JP5809970B2 - Cleaning agent for textile products - Google Patents

Description

  The present invention relates to a detergent for textile products.

In recent years, due to the increase in cleanliness, textile fabric cleaners can remove unpleasant odors generated from textile products in addition to removing dirt adhered to textile products (cleaning effect). Therefore, it is required to prevent the generation of unpleasant odors from textile products (deodorizing effect) (hereinafter, the deodorizing effect and deodorizing effect are collectively referred to as deodorizing effect).
The unpleasant odor emitted from the textile product is often caused by the growth of microorganisms attached to the textile product during drying or storage of the textile product.
In general, cationic surfactants have a bactericidal effect, but there is a problem that the bactericidal effect of the cationic surfactant is not sufficiently exerted when an anionic surfactant is used in combination with the detergent for textile products. there were.

For this reason, conventionally, in order to improve the deodorizing effect or deodorizing effect, for textile products that can sterilize microorganisms adhering to textile products (bactericidal effect) or suppress the growth of adhering microorganisms (antibacterial effect) Cleaning agents have been proposed.
For example, a powder detergent composition for clothing containing a coated sodium percarbonate, a metal catalyst that is a complex of a specific ligand and copper or manganese, an inorganic alkaline agent, and a surfactant has been proposed ( For example, Patent Document 1). According to the invention of Patent Document 1, an excellent odor suppression effect is achieved.
Odor selected from non-complexed cyclodextrins, odor blockers, class I and / or class II aldehydes, flavonoids, metal salts, used in a method for reducing the odor of fabric in laundry or rinse solutions of laundry processes Disclosed is a concentrated non-liquid composition comprising a control agent and an additional component selected from a non-complexed fragrance, a fragrance carrier complex, a cyclodextrin compatible surfactant, an antimicrobial active material, a filler material. (For example, Patent Document 2). According to the invention of Patent Document 2, for example, a concentrated non-liquid composition is applied to an object to be cleaned and washed to remove the odor of the cleaning liquid (for example, the odor derived from the object to be cleaned). It has been.

By the way, in recent years, clothing that uses hollow chemical fibers and has an excellent heat retention effect, and clothing that has a high surface area and easily releases moisture such as sweat are increasing. Such a chemical fiber product is hard to feel when worn and washed repeatedly, and is likely to generate a bad odor from the washed clothes as compared with the clothes made of cotton.
In order to solve these problems, a detergent composition containing an anionic surfactant, a specific hydroxypropyl methylcellulose, a specific bleach activator, and a bleaching agent has been proposed (for example, Patent Document 3). According to the invention of Patent Document 3, both deodorizing action and imparting flexibility (softening action) to chemical fibers are achieved.

JP 2008-31407 A Japanese translation of PCT publication No. 2003-508583 JP 2007-197712 A

However, although the inventions of Patent Documents 1 and 3 are effective in reducing odor derived from microbial growth, they have not been able to reduce all of the odors attached from the outside and odors caused by various causes. If the amount of metal catalyst, bleach activator, or the like is increased in order to enhance the bactericidal effect or antibacterial effect, there is a problem that the quality of the fiber product is likely to deteriorate, such as damage to the fiber product or discoloration.
In addition, in the invention of Patent Document 2, since the concentrated non-liquid composition is used in addition to the cleaning agent, the cleaning process becomes complicated.
Then, this invention aims at the washing | cleaning agent for textiles which is excellent in the softening effect | action and can deodorize a wide range of odor easily.

The detergent for textiles of the present invention comprises an anionic surfactant (A), at least one selected from copper, manganese, nickel, cobalt, iron and zinc (B), and the component (B) and a complex. It contains an aminocarboxylic acid type sequestering agent (C) to be formed and a biguanide polymer (D).
The molar ratio represented by the component (B) / the component (C) is preferably 1/3 to 5.

  According to the detergent for textiles of the present invention, it is excellent in softening action and can easily deodorize a wide range of odors.

(Cleaning agent for textile products)
The detergent for textiles of the present invention is an anionic surfactant (A) (hereinafter sometimes referred to as component (A)) and at least one selected from copper, manganese, nickel, cobalt, iron and zinc ( B) (hereinafter sometimes referred to as component (B)), aminocarboxylic acid-type sequestering agent (C) (hereinafter also referred to as component (C)) that forms a complex with component (B), and And a biguanide polymer (D) (hereinafter sometimes referred to as component (D)).

 The dosage form of the detergent for textile products may be a solid such as granules (powder, granules), tablets, briquettes, sheets or bars, or may be a liquid. From the viewpoint of long-term stability of the component (B) and the component (D), solid is preferable, and granular is more preferable.

When the detergent for textiles is granular, the bulk density is not particularly limited. For example, 0.3 g / cm ³ or more is preferable, 0.4 to 1.2 g / cm ³ is more preferable, and 0.5 -1.0 g / cm ³ is more preferable.
The bulk density is a value measured according to JIS-K3362 (the same applies hereinafter).

 Although the average particle diameter of the granular cleaning agent for textile products is not particularly limited, for example, 200 to 1500 μm is preferable, and 300 to 1000 μm is more preferable. If the average particle size is less than 200 μm, dust may be easily generated, and if it exceeds 1500 μm, the solubility may be insufficient.

 The average particle diameter is a value measured by a classification operation using a 9-stage sieve having openings 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, a sieve with a small opening is stacked in the order of a sieve with a large opening, and a sample of 100 g / time is put on the top of the top 1680 μm sieve. Cover and attach to a low-tap type sieve shaker (manufactured by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute) and vibrate for 10 minutes. Thereafter, the sample remaining on each sieve and the tray is collected for each sieve and the mass of the sample is measured. Then, 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 “a μm”, and the opening of the sieve that is one step larger than a μm is “b μm”. To do. In addition, the integrated value of the mass frequency from the tray to the a μm sieve is “c%”, and the mass frequency on the a μm sieve is “d%”. And an average particle diameter (50 mass% particle diameter) is calculated | required by following (1) Formula, and let this be an average particle diameter of a sample.

The fluidity of the granular textile cleaning agent is preferably 60 ° or less, and more preferably 50 ° or less as an angle of repose. If it exceeds 60 °, the handleability of the particles may deteriorate.
The angle of repose is an angle formed between a sliding surface formed when particles filled in the container flow out and a horizontal plane, and is a value measured by a so-called angle of repose measuring method (the same applies hereinafter). ).

<(A) component>
The component (A) is an anionic surfactant. By containing the component (A), it is possible to satisfactorily remove dirt and odor components adhering to the object to be cleaned, and to improve the deodorizing effect. This is because the (A) component takes in the complex formed by the (B) component and the (C) component in the cleaning liquid in which the cleaning agent for the textile product is dispersed in the cleaning water, and the (D) component. It is considered that a coalescence is formed and this aggregate is adsorbed to the fiber product to exert a deodorizing effect.

A conventionally well-known anionic surfactant can be used as (A) component, For example, the following are mentioned.
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(6) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(8) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(9) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(10) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(11) C14-18 fatty acid methyl ester sulfonate (MES).
(12) A higher fatty acid salt (soap) having 10 to 20 carbon atoms.
These components (A) can be used as alkali metal salts such as sodium salts and potassium salts, amine salts and ammonium salts. Moreover, these anionic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

 Among the components (A), LAS, ABS, MES, or soap is preferable, LAS, MES, and soap (more preferably, sodium salt or potassium salt) are more preferable, and LAS and soap are further preferably included. By using LAS and soap together, the interaction with the components (B) to (D) is enhanced, and the deodorizing effect can be further enhanced. When LAS and soap are used in combination, the mass ratio represented by LAS / soap (LAS / soap ratio) is preferably 20/80 to 95/5, more preferably 40/60 to 95/5, and 70/30. -90/10 is more preferable. If the LAS / soap ratio is within the above range, the deodorizing effect of the textile cleaning agent can be further enhanced.

 Further, the total content of LAS and soap is preferably 6 to 25% by mass and more preferably 10 to 20% by mass in the detergent for textiles. If it is in the said range, a cleaning effect and a deodorizing effect will increase more.

10-80 mass% is preferable, as for content of (A) component in the cleaning agent for textiles, 15-40 mass% is more preferable, 15-35 mass% is further more preferable. If it is less than the said lower limit, there exists a possibility that a cleaning effect may become inadequate. If the value exceeds the upper limit, the content of other components is relatively small, and the effects of the present invention may not be sufficiently obtained.
In the detergent for textile products, the total amount of the component (A) and the nonionic surfactant described later is preferably 50% by mass or more, more preferably 80% by mass or more, and more preferably 95% by mass or more of the total surfactant. Further preferred.
Furthermore, from the viewpoint of improving the deodorizing effect, the content of the component (A) in all the surfactants is preferably 5 to 100% by mass, more preferably 30 to 100% by mass, and further 50 to 90% by mass. 70 to 90% by mass is preferable.

It is preferable that (A) component is mix | blended with the detergent for textiles as surfactant containing particle | grains.
Suitable surfactant-containing particles include surfactant-containing particles (anionic surfactant-containing particles) having component (A) as the main surfactant and surfactants having nonionic surfactant as the main surfactant. And contained particles (nonionic surfactant-containing particles). Any one of these surfactant-containing particles may be used, or both of them may be used in combination, but it is necessary that the component (A) is contained in the final textile product cleaning agent.

≪Anion-containing surfactant particles≫
The anionic surfactant-containing particles are particles in which the component (A) is an essential component and the content of the component (A) is the largest among the surfactants blended in the anionic surfactant-containing surfactant particles. is there.
(A) component mix | blended with an anion-containing surfactant particle | grain is not specifically limited, Any of the (A) component mentioned above may be used. The component (A) blended in the anionic surfactant-containing particles may be one type or two or more types.

 In addition to the component (A), surfactants other than the component (A) (nonionic surfactant, cationic surfactant, amphoteric surfactant, etc.) can be added to the anionic surfactant-containing particles, although the content is limited. is there.

 The content of all the surfactants in the anionic surfactant-containing particles can be determined in consideration of the cleaning effect desired for the fiber product cleaning agent, for example, preferably 10 to 90% by mass, more Preferably it is 15-70 mass%, More preferably, it is 15-50 mass%. If it is in the above-mentioned range, a sufficient cleaning effect can be exhibited.

 Further, in the anionic surfactant-containing particles, the mass ratio represented by (A) component / other surfactant is preferably 100/0 to 50/50, more preferably 100/0 to 55/45, and 95 / 5-70 / 30 is more preferable.

The anionic surfactant-containing particles may contain components other than the surfactant.
Examples of other components that may be contained in the anionic surfactant-containing particles include the components (B) to (D) described later and <other optional components> described later. Among these, surfactants other than the component (A) and inorganic or organic detergency builders are preferable, and surfactants and inorganic builders other than the component (A) are preferable.

As the inorganic builder, potassium salts such as potassium carbonate and potassium sulfate, and alkali metal chlorides such as potassium chloride and sodium chloride are preferable because they have the effect of improving solubility. Among them, potassium carbonate, alkali metal chlorides such as potassium chloride and sodium chloride are preferable from the viewpoint of the balance between the effect of improving solubility and cost.
When mix | blending potassium carbonate, 1-15 mass% is preferable from the point of a solubility improvement effect, 1-15 mass% is more preferable, 2-12 mass% is more preferable, and 3-10 mass% is Further preferred.
When mix | blending an alkali metal chloride, from the point of a solubility improvement effect, 1-10 mass% is preferable, as for content in an anion-containing surfactant particle, 2-8 mass% is more preferable, 3-7 mass % Is more preferable.

Physical properties of the free anionic surfactant particles is not particularly limited, for example, bulk density, 0.3 g / cm ³ or more, more preferably 0.5 to 1.2 g / cm ^3, 0.6 to 1.1 g / cm ³ is more preferable.

 Moreover, 200-1500 micrometers is preferable and, as for the average particle diameter (mass 50%) of an anion-containing surfactant particle | grain, 300-1000 micrometers is more preferable. If the average particle size (mass 50%) is less than 200 μm, dust may be easily generated, and if it exceeds 1500 μm, the solubility may be insufficient.

 The fluidity of the anionic surfactant-containing particles is preferably 60 ° or less, more preferably 50 ° or less as the angle of repose. If the angle of repose exceeds 60 °, the handleability of the particles may deteriorate.

The anionic surfactant-containing particles can be obtained by a known method, and examples of the production method include the following method (1) or (2).
Method (1): A method of granulating a neutralized salt type anionic surfactant.
Method (2): A method in which an acid precursor of an anionic surfactant is dry neutralized and granulated.

Examples of the granulation method used in method (1) include the following methods (1-1) to (1-5).
(1-1) An extrusion granulation method in which a raw material powder of a surfactant and a binder compound (surfactant, water, liquid polymer component, etc.) are kneaded and kneaded, and then extruded and granulated.
(1-2) A kneading and crushing granulation method in which a raw material powder of a surfactant and a binder compound are kneaded and kneaded to obtain a solid detergent, and the resulting solid detergent is crushed and granulated.
(1-3) A stirring granulation method in which a binder compound is added to a raw material powder of a surfactant, and the mixture is stirred with a stirring blade and granulated.
(1-4) A rolling granulation method in which a binder compound is sprayed and granulated while rolling a raw material powder of a surfactant.
(1-5) A fluidized bed granulation method in which a raw material powder of a surfactant is fluidized and a liquid binder is sprayed and granulated.

In the method (2), the acid precursor of the component (A) and the alkaline inorganic powder are neutralized while being contacted and mixed, and granulated. As the granulation method at this time, for example, a granulation method similar to the granulation method mentioned in the method (1) can be used.
As the acid precursor of the component (A), any acid precursor can be suitably used as long as it is the acid precursor of the component (A) described above.

Moreover, it does not specifically limit as alkaline inorganic powder as a neutralizing agent, Alkali metal carbonate, alkali metal silicate, alkali metal phosphate, etc. are mentioned.
Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate / potassium carbonate and the like. Examples of the alkali metal silicate include sodium silicate and layered sodium silicate. Examples of the alkali metal phosphate include sodium tripolyphosphate and sodium pyrophosphate. Of these, alkali metal carbonates are preferable, and sodium carbonate, potassium carbonate, and sodium carbonate / potassium are more preferable.
These neutralizing agents can be used alone or in combination of two or more.

 The anion-containing surfactant particles granulated by the above-described method may be classified as necessary and may be only particles adjusted to a desired particle size.

≪Non-containing surfactant particles≫
The nonionic surfactant particles include a nonionic surfactant, and are particles in which the content of the nonionic surfactant is the largest among the surfactants blended in the nonionic surfactant particles.

The nonionic surfactant to be blended in the nonionic surfactant-containing particles is not particularly limited as long as it is conventionally used in a textile product cleaning agent, and examples thereof include the following various nonionic surfactants.
(1) An average of 3 to 30 moles, preferably 3 to 20 moles, and more preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

 Examples of the fatty acid alkyl ester alkoxylate (3) include those represented by the following general formula (31).

R ⁹ CO (OA) _q R ¹⁰ (31)

[In the formula (31), R ⁹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents an addition unit (oxyalkylene group) of an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, and ethylene oxide, propylene oxide and the like are preferable. q shows the average addition mole number of alkylene oxide, and is generally 3-30, Preferably it is 5-20. R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent. ]

Among the nonionic surfactants described above, the nonionic surfactant (1) is preferable, and among them, polyoxyethylene having an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms added to an aliphatic alcohol having 12 to 16 carbon atoms. Alkylene alkyl ethers or polyoxyalkylene alkenyl ethers are particularly preferred.
The nonionic surfactant blended in the nonionic surfactant-containing particles may be one type or two or more types.

Further, polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and an HLB value of 9 to 16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, fatty acid methyl ester obtained by adding ethylene oxide to fatty acid methyl ester An ethoxylate, a fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester, and the like are preferably used.
The HLB of the nonionic surfactant in the present invention is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991). , Page 234).
The melting point in the present invention is a value measured by a freezing point measurement method described in JIS K8001 “General rules for reagent test methods”.

 The nonionic surfactant-containing particles may contain an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like as surfactants other than the nonionic surfactant, although their contents are limited.

 The content of the total surfactant in the nonionic surfactant-containing particles can be determined in consideration of the cleaning performance desired for the detergent for textile products, and is preferably 5 to 85% by mass, for example. Preferably it is 10-60 mass%. If it is the above-mentioned range, sufficient cleaning effect can be exhibited.

 Further, in the nonionic surfactant particles, the mass ratio of nonionic surfactant / other surfactant is preferably 100/0 to 50/50, more preferably 100/0 to 60/40, and 95/5 to 70. / 30 is more preferable.

 The nonionic surfactant-containing particles may contain components other than the surfactant. The other components are not particularly limited, and for example, those mentioned as other components other than the surfactant in the description of the anionic surfactant-containing surfactant particles can be appropriately blended. Especially, an inorganic or organic detergency builder is mentioned as a component mix | blended suitably in nonionic surfactant particle | grains. The detergency builder is the same as the detergency builder used for the anionic surfactant-containing particles described above. The content of the detergency builder in the nonionic surfactant particles is the same as the content of the detergency builder in the anionic surfactant particles.

Moreover, it is preferable to mix | blend the oil-absorbing support | carrier for carry | supporting a nonionic surfactant in nonionic surfactant particle | grains.
The oil absorbing carrier, oil absorption represented by the JIS-K5101 test method is preferably 80 cm ^3/100 g or more, more preferably 150~600cm ³ / 100g material is preferably used. Examples of such an oil-absorbing carrier include components described in JP-A-5-125400 and JP-A-5-209200. These oil-absorbing carriers may be used alone or in combination of two or more.

 The oil-absorbing carrier is preferably contained in the nonionic surfactant particles in an amount of 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and further preferably 1 to 15% by mass.

Moreover, it is preferable to mix | blend the clay mineral etc. as a granulation adjuvant in nonionic surfactant particle | grains.
As the clay mineral, those belonging to the smectite group and having a crystal structure of a dioctahedral three-layer structure or a trioctahedral three-layer structure are particularly preferable.
Clay minerals of the present invention is preferably less than oil absorption of 80 cm ^3/100 g, more preferably 30~70cm ³ / 100g, bulk density is preferably 0.1 g / cm ³ or more, more preferably 0.2 to 1 0.5 g / cm ³ . Specific examples of such clay minerals include components described in JP-A-9-87691.

 The clay mineral is preferably contained in the nonionic surfactant particles in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass.

Physical properties of the free nonionic surfactant particles are not particularly limited, for example, bulk density, usually, 0.3 g / cm ³ or more, more preferably 0.5 to 1.2 g / cm ^3, 0.6 More preferably, ˜1.1 g / cm ³ .
Moreover, the average particle diameter of the nonionic surfactant particles is preferably 200 to 1500 μm, more preferably 300 to 1000 μm. When the average particle size is less than 200 μm, dust may be easily generated, while when it exceeds 1500 μm, the solubility may be insufficient.
The fluidity of the nonionic surfactant-containing particles is preferably 60 ° or less, more preferably 50 ° or less as the angle of repose. If it exceeds 60 °, the handleability of the particles may deteriorate.

The nonionic surfactant-containing particles can be obtained by the same granulation method as the anionic surfactant-containing particles.
The obtained nonionic surfactant particles may be classified as necessary, and only particles adjusted to a desired particle size may be used.

<(B) component>
The component (B) is at least one selected from copper, manganese, nickel, cobalt, iron, and zinc. The detergent for textiles exhibits an excellent deodorizing effect by containing the component (B). This is presumably because the component (B) forms a complex with the component (C) in the cleaning liquid, and this complex suppresses the growth of microorganisms or adsorbs odors.

  (B) As a component, manganese, copper, or zinc is preferable, copper or zinc is more preferable, and zinc is further more preferable. By using these components (B), the deodorizing effect can be further enhanced.

 (B) A component may be mix | blended as various metal compounds, and may be mix | blended as a complex with (C) component mentioned later. However, it is preferable to mix | blend (B) component as a metal compound from viewpoints, such as the beauty | look of the washing | cleaning agent for textiles, and production efficiency.

 Any metal compound may be used as long as it dissolves in water. Examples of salts forming the metal compound include nitrates, sulfates, chlorides, perchloric acid peroxides, ammonium chlorides, cyanides, and other inorganic salts and acetates. , Organic salts such as gluconate, tartrate, glycine salt and the like.

The manganese compound is not particularly limited as long as it releases manganese ions in water, and examples thereof include manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, and manganese acetylacetonate. Manganese sulfate and manganese chloride are preferable in terms of handling property, cost, raw material supply property and the like.
The copper compound is not particularly limited as long as it releases copper ions in water. For example, copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, copper ammonium chloride, copper gluconate, Examples thereof include copper tartrate, copper perchlorate, etc. Among them, copper sulfate, copper chloride, and copper gluconate are preferable, and copper sulfate is more preferable in terms of handleability, cost, raw material supply ability, and the like.
The zinc compound is not particularly limited as long as it releases zinc ions in water. For example, zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, ammonium zinc chloride, zinc gluconate, Zinc tartrate, zinc perchlorate and the like can be mentioned, and zinc sulfate, zinc chloride and gluconate are preferable, and zinc sulfate is more preferable in terms of handleability, cost, raw material supply property and the like.

 The content of the component (B) in the detergent for textiles can be determined in consideration of the type of the component (B), and is preferably 0.001 to 2% by mass, for example. If it is less than the lower limit, the deodorizing effect may be insufficient, and even if the upper limit is exceeded, the deodorizing effect may not be further improved.

For example, when using manganese as the component (B), the content of manganese in the textile cleaning agent is preferably 0.001 to 0.5 mass%, more preferably 0.01 to 0.3 mass%, 0.02-0.15 mass% is further more preferable. This is because if it is less than the lower limit, the deodorizing effect may be insufficient, and even if the upper limit is exceeded, the deodorizing effect may not be further improved.
Or when using copper as (B) component, 0.001-0.5 mass% is preferable, and, as for copper content in the cleaning agent for textiles, 0.01-0.3 mass% is more preferable, 0.02-0.15 mass% is further more preferable. This is because if it is less than the lower limit, the deodorizing effect may be insufficient, and even if the upper limit is exceeded, the deodorizing effect may not be further improved.
For example, when zinc is used as the component (B), the content of zinc in the detergent for textile products is preferably 0.002 to 2% by mass, more preferably 0.02 to 1% by mass, and More preferably, it is 05-0.5 mass%. This is because if it is less than the lower limit, the deodorizing effect may be insufficient, and even if the upper limit is exceeded, the deodorizing effect may not be further improved.

 (B) When mix | blending a component as a complex with (C) component, a complex can be manufactured with the manufacturing method of the complex as described in international publication 09/078459, for example.

<(C) component>
Component (C) is an aminocarboxylic acid type sequestering agent that forms a complex with component (B). The detergent for textiles exhibits an excellent deodorizing effect by containing the component (C).

 Examples of the component (C) include nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and aminocarboxylates such as iminodisuccinate; serine diacetate, Examples thereof include hydroxyaminocarboxylates such as hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, and dihydroxyethylglycine salt, and preferably an aminocarboxylic acid type sequestering agent having two or more carboxyl groups in the molecule. Yes, more preferably, a compound represented by the following general formula (c1) or the following general formula (c2) may be mentioned.

[In the formula (c1), X ^{11 to} X ¹⁴ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or cationic ammonium, R ² represents a hydrogen atom or a hydroxyl group, and n 1 represents 0 or 1 Represents an integer. ]

[In the formula (c2), A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group or a hydrogen atom, and X ^{21 to} X ²³ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, or Represents cationic ammonium, and n2 represents an integer of 0 to 5. ]

(C1) ^wherein, the alkali metal in the X 11 ^{to X 14,} sodium, potassium, and the like. Examples of the alkaline earth metal include calcium and magnesium. In addition, when at least one of X ^{11 to} X ¹⁴ is an alkaline earth metal, it corresponds to 1/2 atom. For ^example, if ^{X 11} is calcium, -COOX ¹¹ is ^"- 1/2 (Ca) ^- COO".
Examples of the cationic ammonium include alkanolamines such as monoethanolamine and diethanolamine, and examples include those in which 1 to 3 hydrogen atoms of ammonium are substituted with alkanol groups. As for carbon number of an alkanol group, 1-3 are preferable.
Among ^them, X 11 ^{to X 14} are the alkali metal is preferable.
X ^{11 to} X ¹⁴ in the formula (c1) may be the same or different from each other.

(C1) R ² in the formula may be a hydrogen atom or a hydroxyl group.
(C1) n1 in the formula is preferably 1.

 Examples of the compound represented by the formula (c1) include iminodisuccinic acid, 3-hydroxy-2,2'-iminodisuccinic acid, and salts thereof. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt, and sodium salt or potassium salt is more preferable.

(C2) In the formula, the alkali metal, alkaline earth metal, and cationic ammonium in X ^{21 to} X ²³ are the same as the alkali metal, alkaline earth metal, and cationic ammonium in X ^{11 to} X ¹⁴ , respectively. Is mentioned. X ^{21 to} X ²³ are preferably alkali metals.
(C2) X < ²¹ > -X < ²³ > in a formula may be the same respectively, and may differ.

(C2) The alkyl group in A in the formula may be either linear or branched. 1-30 are preferable and, as for carbon number of an alkyl group, 1-18 are more preferable. In the alkyl group, a part of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include a sulfo group (—SO ₃ H), an amino group (—NH ₂ ), a hydroxyl group, and a nitro group (—NO ₂ ).
A may be any of an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group, and a hydrogen atom, and is preferably a hydrogen atom.
(C2) n2 in the formula is preferably an integer of 0 to 2, and more preferably 1.

Examples of the compound represented by the formula (c2) include nitrilotriacetic acid, methylglycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-diacetic acid, serine diacetic acid, hydroxyethyliminodiacetic acid, or the like. Among them, nitrilotriacetic acid, methyl glycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-diacetic acid or a salt thereof is preferable, and methyl glycine diacetic acid or a salt thereof is more preferable. . Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt, and sodium salt or potassium salt is preferable.
These (C) components may be used alone or in combination of two or more.

 Although content of (C) component in the cleaning agent for textiles is not specifically limited, 0.1-1 mass% is preferable, 0.2-0.5 mass% is more preferable, 0.2-0. More preferably, 4% by mass. If content of (C) component is in the said range, a deodorizing effect will be improved more.

 In the detergent for textiles, the molar ratio represented by the component (B) / (C) (hereinafter referred to as (B) / (C) molar ratio) is, for example, preferably 1/3 to 5, 2 to 2 is more preferable. If it is in the said range, a deodorizing effect can be improved more.

<(D) component>
The component (D) is a biguanide polymer. By using the component (D) and the component (A) in combination, the deodorizing effect is enhanced, and the softening action for an object to be cleaned, particularly a chemical fiber product, is excellent.
The reason for exhibiting an excellent deodorizing effect and an excellent softening action by using the component (A) and the component (D) in combination is not clear, but is estimated as follows. In the cleaning liquid, the component (A) and the component (D) form an aggregate (sometimes referred to as an AD aggregate). This AD aggregate is easily adsorbed to the object to be cleaned as compared with the component (D) alone. For this reason, the softening effect | action is exhibited by the (D) component adhering to the to-be-washed object as an AD aggregate.
In addition, in high humidity conditions where bacteria are likely to grow, microorganisms metabolize dirt that could not be removed by washing to produce malodorous components. (D) component adhering to to-be-washed | cleaned material is considered that it contributes to a deodorizing effect by suppressing microbial increase by the microbe growth inhibitory effect.
Furthermore, (A) component takes in the complex formed by (B) component and (C) component, and this (A) component forms an aggregate with (D) component. And the outstanding deodorizing effect is exhibited by the synergistic effect of the complex formed with (B) component and (C) component, and (D) component.

 As the component (D), for example, a biguanide compound such as a polyalkylene biguanide compound represented by the following general formula (d1) is preferable.

(D1) In the formula, n represents an average number of repeating units represented by [(CH ₂ ) ₃ —NH—C (NH) —NH—C (NH) —NH— (CH ₂ ) ₃ ]. It is the number of ~ 40, Preferably it is 2-14, More preferably, it is 11-13, More preferably, it is 12. If n is not less than the above lower limit, the component (D) forms an association with the component (A) incorporating the complex formed by the component (B) and the component (C), and It becomes easy to be adsorbed. For this reason, in addition to the fungus growth inhibitory effect, the deodorizing effect can be further enhanced, and the softening action can be further enhanced. If the average of n is below the said upper limit, the solubility of the component (D) in water will be good, and the liquid stability over time of the liquid textile product cleaning agent can be enhanced.

 In the formula (d1), HY represents an organic acid or an inorganic acid, preferably hydrochloric acid, gluconic acid, or acetic acid, and more preferably hydrochloric acid.

 (D1) In formula, m may be the same as n, and may differ. Since HY is partially bonded to the nitrogen atom of the biguanide group to form a salt, n and m may be different.

As the component (D), a commercially available product can be used, and in the formula (d1), n is 12, HY is HCl, and poly (hexa) which is an aqueous dispersion (pH 4.5) having a pure content of 20% by mass. And methylene biguanide) hydrochloride (Proxel IB (registered trademark), manufactured by Arch Chemicals Japan Co., Ltd.).
(D) A component may be used individually by 1 type and may be used in combination of 2 or more type.

 0.1-10 mass% is preferable, as for content of (D) component in the cleaning agent for textiles, 0.5-8 mass% is more preferable, 1-6 mass% is further more preferable, 2-5 mass % Is particularly preferred. If content of (D) component is more than the said lower limit, a softening effect | action will increase, adsorption | suction to the to-be-washed | cleaned material of the complex of (B) component and (C) component can be accelerated | stimulated, and a deodorizing effect is demonstrated. More enhanced. If it is below the upper limit, the softening action on the chemical fiber can be enhanced and the deodorizing effect can be further enhanced. In addition, if it exceeds the above upper limit value, the softening effect on the chemical fiber is good, but there is a possibility that the removal performance of the odor component is lowered or the reattachment of the odor component is promoted.

In the detergent for textile products, for example, the mass ratio represented by (A) component / (D) component (hereinafter referred to as (A) / (D) mass ratio) is preferably 1 to 70, more preferably. 2-40. When it is 1 or more, even if the component (D) and the component (A) form an aggregate and are adsorbed to the object to be cleaned, sufficient cleaning performance is obtained by the component (A) remaining in the cleaning liquid. If it is 70 or less, the complex of the component (B) and (C) is adsorbed and retained on the object to be cleaned through the AD aggregate, whereby the deodorizing effect can be further enhanced.
In addition, if the complex of (B) component and (C) component is a hydrophobic state, affinity with the hydrophobic part of (A) component will increase, and it will become a to-be-washed object via an AD aggregate. The remaining amount is thought to increase. Whether or not the complex of the component (B) and the component (C) becomes hydrophobic is considered to depend on the (B) / (C) molar ratio.

<(E) component: organic peracid precursor>
The detergent for textiles can contain an organic peracid precursor (E) ((E) component) in addition to the components (A) to (D). The component (E) is combined with the component (F) described later to generate an organic peracid, and this organic peracid acts on the microorganism in the cleaning liquid or the microorganism attached to the object to be sterilized. Bactericidal effect increases. In addition, the bactericidal or sterilizing effect is synergistically enhanced by the presence of the complex of the component (B) and the component (C). For this reason, in the textile product in drying after washing | cleaning, and the textile product after use, the proliferation of microorganisms is suppressed and the deodorizing effect is improved more. Furthermore, the bleaching effect of the textile product is increased.

 (E) As a component, what is represented by the following general formula (I) is preferable.

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

In formula (I), the aliphatic hydrocarbon group for R ¹ may be a saturated aliphatic hydrocarbon group (alkyl group) or an aliphatic hydrocarbon group having an unsaturated bond. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 8 to 11 from the viewpoint of excellent bactericidal and sterilizing effects.
Examples of the salt-forming cation in M include alkali metals, alkaline earth metals, and cationic ammonium mentioned in the description of X ^{11 to} X ¹⁴ in the formula (c1). As M, a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium is preferable, and a hydrogen atom or an alkali metal is more preferable.

In formula (I), the bonding position of X in the benzene ring is not particularly limited. From the viewpoint of the peracid generation rate and manufacturability, the para position (position 4) of the bonding position of R ¹ C (═O) O— is preferred.
Examples of the component (E) include decanoyloxybenzoic acid, sodium dodecanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, etc., and decanoyloxybenzoic acid from the viewpoint of suppressing discoloration of the textile product. , Sodium dodecanoyloxybenzenesulfonate is preferable, and 4-decanoyloxybenzoic acid and sodium 4-dodecanoyloxybenzenesulfonate are more preferable. These (E) components can be used individually by 1 type or in combination of 2 or more types.

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

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

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

 The granulated product or molded product may further contain a film-forming polymer, zeolite, or the like. When the textile cleaning agent contains an alkaline component and water, the presence of these components may cause hydrolysis of the component (E) during storage, which may impair the effect. For this reason, when a film-forming polymer, zeolite, etc. are mix | blended, hydrolysis of (E) component can be suppressed.

The granulated product or molded product can be produced by a known granulation or molding method.
In granulation or molding, it is preferable from the viewpoints of storage stability, manufacturability, and the like that the binder compound is previously melted and added to the component (E) (and, if necessary, a surfactant or the like). At this time, the temperature for melting the binder compound is preferably 40 to 100 ° C, more preferably 50 to 100 ° C, and still more preferably 50 to 90 ° C.
These components are stirred and mixed until uniform, and then granulated or molded to obtain a granulated product or molded product.
A preferred granulation method includes extrusion granulation. In this case, the average particle diameter of the granulated product is preferably 500 to 5000 μm, and more preferably 500 to 3000 μm.
Moreover, as a preferable shaping | molding method in the case of setting it as a molded object, the method etc. which are made into a tablet shape with a briquette machine etc. are mentioned, for example.

 0.1-3 mass% is preferable and, as for content of (E) component in the cleaning agent for textiles, 0.1-2 mass% is more preferable. If it is more than the said lower limit, a bleaching effect, a bactericidal effect, a disinfection effect, etc. will increase further, and a deodorizing effect will increase further. Even if the above upper limit is exceeded, the bleaching effect, bactericidal effect, and sterilizing effect may not be enhanced, and the quality of the fiber product may be deteriorated, or sufficient surfactant content cannot be ensured, and sufficient washing is performed. The effect may not be obtained.

<(F) component>
In addition to the components (A) to (D), the textile cleaning agent can contain hydrogen peroxide or a peroxide (F) that generates hydrogen peroxide in water (component (F)). By containing (F) component, a bleaching effect, a bactericidal effect, and a disinfection effect increase. In addition, the component (F) is used in combination with the component (E), so that the bleaching effect, the bactericidal effect, and the sterilizing effect can be synergistically enhanced.

Among the components (F), peroxides that release hydrogen peroxide in water (hereinafter sometimes referred to simply as peroxides) include sodium percarbonate, sodium perborate, sodium perborate and trihydrate. Among them, sodium percarbonate is preferable from the viewpoint of solubility during use and stability during storage.
When the textile cleaning agent is solid, a peroxide is used as the component (F). At this time, the detergent for textiles may contain a peroxide as it is, and as coated particles (for example, coated sodium percarbonate particles) coated to improve stability during storage. You may mix | blend.
These (F) components may be used individually by 1 type, and may be used in combination of 2 or more type.

 When the textile cleaning agent is liquid, as the component (F), either hydrogen peroxide or peroxide may be used.

As the coated particles, known particles can be used. For example, the coated sodium percarbonate particles are coated with silicic acid and / or silicate and boric acid and / or borate, or a combination of a surfactant such as LAS and an inorganic compound. Are preferred. Specifically, as described in Japanese Patent No. 2,189,991 and the like, it is coated by spraying silicic acid and / or alkali metal silicate aqueous solution and boric acid and / or alkali metal borate aqueous solution. And those coated with an aromatic hydrocarbon sulfonic acid and / or an alkali silicate alkali salt, carbonate, bicarbonate and sulfate having an average particle size of 10 to 500 μm, such as paraffin No. 2871298, paraffin and wax Examples thereof include those coated with a water-insoluble organic compound. For non-hazardous material, it may be used by powder blending with various inorganic materials such as sodium carbonate and sodium hydrogen carbonate.
Furthermore, when the detergent for textiles is a composition having a high water content due to the blending of the component (A), etc., a coating peroxide or aromatic coated with sodium percarbonate and silicic acid and sodium borate It is more preferable to use one coated with hydrocarbon sulfonic acid and alkali silicate, carbonate, bicarbonate and sulfate.
When the textile cleaning agent is solid, the moisture content of the textile cleaning agent is preferably 9% by mass or less in consideration of the stability of the component (F).

As coated sodium percarbonate particles, JP-A 59-196399, USP 4526698 (both sodium percarbonate coated with borate), JP-A-4-31498, JP-A-6-40709 And those produced by the methods described in JP-A Nos. 7-118033 and 2871298.
When blending the component (F) as particles (peroxide particles or coated particles) in a textile cleaning agent, the average particle size of the particles of the component (F) is preferably 200 to 1000 μm, more preferably 500 to 1000 μm. In order to improve solubility and stability, the amount of particles having a particle diameter of less than 125 μm and particles having a particle diameter of more than 1400 μm is preferably 10% by mass or less in the component (F).

The content of the component (F) in the textile cleaning agent can be determined in consideration of the use of the textile cleaning agent.
Moreover, 1-30 mass% is preferable, as for content of the (F) component in the cleaning agent for textiles, 2-20 mass% is more preferable, and 2-15 mass% is further more preferable. If it is less than the said lower limit, a bactericidal effect and disinfection effect will become inadequate and there exists a possibility that a deodorizing effect may not become high. If the upper limit is exceeded, the content of the component (A) becomes insufficient, and the cleaning effect may be reduced.

<Other optional components>
In addition to the components (A) to (F), the detergent for textiles is a surfactant other than the component (A) (optional surfactant), a detergency builder, a sequestering agent other than the component (C), and a fragrance. , Pigments, fluorescent brighteners, enzymes, enzyme stabilizers, other polymers, anti-caking agents, antifoaming agents, reducing agents, pH adjusting agents and the like.

≪Optional surfactant≫
Examples of the optional surfactant include nonionic surfactants exemplified in << nonionic surfactant-containing particles >>, conventionally known cationic surfactants, and amphoteric surfactants.

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

The amphoteric surfactant is not particularly limited as long as it is conventionally used for a detergent for textiles, and various amphoteric surfactants can be used.
Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine are preferable.
These arbitrary surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

≪Detergency Builder≫
Detergency builders are roughly classified into inorganic builders and organic builders.
Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate, alkali metal sulfites such as sodium sulfite and potassium sulfite, and crystalline layered sodium silicate (for example, Clariant Japan Co., Ltd.). Crystalline alkali metal silicates such as trade name [Na-SKS-6] (δ-Na ₂ O.2SiO ₂ )), amorphous alkali metal silicates, sulfates such as sodium sulfate and potassium sulfate, chlorides Examples thereof include alkali metal chlorides such as sodium and potassium chloride, and aluminosilicates.
As the aluminosilicate, either crystalline or amorphous (amorphous) can be used. From the viewpoint of cation exchange ability, crystalline aluminosilicate is preferred.
As the crystalline aluminosilicate, zeolite can be suitably blended, and any of A type, X type, Y type, and P type can be used as the zeolite.
Among the above inorganic builder, sodium carbonate, potassium carbonate, crystalline alkali metal silicate, alkali metal chloride, and aluminosilicate are preferred, potassium carbonate, crystalline alkali metal silicate, alkali metal chloride, crystalline Alkali metal chlorides are particularly preferred.
When mix | blending potassium carbonate, 1-15 mass% is preferable from the point of the effect of a soluble improvement, and, as for content of potassium carbonate in the detergent for textiles, 2-12 mass% is more preferable, and 5-12. More preferred is mass%.
In the case where the crystalline alkali metal silicate is blended, the content of the crystalline alkali metal silicate in the detergent for textile products is preferably 0.5 to 40% by mass, and 1 to 25% by mass from the viewpoint of the cleaning effect. Is more preferable, 3 to 20% by mass is further preferable, and 5 to 15% by mass is particularly preferable.
When blending an alkali metal chloride, the content of the alkali metal chloride in the detergent for textile products is preferably 1 to 10% by mass, more preferably 2 to 8% by mass from the viewpoint of improving the solubility. 3 to 7% by mass is more preferable.
When the crystalline aluminosilicate is blended, the content of the crystalline aluminosilicate in the detergent for textile products is preferably 1 to 40% by mass in terms of powder properties such as cleaning effect and fluidity. -30 mass% is particularly preferred.

Examples of organic builders include hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, and gluconate; cyclocarboxylates such as pyromellitic acid, benzopolycarboxylate, and cyclopentanetetracarboxylate; Ether carboxylates such as carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; polyacrylates, salts of acrylic acid-allyl alcohol copolymers, acrylic acid-maleic acid Salt of polymer, salt of polyacetal carboxylic acid such as polyglyoxylic acid; salt of acrylic acid polymer or copolymer such as hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer; maleic acid, itaconic acid, fumaric acid Acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, Polymers or copolymers of salts such as aspartic acid; starch, cellulose, amylose, polysaccharides derivatives such as polysaccharides oxides pectin etc., and the like. Of these, citrate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, polyacrylate, polyglyoxyl having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) Polyacetal carboxylates such as acids (for example, those described in JP-A No. 54-52196) are suitable.
A detergency builder may be used individually by 1 type, and 2 or more types may be used in combination. For the purpose of improving the cleaning effect and soil dispersibility in the cleaning liquid, it is preferable to use an organic builder such as polyacrylate and acrylic acid-maleic acid copolymer salt in combination with an inorganic builder such as zeolite.
The content of the detergency builder in the detergent for textiles is preferably used within a range that does not impair the effects of the present invention in order to impart sufficient detergency.

≪Metal ion sequestering agent≫
The sequestering agent has an effect of capturing trace metal ions and the like in tap water and enhancing the cleaning effect, and excludes the component (C).
Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid (HEDP-H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1 , 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi Organic phosphonic acid derivatives such as (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or salts thereof; organic acids such as diglycolic acid, tartaric acid, oxalic acid, gluconic acid or the like Examples include salts.
The said sequestering agent may be used individually by 1 type, and may be used in combination of 2 or more type.
Consideration is required so that the content of the sequestering agent in the detergent for textile products is used within a range that does not impair the performance.

≪Perfume≫
The fragrance | flavor in this invention is a mixture (fragrance | flavor composition) which consists of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc.
As this fragrance | flavor, the thing as described in Unexamined-Japanese-Patent No. 2002-146399 and Unexamined-Japanese-Patent No. 2003-89800 etc. can be used, for example.
A fragrance | flavor may be used individually by 1 type and may be used in combination of 2 or more type.
0.001-2 mass% is preferable and, as for content of the fragrance | flavor in the cleaning agent for textiles, 0.01-1 mass% is more preferable.

≪Dye≫
Various dyes can be blended in order to improve the appearance of the detergent for textile products.
As the pigment, either a dye or a pigment can be used. From the viewpoint of storage stability, pigments are preferred, and compounds having oxidation resistance such as oxides are particularly preferred. Such compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine, bitumen, cyanine blue, cyanine green and the like.
A pigment | dye may be used individually by 1 type, and 2 or more types may be combined and used for it.

≪Fluorescent whitening agent≫
Examples of the optical brightener include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- ( Examples thereof include fluorescent whitening agents such as styrylphenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, and bis- (triazinylaminostilbene) disulfonic acid derivatives.
Examples of commercially available fluorescent whitening agents include Whiteex SA, Whitetex SKC (above, trade name; manufactured by Sumitomo Chemical Co., Ltd.), Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS-X (above, trade name; BASF), Lemonite CBUS-3B (above, trade name; manufactured by Khyati Chemicals), and the like. Of these, Tinopearl CBS-X and Tinopearl AMS-GX are preferred.
As the fluorescent brightening agent, one kind may be used alone, or two or more kinds may be used in combination.
The content of the fluorescent whitening agent in the textile cleaning agent is preferably 0.001 to 1% by mass.

≪Enzyme≫
Enzymes that can be incorporated into textile cleaning agents include hydrolases, oxidoreductases, lyases, transferases, and isomerases, classified according to the reactivity of the enzyme. Applicable. Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.
Examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promerin, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like. As commercial products of protease, sabinase, alcalase, cannase, coronase, everase, deozyme (above, trade name; manufactured by Novozymes); API21 (trade name; manufactured by Showa Denko KK); Maxacal, Maxapem, Purefect (above, product) Name; manufactured by Danisco Co.); protease K-14 or K-16 (protease described in JP-A-5-25492), and the like.
Examples of esterases include gastric lipase, bunkreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.
Examples of the lipase include commercially available lipases such as lipolase, Lipex (trade name; manufactured by Novozymes), and liposome (trade name; manufactured by Showa Denko KK).
Cellulases include cellzymes, carezymes, cell clean (trade name; manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K-539, alkaline cellulase K-577, alkaline cellulase K -425, alkaline cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline cellulase K-522, CMCase I, CMCase II, alkaline cellulase E-II, and alkaline cellulase E-III (the cellulase described in JP-A-63-264699) and the like.
Examples of the amylase include commercially available stainzymes, termamyls, duramils (above, trade names: manufactured by Novozymes) and the like.
An enzyme may be used individually by 1 type and may be used in combination of 2 or more type.
In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).
In the detergent for textile products, the content of the enzyme is preferably 0.3 to 2% by mass.

≪Enzyme stabilizer≫
As an enzyme stabilizer, calcium salt, magnesium salt, a polyol, formic acid, a boron compound etc. can be mix | blended, for example. Of these, sodium tetraborate and calcium chloride are preferred.
An enzyme stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the enzyme stabilizer in the detergent for textile products is preferably 0.05 to 2% by mass.

≪Other polymers≫
Polyethylene glycol having an average molecular weight of 200 to 200,000 or a weight average molecular weight of 1,000 to 100,000, as a binder or a powder physical agent when densifying the surfactant-containing particles, and further imparting a recontamination preventing effect on hydrophobic fine particles. Acrylic acid and / or maleic acid polymer, polyvinyl alcohol, cellulose derivatives such as carboxymethyl cellulose, and the like can be blended.
Moreover, as a soil release agent, a copolymer or terpolymer of terephthalic acid and ethylene glycol and / or propylene glycol units can be blended.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer. Among these, polyethylene glycol having an average molecular weight of 1500 to 7000 is preferable.
In particular, a cationized polymer of saccharides such as cationized cellulose may be blended in order to enhance the softening action on cotton fibers.
These polymers may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the polymers in the textile cleaning agent is preferably 0.05 to 5% by mass.

≪Anti-caking agent≫
Examples of the anti-caking agent include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like.
The anti-caking agent may be used alone or in combination of two or more.

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

≪Reducing agent≫
Examples of the reducing agent include sodium sulfite and potassium sulfite.

≪pH adjuster≫
The pH of the detergent for textile products is not particularly limited, but from the viewpoint of cleaning performance, the pH in a 1% by mass aqueous solution of the detergent for textiles is preferably 8 or more, and the pH in the 1% by mass aqueous solution is Is more preferably 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.
As a technique for controlling the pH of the detergent for textile products, the pH is usually adjusted with an alkali agent. In addition to the alkali agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine, etc. Alkanolamine, sodium hydroxide, potassium hydroxide and the like. For example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, manufactured by Rhodia), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio) is used. Is preferred.
Moreover, in order to prevent the pH of the detergent for textiles from becoming too high, it can be adjusted to the above pH range using an acid or the like.
Examples of the acid include the sequestering agent, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid or polycarboxylic acids thereof, sodium hydrogen carbonate, sulfuric acid, hydrochloric acid. Etc. can be used.
Moreover, you may use the buffering agent for preventing the fall of the pH by the acid component derived from the stain | pollution | contamination of a fiber at the time of washing | cleaning.
A pH adjuster may be used individually by 1 type, and 2 or more types may be used in combination.

(Production method)
The production method of the detergent for textiles is not particularly limited. For example, in the case of granular textile detergents, the first step of obtaining surfactant-containing particles, and the obtained surfactant-containing particles and functions It is obtained by the second step of mixing while allowing the particles (for example, sodium percarbonate particles) to flow.

<First step>
The first step is a step of obtaining surfactant-containing particles, and a conventionally known method can be used. For example, a spray-drying slurry is prepared by dispersing and dissolving a surfactant, alkali metal carbonate and optional components in water (slurry preparation operation), and the spray-drying slurry is dried by a spray dryer to form spray-dried particles. What can be obtained (spraying operation). Furthermore, the spray-containing particles obtained by the spraying operation can be granulated (granulating operation) together with the surfactant and optional components to obtain the surfactant-containing particles. If necessary, the obtained surfactant-containing particles may be sieved and adjusted to the desired average particle size and particle size distribution (sieving operation).

In the spraying operation, a high temperature gas is supplied into the spray drying tower at the time of spray drying of the slurry for spray drying. This hot gas is supplied from, for example, the lower part of the spray drying tower and discharged from the top of the spray drying tower. The temperature of the hot gas is preferably 170 to 300 ° C, more preferably 200 to 280 ° C. If it is this range, the slurry for spray-drying can fully be dried, and the spray-drying particle | grains of the desired water content can be obtained easily.
Moreover, 70-125 degreeC is preferable normally and the temperature of the gas discharged | emitted from a spray-drying tower has more preferable 70-115 degreeC.

 In addition, when high temperature gas is supplied from the lower part of a spray-drying tower and discharged | emitted from the tower top of a spray-drying tower (countercurrent type), in order to suppress that the temperature of the spray-dried particle obtained becomes too high, it sprays. Cold air can be supplied from the bottom of the drying tower. At the same time, for example, inorganic fine particles (zeolite, etc.) are introduced from the lower part of the spray drying tower and brought into contact with the spray drying particles, thereby preventing the spray drying particles from adhering to the inner walls of the spray drying tower. The fluidity of spray-dried particles can be improved. The spray drying tower may be a countercurrent type or a cocurrent type, and among them, a countercurrent type is preferable because thermal efficiency and spray-dried particles can be sufficiently dried. Examples of the atomizer for the slurry for spray drying include a pressure spray nozzle, a two-fluid spray nozzle, and a rotary disk type. Among them, it is preferable to use a pressure spray nozzle that can easily obtain a desired average particle size. Here, the “pressure spray nozzle” includes all nozzles used when spraying and atomizing the slurry for spray-drying from the spray port of the nozzle by applying pressure. Among these, a nozzle having a structure in which the slurry for spray drying is guided from one or a plurality of inlets of the nozzle to the spiral chamber in the nozzle and sprayed from the spray port as a swirling flow in the spiral chamber is particularly preferable. The pressure during spraying is preferably 2 to 4 MPa (gauge pressure), more preferably 2.5 to 3 MPa (gauge pressure).

For the granulation operation, a conventionally known method can be used. For example, pulverization granulation for kneading and pulverizing spray-dried particles and other optional components, stirring granulation, rolling granulation, fluidized bed granulation Etc.
In the granulation operation, the spray-dried particles and other optional components can be granulated while spraying water, a nonionic surfactant or an aqueous dispersion of the nonionic surfactant with an arbitrary droplet size.
The temperature of the nonionic surfactant melt or nonionic surfactant aqueous dispersion sprayed in the granulation operation is not particularly limited, but is preferably 70 to 85 ° C.
The droplet diameter is not particularly limited, but is preferably 100 to 200 μm. The droplet diameter can be measured by, for example, a laser particle diameter measuring device. Examples of the laser particle size measuring apparatus include LDSA-1400A manufactured by Tohnichi Computer Applications Co., Ltd.
In the granulation operation, the temperature of the spray-dried particles and other optional components is not particularly limited, but is preferably 20 to 40 ° C.

 For the sieving operation, for example, a plurality of types of sieves are prepared and stacked in the order of a sieve having a small mesh size and a sieve having a large mesh size to form a sieve unit, and the surfactant-containing particles are placed on the top of the sieve unit. Then, the sieve unit is vibrated and sieved. The surfactant-containing particles remaining on the sieve can be collected for each sieve, and the collected surfactant-containing particles can be mixed to obtain surfactant-containing particles having a desired average particle size or particle size distribution.

<Second step>
The second step is a step of mixing the surfactant-containing particles and functional particles, and a conventionally known method can be used. For example, what mixes these particles, making it flow with an agitation granulator, a rolling granulator, and a fluidized-bed granulator is mentioned.

 Examples of the mixing operation include a method in which the particles are added and mixed using a container rotating cylindrical mixer equipped with a stirring blade in a bottomed cylindrical container. Examples of the container rotating cylindrical mixer include a container rotating cylindrical mixer described in JP-A-2005-154648.

 In the mixing operation using the container rotating cylindrical mixer, the Froude number (Fr) represented by the following formula (2) is preferably set to 0.01 to 0.8. By making Fr in the above range, the particles can be mixed well.

Fr = V ² / (R × g) (2)
[However, in the formula (2), V represents the peripheral speed (m / s) of the outermost periphery of the stirring blade of the container-rotating cylindrical mixer. R represents a radius (m) from the rotation center of the outermost periphery in the container rotating cylindrical mixer. g represents a gravitational acceleration (m / s ² ). ]

(Cleaning method)
Examples of a method for cleaning a textile product using a textile product cleaning agent include: Such a method is preferable, and it is particularly preferable to put in a washing machine and wash with a cleaning solution for 5 to 30 minutes. Thereby, while removing the stain | pollution | contamination adhering to a textile product, the deodorizing effect can be provided to a textile product.
Although the density | concentration of the cleaning agent for textiles in a washing | cleaning liquid is not specifically limited, For example, it shall be 0.02-2 mass%. If the amount is less than the above lower limit, the concentration of the component (D) in the cleaning liquid becomes too low, and the effect of the present invention is hardly exhibited.
The textiles washed by the washing method of the present invention can suppress various odors generated in the washing cycle.

Although it does not specifically limit as a textile product which is a to-be-cleaned object, For example, clothing, a fabric, a curtain, a sheet, etc. are mentioned.
Although it does not specifically limit as a raw material of a textile product, Since the effectiveness of the cleaning agent for textile products of this invention is high, the textile product which has mainly chemical fibers, such as an acryl and polyester, is preferable.

 The contact between the textile product cleaning agent and the textile product is preferably carried out under alkaline conditions of pH 8 or more, and more preferably pH 9-11. When the pH is 8 or more, the sterilization effect is enhanced and the deodorizing effect is synergistically enhanced. In addition, pH is pH in 25 degreeC.

As described above, according to the detergent for textiles of the present invention, odor generation from the textiles can be suppressed by the interaction of the components (A) to (D).
The reason why the detergent for textile products of the present invention is excellent in the deodorizing effect is not clear, but is presumed as follows.
When the textile cleaning agent is dispersed in water, the component (B) and the component (C) form a complex (hereinafter sometimes referred to as a metal complex). This metal complex inactivates microorganisms in the cleaning liquid and microorganisms adhering to the object to be cleaned, suppresses the growth of microorganisms in the textile product after cleaning, and suppresses the generation of odor.
In addition, the metal complex is easily incorporated into the component (A) because it has lower water solubility than the component (B) and the component (C). The component (A) incorporating the metal complex forms an association with the component (D), and this association is easily and firmly adsorbed to the object to be cleaned and remains. The metal complex adsorbed on the textile product suppresses the growth of microorganisms attached to the textile product after washing and suppresses the generation of odor.
In the vicinity of the component (B) of the metal complex adsorbed on the textile product, the ligand (C) and the water coordinated with the component (B) are easily replaced with other substances. It is thought that. For this reason, in the metal complex adsorbed on the textile product, the positively charged odor is substituted with the component (B) and combined with the (C) component in the metal complex, and the negatively charged odor is water. Or it is thought that it substitutes with (C) component and couple | bonds with (B) component in a metal complex. Thus, it is estimated that a metal complex captures an odor component well.
And it is thought that various odors, such as a fatty acid type, an amine type, and a thiol type, can be deodorized.
Furthermore, the effect that the odor component is captured by the metal complex is continuously exhibited in the washing cycle.

In the detergent for textiles of the present invention, the component (D) forms an aggregate with the component (A), and the aggregate remains in the textile, so that the textile can be given flexibility.
In addition, since the cleaning agent for textiles of the present invention can enhance the deodorizing effect without significantly increasing the component (B), it can suppress degradation of the quality of the textiles.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, the compounding quantity of the component used in each example is a pure conversion value unless there is particular notice.

(Raw materials used)
<(A) component>
(A-1): MES (palmitic acid methyl ester: stearic acid methyl ester = sodium salt of fatty acid methyl ester sulfonate synthesized from fatty acid methyl ester of 80:20 (mass ratio), pure (AI) = 70 %, Balance is unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc., manufactured by Lion Corporation).
(A-2): LAS salt (LAS-H (linear alkyl (carbon number 10 to 14)) benzenesulfonic acid (product name; Lipon LH-200, pure content 96% by mass, manufactured by Lion Corporation) at a concentration of 48 Neutralized with a mass% aqueous potassium hydroxide solution (the amount in the table indicates mass% as LAS-K (potassium salt)).
(A-3): Soap (fatty acid sodium having 12 to 18 carbon atoms, pure; 67% by mass, titer; 40 to 45 ° C., fatty acid composition; C12 = 11.7% by mass, C14 = 0.4% by mass, C16 = 29.2 mass%, C18F0 (stearic acid) = 0.7 mass%, C18F1 (oleic acid) = 56.8 mass%, C18F2 (linoleic acid) = 1.2 mass%, molecular weight; 289, Lion stock Company-made).
(A-4): LAS-H (LAS acid, trade name: Lipon LH-200). During the production of a liquid textile product cleaning agent, it is neutralized with sodium hydroxide, which is a pH adjusting agent, to form a sodium salt.
<(A ′) component: Comparative product of component (A)>
(A′-1): Nonionic surfactant, Leox CC-150-90 (ethylene oxide average 15 mol adduct of an alcohol having an alkyl group having 12 to 14 carbon atoms, manufactured by Lion Corporation).

<(B) component>
_{(B-1): ZnSO 4} · 1H 2 O ( Zinc monohydrate sulfate, manufactured by Xinyang Ltd.).
(B-2): CuSO ₄ .5H ₂ O (copper sulfate pentahydrate, manufactured by Kanto Chemical Co., Inc.).

<(C) component>
(C-1): MGDA (methylsodium glycine diacetate, product name; Trilon M Compact (86% pure), manufactured by BASF).
(C-2): NTA (Trisodium nitrilotriacetate, product name; Trilon A92R (pure content 92%), manufactured by BASF).

<(D) component>
(D-1): Poly (hexamethylene biguanide) hydrochloride (trade name; Proxel IB (n = 12 in the formula (d1), HY is HCl, and an aqueous dispersion having a pure content of 20% by mass (pH 4.5)) ), A solid product obtained by drying (manufactured by Arch Chemicals Japan Co., Ltd.) at 105 ° C. for 2 hours (pure content: 98% by mass).
<(D ′) Component: Comparative Product of (D) Component>
(D′-1): benzalkonium chloride (manufactured by Kanto Chemical Co., Inc.).

<(E) component>
(E-1): A granulated product of OBS (sodium 4-dodecanoyloxybenzenesulfonate).
≪OBS granulated product manufacturing method≫
As raw materials, sodium p-phenolsulfonate (manufactured by Kanto Chemical Co., Ltd., reagent), N, N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd., reagent), lauric acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent), acetone ( OBS was synthesized by the following method using a reagent manufactured by Kanto Chemical Co., Inc.
100 g (0.46 mol) of dehydrated sodium p-phenolsulfonate was dispersed in 300 g of dimethylformamide, and 111 g (0.51 mol) of lauric acid chloride was added dropwise at 50 ° C. over 30 minutes while stirring with a magnetic stirrer. did. After completion of the dropwise addition, the mixture was reacted for 3 hours, and dimethylformamide was distilled off at 100 ° C. under reduced pressure (0.5 to 1 mmHg). After washing with acetone, recrystallization was performed in a water / acetone (= 1/1 mol) solvent. The yield was 90%.
The obtained OBS and PEG (polyethylene glycol # 6000M, average molecular weight 8300, freezing point 58 degrees, manufactured by Lion Corporation) were mixed by a continuous pro-shear mixer (WA type, manufactured by Taiheiyo Kiko Co., Ltd.) to obtain a mixed powder. It was. The mixed powder was put into a continuous kneader (KRS-S1 type, manufactured by Kurimoto Iron Works Co., Ltd.), kneaded at 60 ° C., and then extruded through a 0.8 mm porous screen to obtain a noodle-like mixture. Crushing using the pulverizer (NEW SPEED MILL, Okada Seiko Co., Ltd.) while mixing the obtained mixture with A-type zeolite (Silton B, pure 80% by mass, manufactured by Mizusawa Chemical Co., Ltd.) as a grinding aid. As a result, a pulverized product was obtained. The pulverized product was sieved to obtain a granulated product having a particle size of 300 to 700 μm.
The blending ratio of each component in the granulated product is as follows.
OBS12: 70.0 mass%, A-type zeolite: 5.0 mass%, PEG: 20.0 mass%.

<(F) component>
(F-1) PC agent: sodium percarbonate particles (trade name; SPCC, effective oxygen amount 13.8% by mass, average particle size 870 μm, manufactured by Zhejiang Jinke Chemicals Co., Ltd.)

(Optional component)
Sodium carbonate: granular ash, average particle size 320 μm, bulk density 1.07 g / cm ³ , manufactured by Asahi Glass Co., Ltd.
Sodium sulfate: neutral anhydrous sodium sulfate A0, manufactured by Shikoku Kasei Co., Ltd.
A-type zeolite: Shilton B (product name), 80% by mass pure, manufactured by Mizusawa Chemical Co., Ltd.
Potassium carbonate: potassium carbonate (powder), average particle size 490 μm, bulk density 1.30 g / cm ³ , manufactured by Asahi Glass Co., Ltd.
MA agent: acrylic acid / maleic anhydride copolymer sodium salt, Aqualic TL-400 (trade name), pure 40% by mass aqueous solution, manufactured by Nippon Shokubai Co., Ltd.
-Ethanol: Ethanol (trade name; specific alcohol 95 degrees), manufactured by Nippon Alcohol Sales Co., Ltd.
PEG: Polyethylene glycol (trade name; PEG # 1000-L60), manufactured by Lion Corporation.
Citric acid: Citric acid (trade name; liquid citric acid), manufactured by Otsuka Kogyo Co., Ltd.
-PH adjuster: NaOH (sodium hydroxide), manufactured by Tsurumi Soda Co., Ltd.

(Examples 1-20, Comparative Examples 1-8)
In accordance with the compositions shown in Tables 1 to 5, granular fiber product cleaners were obtained by the following production methods.
A part of (A'-1) ((A-1) was added to the aqueous slurry (prepared to a water concentration of 25% by mass) obtained by sulfonating and neutralizing the fatty acid ester of the raw material. )), And concentrated under reduced pressure with a thin-film dryer until the water concentration becomes 11% by mass, and a mixed concentrate of (A-1) and (A′-1). Got. In addition, in the following manufacturing method, the component whose compounding quantity is not described in the table shall not be added.

<First step>
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 80 ° C. A surfactant other than (A-1) and (A′-1) was added thereto and stirred for 10 minutes. Subsequently, the MA agent was added. After further stirring for 10 minutes, a part of the A-type zeolite (from the blending amount shown in the table, 1.0% by mass for kneading addition, 5.0% by mass for grinding aid, and charged in the second step) The amount excluding 1.5% by mass for surface modification), sodium carbonate, potassium carbonate and sodium sulfate were added. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38% by mass (slurry preparation operation), and then spray-dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size (mass). 50%) Spray-dried particles having a thickness of 320 μm, a bulk density of 0.30 g / cm ³ and a water content of 5% by mass were obtained (spraying operation).
The resulting spray-dried particles, the above-mentioned mixed concentrate, 1.0% by mass of type A zeolite, nonionic surfactant (0.3% by mass of nonionic surfactant for spray addition sprayed in the second step, and The remaining part excluding the nonionic surfactant in the above mixed concentrate), (B) component, (C) component, (D) component, (D ′) component and water are continuously kneaded (KRC-S12 type, Kurimoto Satoshi Co., Ltd.) And kneaded under conditions of a kneader rotation number of 135 rpm and a jacket temperature of 60 ° C. to obtain a kneaded product containing 6% by mass of water containing a surfactant (kneading treatment). The kneaded product was cut with a cutter (cutter peripheral speed is 5 m / s) while being extruded with a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm, and the length A pellet-shaped molded product of about 5 to 30 mm was obtained.
Next, an amount equivalent to 5.0% by mass of A-type zeolite (average particle size 180 μm) as a grinding aid is added to the obtained pellet-shaped molded product, and in series in the presence of cold air (10 ° C., 15 m / s). Grinding using a Fitzmill (made by Hosokawa Micron Co., Ltd., DKA-3) arranged in three stages, pulverized product (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed : 1st stage / 2nd stage / 3rd stage 4700 rpm) was obtained (granulation operation).

<Second step>
According to the composition of Tables 1 to 5, the pulverized product, (F-1) and the OBS granulated product were simultaneously charged into a container rotating cylindrical mixer at a rate of 15 kg / min and mixed. This container rotating cylindrical mixer has a diameter of 0.7 m, a length of 1.4 m, an inclination angle of 3.0 °, an outlet weir height of 0.15 m, an internal mixing blade of height 0.1 m, and a length. It has a specification in which four 1.4 m flat blades are attached every 90 °. Moreover, the rotation speed of the internal mixing blade was adjusted so that the Froude number was Fr = 0.2.
1.5 mass% A-type zeolite for surface modification was added to the particle group fluidized by rotating the container, and 0.3 mass% nonionic surfactant water dispersion was adjusted in advance to 75 ° C. The liquid was sprayed and rolled for 1 minute to obtain a granular textile product cleaning agent of each example.
About the obtained washing | cleaning agent for textiles, the softening effect | action, the washing | cleaning effect, the deodorizing effect, and the discoloration color suppression effect were evaluated.
In the table, “mmol / 100 g” represents the molar concentration in 100 g of textile cleaning agent.

(Comparative Example 9)
A part of the component (A′-1) (equivalent to 16% by mass) is added to the slurry for spray drying, and a part of the component (A′-1) (equivalent to 4.7% by mass) is added by kneading. A granular detergent for textiles was obtained in the same manner as in Example 1 except for the addition. About the obtained washing | cleaning agent for textiles, the softening effect | action, the washing | cleaning effect, the deodorizing effect, and the discoloration color suppression effect were evaluated.

(Example 21)
According to the composition shown in Table 6, a liquid textile product cleaning agent was obtained by the following production method.
In a 500 mL beaker, (A-4) component, (A′-1) component, (D-1) component, and ethanol and PEG in optional components were placed, and sufficiently stirred with a magnetic stirrer (manufactured by MITAMURA KOGYO INC.). Next, after adding 30% by mass of water, citric acid in the (B-1) component, the (C-1) component, the (D-1) component and the optional component was added, and the pH was adjusted to 9 (25 ° C. with stirring). Sodium hydroxide was added so that After adjusting to pH 9, water is added to 95% by mass of the final product, sodium hydroxide is added to achieve pH 9.5 (25 ° C.), and purified water is added so that the total amount becomes 100% by mass. In addition, a liquid textile cleaner was obtained. About the obtained washing | cleaning agent for textiles, the softening effect | action, the washing | cleaning effect, the deodorizing effect, and the discoloration color suppression effect were evaluated.

(Evaluation method)
<Softening action>
≪Pretreatment of objects to be cleaned≫
Washing objects (acrylic jersey, polyester jersey, cotton towel) using a commercially available synthetic powder detergent top (manufactured by Lion Co., Ltd.), a two-tank washing machine (trade name: CW-C30A1, manufactured by Mitsubishi Electric Corporation) ). Using tap water of 50 ° C. (hardness 3 ° DH) as washing water, washing was performed at a bath ratio of 30 times for 15 minutes, followed by dehydration for 5 minutes twice. After dehydration, the process of rinsing with running water for 15 minutes was carried out 5 times for 5 minutes. After dehydration, it was hung and dried at room temperature (25 ° C.).

≪Test method≫
Using a Haier fully automatic washing machine (JW-Z23A), bathing ratio 20 times, water temperature 23 ° C, 3 acrylic jerseys (41 g / sheet), 3 polyester jerseys (39 g / sheet), cotton towel 4 Sheets (90 g / sheet) (total 600 g) were washed (cleaning treatment). As the cleaning solution, a solution obtained by dissolving 8 g of the cleaning agent for textile products in each example in 12 L of tap water (hardness 3 ° DH) was used. After washing on a normal course, each fabric was shaded for 12 hours. Thereafter, each fabric was left in a constant temperature and humidity chamber at 25 ° C. and a humidity of 65% RH for 2 days. The acrylic jersey and polyester jersey subjected to the above treatment were used as test cloths to evaluate the softening action.
In addition, it replaced with the textiles cleaning agent of each example, the acrylics processed similarly to said washing | cleaning process using the cleaning agent (reference | standard cleaning agent) except (C) component and (D) component from the comparative example 1. A jersey and a polyester jersey were used as evaluation control cloths. For the evaluation of the softening action, a pairwise comparison with the evaluation control cloth was performed by a sensory method according to the following evaluation criteria. The average value of 10 professional panelists was determined, and was given as ◎: 4 points or more, ○: 3.5 points or more and less than 4 points, Δ: 3 points or more and less than 3.5 points, and X: less than 3 points. "◎", "○", and "△" were determined to be acceptable.

[Evaluation criteria]
1 point: The control cloth is softer.
2 points: equivalent to the control fabric.
3 points: Slightly softer than the control cloth.
4 points: Softer than the control cloth.
5 points: considerably softer than the control cloth.

<Cleaning effect, deodorizing effect>
≪Pretreatment of objects to be cleaned≫
In the same manner as the processing method described in “<< Pretreatment of an object to be cleaned” ”of“ <Softening action> ”, clothing (Heattech Crew neck short-sleeved T-shirt, L size, 00 White, material configuration; 40% acrylic, 33% polyester, 21% rayon, 6% polyurethane, 120 g / sheet, manufactured by UNIQLO CO., LTD.).

≪Test method≫
After pretreatment, the 10 pieces of clothing were repeatedly worn and washed at home for 3 months. Thereafter, the clothes worn for 2 days without washing were collected (10 sheets) and cut in half to obtain an article to be washed. One half to-be-cleaned object (total of 10 sheets, total 600g) and 5cm square wet artificially contaminated cloth using Haier fully automatic washing machine (JW-Z23A), bath ratio 20 times, water temperature Washed at 15 ° C. on a normal course (cleaning treatment). The cleaning liquid used was a dispersion of 8 g of textile cleaning agent in each example in 12 L of tap water (hardness 3 ° DH). In this way, the half-cut T-shirt (odor evaluation cloth) and the wet artificial contamination cloth (cleaning evaluation cloth) washed with the textile product cleaning agent of each example were obtained. The reflectance of the obtained cleaning evaluation cloth and the wet artificial contamination cloth before washing are measured with a color difference meter (SE200 type, manufactured by Nippon Denshoku Co., Ltd.), and the washing ratio (%) is calculated by the following equation (3). Calculated. Cleaning evaluation The average value of the cleaning rate (%) of the five pieces of cloth was classified into the following evaluation criteria, and the cleaning effect was evaluated.

Cleaning rate (%) = {(K / S of wet artificial contaminated cloth before cleaning) − (K / S of evaluation cloth for cleaning)} ÷ (K / S of wet artificial contaminated cloth before cleaning) (3) )
However, K / S is a value obtained by (1−R / 100) ² ÷ (2R / 100) (Kubermunk formula), and R is reflectance (%).

≪Evaluation criteria≫
○: Cleaning rate of 70% or more.
Δ: The cleaning rate is 50 or more and less than 70%.
X: The washing rate is less than 50%.

In addition, using the cleaning agent (reference cleaning agent) excluding the components (C) and (D) from Comparative Example 1, the other object to be cleaned (half-finished) (similar to the cleaning agent for textile products in each example) A total of 10 sheets) were washed. In this way, the reference | standard cloth wash | cleaned with the reference | standard cleaning agent was obtained.
About the obtained odor evaluation cloth and the reference cloth, 10 expert panelists compared the odor (bad odor) between the odor evaluation cloth and the reference cloth paired with the odor evaluation cloth in the following four scenes. Evaluated according to. The sum of the evaluation points of the 10 panelists was classified into the following criteria for determining the deodorizing effect, and the deodorizing evaluation was made.
By confirming the deodorizing effect in the following four scenes, the deodorizing effect against various bad odors generated from after washing to before use was confirmed.

In addition, the following are mentioned as a kind of malodor, It is thought that these kinds of malodor and the composition balance differ for every scene.
(1) Bad odor mixed with fatty acids, aldehydes, thiols, amines, etc. that could not be removed and deodorized by washing.
(2) Occurs mainly with medium-chain fatty acid and amine odors caused by the growth of microorganisms due to indoor drying (generated by microorganisms metabolizing trace amounts of sebum (lipids and proteins) that cannot be completely removed during washing) Estimated).
(3) Odor remaining after drying mainly consisting of medium chain fatty acid odor.
(4) Raw odors mainly composed of amine-based odor components (estimated to be metabolized by microorganisms using proteins adhering to the substrate as a substrate).

≪Scene with deodorant evaluation≫
Scene 1: When taken out of the washing machine immediately after washing.
Scene 2: After cleaning, after drying in a room of about 28 ° C. and 90% RH for 8 hours.
Scene 3: After drying in Scene 2, after moving to a room of about 20 ° C. and a relative humidity of 45% RH and drying for 8 hours.
Scene 4: After cleaning, dry in a room at about 20 ° C and relative humidity of 45% RH for one day, connect paired odor evaluation cloths or reference cloths, and use them at home for 3 days without washing. . Then cut in half, collected separately in a plastic bag with a chuck, and stored for 2 days at 25 ° C (contained before washing the textile before washing (contamination adhered to the object to be cleaned) After assuming).

≪Evaluation criteria for deodorizing effect≫
+1 point: The odor detected from the odor evaluation cloth is relatively weaker than the odor detected from the reference cloth (in general, the deodorizing effect of the detergent for textile products in each case is higher than that of the reference detergent) .
0 point: There is almost no difference between the bad odor detected from the odor evaluation cloth and the bad odor detected from the reference cloth (the deodorizing effect of the reference cleaning agent and the cleaning agent for textile products in each example is substantially the same). .
-1 point: The odor detected from the odor evaluation cloth is relatively stronger than the odor detected from the reference cloth (in comparison with the reference detergent, the deodorizing effect of the cleaning agents for textile products in each example is generally low) ).

≪Judgment criteria≫
A: The total score of 10 people is 10.
A: The total score of 10 people is 8 or 9 points.
○: The total score of 10 people is 5 to 7 points.
(Triangle | delta): The total score of 10 people is 2-4 points.
X: The total score of 10 people is 1 point or less.

<Discoloration suppression effect>
≪Normal conditions≫
Ten cotton cloths (# 100, 6 cm × 6 cm) dyed with Reactive Red 21 were washed under the same washing conditions as in the evaluation of “<Deodorizing effect>”. About the cotton cloth after washing | cleaning, it evaluated visually according to the evaluation criteria of the following discoloration color, and made 2 or more points a pass.

≪Evaluation criteria of discoloration color≫
3 points: No discoloration of the cotton cloth was observed.
2 points: A slight discoloration of the cotton cloth was observed.
1 point: Some discoloration of cotton cloth was observed.
0 point: Discoloration of cotton cloth was clearly recognized

≪Severe conditions≫
A cotton cloth (# 100) 6 cm × 6 cm dyed with Reactive Red 21 was placed on a plastic petri dish (diameter 9 cm, height 1.5 cm). 1 g of the detergent for textile products in each example was placed on a cotton cloth and further covered with a dyed cotton cloth. Thereafter, 2 mL of 40 ° C. tap water (hardness 3 ° DH) was gently applied on the covered cotton cloth, left at room temperature (25 ° C.) for 2 hours, and then gently rinsed. Next, a normal course (rinse twice tap water) of a washing machine (JW-Z23A type, manufactured by Haier) was performed and dried with an iron. About the cotton cloth after washing | cleaning, it evaluated visually according to evaluation criteria of said discoloration color, and made 2 or more points a pass.

As shown in Tables 1 to 6, in Examples 1 to 21 to which the present invention is applied, the cleaning effect is “◯”, and the deodorizing effect is “◯” to “◎◎” in any of the scenes 1 to 4. And “discoloration suppression” was 2 or more. In addition, in Examples 1 to 21, the softening action was “Δ” to “◎”. Among Examples 1 to 20 which are granular fiber product cleaning agents, Examples 19 to 20 in which the component (E) and the component (F) are used in combination have particularly excellent deodorizing effects.
On the other hand, in Comparative Examples 1 to 3 which did not contain the component (B) and / or the component (C), the deodorizing effect was “x” to “Δ”.
In Comparative Examples 4 and 8, which did not contain the component (D), the deodorizing effect was “Δ” and the softening action was “x”.
In Comparative Example 7 using (D′-1) which is a cationic fungicide instead of the component (D), the deodorizing effect was “Δ”.
The comparative example 5 which does not contain (C) component and (D) component, and the comparative example 6 which does not contain (B) component and (D) component have a deodorizing effect "x", and a softening effect | action is "x". Met.
In Comparative Example 9 using (A′-1) instead of the component (A), the deodorizing effect was “×” to “Δ”.
From these results, it was found that both the softening action and the deodorizing effect can be achieved by a simple operation of washing with the textile product cleaning agent to which the present invention is applied.

Claims (2)

 An anionic surfactant (A), at least one selected from copper, manganese, nickel, cobalt, iron, and zinc (B), and an aminocarboxylic acid type sequestering agent that forms a complex with the component (B) A detergent for textiles containing (C) and a biguanide polymer (D).  The cleaning agent for textiles according to claim 1, wherein a molar ratio represented by the component (B) / the component (C) is 1/3 to 5.