JP6288840B2 - Cleaning agent for clothing - Google Patents

Description

The present invention relates to a cleaning agent for clothes .

For example, mud dirt adhering to socks and the like is known as dirt that is difficult to remove by ordinary washing, and various techniques for removing such dirt have been studied.
For example, Patent Document 1 proposes a composition containing a surfactant and / or a bleaching agent and cellulase, and Patent Document 2 discloses a protopectinase as a detergent composition having a high cleaning effect on mud dirt. And a composition containing cellulase, protease, and an acidic substance such as organic phosphonic acid is proposed in Patent Document 3.

  However, it is very difficult to remove mud stains in which inorganic particles generally called black soil and organic polymer compounds called humus are mixed, and even using the techniques described in Patent Documents 1 to 3, these mud stains are satisfied. It cannot be removed to the level possible.

  On the other hand, Patent Document 4 proposes a composition containing a reducing agent, a fluoride, a nitrogen-containing surfactant and at least one of a specific polymer compound, and the composition contains inorganic particles. It is said that it is also effective against mud stains that contain organic polymer compounds. However, when a reducing agent capable of obtaining a high cleaning effect is employed, there is a risk of causing discoloration of colored clothing.

JP 2000-319688 A Japanese Patent Application Laid-Open No. 11-1404089 JP-A-61-231094 JP 2006-111869 A

  The present invention has been made in view of the above circumstances, and exhibits a high cleaning effect against mud stains in which inorganic particles and organic polymer compounds are mixed, and also causes discoloration of objects to be washed such as colored clothing. The problem is to provide a cleansing agent that does not have any.

The present invention has the following configuration.
[1] A cleaning agent comprising cellulase (A) and water-soluble fluoride (B).
[2] One or more compounds selected from the group consisting of phosphonic acids, phosphonates, phosphoric acids, phosphates, and aminocarboxylic acid-based chelating agents having an Fe ³⁺ chelate stabilization constant of 20 or more ( The cleaning agent according to [1], further comprising C).

  According to the cleaning agent of the present invention, it exhibits a high cleaning effect against mud stains in which inorganic particles and organic polymer compounds are mixed, and does not cause discoloration of objects to be cleaned such as colored clothing.

<Cleaning agent>
The cleaning agent of the present invention comprises cellulase (A) (hereinafter also referred to as “component (A)”) and water-soluble fluoride (B) (hereinafter referred to as “component (B)” or simply “fluoride (B)”). At least).
The dosage form of the cleaning agent of the present invention may be liquid or solid, such as granular, tablet, briquette, sheet or bar.
In the case of a liquid cleaning agent (hereinafter, also referred to as “liquid cleaning agent”), the component (A) and the component (B) may both be a one-component type mixed in a dispersion medium such as water, A two-component type composed of a first liquid containing the component (A) and a second liquid containing the component (B) may be used.
In the case of a granular detergent (hereinafter also referred to as “granular detergent”), the component (A) and the component (B) may be mixed, and the component (A) and the component (B) are each It may be prepared as a separate granular material.

[Cellulase (A)]
Cellulase (A) is an action that cuts fibers (fibers that constitute an object to be washed) such as cotton fibers in a state where organic polymer compounds contained in mud soil are bound (hereinafter referred to as “fiber cutting action”). Is considered to play. Mud dirt in which inorganic particles and organic polymer compounds are mixed has a structure in which the organic polymer compound covers the inorganic particles adhering to the fibers. Therefore, the organic polymer compound becomes an obstacle only by allowing the later-described component (B), which has a high effect of removing inorganic particles, to act on mud soil, and the inorganic particles are not easily removed. On the other hand, when the component (A) is used together with the component (B), the component (A) cuts the fiber bonded with the organic polymer compound, and the component (B) described later can act on the inorganic particles from the cut surface. It becomes like this. As a result, it is considered that the component (B) effectively removes the metal contained in the inorganic particles.

As cellulase (A), for example, a commercially available cellulase preparation such as a cellulase preparation available from Novozymes, a cellulase preparation available from Genencor, or the like can be used. Cellulase preparations include granule preparations and liquid preparations, both of which can be used.
Examples of cellulase preparations available from Novozymes include “Celluclean 4500T”, “Celluclean 5000L”, “Cellucian Classic 400L”, “Carezyme Premium 4500L”, “Carezyme 4500L”, etc. Examples of cellulase preparations include “Puradux EG L” as a trade name. (A) 1 or more types can be used for a component.

Among these, an endoglucanase that degrades the non-crystalline part of cellulose is preferable, and an endoglucanase having a high enzymatic activity, that is, an endoglucanase having a high value of the amount of Glu-like reducing end produced by the cellulose decomposition reaction is preferable. Specifically, it is an endoglucanase having a Glu-like reducing end production amount of 50 μM or more, preferably 80 μM or more, more preferably 100 μM or more. Examples of such endoglucanases include “Celluclean 4500T, Glu-like reducing end production amount: 104 μM”, “Carezyme Premium 4500 L, Glu-like reducing end production amount: 85 μM”, “Celluclean 5000 L, Glu-like reducing end production amount: 127 μM. “Carezyme 4500L, Glu-like reducing end generation amount: 69 μM” is preferable, “Celluclean 4500T”, “Carezyme Premium 4500L”, “Celluclean 5000L” are more preferable, and “Celluclean 4500T” and “Celluclean 5000L” are most preferable.
In addition, the measuring method of the amount of Glu-like reducing terminal production | generation in this invention is described in the below-mentioned Example.

As will be described in detail later, the cleaning agent of the present invention is preferably used by diluting with water to form a cleaning liquid and immersing an object to be cleaned in the cleaning liquid. More preferably, the object to be washed is washed with a washing machine or the like after the immersion.
The cellulase is preferably blended so that the amount of Glu-like reducing terminal generated in the above-mentioned washing solution is 0.018M or more, preferably 0.18M or more, more preferably 0.9M or more. The cellulase preparation is preferably blended in the cleaning solution in an amount of 100 to 20000 ppm, more preferably 1000 to 10,000 ppm, and particularly preferably 5000 to 10,000 ppm so as to satisfy this enzyme activity amount. When it is at least the lower limit of the above range, a high mud removing effect can be obtained. In addition, even if it mixes exceeding the upper limit of the said range, the improvement of a mud removal effect is hard to be recognized. Moreover, ppm is a mass reference | standard in this specification.

When the cleaning agent of the present invention is a liquid cleaning agent, the blending amount of the component (A) in the liquid cleaning agent can be appropriately set, but is preferably 0.01 to 10% by mass, and 2.5 to 10% by mass. More preferred. When the liquid cleaning agent of the present invention is diluted with water and used at the time of washing as will be described in detail, the amount of use of the liquid cleaning agent of the present invention is measured and the like when it is equal to or more than the lower limit of the above range. It can be easily reduced to an appropriate amount. It is preferable from a viewpoint of human body safety that it is below the upper limit of the said range.
When the cleaning agent of the present invention is a granular cleaning agent, the blending amount of the component (A) in the granular cleaning agent can be appropriately set, but is preferably 0.1 to 10% by mass, and 2.5 to 10% by mass. More preferred. When it is at least the lower limit of the above range, the amount of the granular detergent of the present invention can be suppressed to an appropriate amount that can be easily measured. Moreover, (A) component is easy to disperse | distribute uniformly in a granular cleaning agent, and the presence nonuniformity of (A) component in a granular cleaning agent can be suppressed. It is preferable from a viewpoint of human body safety that it is below the upper limit of the said range.

[Water-soluble fluoride (B)]
The water-soluble fluoride (B) forms a chelate with a metal such as aluminum contained in the inorganic particles in the mud soil, and traps and removes the metal (hereinafter, sometimes referred to as “metal trapping action”). It is thought to play. The water-soluble fluoride (B) refers to a fluoride that dissolves 100 mg or more in 100 g of water at 20 ° C. The fluoride (B) is a compound that releases fluoride ions when dissolved in water. For example, in addition to a compound that forms a fluoride salt, the fluoride (B) may have fluoride ions as counter ions of the compound. .

Fluoride (B) includes hydrogen fluoride, sodium fluoride, potassium fluoride, lithium fluoride, rubidium fluoride, cesium fluoride, ammonium fluoride, and sodium acid fluoride (NaHF ₂ ) from the viewpoint of metal capture action. ), Acidic potassium fluoride (KHF ₂ ), sodium silicofluoride (Na ₃ SiF ₆ ), cryolite (Na ₃ AlF ₆ ), sodium fluoride, potassium fluoride, and ammonium fluoride are more preferable. Sodium chloride is particularly preferred. (B) 1 or more types can be used for a component.

  It is preferable to mix | blend the compounding quantity of water-soluble fluoride (B) so that it may become 1500-5000 ppm in the above-mentioned washing | cleaning liquid, and it is further more preferable to mix | blend so that it may become 3000-5000 ppm. High mud removal performance is obtained by setting it to be equal to or higher than the lower limit of the above range, and the effects of other components are not hindered by setting the upper limit of the above range.

When the cleaning agent of the present invention is a liquid cleaning agent, the blending amount of the component (B) in the liquid cleaning agent can be appropriately set, but is preferably 0.5 to 3% by mass, and more preferably 1.5 to 3% by mass. More preferably, 1.5-2.5 mass% is further more preferable. When the liquid cleaning agent of the present invention is diluted with water and used at the time of washing as will be described in detail, the amount of use of the liquid cleaning agent of the present invention is measured and the like when it is equal to or more than the lower limit of the above range. It can be easily reduced to an appropriate amount. If it is not more than the upper limit of the above range, the liquid stability (liquid appearance) of the liquid detergent is excellent.
When the cleaning agent of the present invention is a granular cleaning agent, the blending amount of the component (B) in the granular cleaning agent can be appropriately set, but is preferably 1.0 to 25% by mass, and 1.0 to 15% by mass. More preferably, 5.0-15 mass% is further more preferable, and 5.0-10 mass% is especially preferable. When it is at least the lower limit of the above range, the amount of the granular detergent of the present invention can be suppressed to an appropriate amount that can be easily measured. Moreover, the (B) component is easily dispersed uniformly in the granular cleaning agent, and the presence unevenness of the (B) component in the granular cleaning agent can be suppressed. It is easy to mix | blend another component while being able to hold down cost as it is below the upper limit of the said range.

[(B) component / (A) component ratio]
The mass ratio ((B) / (A)) of (B) component concentration / (A) component concentration in the cleaning agent is preferably 0.3 to 50, more preferably 0.6 to 15, and 1 to 5 Further preferred. When it is within the above range, a mechanism in which the component (B) acts more effectively works from the cut surface of the fiber generated by the fiber cutting action of the component (A), and mud dirt can be removed better.

[Compound (C)]
The cleaning agent of the present invention is one selected from the group consisting of phosphonic acids, phosphonates, phosphoric acids, phosphates, and aminocarboxylic acid chelating agents having a logarithmic value of the chelate stabilization constant of Fe ³⁺ of 20 or more. It is preferable to further contain the above compound (C) (hereinafter also referred to as “component (C)”). The compound (C) is a chelating agent, and is considered to form a chelate with a metal such as aluminum or iron contained in the inorganic particles in the mud soil and exert a metal capturing action. When the compound (C) is used together with the fluoride (B), the detailed reason is not clear, but the organic polymer compound in the mud soil becomes a steric hindrance and is difficult to chelate only with the component (B). It can be considered that the component (C) can be chelated so that the metal capturing action becomes efficient and the effect is synergistically improved. In particular, phosphonic acids, phosphonates, phosphoric acids, and phosphates easily form chelates with metals such as aluminum, and aminocarboxylic acid chelating agents easily form chelates with metals such as iron. The compound (C) has at least one selected from the group consisting of phosphonic acids, phosphonates, phosphoric acids, phosphates and a chelate stabilization constant of Fe ^{3+ in that} the cleaning effect on mud dirt is further improved. It is preferable to use in combination with an aminocarboxylic acid chelating agent having a logarithmic value of 20 or more.

Examples of phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonate, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, Examples include ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, and one or more of them can be used. Examples of the phosphonates include salts of the above-described phosphonic acids. Examples of the salt include an alkali metal salt whose counter ion is an alkali metal ion such as sodium ion or potassium ion.
Among the above-described phosphonic acid-based chelating agents such as phosphonic acids and phosphonic acid salts, 1-hydroxyethane-1 exhibits a high metal-capturing action and is excellent in combined effect when used in combination with the component (B). 1,1-diphosphonic acid and ethylenediaminetetrakismethylenephosphonic acid are preferred, and 1-hydroxyethane-1,1-diphosphonic acid is particularly preferred.

  As 1-hydroxyethane-1,1-diphosphonic acid, commercially available products can be used. For example, “Feliox 115 (trade name)” manufactured by Rhodia Japan, Inc .; “BRIQUEST ADPA-60A” manufactured by Albright Wilson Co., Ltd. (Trade name) ”;“ Chillest PH-210 (trade name) ”manufactured by Kirest Co., Ltd .;“ DEQUEST 2010 (trade name) ”manufactured by Monsanto, and the like.

Examples of phosphoric acids include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid (STPP), metaphosphoric acid, hexametaphosphoric acid, phytic acid, and the like, and one or more can be used. Examples of the phosphates include salts of the above-described phosphoric acids. Examples of the salt include an alkali metal salt whose counter ion is an alkali metal ion such as sodium ion or potassium ion.
Among the phosphoric acid-based chelating agents such as phosphoric acids and phosphates described above, tripolyphosphate and pyrophosphoric acid are used because they exhibit a high metal scavenging action and have excellent combined effects when used in combination with component (B). Salts are preferred. Commercially available products can be used as the tripolyphosphate and pyrophosphate. For example, as sodium tripolyphosphate, “sodium tripolyphosphate” manufactured by Wako Pure Chemical Industries, Ltd .; “tripolyphosphate manufactured by Mitsui Chemicals, Inc.” Examples of “soda” and sodium pyrophosphate include “sodium pyroacid” manufactured by Mitsui Chemicals.

The aminocarboxylic acid chelating agent having a logarithmic value of Fe ³⁺ chelate stabilization constant of 20 or more includes ethylenediaminetetraacetic acid (logarithmic value: 25.1, from the Dojin Chemical Laboratory Chelate Stability Constant), trans-1, 2-diaminocyclohexane-N, N, N ′, N′-4 acetic acid (logarithmic value: 28.05), diethylenetriaminepentaacetic acid (logarithmic value: 28.6), glycol ether diamine tetraacetic acid (logarithmic value: 20.5) ), Triethylenetetramine hexaacetic acid (logarithmic value: 26.8), ethylenediamine-N ′, N-disuccinic acid (logarithmic value: 20.6), and the like, and one or more can be used. Among these, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine-N ′, N-disuccinic acid are preferred, and diethylenetriaminepentaacetic acid, ethylenediamine-N ′, N-disuccinic acid are preferred. Most preferred.

As a compounding quantity of a compound (C), it is preferable to mix | blend so that it may become 1500-10000 ppm in the above-mentioned washing | cleaning liquid, More preferably, it becomes 1500-5000 ppm, More preferably, it becomes 2000-4500 ppm, Most preferably, it becomes 2000-4000 ppm. Blend as follows. By making it 1500 ppm or more, high mud removal performance is obtained, and by making it 10000 ppm or less, costs can be suppressed and the burden on the environment can be reduced.
When the cleaning agent of the present invention is a liquid cleaning agent, the blending amount of the component (C) in the liquid cleaning agent can be appropriately set, but is preferably 0.5 to 10% by mass, and 1.0 to 6% by mass. More preferably, 1.0-5 mass% is further more preferable. When the liquid cleaning agent of the present invention is diluted with water and used at the time of washing as will be described in detail, the amount of use of the liquid cleaning agent of the present invention is measured and the like when it is equal to or more than the lower limit of the above range. It can be easily reduced to an appropriate amount. If it is not more than the upper limit of the above range, the liquid stability (liquid appearance) of the liquid detergent is excellent.
When the cleaning agent of the present invention is a granular cleaning agent, the blending amount of the component (C) in the granular cleaning agent can be appropriately set, but is preferably 1.0 to 30% by mass, and 5.0 to 25% by mass. More preferred is 6.0 to 25% by mass. When the amount is not less than the lower limit of the above range, the amount of the granular detergent of the present invention can be suppressed to an appropriate amount, and the component (C) can easily be uniformly dispersed in the granular detergent. The presence unevenness of the component (C) in the granular cleaning agent can be suppressed. It is easy to mix | blend another component while being able to hold down cost as it is below the upper limit of the said range.

[Molar ratio of component (C) / component (B)]
When (C) component is mix | blended with the cleaning agent of this invention, 0.05-2 are preferable as for the molar ratio ((C) / (B)) of (C) component / (B) component in cleaning agent, 0 .10 to 1.5 is more preferable, and 0.15 to 1 is more preferable. Within the above range, the metal trapping action by the component (B) and the component (C) is more synergistically exhibited.

[Component (D)]
The cleaning agent of the present invention is one or more selected from the group consisting of amphoteric surfactants, semipolar surfactants, and amine compounds represented by the following general formula (2) (hereinafter also referred to as “amine compounds”). It is preferable to further contain (D) as a component. The component (D) is considered to have an effect of dispersing the organic polymer compound separated from the fibers of the washing object by the action of the component (A).

Examples of amphoteric surfactants include N-alkyl amino acids, alkenyl amino acids, their salts, betaines, and the like, and one or more can be used.
In N-alkylamino acids and N-alkenylamino acids, an alkyl group or an alkenyl group is bonded to a nitrogen atom, and one or two “—R—COOH” (wherein R represents a divalent hydrocarbon group). , Preferably an alkylene group, and particularly preferably having 1 to 2 carbon atoms.). In a compound in which one “—R—COOH” is bonded, a hydrogen atom is further bonded to the nitrogen atom.
One “—R—COOH” is called a mono form, and two are called a di form. As the component (D), any of these mono and di forms can be used.
In the N-alkyl amino acid and alkenyl amino acid, the alkyl group and the alkenyl group preferably have 10 to 20 carbon atoms, and these may be linear or branched.
The salt is preferably an alkali metal salt such as sodium or potassium, and is preferably a sodium salt.

  Preferable examples of the amphoteric surfactant include alkylaminopropionic acid, alkenylaminopropionic acid, and salts thereof, and laurylaminopropionic acid and its sodium salt are more preferable. Examples of commercially available products include Naurylaminopropionic acid Na (manufactured by Yushi Kogyo Co., Ltd.). This is a 90% by mass: 10% by mass mixture of mono and di.

  Examples of betaines include alkylbedines, carbobetaines, amide betaines, sulfobetaines, amide sulfobetaines, imidazolinium betaines, phosphobetaines, and the like. Specifically, fatty acid amide propyl betaines such as amide propyl betaine laurate, 2 -Alkyldimethylbetaine such as alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldimethylaminoacetic acid betaine, alkylhydroxysulfobetaine, lauryldimethylbetaine and the like. Among these, alkylbedine, amidebedine, and sulfobedine are preferable, and amidepropylbetaine laurate and lauryldimethylbetaine are particularly preferable.

  Examples of commercially available products include lauric acid amidopropyl betaine (trade name “Softazoline LPB”; manufactured by Kawaken Fine Chemical Co., Ltd.), lauryl dimethyl betaine (trade name “Amphithol 24B”; manufactured by Kao Corporation), and the like.

  Examples of the semipolar surfactant include amine oxide surfactants represented by the following general formula (1).

In Formula (1), R ¹ is a linear or branched alkyl group or alkenyl group, and has 8 to 18 carbon atoms, preferably 8 to 16, and more preferably 10 to 14.
R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group.
R ⁴ is an alkylene group having 1 to 4 carbon atoms.
A is a group selected from —CO—NH—, —NHCO—, —COO—, —OCO— or —O—, and n ′ is 0 or 1.

  Specific examples of the amine oxide surfactant include alkyldimethylamine oxide, alkylamidopropyldimethylamine oxide, and the like, and one or more of them can be used. Among these, alkyldimethylamine oxide is preferable from the viewpoint of the dispersibility of the organic polymer compound in the mud soil, and n-dodecyldimethylamine oxide and myristyldimethylamine oxide are particularly preferable. For example, n-dodecyldimethylamine oxide and myristyldimethylamine oxide are commercially available from Lion Akzo Corporation.

  The amine compound is a compound represented by the following general formula (2).

In the formula (2), R ⁵ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, PO is an oxypropylene group, and EO is an oxyethylene group. x, y, a and b represent the average number of repetitions, respectively, and x + y = 0 to 10, a + b = 2 to 50, a ≧ 1, and b ≧ 1.

R ⁵ is an alkyl group or alkenyl group having 8 to 22 carbon atoms. R ⁵ may be linear or branched. The number of carbon atoms in R ⁵ is preferably 10 to 20, 12 to 18 is more preferable. When the carbon number of R ⁵ is within the above range, the organic polymer compound contained in the mud can be sufficiently dispersed.

PO is an oxypropylene group, and EO is an oxyethylene group. The addition form of EO and PO in Formula (2) may be random addition or block addition.
x, y, a and b each represent an average number of repetitions. x + y is 0 to 10, preferably 0 to 4. a + b is 2-50, and 10-20 are preferable. Moreover, 0-10 are preferable and 0-5 are more preferable. y is preferably 0 to 10, and more preferably 0 to 5. a is preferably from 1 to 25, and more preferably from 5 to 10. 1-25 are preferable and, as for b, 5-10 are more preferable. The “average number of repetitions” is sometimes referred to as “average number of added moles”.

  As a commercial item of an amine compound, for example, Lion Akzo Co., Ltd., trade name “Esomine C15” (R: coconut palm-derived alkyl group (carbon number 12 to 14), x + y = 0, a + b = 5 (a = 2) -3, b = 2-3)), trade name "Esomine C25" (R: coconut-derived alkyl group (carbon number 12-14), x + y = 0, a + b = 15 (a = 7-8, b = 7) -8)), trade name "Esomine T15" (R: tallow-derived alkyl group (carbon number 14-18), x + y = 0, a + b = 5 (a = 2-3, b = 2-3)), product Name “Esomin T25” (R: tallow-derived alkyl group (carbon number 14-18), x + y = 0, a + b = 15 (a = 7-8, b = 7-8)), trade name “Esopropomine C18 / 18” (R: an alkyl group derived from coconut (carbon number: 12 to 14), x + y = (X = y = 4), a + b = 8 (a = b = 4)) and the like.

  As the component (D), an amine compound is preferable. When the cleaning agent contains the component (E) described later, the amphoteric surfactant or the semipolar surfactant forms a complex with the component (E), and the effect obtained from each component may decrease. On the other hand, since it is difficult to form a complex with the component (E) if it is an amine compound, the effects of both the component (D) and the component (E) can be sufficiently obtained.

  (D) As a compounding quantity of a component, it is preferable to mix | blend so that it may become 100-10000 ppm in the above-mentioned washing | cleaning liquid, 500-5000 ppm is more preferable, 1000-5000 ppm is further more preferable. By making it 100 ppm or more, the effect of dispersing the organic polymer compound can be sufficiently obtained, and the recontamination of the object to be washed by the organic polymer compound can be suppressed. When it is 10000 ppm or less, the rinsing time of the article to be washed does not become long.

When the cleaning agent of the present invention is a liquid cleaning agent, the blending amount of the component (D) in the liquid cleaning agent can be appropriately set, but is preferably 0.1 to 10% by mass, and preferably 0.5 to 5.0% by mass. % Is more preferable. When the liquid cleaning agent of the present invention is diluted with water and used at the time of washing as will be described in detail, the amount of use of the liquid cleaning agent of the present invention is measured and the like when it is equal to or more than the lower limit of the above range. It can be easily reduced to an appropriate amount. It is easy to mix | blend another component while being able to hold down cost as it is below the upper limit of the said range.
When the cleaning agent of the present invention is a granular cleaning agent, the blending amount of the component (D) in the granular cleaning agent can be appropriately set, but is preferably 0.1 to 25% by mass, and 1.0 to 13% by mass. More preferred. When the amount is not less than the lower limit of the above range, the amount of the granular detergent of the present invention can be suppressed to an appropriate amount and the component (D) is easily dispersed uniformly in the granular detergent. The presence unevenness of the component (D) in the cleaning agent can be suppressed. It is easy to mix | blend another component while being able to hold down cost as it is below the upper limit of the said range.

[Anionic surfactant (E)]
The cleaning agent of the present invention preferably further contains an anionic surfactant as the component (E). The component (E) prevents the organic polymer compound from being recontaminated on the fiber to which the mud dirt of the object to be washed is not attached.

  Examples of the anionic surfactant include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; Alkane sulfonate having a group; α-sulfo fatty acid ester salt and the like. Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine, and one or more of them can be used.

Preferable examples of the anionic surfactant include the following.
As the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide added (ie, A polyoxyethylene alkyl ether sulfate salt or a polyoxyethylene alkenyl ether sulfate ester salt having an oxyethylene group having an average repeating number of 1 to 10) is preferred.
As the alkane sulfonate, a secondary alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms, is particularly preferable.
The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.
Among these, linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate are preferable, and linear alkyl benzene sulfonic acid is particularly preferable.

  It is preferable to mix | blend so that it may become 200-2500 ppm in the above-mentioned washing | cleaning liquid as a compounding quantity of an anionic surfactant, Preferably it is 200-1000 ppm, More preferably, it mix | blends so that it may become 200-500 ppm. By setting it to 200 ppm or more, recontamination of the organic polymer compound can be effectively suppressed. By making it 2500 ppm or less, inhibition of the effect of the component (A) can be suppressed.

When the cleaning agent of the present invention is a liquid cleaning agent, the blending amount of the component (E) in the liquid cleaning agent can be appropriately set, but is preferably 0.1 to 1.5% by mass, preferably 0.1 to 0. 5 mass% is more preferable and 0.1-0.25 mass% is further more preferable. Within the above range, it is possible to suppress denaturation of the component (A) by the component (E) while effectively suppressing recontamination of the organic polymer compound, so that high performance can be obtained even after storage.
When the cleaning agent of the present invention is a granular cleaning agent, the blending amount of the component (E) in the granular cleaning agent can be appropriately set, but is preferably 0.5 to 6.5% by mass, and preferably 0.5 to 2. 5 mass% is more preferable. When the amount is not less than the lower limit of the above range, the amount of the granular detergent of the present invention can be controlled to an appropriate amount, and the component (E) is easily dispersed uniformly in the granular detergent. The presence unevenness of the component (E) in the cleaning agent can be suppressed. It is easy to mix | blend another component while being able to hold down cost as it is below the upper limit of the said range.

[Other optional ingredients]
In the cleaning agent of the present invention, a nonionic surfactant other than the amine compound (other nonionic surfactant), an enzyme other than cellulase (A) (other enzyme), an enzyme stabilizer, a reducing agent, etc. are optional. It may be included as a component.

(Other nonionic surfactants)
Although there is no restriction | limiting in particular as nonionic surfactants other than the said amine compound, For example, the polyoxyalkylene type nonionic surfactant represented by following General formula (3) is used suitably.
_{^{R 6 -Y- (EO) s /}} (PO) t -R 7 ··· (3)

In the formula (3), R ⁶ is a hydrophobic group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and may be linear or branched. Examples of the hydrophobic group include those derived from primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like. Specifically, alkyl groups and alkenyl groups are preferable. R ⁷ is a hydrogen atom or an alkyl or alkenyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl or alkenyl group having 1 to 3 carbon atoms.

-Y- is a divalent group such as -O-, -COO-, and -CONH-.
EO is an oxyethylene group and PO is an oxypropylene group.
s shows the average repeating number of an oxyethylene group, is 3-20, and 5-18 are preferable. s corresponds to the average number of moles of ethylene oxide added. t shows the average repeating number of an oxypropylene group, is 0-6, and 0-3 are preferable. t corresponds to the average number of moles of propylene oxide added. When s is in the above range, the dispersibility of mud soil is excellent, the HLB value is moderate without being too high, and the dispersibility of the organic polymer compound is excellent. When t is in the above range, the dispersibility of mud dirt is excellent.

In the formula (3), when EO and PO coexist in the same molecule, EO and PO may be added randomly or in blocks. The order of adding EO and PO is not particularly limited.
In the present specification, the “HLB value” refers to the relative strength between the hydrophilicity and lipophilicity of the surfactant molecule, and represents the hydrophilic-lipophilic balance in a quantitative manner. .

The distribution of the number of repetitions of EO and PO is likely to vary depending on the reaction method in producing the nonionic surfactant. For example, the repetition number distribution of EO or PO is relatively wide when ethylene oxide or propylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. It tends to be distributed. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution tends to be relatively narrow. The distribution of the number of repetitions of EO and PO is not particularly limited.

In Formula (3), when -Y- is -O-, the nonionic surfactant is an alcohol ethoxylate. In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R ⁶ is 10 to 22, preferably 10 to 20, and more preferably 10 to 18. R ⁶ may have an unsaturated bond. In this case, R ⁷ is preferably a hydrogen atom.

  Specific examples of the nonionic surfactant represented by the formula (3) are manufactured by Mitsubishi Chemical Corporation: trade name Diadol (C13 (indicating that the carbon number is 13; the same applies hereinafter)), Shell Product: Neodol (C12 / C13), manufactured by Sasol: Alcohol of 12 mole equivalent or 15 moles of ethylene oxide added to alcohol such as trade name Safol23 (C12 / C13); manufactured by P & G: A product obtained by adding ethylene oxide corresponding to 5 mol, 6 mol, 7 mol, 12 mol, or 15 mol of ethylene oxide to natural alcohols such as trade names CO-1214 and CO-1270; C12 obtained by trimerizing butene A product obtained by adding 7 moles of ethylene oxide to C13 alcohol obtained by subjecting alkene to oxo method (BASF Corporation: trade name Lutensol T) 7); C10 alcohol obtained by subjecting pentanol to gerbet reaction to addition of 7 moles of ethylene oxide (BASF: trade name Lutensol XL70); C10 alcohol obtained by subjecting pentanol to gerbet reaction To which 6 mol equivalent ethylene oxide was added (BASF: trade name Lutensol XA60); 9 mol equivalent or 15 mol equivalent ethylene oxide added to secondary alcohol having 12 to 14 carbon atoms (Nippon Shokubai Co., Ltd .: trade name Softanol 90 or Softanol 150); Furthermore, to the palm fatty acid methyl (lauric acid / myristic acid = 8/2), using an alkoxylation catalyst, 15 mol equivalent of ethylene oxide added (polyoxyethylene palm fatty acid methyl ester (hereinafter, “ Also referred to as “MEE”) EO 15 mol). Examples of the natural alcohol added with 7 moles of ethylene oxide include Leox CL-70 manufactured by Lion Chemical Co., Ltd. One or more of these can be used.

  It is preferable to mix | blend so that it may become 100-10000 ppm in the above-mentioned washing | cleaning liquid as a compounding quantity of a nonionic surfactant, Preferably it is 500-5000 ppm, More preferably, it mix | blends so that it may become 1000-2500 ppm.

(Other enzymes)
Examples of the enzyme other than the component (A) include protease, amylase, lipase, cellulase, mannanase, and pectinase, and one or more kinds can be used. Specific examples include the following.
As proteases, protease preparations available from Novozymes: Tradenames Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type EX 2.5, Ultra Ul 16L, Erase Ultra 16L, Esperase 8L , Liquidase Ultra 2.5L, Liquidase Ultra 2.5XL, Coronase 48L, Protease preparations available from Genencor Corporation: Tradenames Purefect L, Perfect Prime, Properase L and the like.
As the amylase, amylase preparations available from Novozymes: trade name Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, amylase preparation available from Genencor Corp. Examples include amylase preparations available from Enzyme Co., Ltd .: trade name pullulanase Amano, amylase preparations available from Seikagaku Corporation, trade name DB-250, and the like.
Examples of the lipase include lipase preparations available from Novozymes: trade names Lipex 100L, Lipolase 100L, and the like.
Examples of mannanases include mannanase preparations available from Novozymes: trade name Mannaway 4L.
Examples of the pectinase include a pectinase preparation available from Novozymes, such as trade name Xspect 1000L.

(Enzyme stabilizer)
The cleaning agent of the present invention includes boric acid, borax, formic acid and salts thereof, calcium salts such as calcium chloride, calcium carbonate, and calcium sulfate that improve the stability of component (A) and other enzymes that are optionally blended. May be blended as an enzyme stabilizer. One or more enzyme stabilizers can be used.

(Reducing agent)
The cleaning agent of the present invention may contain a reducing agent having a reducing power that does not cause discoloration of the object to be washed. Examples of such a reducing agent include sodium sulfite, ascorbic acid, sodium thiosulfate, and the like. 1 type or more can be used. Of these, ascorbic acid is preferred.

  As a compounding quantity of a reducing agent, it is preferable to mix | blend so that it may become 100-10000 ppm in the above-mentioned washing | cleaning liquid, Preferably it is 500-5000 ppm, More preferably, it mix | blends so that it may become 1000-2500 ppm.

[Liquid cleaning agent]
When the cleaning agent of the present invention is a one-component liquid cleaning agent, the dispersion medium is preferably water.
Moreover, 4-9 are preferable and, as for pH at 25 degreeC of a liquid detergent, 4-8 are more preferable.
The pH in the present specification is a value measured by a pH meter (HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.

[Action]
It is considered that the excellent cleaning action of the cleaning agent of the present invention is expressed as follows.
As described above, the mud stain in which inorganic particles and organic polymer compounds are mixed has a structure in which the organic polymer compounds cover the inorganic particles attached to the fibers. When the component (A) is allowed to act on such mud soil, the component (A) cuts the fiber to which the organic polymer compound is bonded. The component (B) acts on the inorganic particles from the cut surface. As a result, it is considered that mud dirt can be washed well by the synergistic action of these components.
Furthermore, when the cleaning agent of the present invention contains the component (C), the detailed reason is not clear, but as described above, the organic polymer compound in the mud soil becomes a steric hindrance, and only the component (B) It is considered that the component (C) can be chelated against a metal that is difficult to chelate, so that the metal capturing action becomes efficient and the effect is synergistically improved.

Moreover, when the component (D), which is an optional component, is used, the organic polymer compound is dispersed by the component (D). And when an organic polymer compound is removed from a fiber in this way, (A) component will cut | disconnect the fiber to which the organic polymer compound which exists in the back of a fiber adheres again, and from there ( It is considered that the component B) and the component (C) act on the inorganic particles.
Moreover, when (E) component which is an arbitrary component is used, (E) component adsorb | sucks to the organic polymer compound removed from the fiber of the to-be-washed object, and the mud dirt of the to-be-washed object has not adhered. Prevents re-contamination on the part, so that the mud dirt removing effect can be further enhanced.
Moreover, since the cleaning agent of the present invention does not contain a reducing agent as an essential component, it does not cause discoloration of objects to be cleaned such as colored clothing.

As described above, in the cleaning agent of the present invention, it is considered that the component (A) cuts the fiber to which the organic polymer compound is bonded. In order to sufficiently act such a fiber cutting action of the component (A), it is preferable not to add a high molecular weight compound that inhibits such action to the cleaning agent of the present invention. That is, the cleaning agent of the present invention preferably does not contain a high molecular compound having a mass average molecular weight of 10,000 or more, and more preferably does not contain a high molecular compound of 5000 or more.
The cleaning agent of the present invention exhibits high mud removal performance even when the cleaning agent is used alone for cleaning, or blended with a normal granular cleaning composition or liquid cleaning composition.

<Manufacturing method of cleaning agent>
When the cleaning agent of the present invention is a one-component liquid cleaning agent, a method of adding the components (A) and (B) and optional components used as necessary to a solvent such as water can be mentioned. . At that time, it is preferable to add the component (A) after adjusting the pH, since its denaturation is suppressed.
When the cleaning agent of the present invention is a granular cleaning agent, it is not particularly limited, and a conventionally known production method can be used. For example, the powder (A), the component (B), and the powder or granulated product of the optional component are mixed using a powder mixer, the liquid component (A), the component (B) and the optional component are mixed with zeolite or A method of impregnating a porous material such as clay minerals or retaining it between inorganic salt particles such as sodium sulfate and sodium silicate, mixing them using a powder mixer, binder compounds such as polyethylene glycol Examples thereof include a method of obtaining a granulated product or a molded product by dissolving in advance, adding the component (A), the component (B) and an optional component, stirring and mixing, and granulating or molding. Moreover, in the case of a tablet, the method of tableting the powder obtained by mixing each component as mentioned above using a tableting machine is mentioned.

<How to wash>
As a washing method using the cleaning agent of the present invention, a method including a step of immersing an object to be cleaned in a cleaning liquid containing the cleaning agent is suitable. After the step of immersing, mud soil can be more effectively removed by performing a step of washing the article to be washed with a washing machine or the like.
Although the cleaning agent of the present invention can be used as it is as a cleaning solution, it is preferable to use the cleaning agent diluted with water from the viewpoint of usability. The concentration of the cleaning agent of the present invention in the cleaning liquid is preferably in a range where the total concentration of the component (A) and the component (B) is 1600 to 13000 ppm, more preferably 2500 to 8000 ppm, and further preferably 2500 to 4000 ppm. By setting it as 1600 ppm or more, the contact frequency of the fiber which (A) component and the organic polymer compound couple | bonded improves, The fiber cutting action of (A) component fully works, and the metal removal effect by (B) component Can also be obtained sufficiently. Therefore, a high effect is obtained even by short-time immersion, and by making it 13000 ppm or less, it becomes economically favorable.
Moreover, when (C) component is contained in the cleaning agent, the concentration of the cleaning agent of the present invention in the cleaning liquid has a range in which the total concentration of the (A) component, the (B) component, and the (C) component is 3100 to 23000 ppm. Preferably, 3100 to 10500 ppm is more preferable, 3600 to 9500 ppm is more preferable, and 4500 to 8000 ppm is particularly preferable.
In addition, the suitable ratio of each component in a washing | cleaning liquid is as having described as a suitable ratio of each component in a cleaning agent previously.

  The pH of the cleaning liquid is preferably 5.0 to 10.0, and more preferably 5.0 to 8.0. When the pH is at least the lower limit of the above range, the activity of the component (A) is excellent. When the pH is not more than the upper limit of the above range, the possibility that the organic polymer compound in the mud soil once removed from the fiber causes re-contamination to the fiber is suppressed. Therefore, the pH of the cleaning agent of the present invention is preferably designed so that the pH when used as a cleaning liquid is 5.0 to 10.0, and is designed to be 5.0 to 8.0. More preferred.

The immersion time is preferably 30 minutes to 24 hours, more preferably 2 hours to 18 hours, and even more preferably 6 hours to 15 hours. When it is at least the lower limit of the above range, the high mud stain removing effect of the cleaning agent of the present invention is exhibited. If it is below the upper limit of the said range, possibility that the organic polymer compound in the mud stain once removed from the fiber will cause re-contamination to the fiber is suppressed.
The immersion temperature is preferably 15 ° C to 40 ° C, and more preferably 25 ° C to 35 ° C. When it is at least the lower limit of the above range, the activity of the component (A) is excellent, and the metal removal rate of the component (B) and the optional component (C) can be sufficiently secured. When the amount is not more than the upper limit of the above range, the modification of the component (A) is suppressed.

  As described above, according to the cleaning agent of the present invention, it exerts a high cleaning effect against mud stains in which inorganic particles and organic polymer compounds are mixed, and the color of clothes to be washed such as colored clothes is also changed. Does not occur.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
[Examples 1-37, Comparative Examples 1-2]
Each component shown in Table 1 was mix | blended by the mass part shown in Tables 2-6, and the liquid detergent of each example was prepared.
Specifically, among the components shown in Tables 2 to 6, components other than purified water were mixed, and then water was added so that the total amount became 100 parts by mass. An appropriate amount of sulfuric acid or sodium hydroxide was added to the cleaning agent as a pH adjusting agent, and the pH was adjusted to 7.0.
Using the cleaning agent of each example, the mud-stained cloth (model mud-stained cloth) is washed by the following method, and the mud-stain cleaning rate (%) at that time is determined. Evaluated.
In addition, the compounding quantity of each component is a pure part conversion.

[Examples 38 and 39]
A granular detergent was produced using each component shown in Table 5.
Specifically, sodium sulfate was charged into a small pulverizer, and component (C) was gradually added over 5 minutes while stirring, and then stirring was continued for 3 minutes to obtain a granulated product. The granulated product was dried for 1 day and then passed through a sieve (JIS-Z8801) having an opening of 850 μm. The portion that did not pass through the sieve was pulverized with Trio Blender (manufactured by Trio Science), passed through a sieve with an opening of 850 μm, and passed through the sieve. After passing all of the granulated material through the sieve in this way, add optional components other than (A) component, (B) component, (D) component, (E) component and sodium sulfate to the granulated product. The mixture was thoroughly mixed with a pulverizer to obtain a granular detergent.
Using the cleaning agent of each example, the mud-stained cloth (model mud-stained cloth) is washed by the following method, and the mud-stain cleaning rate (%) at that time is determined. Evaluated.
The pH of the cleaning liquid in which the granular cleaning agent of Example 38 was added to water so as to have a concentration of 40000 ppm was 7, and the pH of the cleaning liquid in which the granular cleaning agent of Example 38 was added to water so as to have a concentration of 40000 ppm was It was 9.5.
In addition, the compounding quantity of each component is a pure part conversion.

[Examples 40 to 49]
Each component shown in Table 1 was mix | blended by the mass part shown in Table 7, and the liquid cleaning agent of each example was prepared.
Specifically, among the components shown in Table 7, components other than purified water were mixed, and then water was added so that the total amount became 100 parts by mass. An appropriate amount of sulfuric acid or sodium hydroxide was added to the cleaning agent as a pH adjusting agent, and the pH was adjusted to 7.0.
Using the cleaning agent of each example, the mud-stained cloth (model mud-stained cloth) is washed by the following method, and the mud-stain cleaning rate (%) at that time is determined. Evaluated. Furthermore, the recontamination prevention property was evaluated by the following method.
In addition, the compounding quantity of each component is a pure part conversion.

Example 50
A granular detergent was manufactured using each component shown in Table 7.
Specifically, polyethylene glycol having an average molecular weight of 2600 to 3800 was placed in a beaker and dissolved in a hot water bath at 80 ° C. The components (C) and (D) were added and stirred there, and after sufficiently stirring, they were taken out from the hot water bath, spread thinly on a vat and hardened at room temperature. This was pulverized with Trio Blender (manufactured by Trio Science), passed through a sieve having an opening of 850 μm, and passed through the sieve to obtain a granulated product. (A) component, (B) component, (E) component, sodium sulfate, and sodium carbonate were added to this, and it mixed well with the table-top grinder, and obtained the granular detergent.
Using this cleaning agent, the mud-stained cloth (model mud-stained cloth) is cleaned by the method shown below, and the mud-stain cleaning rate (%) at that time is determined to evaluate the cleaning ability of the cleaning agent. did. Furthermore, the recontamination prevention property was evaluated by the following method.
In addition, the compounding quantity of each component is a pure part conversion.

Example 51
A granular detergent was manufactured using each component shown in Table 7.
Specifically, polyethylene glycol having an average molecular weight of 2600 to 3800 was placed in a beaker and dissolved in a hot water bath at 80 ° C. The component (D) was added and stirred there, and after sufficiently stirring, it was taken out from the hot water bath, spread thinly on a vat and hardened at room temperature. This was pulverized with Trio Blender (manufactured by Trio Science), passed through a sieve having an opening of 850 μm, and passed through the sieve to obtain a granulated product. (A) component, (B) component, (C) component, (E) component, sodium sulfate, and sodium carbonate were added to this, and it mixed well with the table-top grinder, and obtained the granular detergent.
Using this cleaning agent, the mud-stained cloth (model mud-stained cloth) is cleaned by the method shown below, and the mud-stain cleaning rate (%) at that time is determined to evaluate the cleaning ability of the cleaning agent. did. Furthermore, the recontamination prevention property was evaluated by the following method.
In addition, the compounding quantity of each component is a pure part conversion.

(Evaluation)
(1) Production of model mud soil cloth 10 g of black soil for gardening (manufactured by kyotochiya) was weighed and put into 500 g of tap water, and homogenizer (manufactured by KINEMATICA Switzerland, trade name: Polytron Type PT 10/35). Dispersion was carried out at 80 rpm for about 5 minutes. In the obtained dispersion, 15 pieces of cotton knitted fabric (made by Tanigami Shoten Co., Ltd., dyed sample, unsilled cotton knit) cut into 10 cm x 25 cm are immersed, and the fabric is thoroughly rubbed by hand. The mud dispersion was uniformly contained throughout. Then, the cloth was taken out and lightly squeezed with a roller. After naturally drying for 1 hour, it was further dried for 1 hour in a thermostatic bath at 105 ° C. Finally, the surface of the cloth was rubbed with a urethane sponge and the excess mud particles were removed for evaluation as a model mud soil cloth.
Each model mud soil cloth prepared above was cut to obtain 12 sheets of 4 cm × 4 cm detergency evaluation cloth (dirt cloth) from one model mud soil cloth. From a total of 180 detergency evaluation cloths, 5 sheets were randomly selected and used for the experiment.
(2) Evaluation of mud dirt cleaning power Cleaning agents in 150 mL of ion-exchanged water prepared by adjusting the liquid cleaning agents prepared in Examples 1 to 37 and 40 to 49 and Comparative Examples 1 and 2 to a hardness of 3 ° DH and a water temperature of 15 ° C. Was added so as to have a concentration of 200,000 ppm, and this was used as a cleaning solution.
The granular detergent prepared in Examples 38, 39, 50 and 51 was added to 150 mL of ion-exchanged water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C. so that the concentration of the detergent would be 40000 ppm. did.
5 sheets of the cleaning power evaluation cloths were put on each of these cleaning liquids for 10 hours, and then TG-O-Tometer (manufactured by UNITED STATES TESTING) containing 750 mL of ion-exchanged water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C. The whole cleaning solution was put in a cleaning bath and washed at 120 rpm for 10 minutes (bath ratio 20 times).
Thereafter, the contents in the washing bath were emptied into a colander, the washing solution was removed, and the washing power evaluation cloth was dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation).
After dehydration, the cloth for evaluating detergency was further rinsed for 3 minutes in a Terg-O-Tometer bath containing 900 mL of ion-exchanged water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C. Dehydrated.
The detergency test cloth is rinsed again for 3 minutes in a Terg-O-Tometer bath containing 900 mL of ion-exchanged water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C. After dehydration, it was air-dried.
The Z value of the cloth before adhesion of dirt and the cloth for evaluating the washing power before and after washing is measured using a colorimetric color difference meter (trade name: SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.). The washing rate (%) was calculated. And the average value of the mud dirt cleaning rate (%) of 5 sheets of cleaning power evaluation cloth was calculated | required, and it described in Tables 2-7.
Mud dirt cleaning rate (%) = (Z value of cleaning power evaluation cloth after cleaning−Z value of cleaning power evaluation cloth before cleaning) / (Z value of raw cloth−Z value of cleaning power evaluation cloth before cleaning) × 100

(3) Preparation of recontamination evaluation cloth Using a commercially available detergent for clothes (product name: Blue Diamond), a skin shirt (manufactured by BVD, white), two-tank washing machine And 15 minutes of washing and 1 minute dehydration were repeated three times. Thereafter, rinsing with running water for 15 minutes and 1-minute dehydration were repeated 5 times. After the final dehydration was completed, the room was naturally dried indoors. This was cut into 5 cm × 5 cm, and 5 pieces were selected at random from these, and these were subjected to evaluation as a recontamination evaluation cloth.
(4) Evaluation of recontamination prevention property After putting 5 sheets of the above-mentioned recontamination evaluation cloth into the cleaning liquid prepared in the same manner as the evaluation of the mud dirt cleaning power, 5 sheets of the cleaning power evaluation cloth prepared in (1) are used. After 10 hours, put the entire cleaning solution in a cleaning bath of Terg-O-Tometer (made by UNITED STATES TESTING) containing 750 mL of ion-exchanged water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C., and 10 at 120 rpm. Washed for a minute (bath ratio 20 times).
Thereafter, the contents in the washing bath were emptied into a colander, the washing liquid was removed, and the recontamination evaluation cloth was dehydrated for 1 minute in a dehydration tank of a two-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation).
After dehydration, the re-contamination evaluation cloth is further rinsed for 3 minutes in a Terg-O-Tometer bath containing 900 mL of ion-exchanged water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C. for 1 minute in a 2-tank washing machine dewatering tub. Dehydrated.
Then, the re-contamination evaluation cloth is rinsed again for 3 minutes in a Terg-O-Tometer bath containing 900 mL of ion-exchanged water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C. for 1 minute in a dewatering tank of a 2-bath washing machine. After dehydration, it was air-dried.
The Z value of the re-contamination evaluation cloth before and after washing was measured using a colorimetric color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: SE2000), and ΔZ was calculated according to the following equation. And the average value of (DELTA) Z of five sheets of re-contamination evaluation cloth was calculated | required, and it described in Table 7. A smaller value of ΔZ means higher anti-recontamination property.
ΔZ = Z value of re-contamination evaluation cloth before washing−Z value of re-contamination evaluation cloth after washing

In addition, the measuring method of the amount of Glu-like reducing terminal production | generation about (A) component is as follows.
17.6 g of sodium dihydrogen phosphate dihydrate (manufactured by Junsei Chemical Co., Ltd.) is dissolved in 900 mL of ion exchange water, adjusted to pH 7.0 with 1M aqueous sodium hydroxide solution, and then ion exchange water. The volume was made up to 1000 mL with 0.1 M phosphate buffer.
The cellulase enzyme sample was dissolved or diluted with 0.1 M phosphate buffer to 30 ppm to prepare an enzyme solution.
5 g of powdered cellulose (cotton linter: manufactured by Sigma) was dispersed in 495 g of ion-exchanged water to prepare a substrate solution.
PAHBAH (p-hydroxybenzhydrazide, manufactured by Wako Pure Chemical Industries, Ltd.) 1.8 g, (+)-potassium sodium tartrate tetrahydrate (produced by Junsei Kagaku Co., Ltd.) 6.0 g, Bismuth (III) acetate ( Alfa AESAR017574) 0.23 g was dissolved in 2% by mass sodium hydroxide and made up to 120 mL to prepare a PAHBAH solution.
The sample was measured by the following procedure. After 2 mL of the enzyme solution, 2 mL of 0.1 M phosphate buffer, and 2 mL of the substrate solution were added to the test tube and stirred, the enzyme reaction was performed in a 25 ° C. water bath for 15 hours. After completion of the reaction, 1 mL of 2% by mass sodium hydroxide was added to each sample to stop the reaction. Then, after centrifuging at 4000 rpm and 25 ° C. for 10 minutes with a centrifuge (manufactured by Hitachi, Ltd., himac CF7D2), 4 mL of the supernatant was taken, 2 mL of PAHBAH solution was added, and the mixture was added in boiling water for 10 minutes. After heating and cooling with water, the absorbance at 410 nm was measured using an absorptiometer (manufactured by Hitachi, Ltd., U-3010) with water as a control.
The blank was measured by the following procedure. After 2 mL of the enzyme solution and 2 mL of 0.1 M phosphate buffer were added to the test tube and stirred, the enzyme reaction was performed in a 25 ° C. water bath for 15 hours. After completion of the reaction, 1 mL of 2% by mass sodium hydroxide was added to each sample to stop the reaction, and 2 mL of the substrate solution was added. Then, after centrifuging at 4000 rpm and 25 ° C. for 10 minutes with a centrifuge (manufactured by Hitachi, Ltd., himac CF7D2), 4 mL of the supernatant was taken, 2 mL of PAHBAH solution was added, and the mixture was added in boiling water for 10 minutes. After heating and cooling with water, the absorbance at 410 nm was measured using an absorptiometer (manufactured by Hitachi, Ltd., U-3010) with water as a control.
The difference in absorbance between the sample and the blank was used as a measurement value, and the amount of reducing sugar produced was calculated from a calibration curve prepared using glucose at a predetermined concentration.

As shown in Tables 2-7, the cleaning agent of each Example had excellent mud dirt cleaning power. The cleaning agents of Examples 40 to 51 were also excellent in recontamination preventing property.
Further, the cleaning agent of Comparative Example 1 not containing the component (A) had a mud dirt cleaning rate of 15%, and the cleaning agent of Comparative Example 2 not containing the component (B) had a mud soil cleaning rate of 18%. The cleaning agent of Example 12 containing the component (A) and the component (B) has a mud dirt cleaning rate of 42%. By using the component (A) and the component (B) in combination, the mud dirt cleaning rate can be increased. Greatly improved.
In addition, for example, from comparison between Example 1 and Example 12, it was found that the mud dirt cleaning rate is greatly improved by using the component (C) in addition to the component (A) and the component (B). .

Claims (2)

A cleaning agent for clothes, comprising cellulase (A) and at least one water-soluble fluoride (B) selected from sodium fluoride, potassium fluoride and ammonium fluoride. One or more compounds (C) selected from the group consisting of phosphonic acids, phosphonates, phosphoric acids, phosphates, and aminocarboxylic acid chelating agents having a logarithm of the chelate stabilization constant of Fe ³⁺ of 20 or more Furthermore, it contains , The washing | cleaning agent for clothes of Claim 1 characterized by the above-mentioned.