and the oil stain can be sufficiently washed.

<Evaluation of disinfection and bactericidal power>
[Evaluation method]
The equipment, water, etc. used in this evaluation were sterilized in advance by an autoclave. In addition, “ppm” described below is based on mass.
Using the detergent compositions of Examples 11 to 13 and Comparative Example 6, 9.9 mL of a liquid test solution having a detergent composition concentration of 2000 ppm and a hydrogen peroxide concentration of 1000 ppm was prepared.
To the test solution, 0.1 mL of E. coli mother liquor (IFO 3972) prepared so that the number of bacteria was 10 ⁸ cells / mL was added and stirred uniformly (E. coli sterilization and sterilization tests were performed at 25 ° C.) .
In addition, 0.1 mL of Staphylococcus aureus mother solution (NBRC12732) prepared so that the number of bacteria becomes 10 ⁷ cells / mL was added to the test solution and stirred uniformly (the sterilization test of staphylococcus aureus was performed Performed at 45 ° C.).
Ten minutes after each mother liquor was added to the test solution, 1 mL collected from each was added to 9 mL of SCDLP medium (Soybean-Casein Digest Broth Wectin & Polysorbate 80: manufactured by Wako Pure Chemical Industries, Ltd.). It was.
The operation of further diluting the obtained diluted solution 10 times was repeated 4 times in the same manner as described above to obtain 10 to 100000 times diluted solutions.
1.0 mL from each of these dilutions is collected in a petri dish, and 15 mL of SCDLP agar medium (Soybean-Casein Digest Ager with Lectin & Polysorbate 80: manufactured by Wako Pure Chemical Industries, Ltd.) is added thereto and homogenized at 37 ° C. for 2 days. After culturing, those in the range of 70 to 300 colonies were selected, and the number of viable bacteria was determined by counting the colonies.
And the viable count (about 10 ⁶ to 10 ⁷ ) when treated with Tween 80 (Polysorbate 80, manufactured by Kanto Chemical Co., Ltd.) 500 ppm, and the viable count when treated with the test solution of each example, The sterilization and bactericidal power was calculated by expressing the difference in the number of bacteria from the control (the number of bacteria decreased) by the common logarithm determined by the following formula, and the sterilization and bactericidal power was evaluated based on the following evaluation criteria. .
Sterilization and bactericidal power = Log [(Number of viable bacteria when treated with Tween 80) / (Number of viable bacteria when treated with the test solution of each example)]

(Evaluation criteria)
Compared with the number of viable bacteria when treated with Tween 80, sterilization and bactericidal activity were evaluated in the following four stages. The results are shown in Table 3.
A: The difference in the number of bacteria was 3 digits or more (Log 3 ≦ bactericidal / sterilizing power).
○: The difference in the number of bacteria was 2 digits or more and less than 3 digits (Log2 ≦ bactericidal / sterilizing power <Log3).
Δ: The difference in the number of bacteria was 1 digit or more and less than 2 digits (Log1 ≦ sterilization / bactericidal power <Log2).
X: The difference in the number of bacteria was less than one digit (disinfection / bactericidal power <Log1).

From the results of Table 3, it was confirmed that the detergent compositions of Examples 11 to 13 were able to sufficiently wash oil stains in combination with an oxygen-based bleach and to obtain a high sterilizing / sterilizing effect.
In particular, by selecting alkylaminodiacetic acid as the component (B) from the comparison between Example 11 and Example 13, the disinfection / bactericidal effect is improved, not only against Escherichia coli but also against Staphylococcus aureus. It was confirmed that a high sterilizing and bactericidal effect was obtained.

Claims (6)

A granular water-soluble salt (A) containing a transition element, zinc or silver in the fourth period of the periodic table, an alkylaminodiacetic acid or a salt thereof (B), and an alkali agent (C) are blended,
The water-soluble salt (A) contains 30% by mass or more of particles having a particle size of 300 μm or less. The said (A) component is a detergent composition of Claim 1 sprayed and mix | blended as aqueous solution with respect to the detergent raw material mixture in which the said (A) component is not mix | blended .   The detergent composition according to claim 1 or 2, further comprising a polycarboxylic acid polymer compound (D).   A combination of the detergent composition according to any one of claims 1 to 3, and at least one selected from the group consisting of a compound that dissolves in water to generate hydrogen peroxide and hydrogen peroxide. And washing method. A detergent composition comprising a granular water-soluble salt (A) containing a transition element, zinc or silver in the fourth period of the periodic table, alkylaminodiacetic acid or a salt thereof (B), and an alkaline agent (C). A manufacturing method of
The method for producing a detergent composition, wherein the water-soluble salt (A) contains 30% by mass or more of particles having a particle size of 300 μm or less. The manufacturing method of the detergent composition of Claim 5 which prepares the aqueous solution which melt | dissolved the said (A) component in water, and sprays this aqueous solution with respect to the detergent raw material mixture in which the said (A) component is not mix | blended.