TW201930577A - Washing agent composition for textile product - Google Patents

Abstract

The present invention is a washing agent composition for textile products which comprises component (A) and component (B), wherein the mass ratio of the content of component (A) to the content of component (B) (content of component [A]/content of component [B]) is 2 to 100. Component (A): A nonionic surfactant having a clouding point of 45 DEG C or higher and an HLB according to Griffin of 18.0 or less. Component (B): A polysaccharide derivative having a hydrocarbon group of 5 to 16 carbon atoms.

Description

Detergent composition for fiber products

The present invention relates to a detergent composition for a fibrous product and a method for cleaning a fibrous product.

It is known that a detergent for a fibrous product uses a detergent. As for the term "detergent", there is a case called a soil release agent. The detergent is used to pre-attach the detergent to the fiber product before use by wearing the fiber product, and even if the fiber product adheres to the dirt during use, the dirt can be further improved from the fiber after use. Compounds from which the product is detached are known.

A polysaccharide derivative having an alkyl group having a carbon number of 10 to 43 or the like, a carboxymethyl group or the like, and a quaternary ammonium group to improve the detergency is disclosed in Japanese Laid-Open Patent Publication No. 2000-178303. A lotion composition containing a specific weight ratio of an anionic surfactant and a nonionic surfactant, and a soil release ether selected from a specific cellulose ether is disclosed in Japanese Laid-Open Patent Publication No. SHO 51-142007. The ingredients and optional cleaning aid ingredients provide excellent fabric cleansing performance. A polysaccharide derivative having an alkyl group having 4 to 30 carbon atoms or the like is disclosed in Japanese Laid-Open Patent Publication No. 2007-145903. Specifically, a detergent composition in which a nonionic surfactant is used in combination is described. Japanese Laid-Open Patent Publication No. 2001-507396 discloses a detergent surfactant, an organic or inorganic detergency adjuvant, and a cellulose ether having an alkyl group having 8 to 24 carbon atoms for imparting an appearance to the fabric. An advantageous detergent lotion composition. As the lotion surfactant, a nonionic surfactant is described.

The present invention provides a detergent composition for a fibrous product which is more effective for removing dirt from a fibrous product, particularly a fibrous product containing chemical fibers, by using a detergent, even if the dirt load is high. Under the conditions, it is also excellent in re-contamination resistance during washing.

The present invention relates to a detergent composition for a fibrous product comprising the following component (A) and the following component (B), and the mass ratio of the component (A) to the component (B) is (A) The content of the component / the content of the component (B) is 2 or more and 100 or less.
(A) component: nonionic surfactant with a cloud point of 45 ° C or higher and a Griffin HLB of 18.0 or less
(B) component: a polysaccharide derivative having a hydrocarbon group having 5 or more and 16 or less carbon atoms

Further, the present invention relates to a method for cleaning a fibrous product, which comprises washing a fibrous product comprising a chemical fiber, in particular, a detergent composition for a fibrous product according to the present invention.

According to the present invention, it is possible to obtain dirt for adhering to a fibrous product, particularly a fibrous product containing chemical fibers, and to improve the decontamination property of the detergent using the component (B) even under conditions of high dirt load A detergent composition for a fibrous product which is excellent in recontamination resistance during washing.

<Detergent composition for fiber products>
<(A) component>
The component (A) is a nonionic surfactant having a cloud point of 45 ° C or higher and a Griffin HLB of 18.0 or less.
In the present invention, the cloud point of the component (A) is an aqueous solution of 35 ° C prepared by using ion-exchanged water at a concentration of 2% by mass of the non-ionic surfactant to be measured, at 1 ° C/min. When the ratio is raised, the aqueous solution is uniformly turbid, and when it is naturally cooled at a room temperature of 20 ° C, the temperature becomes transparent again. Specifically, the measurement can be carried out by the method described in the examples.

In water-containing cleaning liquids, fibrous products are more hydrophobic than water, and in particular, fibrous products containing chemical fibers tend to be more hydrophobic. When the fibrous product containing the chemical fiber is preliminarily attached to the fiber product containing the chemical fiber of the present invention, the detergent component is preferably washed with the detergent product for the fibrous product. More fibrous products are selectively attached to the soil. The present inventors have found that controlling the cloud point of the nonionic surfactant and synergistic effect of the polysaccharide derivative having an aliphatic hydrocarbon group having 5 or more and 16 or less and a nonionic surfactant having a moderate cloud point Further, the soil is reformed to a state in which it is easily peeled off, whereby the stain release property of the polysaccharide derivative of the component (B) is improved. Further, it has been found that the HLB of the Griffin of the component (A) of the present invention is controlled to a specific value or less, and synergistically functions with a polysaccharide derivative containing an aliphatic hydrocarbon group having 5 or more carbon atoms and 16 or less. This facilitates the distribution of the dirt and the component (B) from the fibrous product to the cleaning liquid, whereby the stain removal property of the component (B) is improved.

The cloud point of the component (A) is more preferably 45 ° C or higher, more preferably 47 ° C or higher, more preferably 50 ° C or higher, and still more preferably 55, from the viewpoint of further improving the stain release property of the component (B). More preferably, it is 60 ° C or more, more preferably 70 ° C or more, still more preferably 80 ° C or more, and still more preferably 90 ° C or more.

The HLB of the component (A) of the present invention represents the HLB of Griffin. The value of HLB is more preferably 18.0 or less, more preferably 17.5 or less, still more preferably 17.0 or less, and still more preferably 12.0 or more, and still more preferably 12.5 or more, from the viewpoint of further improving the stain release property of the component (B). It is preferably 13.0 or more, more preferably 14.0 or more, still more preferably 14.5 or more, still more preferably 15.5 or more.

The HLB of the component (A) is determined by the HLB of Griffin represented by the following Formula 1.
HLB (Griffin) = [(molecular weight of polyoxyethylene) / (molecular weight of (A) component)] × 20
Further, the molecular weight of the polyoxyethylene group is calculated by using the value of the average addition mole number of the polyoxyethylene group.

More specifically, the component (A) is a nonionic surfactant represented by the following formula (1), and from the viewpoint of further improving the stain release property of the component (B), the following nonionic surfactant is exemplified. That is, the cloud point is 45 ° C or higher, preferably 47 ° C or higher, more preferably 50 ° C or higher, further preferably 55 ° C or higher, more preferably 60 ° C or higher, and still more preferably 70 ° C or higher, and thus more preferably It is 80 ° C or more, and the HLB of Gurley is 18.0 or less, preferably 17.5 or less, more preferably 17.0 or less, and further preferably 12.0 or more, more preferably 12.5 or more, still more preferably 13.0 or more, and still more preferably It is 14.0 or more, and more preferably 14.5 or more.
R ¹ (CO) _m O-(A ¹ O) _n -R ² (1)
In the formula, R ¹ is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms, R ² is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, and an A ¹ O group is a ethoxy group. The alkylene group having a carbon number of 2 or more and 4 or less; n is an average addition molar number of 3 or more and 50 or less].

In the formula (1), R ¹ is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms. When the other structures are the same, the carbon number of R ¹ becomes larger, the value of HLB becomes lower, and the smaller the value becomes, the higher the value of HLB becomes. When the other structures are the same, the carbon number of R ¹ becomes larger, the value of the cloud point becomes lower, and the smaller the value becomes, the higher the value of the cloud point becomes. From the viewpoint of controlling the cloud point and the value of HLB to further improve the stain release property of the component (B), the carbon number of R ¹ is 9 or more, preferably 10 or more, more preferably 11 or more, and preferably 18 or less, more preferably 16 or less, further preferably 15 or less, and still more preferably 14 or less.
Examples of the aliphatic hydrocarbon group of R ¹ include a group selected from an alkyl group and an alkenyl group.

In the formula (1), the A ¹ O group is an alkyleneoxy group having a carbon number of 2 or more and 4 or less. Include groups selected A ¹ O and extending ethoxy propoxy extending in the one or more kinds of groups. The A ¹ O group may be only an ethoxy group, or may be an alkoxy group containing an ethoxy group and another alkoxy group, for example, a propoxy group. The other alkoxy group is preferably a propoxy group. In the case of containing an ethoxy group and a propoxy group, the ethoxy group and the propoxy group may be a block type bond or a random type bond. The ethoxy group is more extended than the propoxy group, so that the value of HLB is increased. The ethoxy group is more extended than the propoxy group, so that the value of the cloud point becomes higher.

Formula (1), n is the number of A ¹ O group average addition molar number of 3 or more and 50 or less atoms. If the other structures are the same, the number of n becomes larger, and the value of HLB becomes higher, and the smaller the value becomes, the lower the value of HLB becomes. The larger the number of n becomes, the higher the value of the cloud point becomes, and the smaller the value becomes, the lower the value of the cloud point becomes. From the viewpoint of controlling the cloud point and the value of HLB and further improving the detergency of the component (B), n is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and still more preferably 8 or more and 50 or less, preferably 40 or less.

[Component (B): Polysaccharide derivative having a hydrocarbon group having 5 or more and 16 or less carbon atoms]
The component (B) is a polysaccharide derivative having a hydrocarbon group having 5 or more and 16 or less carbon atoms.
The component (B) of the present invention is characterized in that it is bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a polysaccharide of a precursor compound of the component (b) or a derivative thereof, or a carbon number 5 bonded directly or via a linking group. A polysaccharide derivative of a hydrocarbon group of 16 or more and above.

The polysaccharide may, for example, be one or more polysaccharides selected from the group consisting of cellulose, guar gum and starch. The component (B) is a polysaccharide derivative, but a polysaccharide derivative can be used as the precursor compound for obtaining the component (B). That is, the component (B) may also be a derivative of a polysaccharide derivative. The polysaccharide derivative which is a precursor compound of the component (B) may, for example, be a polysaccharide derivative in which one or all of the hydrogen atoms of the hydroxyl group of the polysaccharide are substituted with a hydroxyalkyl group having 1 or more and 4 or less carbon atoms (hereinafter also referred to as Is a hydroxyalkyl substituent). The hydroxyalkyl group having 1 or more and 4 or less carbon atoms is preferably a hydroxyalkyl group having 2 or more and 4 or less carbon atoms. The hydroxyalkyl group having 2 or more and 4 or less carbon atoms may, for example, be one or more selected from the group consisting of hydroxyethyl, hydroxypropyl and hydroxybutyl, and is preferably selected from the group consisting of hydroxyethyl and hydroxypropyl. One or more kinds of bases. The component (B) may be one selected from the group consisting of cellulose, guar gum or starch, or a polysaccharide or polysaccharide derivative selected from the group consisting of the hydroxyalkyl group-substituted polysaccharides And a compound of one or more of a hydrocarbon group and a cationic group of 18 or less.

In the component (B), the polysaccharide or the derivative thereof as the precursor compound of the component (B) may be bonded to the carbon number of 5 or more and 16 or less directly or via a linking group (hereinafter referred to as a linking group (1) component]. Hydrocarbyl polysaccharide derivative.

The above-mentioned linking group (1) may, for example, be a polyoxyalkylene group selected from an alkylene group having a carbon number of 1 or more and 3 or less and an alkylene group having an alkyl group having 1 or more and 3 or less carbon atoms. And one or more of a carbonyl group, a carbonyloxy group and an oxycarbonyl group. One of the linking groups (1) may be one of the above-mentioned linking groups, or a plurality of them may be combined. Further, the linking group (1) contained in the polysaccharide derivative may be one type or plural kinds.

In the present invention, when the hydrocarbon group is bonded to the oxygen atom of the linking group (1), the carbon number of the hydrocarbon group of the component (B) represents the carbon number of the hydrocarbon group bonded to the oxygen atom. In the case where the above hydrocarbon group is bonded via a carbonyl group, a structure in which a mercapto group is bonded is obtained. In this case, the carbon number of the hydrocarbon group of the component (B) represents the carbon number of the mercapto group. That is, when it is convenient to connect via a carbonyloxy group and an oxycarbonyl group, the carbon number is similarly included. In the case of introducing a hydrocarbon group to a polysaccharide or a polysaccharide derivative, in the case of using a 1,2-alkylene oxide, it means the carbon number of the aliphatic hydrocarbon group bonded to the ether group derived from the epoxy group. The epoxy group becomes a linking group (1). For example, when a hydrocarbon group is introduced into a polysaccharide or a polysaccharide derivative using 1,2-epoxytetradecane, the carbon number of the hydrocarbon group is set to 12. That is, the oxyethylene group as the linking group (1) is bonded to the hydroxyl group of the polysaccharide or the polysaccharide derivative, and the alkyl group having 12 carbon atoms (dodecyl group) is bonded via the linking group. The same applies to the case of using an alkyl glycidyl ether.

The polysaccharide derivative having a hydrocarbon group having 5 or more and 16 or less carbon atoms as the component (B) may, for example, be directly or via an oxygen atom obtained by removing a hydrogen atom from a part or all of a hydroxyl group of one or more of the above hydroxyalkyl substituents. The linking group (1) is preferably a polysaccharide derivative in which a hydrocarbon group having 5 or more and 16 or less carbon atoms is bonded via the linking group (1).

The hydrocarbon group having a carbon number of 5 or more and 16 or less is preferably a property of imparting hydrophobicity to the component (B), and by further improving the adsorptivity to the fiber product, particularly the fiber product containing the chemical fiber, It can improve the properties of dirt easily falling into the fiber product. The carbon number of the hydrocarbon group having 5 or more and 16 or less carbon atoms is preferably 6 or more and 16 or less from the viewpoint of easily dropping the dirt adhering to the fiber product. The hydrocarbon is preferably an aliphatic hydrocarbon group based on the viewpoint of easily interacting with the component (A).

The degree of substitution of the hydrocarbon group having a carbon number of 5 or more and 16 or less in the component (B) is preferably 0.0001 or more from the viewpoint of easily interacting with the hydrocarbon group of the component (A). It is more preferably 0.001 or more, further preferably 0.005 or more, and is preferably 1 or less, more preferably 0.4 or less, more preferably 0.4 or less, from the viewpoint of removal of a fiber product, particularly a fiber product containing chemical fibers. 0.2 or less, more preferably 0.1 or less, still more preferably 0.09 or less.

The component (B) may also have a cationic group within the range which does not impair the effects of the present invention. When the component (B) has a cationic group, the component (B) is bonded to the group obtained by removing a hydrogen atom from the hydroxyl group of the polysaccharide of the precursor compound (B) or a derivative thereof, via a linking group. A cationic derivative of a cationic group. A compound obtained by removing a hydrogen atom from a hydroxyl group of a polysaccharide or a derivative thereof, that is, a compound in which a cationic atom of a cationic group directly covalently bonded to an oxygen atom, such as a nitrogen cation, is bonded is not considered to have a cationic group. (B) ingredients.
It is also possible to pass a carbon which may contain a hydroxyl group as a linking group on a group obtained by removing a hydrogen atom from a polysaccharide of the precursor compound (B), preferably a hydroxyl group of the above hydroxyalkyl substituent. The alkylene group having a number of 1 or more and 4 or less (hereinafter referred to as a linking group (2)) is bonded with a cationic group.
The cationic group is preferably a group containing a nitrogen cation, and is more preferably a quaternary ammonium group in terms of being easily detached from the fibrous product by interaction with the component (A).

The linking group (2) may contain an alkylene group having 1 or more and 4 or less carbon atoms of a hydroxyl group. Examples of the alkylene group having 1 or more and 4 or less carbon atoms include an alkylene group selected from a straight chain having a hydroxyl group of 1 or more and 4 or less, and a carbon number of 3 or more and 4 or more. One or more kinds of alkylene groups in the alkylene group below.

In the case where the cationic group is a quaternary ammonium group, the three hydrocarbon groups bonded to the linking group (2) of the quaternary ammonium group are each independently, and a linear hydrocarbon group or carbon having 1 or more and 4 or less carbon atoms is exemplified. A branched hydrocarbon group of 3 or more and 4 or less. Examples of the linear hydrocarbon group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, a n-propyl group, and an n-butyl group. Examples of the hydrocarbon group having a carbon number of 3 or more and 4 or less include an isopropyl group, a second butyl group, a third butyl group, and an isobutyl group. The linear hydrocarbon group having 1 or more and 4 or less carbon atoms is preferably a methyl group or an ethyl group.
Examples of the counter ion of the quaternary ammonium group include an alkyl sulfate ion having a carbon number of 1 or more and 3 or less, a sulfate ion, a phosphate ion, a fatty acid ion having 1 or more and 3 or less carbon atoms, and a halide ion. One or more relative ions in the middle. Among these, from the viewpoints of easiness of production and easiness of obtaining raw materials, it is preferably one selected from the group consisting of alkylsulfate ions, sulfate ions, and halide ions having a carbon number of 1 or more and 3 or less. More than the above, more preferably a halide ion. Examples of the halide ion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion. From the viewpoint of water solubility and chemical stability of the polysaccharide derivative of the component (B), it is preferably one or more selected from the group consisting of chloride ions and bromide ions, and more preferably chloride ions. Further, the relative ions may be used alone or in combination of two or more.

The degree of substitution of the cationic group optionally contained in the polysaccharide derivative of the component (B) is preferably 1 or less, more preferably from the viewpoint of improving the stain release property of the component (B) of the component (A). It is 0.7 or less, more preferably 0.4 or less, still more preferably 0.35 or less, still more preferably 0.3 or less, still more preferably 0.25 or less, still more preferably 0.2 or less. The degree of substitution of the cationic group is a trace amount exceeding 0, and may be, for example, 0.001 or more, or may be 0.

In the present invention, the degree of substitution of the hydrocarbon group having 5 or more and 16 or less carbon atoms of the component (B) means the substitution number of the group constituting the monosaccharide unit, that is, the degree of substitution (MS) of the molar average. For example, in the case where the polysaccharide is cellulose, the "degree of substitution" means the average number of moles of the group introduced relative to the anhydroglucose unit. The degree of substitution of the cationic group of the component (B) is also the same. The degree of substitution of the hydrocarbon group having a carbon number of 5 or more and 16 or less and the degree of substitution of the cationic group of the polysaccharide derivative of the component (B) are respectively determined by the methods described in the examples.

The component (B) may be a polysaccharide derivative having both a hydrocarbon group and a cationic group having 5 or more and 16 or less carbon atoms. The degree of substitution of each group in this case is as shown above.

The component (B) may have an anionic group, but the ratio of the degree of substitution of the anionic group in the component (B), the degree of substitution with the cationic group, and the degree of substitution of the hydrocarbon group having a carbon number of 5 or more and 16 or less is an anionic group. The degree of substitution / (degree of substitution of a cationic group + degree of substitution of a hydrocarbon group having 5 or more carbon atoms and 16 or less) is preferably 3 or less, more preferably 1.7 or less, more preferably 1.7 or less, from the viewpoint of cleaning performance. It is 1.5 or less, more preferably 1 or less, still more preferably 0.5 or less, still more preferably 0.1 or less, and may be 0 or more, and preferably 0.

The weight average molecular weight of the polysaccharide or the derivative thereof as the precursor compound of the component (B) of the present invention is preferably 1,000 or more, more preferably 10,000 or more, and still more preferably 30,000, from the viewpoint of improving the washing performance. The above is more preferably 50,000 or more, further preferably 70,000 or more, more preferably 100,000 or more, still more preferably 300,000 or more, and from the viewpoint of easiness of handling, 300 is more preferable. Less than 10,000, more preferably less than 2.5 million. The weight average molecular weight of the polysaccharide derivative of the precursor compound can be calculated by conversion of polyethylene glycol by GPC (gel permeation chromatography).

<fiber>
The fiber constituting the fiber product to be washed by the detergent composition for a fiber product of the present invention may be either a chemical fiber or a natural fiber. Examples of the chemical fiber include polyaniline fibers (such as nylon), polyester fibers (such as polyester), polyacrylonitrile fibers (such as acrylic acid), polyvinyl alcohol fibers (such as vinylon), and poly Vinyl chloride fiber (polyvinyl chloride), polyvinylidene chloride fiber (vinylidene, etc.), polyolefin fiber (polyethylene, polypropylene, etc.), polyurethane fiber (polyamine base) An acid ester or the like, a polyvinyl chloride/polyvinyl alcohol copolymer fiber (such as polyvinyl chloride fiber). Examples of the natural fiber include hair fiber (cotton, wood wool, kapok seed, etc.), bast fiber (hemp, flax, ramie, hemp, jute, etc.), vein fiber (Manila hemp, Qiongma, etc.), and coconut fiber. , rush, stalk, animal hair fiber (wool, mohair, cashmere wool, camel hair, Alpaca, llama hair, Angora rabbit hair, etc.), silk fiber (silk silk, wild silk), feather, cellulose Fiber (嫘萦, high-moisture modulus viscose fiber, copper ammonia fiber, acetate fiber, etc.). The fiber to be the object of the present invention is preferably a chemical fiber.

<Fiber Products>
The term "fibrous product" as used in the present invention means a woven fabric, a knitted fabric, a non-woven fabric, or the like which is obtained by using the above chemical fiber or natural fiber, and a sweatshirt, a t-shirt, a shirt, a blouse, a trousers, a hat, a handkerchief, a towel, and the like obtained using the same. Knitwear, socks, underwear, tights and other products. The fiber product is preferably a fiber product containing chemical fibers from the viewpoint of more easily and reliably feeling the improvement in the detergency of the component (B) by using the component (A) of the present invention. The content of the chemical fiber in the fiber product is preferably 5% by mass or more, more preferably 5% by mass or more, from the viewpoint of further improving the detergency of the component (B) by using the component (A) of the present invention. It is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 50% by mass or more, and still more preferably 100% by mass or less. The content of the chemical fiber in the fiber product may also be 100% by mass.

<composition, etc.>
The detergent composition for a fiber product of the present invention may be a detergent composition for a fiber product which is used for (1) a product which is diluted in water, that is, a detergent composition for a fiber product which is diluted in water [ It is also called a detergent composition (1) for a fiber product, and (2) a detergent for a fiber product in which a detergent product for a fiber product is directly used as a cleaning liquid to clean a fiber product. A composition, that is, a detergent composition for a fibrous product which is used as a cleaning liquid without being diluted, is hereinafter referred to as a detergent composition (2) for a fibrous product. In the case of the "cleaning agent composition for a fibrous product" or the "cleaning agent composition for a fibrous product of the present invention", the detergent composition (1) for such a fibrous product is included. 2).

The content of the component (A) in the detergent composition (1) for a fiber product is preferably 5% by mass or more from the viewpoint of improving the stain release property of the component (B) when the fiber is washed. It is more preferably 7 mass% or more, further preferably 10 mass% or more, and is preferably 60 mass% or less, more preferably 50 mass% or less, still more preferably 40 mass% or less.
In addition, the content of the component (A) in the detergent composition (2) for a fiber product is preferably 0.005% by mass or more, more preferably from the viewpoint of further improving the detergency when the fiber is washed. 0.01% by mass or more, more preferably 0.1% by mass or more, and from the viewpoint of economy, it is preferably 1% by mass or less, and more preferably 0.8% by mass or less.

The content of the component (B) in the detergent composition (1) for a fiber product of the present invention is further increased by the fiber adhering to the fiber per unit mass of the detergent composition (1) for a fiber product. In terms of the detergency, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and more preferably 5% by mass or less, more preferably 3%, from the viewpoint of further improving the anti-recontamination property. % or less, further preferably 1% by mass or less.
In addition, the content of the component (B) in the detergent composition (2) for a fiber product is preferably 0.1 mg/kg or more, and more preferably 0.5, from the viewpoint of improving the detergency when the fiber is washed. Mg/kg or more, further preferably 1.0 mg/kg or more, more preferably 3.0 mg/kg or more, and from the viewpoint of economy, it is preferably 800 mg/kg or less, more preferably 500 mg/kg. Hereinafter, it is preferably 100 mg/kg or less, more preferably 50 mg/kg or less, still more preferably 30 mg/kg or less, still more preferably 10 mg/kg or less, and still more preferably 5 mg/kg. the following.

The mass ratio of the content of the component (A) to the content of the component (B) in the detergent composition for a fiber product of the present invention, that is, the content of the component (A) / the content of the component (B), improves the anti-recontamination property. In view of the above, it is 2 or more, preferably 5 or more, more preferably 7 or more, still more preferably 10 or more, and more preferably 100 or less from the viewpoint of improving the detergency of the component (B). It is preferably 80 or less, more preferably 60 or less, further preferably 50 or less, and still more preferably 40 or less.

The detergent composition for a fibrous product of the present invention may contain water. For example, water may be contained in order to make the composition of the present invention into a liquid state at a temperature of 4 ° C or more and 40 ° C or less. Water may be added to ion-exchanged water by adding deionized water (also referred to as ion-exchanged water) of 1 mg/kg or more and 5 mg/kg or less or sodium hypochlorite. Also, tap water can be used.

The detergent composition for a fibrous product of the present invention contains an anionic surfactant as the component (C) within the range which does not impair the effects of the present invention.
The (C) component is an anionic surfactant selected from one or more of the following (c1) component, (c2) component, (c3) component, and (c4) component.
Component (c1): alkyl or alkenyl sulfate
(c2) component: polyoxyalkylene alkyl ether sulfate or polyoxyalkylene ether sulfate
(c3) component: an anionic surfactant having a sulfonate group
(c4) Ingredients: fatty acids or their salts

Specific examples of the component (c1) include an alkylsulfate salt having an alkyl group having 10 or more and 18 or less carbon atoms, and an alkenyl sulfate having an alkenyl group having 10 or more and 18 or less carbon atoms. One or more anionic surfactants in the ester salt. In view of improving the detergency, the component (c1) is preferably an anionic surfactant selected from the group consisting of an alkyl sulfate having an alkyl group having 12 or more and 14 or less carbon atoms, more preferably an anionic surfactant. One or more kinds of anionic surfactants derived from sodium alkyl sulfate having an alkyl group having 12 or more and 14 or less carbon atoms.

More specifically, the component (c2) may, for example, be a polyoxyalkylene alkyl group selected from the group consisting of an alkyl group having 10 or more and 18 or less carbon atoms and an average alkylene oxide addition molar number of 1 or more and 3 or less. One or more of the polyoxyalkylene alkyl ether ether sulfates having a carbon number of 10 or more and 18 or less and an average number of moles of alkylene oxide of 1 or more and 3 or less Anionic surfactant. From the viewpoint of improving the detergency, the component (c2) is preferably a polyoxyethylene alkyl sulfate having an average addition molar number of ethylene oxide of 1 or more and 2.2 or less, more preferably an alkyl carbon. The number is 12 or more and 14 or less, and the polyoxyethylene alkyl sulfate having an average addition molar number of ethylene oxide of 1 or more and 2.2 or less is more preferably the sodium salt.

The anionic surfactant having a sulfonate group as the component (c3) means an anionic surfactant having a sulfonate as a hydrophilic group.
Specific examples of the component (c3) include an alkylbenzenesulfonate having an alkyl group having 10 or more and 18 or less carbon atoms, and an alkenylbenzene having an alkenyl group having 10 or more and 18 or less carbon atoms. The sulfonate or the alkyl group has an alkanesulfonate having 10 or more and 18 or less carbon atoms, an α-olefin sulfonate having 10 or more and 18 or less carbon atoms in the α-olefin portion, and a carbon number of 10 or more in the fatty acid portion. And an α-sulfo fatty acid salt of 18 or less and one of the α-sulfo fatty acid lower alkyl ester salts having a carbon number of 10 or more and 18 or less and a carbon number of the ester moiety of 1 or more and 5 or less The above anionic surfactant. In view of improving the detergency, the component (c3) is preferably an alkylbenzenesulfonate having an alkyl group having 11 or more and 14 or less carbon atoms, more preferably an alkyl group having 11 or more and 14 or less carbon atoms. Sodium alkylbenzene sulfonate.

The fatty acid or a salt thereof as the component (c4) may, for example, be a fatty acid having a carbon number of 10 or more and 20 or less or a salt thereof. The carbon number of the component (c4) is preferably 10 or more, preferably 12 or more, more preferably 14 or more, and 20 or less, and preferably 18 or less, from the viewpoint of not easily inhibiting the detergency.

The salt of the anionic surfactant as the component (c1) to the component (c4) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and still more preferably a sodium salt.

In the case where the detergent composition for a fiber product of the present invention contains the component (C), the content of the component (C) in the composition is preferably 0.5% by mass or more and 15% by mass or less.

Further, the following (d1) to (d7) components may be blended in the detergent composition for a fiber product of the present invention.
(d1) 0.01% by mass or more and 10% by mass or less of the anti-recontaminant and dispersant of polyacrylic acid, polymaleic acid, carboxymethylcellulose, etc. in the composition
(d2) a bleaching agent such as 0.01% by mass or more and 10% by mass or less of hydrogen peroxide, sodium percarbonate or sodium perborate in the composition
(d3) The bleaching activation represented by the formula (I-2) to (I-7) of 0.01% by mass or more and 10% by mass or less of the composition, and the formula (I-2) to (I-7) of JP-A-6-316700 Bleach activator
(d4) The composition is 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, and 2% by mass or less, preferably 1% by mass or less. One or more enzymes selected from the group consisting of cellulase, amylase, pectinase, protease, and lipase, preferably one or more enzymes selected from the group consisting of amylase and protease
(d5) The fluorochemical dye of 0.001% by mass or more and 1% by mass or less of the composition is commercially available, for example, in the form of Tinopal CBS (trade name, manufactured by Ciba Specialty Chemicals) or Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.). Fluorescent dye
(d6) 0.01% by mass or more and 2% by mass or less of an antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite, and sodium hydrogen sulfite in the composition
(d7) Appropriate amount of pigment, flavor, antibacterial preservative, polyfluorene and other antifoaming agents.

The detergent composition for a fibrous product of the present invention is preferably a liquid. When the detergent composition for a fibrous product of the present invention is a liquid, the pH at 20 ° C is preferably 3 or more, more preferably 4 or more, and preferably 10 or less, more preferably 9 or less. It is preferably 8 or less. The pH value was measured in accordance with the pH measurement method described below.
<Measurement method of pH>
A composite electrode for pH measurement (a glass polishing sleeve type manufactured by HORIBA) was connected to a pH meter (pH/ion meter F-23 manufactured by HORIBA) and charged. As the internal liquid of the pH electrode, a saturated aqueous solution of potassium chloride (3.33 mol/L) was used. Then, the pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), pH 9.18 standard solution (borate standard solution) were respectively filled into a 100 mL beaker. Immerse in a thermostat at 25 ° C for 30 minutes. The electrode for pH measurement was immersed in a standard solution adjusted to a constant temperature, and the calibration operation was performed in the order of pH 6.86 → pH 9.18 → pH 4.01. The sample to be measured was adjusted to 25 ° C, and the electrode of the above pH meter was immersed in the sample, and the pH value after 1 minute was measured.

The present invention provides a method for cleaning a fibrous product, which comprises washing a fibrous product comprising chemical fibers by using the above-described detergent composition for a fibrous product of the present invention. More specifically, the present invention provides a method for cleaning a fibrous product, which comprises washing a fibrous product comprising chemical fibers by using the detergent composition for a fibrous product of the present invention and a washing liquid for water. This washing method can suitably apply the matters described in the detergent composition for a fibrous product of the present invention. In the above-mentioned cleaning liquid, the mass ratio of the content of the component (A) to the content of the component (B), that is, the content of the component (A) / the content of the component (B), is 2, from the viewpoint of improving the anti-recontamination property. The above is preferably 5 or more, more preferably 7 or more, still more preferably 10 or more, and more preferably 100 or less, more preferably 80 or less, from the viewpoint of further improving the stain release property of the component (B). It is preferably 60 or less, and more preferably 40 or less. Further, the content of the component (A) in the cleaning liquid is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, and preferably 1% by mass or less, more preferably It is 0.8% by mass or less. In addition, the content of the component (B) in the cleaning liquid is preferably 0.1 mg/kg or more, more preferably 0.5 mg/kg or more, and more preferably from the viewpoint of improving the detergency when the fiber is washed. 1.0 mg/kg or more, more preferably 3.0 mg/kg or more, and from the viewpoint of economy, it is preferably 800 mg/kg or less, more preferably 500 mg/kg or less, and further preferably 100 mg/kg. The amount of k or less is more preferably 50 mg/kg or less, further preferably 30 mg/kg or less, more preferably 10 mg/kg or less, and still more preferably 5 mg/kg or less. The above cleaning solution may also be the detergent composition (2) for a fibrous product of the present invention. Further, the above-mentioned cleaning liquid can also be prepared by diluting the detergent composition (1) for a fibrous product of the present invention.

The water used in the method for cleaning the fibrous product of the present invention is preferably water having hardness. The hardness of the water is more preferably 1°dH or more, more preferably 2°dH or more, and still more preferably 3.5°dH from the viewpoint of the effect of imparting a texture to the fiber product. The above is more preferably 5°dH or more, still more preferably 7°dH or more, and is preferably 20°dH or less, more preferably 18°dH or less, still more preferably 15°dH or less. Here, the German hardness (°dH) in this specification means that the concentration of calcium and magnesium in water is 1 mg/L (ppm) = about 0.056 ° dH (1 ° dH = 17.8 ppm) in terms of CaCO ₃ conversion concentration. Representation.
The concentrations of calcium and magnesium used in the German hardness were determined by a chelate titration method using disodium ethylenediaminetetraacetate.
The specific measurement method of the German hardness of the water in the present specification is shown below.
<Method for measuring the hardness of water in Germany>
[Reagents]
・0.01 mol/l EDTA・2Na solution: 0.01 mol/l aqueous solution of disodium edetate (titration solution, 0.01 M EDTΑ-Na2, manufactured by SIGMΑ-ALDRICH)
・Universal BT indicator (product name: Universal BT, manufactured by Tongren Chemical Research Institute Co., Ltd.)
・Ammonia buffer for hardness measurement (67.5 g of ammonium chloride is dissolved in 570 ml of 28 w/v% ammonia water, and the total amount is 1000 ml by ion-exchanged water)
[Measurement of hardness]
(1) 20 ml of water to be a sample was collected into a conical beaker using a full pipette.
(2) Add 2 ml of ammonia buffer for hardness measurement.
(3) Add 0.5 ml of Universal BT indicator. Confirm that the added solution is reddish purple.
(4) While fully mixing the mixing cone beaker and mixing, a 0.01 mol/l EDTA·2Na solution was dropped from the burette, and the point at which the water of the sample was discolored to blue was set as the end point of the titration.
(5) The total hardness is obtained by the following calculation formula.
Hardness (°dH)=T×0.01×F×56.0774×100/A
T: 0.01 mol/l EDTA・2Na solution titration (mL)
A: sample capacity (20 mL, the capacity of the sample water)
F: 0.01 mol/l EDTA・2Na solution factor

The cleaning liquid used in the present invention is preferably a cleaning liquid obtained by mixing (A) component, (B) component, and water having a German hardness of 1° dH or more and 20° dH or less. Further, the cleaning liquid may be a cleaning liquid obtained by mixing the detergent composition (1) for a fiber product of the present invention with water having a German hardness of 1° dH or more and 20° dH or less.

In the method for cleaning a fibrous product of the present invention, the ratio of the bath ratio expressed by the ratio of the mass of the fibrous product (kg) to the amount of the cleaning liquid (liter), that is, the amount of the cleaning liquid (liter) / the fiber product The value of the mass (kg) (hereinafter, the ratio is also referred to as the bath ratio) is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, and preferably It is 400 or less, more preferably 300 or less.

In the method for cleaning a fibrous product of the present invention, the time for washing the fibrous product can further improve the effect of imparting a texture to the fibrous product, and is preferably 1 minute or longer, more preferably 2 The minute or more is more preferably 3 minutes or longer, and is preferably 12 hours or shorter, more preferably 8 hours or shorter, further preferably 6 hours or shorter, further preferably 3 hours or shorter, and still more preferably 1 hour or shorter.

The method of washing the cloth of the present invention is also suitable for a rotary washing method. The rotary cleaning method means a cleaning method in which a fiber product that is not fixed to a rotating machine rotates around a rotating shaft together with a cleaning liquid. The rotary washing method can be carried out by a rotary washing machine. Specific examples of the rotary washing machine include a drum type washing machine, a pulsator type washing machine, and a stirring type washing machine. These rotary washing machines can be used separately as a home marketer. In recent years, the drum type washing machine has been rapidly popularized in terms of reducing the amount of water used for one washing, and the drum type washing machine particularly reduces the amount of water during washing.

<The aspect of the invention>
The aspect of the invention is exemplified below. The above-described aspects can be suitably applied to the detergent composition for a fibrous product of the present invention and the method for washing the fibrous product.

<1>
A detergent composition for a fibrous product comprising the following component (A) and the following component (B), and the mass ratio of the content of the component (A) to the content of the component (B) is the content of the component (A) The content of the /(B) component is 2 or more and 100 or less.
(A) component: nonionic surfactant with a cloud point of 45 ° C or higher and a Griffin HLB of 18.0 or less
(B) component: a polysaccharide derivative having a hydrocarbon group having 5 or more and 16 or less carbon atoms

<2>
The detergent composition for a fibrous product according to the above aspect, wherein the HLB of the Griffin of the component (A) is 12.0 or more.

<3>
The detergent composition for a fibrous product according to the above aspect (1), wherein the HLB of the component (A) has a HLB of 17.5 or less, preferably 17.0 or less, and preferably 12.5 or more, more preferably It is 13.0 or more, more preferably 14.0 or more, still more preferably 14.5 or more, and still more preferably 15.5 or more.

<4>
The detergent composition for a fibrous product according to any one of the above aspects, wherein the component (A) has a cloud point of 47 ° C or higher, preferably 50 ° C or higher, more preferably 55 ° C or higher. Further, it is preferably 60 ° C or higher, more preferably 70 ° C or higher, still more preferably 80 ° C or higher, and still more preferably 90 ° C or higher.

<5>
The detergent composition for a fibrous product according to any one of the above aspects, wherein the component (A) is a nonionic surfactant represented by the following formula (1), and the cloud point is 45. Above C °, preferably 47 ° C or higher, more preferably 50 ° C or higher, further preferably 55 ° C or higher, more preferably 60 ° C or higher, still more preferably 70 ° C or higher, and still more preferably 80 ° C or higher, and The HLB of Griffin is 18.0 or less, preferably 17.5 or less, more preferably 17.0 or less, and is preferably 12.0 or more, more preferably 12.5 or more, still more preferably 13.0 or more, still more preferably 14.0 or more, and further more. Good is 14.5 or more.
R ¹ (CO) _m O-(A ¹ O) _n -R ² (1)
In the formula, R ¹ is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms, R ² is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, and an A ¹ O group is a ethoxy group. The alkylene group having a carbon number of 2 or more and 4 or less; n is an average addition molar number of 3 or more and 50 or less].

<6>
The detergent composition for a fibrous product according to the above formula (1), wherein the carbon number of R ^{1 in} the formula (1) is 10 or more, preferably 11 or more, and 16 or less, preferably 15 or less, more preferably It is preferably 14 or less, and preferably the aliphatic hydrocarbon group of R ¹ is a group selected from the group consisting of an alkyl group and an alkenyl group.

<7>
The detergent composition for a fibrous product according to the above-mentioned item (1), wherein, in the formula (1), the alkylene group having a carbon number of 2 or more and 4 or less is contained as an A ¹ O group. The group is one or more selected from the group consisting of an ethoxy group and a propoxy group.

<8>
The detergent composition for a fibrous product according to any one of the above-mentioned items, wherein, in the formula (1), n is 4 or more, preferably 5 or more, more preferably 6 or more, and further It is preferably 8 or more and 40 or less.

<9>
The detergent composition for a fibrous product according to any one of <1> to <8> wherein
The component (B) is a polysaccharide derivative obtained by removing a hydrogen atom from a hydroxyl group of a polysaccharide or a derivative thereof as a precursor compound, or a hydrocarbon group having 5 or more and 16 or less carbon atoms bonded thereto via a linking group (1). ,
The linking group (1) is a polyoxyalkylene group, a carbonyl group, a carbonyl group selected from the group consisting of an alkylene group having 1 or more and 3 or less carbon atoms and a alkyl group having an alkyl group having 1 or more and 3 or less carbon atoms. One or more of an oxy group and an oxycarbonyl group.

<10>
The detergent composition for a fiber product according to the item (9), wherein the polysaccharide derivative of the precursor compound of the component (B) is a part or all of a hydrogen atom of a hydroxyl group of the polysaccharide, and a hydroxyalkane having a carbon number of 1 or more and 4 or less A substituted hydroxyalkyl substituent.

<11>
The detergent composition for a fibrous product according to <10>, wherein the hydroxyalkyl group having 1 or more and 4 or less carbon atoms is a hydroxyalkyl group having 2 or more and 4 or less carbon atoms, preferably selected from the group consisting of hydroxyethyl and hydroxy groups. One or more groups of the propyl group and the hydroxybutyl group are more preferably one or more selected from the group consisting of a hydroxyethyl group and a hydroxypropyl group.

<12>
The detergent composition for a fibrous product according to any one of <1> to <11> wherein the polysaccharide is one or more polysaccharides selected from the group consisting of cellulose, guar gum and starch.

<13>
The detergent composition for a fiber product according to any one of the above aspects, wherein the degree of substitution of the hydrocarbon group having 5 or more and 16 or less carbon atoms of the component (B) is 0.0001 or more and 1 or less.

<14>
The detergent composition for a fibrous product according to any one of the above aspects, wherein the carbon derivative having a hydrocarbon group having 5 or more and 16 or less carbon atoms as the component (B) has a carbon number of 5 or more. Further, the degree of substitution of the hydrocarbon group of 16 or less is 0.001 or more, more preferably 0.005 or more, and 0.4 or less, preferably 0.2 or less, more preferably 0.1 or less, still more preferably 0.09 or less.

<15>
The detergent composition for a fibrous product according to any one of the above aspects, wherein the component (B) further has a cationic group.

<16>
The detergent composition for a fibrous product according to <15>, wherein the component (B) is bonded via a linking group (2) on a group obtained by removing a hydrogen atom from a hydroxyl group of a polysaccharide or a derivative thereof as a precursor compound. The polysaccharide derivative having a cationic group, and the linking group (2) is an alkylene group having 1 or more and 4 or less carbon atoms which may have a hydroxyl group.

<17>
The detergent composition for a fibrous product according to <15>, wherein the cationic group is a group containing a nitrogen cation, preferably a quaternary ammonium group.

<18>
The detergent composition for a fibrous product according to <16>, wherein the cationic group is a quaternary ammonium group, and the three hydrocarbon groups other than the linking group (2) bonded to the quaternary ammonium group are independently a linear hydrocarbon group having 1 or more and 4 or less carbon atoms or a branched hydrocarbon group having 3 or more and 4 or less carbon atoms, preferably a linear hydrocarbon group having 1 or more and 4 or less carbon atoms is selected from a methyl group and an ethyl group. The group in the n-propyl group and the n-butyl group, preferably a hydrocarbon group having a carbon number of 3 or more and 4 or less is a group selected from the group consisting of an isopropyl group, a second butyl group, a third butyl group, and an isobutyl group.

<19>
The detergent composition for a fibrous product according to any one of <16>, wherein the number of carbon atoms in the alkylene group having 1 or more and 4 or less carbon atoms which may have a hydroxyl group as the linking group (2) The alkylene group of 1 or more and 4 or less is selected from the group consisting of an alkylene group having 1 or more and 4 or less carbon atoms which may have a linear chain of a hydroxyl group, and an alkylene group having 3 or more and 4 or less carbon atoms which may have a branched chain of a hydroxyl group. One or more kinds of alkylene groups.

<20>
The detergent composition for a fibrous product according to any one of the above aspects, wherein the cationic group of the cationic derivative having a cationic group as the component (B) has a degree of substitution of 1 or less, preferably 0.7 or less, more preferably 0.4 or less, still more preferably 0.35 or less, still more preferably 0.3 or less, still more preferably 0.25 or less, still more preferably 0.2 or less, and the degree of substitution of the cationic group is a trace amount exceeding 0, for example It can be 0.001 or more, and can also be 0.

<21>
The detergent composition for a fibrous product according to any one of the above aspects, wherein the polysaccharide having a precursor compound of the component (B) or a derivative thereof has a weight average molecular weight of 1,000 or more, preferably 1 More than 10,000, more preferably 30,000 or more, further preferably 50,000 or more, more preferably 70,000 or more, still more preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 500,000 or more. And it is 3 million or less, preferably 2.5 million or less.

<22>
The detergent composition for a fibrous product according to any one of the above aspects, wherein the detergent composition for a fibrous product is a detergent composition for a fibrous product which is diluted in water (1) The content of the component (A) in the detergent composition (1) for a fiber product is 5% by mass or more, preferably 7% by mass or more, more preferably 10% by mass or more, and 60% by mass or less. The content is preferably 50% by mass or less, more preferably 40% by mass or less, and the content of the component (B) is 0.1% by mass or more, preferably 0.2% by mass or more, and 10% by mass or less, preferably 5% by mass or less. More preferably, it is 3% by mass or less, and further preferably 1% by mass or less.

<23>
The detergent composition for a fibrous product according to any one of <1> to <22> wherein the mass ratio of the content of the component (A) to the content of the component (B) is the content of the component (A) / (B) The content of the component is 5 or more, preferably 7 or more, more preferably 10 or more, and 80 or less, preferably 60 or less, more preferably 40 or less.

<24>
The detergent composition for a fibrous product according to any one of <1> to <23>, wherein the content of the chemical fiber in the fiber product is 5% by mass or more, and the content of the chemical fiber in the fiber product is preferably 5% by mass or more. It is more preferably 10% by mass or more, further preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and still more preferably 100% by mass or less.

<25>
A method of cleaning a fibrous product, which comprises washing a fibrous product containing chemical fibers with the detergent composition for a fibrous product according to any one of <1> to <24>.

<26>
The method for cleaning a fibrous product according to the above, wherein the content of the chemical fiber in the fibrous product is 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and still more preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 100% by mass or less.

EXAMPLES <Mixing Composition>
[(A) component or (A') component]
・(A) component
(a-1): Polyoxyethylene lauryl ether (the average addition molar number of oxyethylene groups is 9 moles, HLB=13.6, cloud point 83 ° C)
(a-2): Polyoxyethylene lauryl ether (the average addition molar number of oxyethylene groups is 10 moles, HLB=14.1, cloud point above 90 °C)
(a-3): polyoxyethylene lauryl ether (the average addition molar number of oxyethylene groups is 14 moles, HLB = 15.4, cloud point above 90 °C)
(a-4): Polyoxyethylene lauryl ether (the average addition mole number of oxyethylene groups is 21 moles, HLB=16.6, cloud point above 90 °C)
(a-5): Polyoxyethylene lauryl ether (the average addition molar number of oxyethylene groups is 30 moles, HLB=17.5, cloud point above 90 °C)
(a-6): polyoxyalkylene lauryl ether (relative to lauryl alcohol 1 mol, the ethoxy group is added to add an average of 7 moles, and the propoxyl group is added to the average of 2 moles, After that, the ethoxy group is added to a compound of 7 moles on average, HLB=13.4, and the cloud point is above 90 °C.
(a-7): polyoxyalkylene lauryl ether (relative to lauryl alcohol 1 mol, the ethoxy group is added to the average of 9 moles, and the propoxyl group is added to the average of 2 moles. After that, the ethoxy group is added to a compound of 9 moles on average, HLB = 14.5, and the cloud point is above 90 °C.
(a-8): a polyoxyethylene alkyl ether (alkyl-based lauryl/myristyl=7/3 (mass ratio) mixed alkyl group, and an average addition mole number of oxyethylene groups of 12 moles, HLB=14.6, cloud point above 90 °C)
(a-9): a polyoxyethylene alkyl ether (alkyl palmitoyl/stearyl group = 8/2 (mass ratio) mixed alkyl group, and an average addition mole number of oxyethylene groups of 7 moles, HLB=11.1, cloud point 52°C)

・(A') component
(a'-1): polyoxyethylene lauryl ether (the average addition molar number of oxyethylene groups is 6 moles, HLB = 11.7, cloud point 40 ° C)
(a'-2): Polyoxyethylene lauryl ether (the average addition molar number of oxyethylene groups is 40 moles, HLB = 18.1, cloud point above 90 °C)

[Method for measuring cloud point of (A) component or (A') component]
The cloud point was measured by the following method.
(1) A 2% by mass aqueous solution of the component (A) or the component (A') was prepared, and the temperature was adjusted to 35 °C. The water system uses ion exchange water.
(2) 80 g of the aqueous solution prepared in the above (1) was placed in a transparent glass vessel having a diameter of 30 mm and a height of 150 mm.
(3) Install a stir bar and a thermometer and heat at 1 ° C / 1 min in a constant temperature bath.
(4) If the temperature of the solution approaches the roughly estimated cloud point, the mixture is stirred at a ratio of 1 to 2 times per second, and the turbidity of the solution becomes uniform.
(5) The glass container was taken out from the constant temperature bath, and slowly cooled while stirring at room temperature of 20 ° C to read the temperature at which the solution became transparent, and was set to be a cloud point.

[(B) ingredients]
・(b-1) Synthesis hydroxyethyl cellulose (Dow, QP-100MH, weight average molecular weight: 2.1 million, degree of substitution of hydroxyethyl (MS): 2.5) 90 g was added to a 1 L separation flask. Medium and carry out nitrogen flow. 77.2 g of ion-exchanged water and 414.5 g of isopropyl alcohol (hereinafter referred to as IPA) were added, and after stirring for 5 minutes, 10.9 g of a 48% aqueous sodium hydroxide solution was added, and the mixture was further stirred for 15 minutes. Then, 5.3 g of 1,2-epoxytetradecane (Wako Pure Chemical Industries, Ltd.) was added, and the alkylation reaction was carried out at 80 ° C for 13 hours. Thereafter, 10.9 g of a 90% aqueous acetic acid solution was added and stirred for 30 minutes, whereby a neutralization reaction was carried out.
The obtained suspension was equally transferred to two 500 mL centrifuge tubes, and centrifuged using a high-speed cooling centrifuge (Hitachi Machine Co., Ltd., CR21G III). The supernatant was removed by decantation, and an 85% aqueous solution of IPA equivalent to the supernatant removed was added to carry out redispersion. The centrifugation and redispersion were repeated again, and the precipitate was taken out after the third centrifugation. The obtained precipitate was dried under reduced pressure at 80 ° C for one night using a vacuum dryer (Advantech, VR-420), and crushed by Xtreme Mix (Waring Co., Ltd., MX-1200XTM), thereby obtaining as a powder. (b-1) of the cellulose derivative composition. The degree of substitution of the obtained (b-1) lauryl group was 0.015.

・Synthesis of (b-2) to (b-4) in the synthesis of (b-1) above, using various 1,2-alkylene oxides having different hydrocarbon groups (the number of carbon atoms of the hydrocarbon group and the hydrocarbon group of each compound) In place of 1,2-epoxytetradecane, the amount of addition, the reaction conditions, and the like are appropriately changed, whereby the following (b-2) to (b-4) are obtained.
・(b-2)
The degree of substitution of the hexyl group of (b-2) is 0.023.
・(b-3)
The degree of substitution of the thiol group of (b-3) is 0.012.
・(b-4)
The degree of substitution of the palm base of (b-4) was 0.006.

・(b-5) Synthesis hydroxyethyl cellulose (Ashland, Natrosol 250 GR, weight average molecular weight: 300,000, degree of substitution of hydroxyethyl (MS): 2.5) 90 g was added to a 1 L separation flask. Medium and carry out nitrogen flow. 77.2 g of ion-exchanged water and 414.5 g of isopropyl alcohol (hereinafter referred to as IPA) were added and stirred for 5 minutes, and then 10.9 g of a 48% aqueous sodium hydroxide solution was added, followed by stirring for 15 minutes. Then, 5.6 g of lauryl glycidyl ether (Siichi Synthetic Co., Ltd., LA-EP) was added, and the alkylation reaction was carried out at 80 ° C for 13 hours. Further, 12.9 g of glycidyl trimethylamine chloride (Sakamoto Pharmaceutical Co., Ltd., SY-GTA80) was added, and a cationization reaction was carried out at 50 ° C for 1.5 hours. Thereafter, 10.9 g of a 90% aqueous acetic acid solution was added and stirred for 30 minutes, whereby a neutralization reaction was carried out.
The obtained suspension was equally transferred to two 500 mL centrifuge tubes, and centrifuged using a high-speed cooling centrifuge (Hitachi Machine Co., Ltd., CR21G III). The supernatant was removed by decantation, and an 85% aqueous solution of IPA equivalent to the supernatant removed was added to carry out redispersion. The centrifugation and redispersion were repeated again, and the precipitate was taken out after the third centrifugation. The obtained precipitate was dried under reduced pressure at 80 ° C for one night using a vacuum dryer (Advantech, VR-420), and crushed by Xtreme Mix (Waring Co., Ltd., MX-1200XTM), thereby obtaining as a powder. (b-2) of the cellulose derivative composition. The degree of substitution of the obtained lauryl group of (b-2) was 0.030, and the degree of substitution of the cationic group was 0.023.

The degree of substitution of the component (B) and the weight average molecular weight of the precursor compound of the component (B) were measured by the following methods.
(1) Measurement of degree of substitution ・Pretreatment of polysaccharide derivative 1 g of the polysaccharide derivative as the component (B) was dissolved in 100 g of water, and then the aqueous solution was placed in a dialysis membrane (Spectra/Por, molecular weight: 1000) , 2 days of dialysis. The obtained aqueous solution was freeze-dried using a freeze dryer (eyela, FDU1100), thereby obtaining a pretreated polysaccharide derivative.

・Using the calculation of the cationic base mass of the Kjeldahl method, we accurately weigh 200 mg of the polysaccharide derivative pretreated by the above method, add 10 mL of concentrated sulfuric acid and 1 ingot of Merck, and use the Kjeldahl decomposition unit (BUCHI). Manufactured, K-432) was subjected to thermal decomposition. After the completion of the decomposition, 30 mL of ion-exchanged water was added to the sample, and the nitrogen content (% by mass) of the sample was determined using an automatic Kjeldahl distillation apparatus (K-370, manufactured by BUCHI Co., Ltd.) to calculate the mass of the cationic group.

・Using the calculation of the hydrocarbyl (alkyl) mass of the Caier method, the polysaccharide derivative 200 mg pretreated by the above method and the adipic acid 220 mg to 10 mL vial (MIGHTY VIALS No. 3) were accurately weighed. Add 3 mL of internal standard solution (tetradecane/o-xylene = 1/25 (v/v)) and 3 mL of hydroiodic acid and stopper. Further, a sample for the calibration curve in which 1-iodododecane 2.4 mg or 9 mg was added instead of the polysaccharide derivative was prepared. While stirring each sample by a stirrer tip, heating was carried out using a heating block (Reacti-Therm III Heating/Stirring module, manufactured by PIERCE Co., Ltd.) at 160 ° C for 2 hours. After the sample was allowed to stand for cooling, the upper layer (o-xylene layer) was collected and analyzed by gas chromatography (GC) (Shimadzu Corporation, QD2010plus) under the following conditions.
・GC analysis condition column: Agilent HP-1 (length: 30 m, liquid film thickness: 0.25 μL, inner diameter: 32 mm)
Split ratio: 20
Column temperature: 100 ° C (2 min) → 10 ° C / min → 300 ° C (15 min)
Injector temperature: 300 ° C
Detector: HID
Detector temperature: 330 ° C
Injection volume: 2 μL
The mass of the alkyl group in the sample was determined from the amount of 1-iododecane obtained by GC.

The measurement of the mass of the hydroxyalkyl group is carried out by quantifying the iodine derived from the hydroxyalkyl group in the same manner as the measurement of the mass of the above alkyl group.

・Calculation of Degree of Substitution of Cationic Group and Alkyl Group The mass of the skeleton of the polysaccharide derivative is calculated based on the mass of the above-mentioned cationic group and the alkyl group and the mass of the total sample, and converted into mass (mol), respectively, thereby using the molar average The degree of substitution of the cationic group with the alkyl group was calculated.

- Measurement of Weight Average Molecular Weight The weight average molecular weight of the hydroxyethyl cellulose (HEC) as the precursor compound of the component (B) was calculated by conversion of polyethylene glycol by GPC (gel permeation chromatography).
The measurement conditions are as follows.
・Tube: TSKgel α-M
・Solution: 50 mmol/L LiBr, 1% CH ₃ COOH, ethanol/water = 3/7
・Temperature: 40°C
・Flow rate: 0.6 mL/min

[arbitrary ingredients]
Ion exchange water

<Preparation of detergent composition for fiber products>
The detergent composition for a fiber product shown in Table 1 was prepared using the above-mentioned compounding ingredients, and the following items were evaluated. The results are shown in Table 1. In Table 1, the component (A') is referred to as the component (A) and represents the mass ratio of (A)/(B).
The detergent composition for a fibrous product shown in Table 1 was specifically prepared in the following manner. The stirrer piece of Teflon (registered trademark) having a length of 5 cm was placed in a glass beaker having a capacity of 200 mL, and the mass was measured. Then, 80 g of ion-exchanged water at 20 ° C, (A) component or (A') component, and (B) component were put, and the upper surface of the beaker was sealed with Saran Wrap (registered trademark).
The beaker containing the contents was placed in a water bath set at 60 ° C in a magnetic stirrer, and stirred at 100 r/min for 30 minutes in a temperature range of water temperature of 60 ± 2 ° C in the water bath. Then, the water in the water bath was replaced with tap water at 5 ° C, and cooling was performed until the temperature of the composition in the beaker became 20 °C. Then, Saran Wrap (registered trademark) was taken, ion-exchanged water was added in such a manner that the mass of the contents became 100 g, and the mixture was further stirred at 100 r/min for 30 seconds to obtain a detergent composition for the fibrous product described in Table 1. Things.

<Evaluation of decontamination>
The detergency was evaluated using the detergent composition for fiber products shown in Table 1. The results are shown in Table 1.

(1) Pretreatment of fiber products containing chemical fibers Polyester grosgrain (fiber composition: polyester 100%, dyed test materials (shares)) using a standard process of a fully automatic washing machine (NA-F70PB manufactured by Panasonic) 5 times of cumulative washing (Emulgen 108 (manufactured by Kao)), 4.8 g of water, 48 L of water, 12 minutes of washing, 2 times of washing, and 3 minutes of dehydration. Then, it was washed only once with water (48 L of water, 12 minutes of washing, 2 times of washing, and 3 minutes of dehydration), and then a double-tank washing machine (manufactured by Hitachi, PS-H45L) was used to rinse the water until the bubble completely disappeared. Dry at 24 ° C, 55% RH for 24 hours. Thereafter, it is cut to a size of 6 cm × 6 cm.

(2) Preparation of fiber products for evaluation of detergency
(2-1) Preparation of Decontamination Treatment Fabric Desmut treatment was carried out using a vibrator (Yamato Scientific, model: SA300). Regarding the water used for the treatment, calcium chloride and magnesium chloride were introduced into ion-exchanged water at a mass ratio of 8:2, and the hardness was adjusted to 4 °dH to obtain washing water. The washing water is mixed with the washing water in a concentration of 150 mg/kg in the concentration of the component (A) and the component (B) in the detergent composition for a fiber product as described in Table 1 Obtain a cleaning solution. Further, a blank composition in which the component (B) was removed from the detergent composition for a fiber product of the examples and the comparative examples and replaced with water was prepared. Furthermore, the component (A) was mixed with the washing water so that the concentration in the washing liquid was 150 mg/kg, and a blank washing liquid was obtained. In a 100 mL spiral tube (Maruemu, No. 8, 40 mm × 120 mm), 50 mL of the washing liquid (24 ° C) and 5 pieces of the fiber product obtained in the above (1) were placed. The bath ratio is 20. The fiber product was subjected to horizontal reciprocating vibration treatment at 300 rpm for 10 minutes using a vibrator. After the treatment, dehydration was performed for 1 minute using a double-tank washing machine (manufactured by Hitachi, Ltd., PS-H45L shape). Then, 50 mL (24 ° C) of the washing water and the obtained fiber product were placed in a 100 mL spiral tube. The fabric was rinsed for 3 minutes at 340 rpm using a vibrator. After rinsing, the mixture was dehydrated by a two-tank washing machine for 1 minute, and dried at 24 ° C and 55% RH for 24 hours to prepare a fibrous product for evaluation of detergency.

(2-2) Preparation of decontaminated treated sebum artificial stains 0.02% of Sudan III (manufactured by Tokyo Chemical Industry Co., Ltd.) in oleic acid (Wako Pure Chemical Industries, Ltd.) is used as a pigment. The model sebum artificial contamination solution 0.1 mL is applied to the center portion of the fiber product obtained in the above (2-1) to a circular shape of 4 cm in diameter, and the air temperature constant temperature dryer (ADVANTEC) is used in an environment of 40 ° C. Manufactured, DRM420DA) was dried for 1 hour. Thereafter, it was dried in an environment of 20 ° C and 70% RH for 24 hours to prepare a stain-treated artificial sebum artificial stained cloth.

(2-3) Washing test A washing operation was carried out using a Terg-O-Tometer (manufactured by Ushimashima Manufacturing Co., Ltd., MS-8212). Regarding the water used for the washing, calcium chloride and magnesium chloride were supplied to ion-exchanged water at a mass ratio of 8:2, and the hardness was adjusted to 4 °dH to obtain washing water. In the detergent composition for a fiber product according to Table 1, the total amount of the components (A) and (B) in the detergent composition is mixed with the washing water so that the concentration in the cleaning liquid is 150 mg/kg. Obtain a cleaning solution. In addition, in the same manner as in the above (2-1), the component (A) in the detergent composition for a fiber product is mixed with the washing water so as to have a concentration of 150 mg/kg in the cleaning liquid. Obtain a blank detergent. In a 1 L stainless steel beaker for the washing test, 600 mL of the washing liquid and 5 pieces of the model sebum artificial stain obtained in the above (2-2) (bath ratio 300) were placed. The temperature of the washing liquid was 20 °C. The model sebum artificial stain was washed with a tarp instrument (Terg-O-Tometer) at 85 rpm for 10 minutes. Rinse with 5 L of water after washing. After rinsing, dehydration was carried out, and drying was carried out at 24 ° C, 55% RH for 24 hours.

(2-4) Evaluation of washing rate The washing rate of the model sebum artificial stain obtained in the washing test of the above (2-3) was measured by the following method, and the average value of the five pieces was determined. The results are shown in Table 1. The reflectance of the original cloth before contamination and before and after washing at 460 nm was measured by a colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd., SE-2000), and the washing rate was determined by the following formula. (%). Calibration was performed using standard reflectors (white, X94.03, Y95.96, Z113.16). The washing rate was also calculated when a blank washing solution was used.
Washing rate (%) = 100 × [(reflectance after washing - reflectance before washing) / (reflectivity of original cloth - reflectance before washing)]

(2-5) Evaluation of detergency The decontamination property of the decontamination treatment cloth obtained in the above-mentioned (2-3) washing test was determined as the difference from the washing rate using the blank washing liquid. The average value of the pieces. The results are shown in Table 1.
Detergency (%) = [washing rate (%) of cloth treated with the cleaning solution prepared by the composition of the embodiment or the comparative example (containing the component (B)) - washing prepared by the blank composition Washing rate (%) of cloth treated with liquid (excluding component (B))

<Evaluation of anti-recontamination>
(1) Anti-contamination test A re-contamination operation was carried out using a Terg-O-Tometer (manufactured by Ushimashima Manufacturing Co., Ltd., MS-8212). Regarding the water used for the washing, calcium chloride and magnesium chloride were put into ion-exchange water at a mass ratio of 8:2, and the hardness was adjusted to 4 °dH to obtain washing water. The washing water is mixed with the washing water in a concentration of 150 mg/kg in the concentration of the component (A) and the component (B) in the detergent composition for a fiber product as described in Table 1. And get a cleaning solution. To the 600 mL of the cleaning solution, a carbon black (standard carbon black for Asahi Wash, manufactured by Asahi Carbon Co., Ltd.) selected by the Japan Oil Chemical Association was added, and an ultrasonic cleaner (model: BRANSON M2800-J, Emerson Japan (s)) was subjected to ultrasonic irradiation for 1 hour to obtain a carbon black dispersion. 5 pieces of the decontamination treatment cloth (bath ratio 300) obtained by adding 600 mL of the carbon black dispersion to the 1 L stainless steel beaker for the washing test and (2-1) of the above <Detergency Evaluation> ). The temperature of the dispersion was 20 °C. The model sebum artificially contaminated cloth was washed with a tarp meter (Terg-O-Tometer) at 85 rpm for 10 minutes. Rinse with 5 L of water after washing. After rinsing, dehydration was carried out, and drying was carried out at 24 ° C, 55% RH for 24 hours.

(2) Evaluation of the anti-recontamination rate The anti-recontamination rate of the decontamination treatment cloth obtained in the recontamination test of the above (1) was measured by the following method, and the average value of the five pieces was determined. Using a colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd., SE-2000), the original cloth before contamination and the reflectance at 550 nm before and after washing were measured, and the washing rate was determined by the following formula (%). ). Calibration was performed using standard reflectors (white, X94.03, Y95.96, Z113.16). The higher the value of the anti-recontamination rate, the more excellent the anti-recontamination property.
Anti-carbon re-pollution rate (%) = 100 × (reflectance after re-contamination / reflectance of original cloth)

[Table 1]

Claims (19)

A detergent composition for a fibrous product comprising the following component (A) and the following component (B), and the mass ratio of the content of the component (A) to the content of the component (B) is the content of the component (A) The content of the /(B) component is 2 or more and 100 or less, (A) component: nonionic surfactant with a cloud point of 45 ° C or higher and a Griffin HLB of 18.0 or less (B) component: a polysaccharide derivative having a hydrocarbon group having 5 or more and 16 or less carbon atoms. The detergent composition for a fibrous product according to claim 1, wherein the HLB of the above-mentioned (A) component is 12.0 or more. The detergent composition for a fibrous product according to claim 1 or 2, wherein the HLB of the above-mentioned (A) component is 17.5 or less and 12.5 or more. The detergent composition for a fiber product according to any one of claims 1 to 3, wherein the component (A) is a nonionic surfactant represented by the following formula (1), and the cloud point is 45 ° C or higher. The HLB of Griffin is 18.0 or less, and R ¹ (CO) _m O-(A ¹ O) _n -R ² (1) wherein R ¹ is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms, and R ² Is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, and the A ¹ O group is an alkylene group having a carbon number of 2 or more and 4 or less containing an ethoxy group; n is an average addition mole The number is 3 or more and 50 or less]. The detergent composition for a fibrous product according to claim 4, wherein in the formula (1), the alkylene group having a carbon number of 2 or more and 4 or less as the A ¹⁰ O group is selected from the group consisting of One or more groups of an ethoxy group and a propoxy group. A detergent composition for a fibrous product according to any one of claims 1 to 5, wherein The component (B) is a polysaccharide derivative obtained by removing a hydrogen atom from a hydroxyl group of a polysaccharide or a derivative thereof as a precursor compound, or a hydrocarbon group having 5 or more and 16 or less carbon atoms bonded thereto via a linking group (1). , The linking group (1) is selected from the group consisting of a polyalkylene group having a carbon number of 1 or more and 3 or less and an alkylene group having a carbon number of 1 or more and 3 or less and a carbonyl group and a carbonyl group. One or more of an oxy group and an oxycarbonyl group. The detergent composition for a fiber product according to claim 6, wherein a part or all of the hydrogen atom of the hydroxyl group of the polysaccharide as the precursor compound of the component (B) is substituted with a hydroxy group having 1 or more and 4 or less carbon atoms. A hydroxyalkyl substituent of an alkyl group. The detergent composition for a fibrous product according to any one of claims 1 to 7, wherein the polysaccharide is one or more polysaccharides selected from the group consisting of cellulose, guar or starch. The detergent composition for a fiber product according to any one of claims 1 to 8, wherein the degree of substitution of the hydrocarbon group having 5 or more and 16 or less carbon atoms of the component (B) is 0.0001 or more and 1 or less. The detergent composition for a fibrous product according to any one of claims 1 to 9, wherein the component (B) further has a cationic group. The detergent composition for a fibrous product according to claim 10, wherein the component (B) is bonded to the group obtained by removing a hydrogen atom from a hydroxyl group of a polysaccharide or a derivative thereof as a precursor compound via a linking group (2). The cationic derivative of the cationic group, the linking group (2) may contain an alkylene group having 1 or more and 4 or less carbon atoms of a hydroxyl group. The detergent composition for a fibrous product according to claim 11, wherein the cationic group is a quaternary ammonium group, and the three hydrocarbon groups other than the linking group (2) bonded to the quaternary ammonium group are each independently a carbon number of 1 or more. a linear hydrocarbon group of 4 or less or a branched hydrocarbon group having 3 or more and 4 or less carbon atoms, and a linear hydrocarbon group having 1 or more and 4 or less carbon atoms is selected from the group consisting of methyl, ethyl, n-propyl and n-butyl groups. The hydrocarbon group having a carbon number of 3 or more and 4 or less is a group selected from the group consisting of an isopropyl group, a second butyl group, a third butyl group, and an isobutyl group. The detergent composition for a fibrous product according to any one of claims 10 to 12, wherein the degree of substitution of the cationic group of the cationic derivative having the cationic group as the component (B) is 1 or less. The detergent composition for a fibrous product according to any one of claims 10 to 13, wherein the polysaccharide having a precursor compound of the component (B) or a derivative thereof has a weight average molecular weight of 1,000 or more and 3,000,000 or less. The detergent composition for a fibrous product according to any one of claims 1 to 14, wherein the detergent composition for a fibrous product is a detergent composition (1) for a fibrous product which is diluted in water, a fibrous product The content of the component (A) in the detergent composition (1) is 5% by mass or more and 60% by mass or less, and the content of the component (B) is 0.1% by mass or more and 10% by mass or less. The detergent composition for a fibrous product according to any one of claims 1 to 15, wherein the mass ratio of the content of the component (A) to the content of the component (B) is the content of the component (A) / the component (B) The content is 5 or more and 60 or less. A detergent composition for a fibrous product according to any one of claims 1 to 16, which is for use in a fibrous product comprising chemical fibers. A method of cleaning a fibrous product, which comprises washing a fibrous product comprising chemical fibers with the detergent composition for a fibrous product according to any one of claims 1 to 17. The method for cleaning a fibrous product according to claim 18, wherein the content of the chemical fiber in the fibrous product is 5% by mass or more and 100% by mass or less.