RU2776376C2 - Washing composition for textile products - Google Patents

Abstract

FIELD: textile industry.

SUBSTANCE: present invention relates to a washing composition for textile products, containing the following component (A), the following component (B), and the following component (C). The component (A) is: inner olefinsulfonate containing 16 or more, and 24 or less carbon atoms, where the ratio of the weight of inner olefinsulfonate (IO-1S) containing 16 or more, and 24 or less carbon atoms, containing a sulfonate group in position 2 or further and position 4 or closer, to the weight of inner olefinsulfonate (IO-2S) containing 16 or more, and 24 or less carbon atoms, containing a sulfonate group in position 5 or further, which has the form (IO-2S)/(IO-1S), is equal to 0.30 or more, and 3 or less. The component (B) is: one or more dirt-repellent agents. The component (C) is: non-ionogenic surfactant with HLB indicator equal to 7 or more, and 20 or less, described by the following general formula (C): R¹(CO)_mO-(A¹O)_n-R², in which R¹ is an aliphatic hydrocarbon group containing 9 or more, and 16 or less carbon atoms; R² is a hydrogen atom or a methyl group; CO is a carbonyl group; m is a number equal to 0 or 1; A¹O group is one or more groups selected from a group including an ethyleneoxy group and a propyleneoxy group; and n is an average number of added moles, and it is a number equal to 3 or more, and 50 or less. The ratio, wt., of (C)/(B) of the content of the component (C) to the content of the component (B) is equal to 2 or more, and 100 or less.

EFFECT: creation of a washing composition for textile products with excellent capability of wash off dirt stuck to textile products, in particular to textile products containing chemical fibers.

12 cl, 4 tbl

Description

The technical field to which the invention belongs

[0001]

The present invention relates to a detergent composition for textiles and to a method for washing textiles.

State of the art

[0002]

It is known that soil-repellent agents are used in detergents for textiles. Soil repellant agents may also be referred to as soil separating agents. Soil repellant agents are known as agents that can be applied to textiles in advance before use of the textiles, such as wearing, and thereby, even if dirt has adhered to the textiles during use, to facilitate the desorption of dirt from the textiles in laundering after use.

[0003]

JP-A 2001-172673 discloses a soil repellant comprising a monosaccharide unit containing a special cationic group and a detergent containing a soil repellant. JP-A S51-142007 discloses a detergent composition that contains an anionic surfactant and a nonionic surfactant in a specific weight ratio, a soil-repellent ether component selected from specific cellulose ethers, and an optional component to improve detergent action, the composition provides excellent garment washing performance.

[0004]

At the same time, internal olefin sulfonates, which are used as raw materials, internal olefins containing a double bond not at the end of the olefin chain, but inside it, have been widely used as household and industrial detergent components. JP-A 2015-28123 and JP-A 2014-77126 disclose compositions of internal olefin sulfonates with excellent foaming ability and the like, compositions containing an internal olefin sulfonate having 16 carbon atoms and an internal olefin sulfonate having 18 carbon atoms in a specific ratio and having a specific hydroxy form/olefin form.

The essence of the invention

[0005]

The present invention relates to a detergent composition for textiles with excellent ability to wash dirt adhering to textiles, especially textiles containing chemical fibers.

[0006]

The present invention relates to a detergent composition for textiles containing the following component (A) and the following component (B):

component (A): an internal olefin sulfonate containing 16 or more and 24 or less carbon atoms, where the ratio of the mass of an internal olefin sulfonate (IO-1S) containing 16 or more and 24 or less carbon atoms containing a sulfonate group at position 2 or further and position 4 or closer, to the mass of internal olefinsulfonate (IO-2S) containing 16 or more and 24 or less carbon atoms, containing a sulfonate group in position 5 or more, which has the form (IO-2S)/(IO-1S), equal to 0.30 or more and 5 or less; and

component (B): soil-repellent agent.

[0007]

The present invention also relates to a method for washing textiles, including washing textiles with a washing liquid containing the above washing composition for textiles according to the present invention and water, wherein the content of component (A) in the above washing liquid is 0.005 wt.%. or more and 1 mass% or less, and the content of the component (B) in the above washing liquid is 0.1 mg/kg or more and 800 mg/kg or less.

[0008]

According to the present invention, it is possible to obtain a washing composition for textiles with an excellent ability to wash dirt adhering to textiles, especially textiles containing chemical fibers.

Embodiments of the invention

[0009]

<Detergent composition for textiles>

The present inventors have found that the soil repellency provided by soil repellants can be further enhanced by using, along with soil repellants, an internal olefin sulfonate containing 16 or more and 24 or less carbon atoms, where the mass ratio of the internal olefin sulfonate (IO-1S) containing 16 or more and 24 or less carbon atoms containing a sulfonate group at position 2 or more and position 4 or closer, to the mass of internal olefinsulfonate (IO-2S) containing 16 or more and 24 or less carbon atoms containing a sulfonate group at position 5 or more, which is (IO-2S)/(IO-1S), is 0.30 or more and 5 or less. It has not previously been known that different attachment positions of the sulfonate groups in internal olefin sulfonates lead to differences in the washing power of a textile detergent composition formulated with internal olefin sulfonates and soil repellants.

[0010]

<Component (A)>

Component (A) proposed in the present invention is an internal olefinsulfonate containing 16 or more and 24 or less carbon atoms, where the mass ratio of the internal olefinsulfonate (IO-1S) containing 16 or more and 24 or less carbon atoms, containing sulfonate a group at position 2 or more and position 4 or closer, to the mass of an internal olefinsulfonate (IO-2S) containing 16 or more and 24 or less carbon atoms containing a sulfonate group at position 5 or more, which is of the form (IO-2S) /(IO-1S) is equal to 0.30 or more and 5 or less, and provides additional enhancement of the action of soil-repellent agents desorbing dirt adhering to its fibers from textiles. Generally, anionic surfactants can be adsorbed even on textiles in the washing liquid and can reduce the proportion adsorbed on dirt adhering to textiles. It is assumed that the greater the relative content of internal olefinsulfonate (IO-2S) containing 16 or more and 24 or less carbon atoms containing a sulfonate group at position 5 or further in the component (A) proposed in the present invention, the more the component (A) is selectively adsorbed on dirt adhering to textiles, especially textiles containing chemical fibers, and thus the dirt is modified into a state in which it is easily desorbed into the washing liquid, and the dirt repellency of the component (B) further improved.

[0011]

Component (A) can be obtained by sulfonating an internal olefin containing 16 or more and 24 or less carbon atoms. Component (A) is an internal olefinsulfonate containing 16 or more and 24 or less carbon atoms. The above internal olefin is an olefin containing a double bond in position 2 or inside. The internal olefin can be obtained, for example, by isomerization of a 1-olefin obtained by dehydration of a 1-alcohol. If the internal olefin is sulfonated, a β-sultone is formed quantitatively and part of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are then converted to hydroxyalkane sulfonate and olefin sulfonate by the course of neutralization and hydrolysis (e.g., J. Am. Oil Chem. Soc. 69 , 39 (1992)). In this case, the hydroxy group of the resulting hydroxyalkane sulfonate is located inside the alkane chain and the double bond of the olefin sulfonate is located inside the olefin chain. In addition, although the resulting product is generally a mixture of the two, in some cases it may include a trace amount of a hydroxyalkane sulfonate containing a hydroxy group at the end of its carbon chain or an α-olefin sulfonate containing a hydroxy group at the end of its carbon chain. In the present description, each of these products and their mixture is collectively referred to as internal olefinsulfonate (component (A)). In addition, hydroxyalkane sulfonate is referred to as the hydroxy group-containing form (hereinafter also referred to as HAS) of the internal olefin sulfonate, and the olefin sulfonate is referred to as the olefin form (also referred to as IOS in the present invention) of the internal olefin sulfonate.

Thus, the component (A) includes an internal olefin sulfonate (IO-1S) containing 16 or more and 24 or less carbon atoms, containing a sulfonate group at position 2 or further and position 4 or closer, and an internal olefin sulfonate (IO-2S) containing 16 or more and 24 or less carbon atoms, containing a sulfonate group at position 5 or further, where the mass ratio of the form (IO-2S)/(IO-1S) is 0.30 or more and 5 or less.

[0012]

(IO-2S)/(IO-1S), the ratio of the mass of (IO-2S) contained to the mass of (IO-1S) (IO-1S) contained in component (A), in terms of selective adsorption on dirt, thereby modifying dirt into a state in which it is easily desorbed into the washing liquid, and further enhancing the dirt-repellency of the component (B), and thus further enhancing the ability to wash dirt adhering to textiles containing chemical fibers, is equal to 0.30 or more preferably 0.35 or more, more preferably 0.40 or more, more preferably 0.50 or more, even more preferably 0.60 or more, even more preferably 0.70 or more, even more preferably 0.80 or more more, even more preferably 0.90 or more, and even more preferably 1.0 or more and 5 or less, preferably 4 or less, and more preferably 3 or less.

[0013]

It should be noted that the content of each compound containing a sulfonate group at a different position in the component (A) can be determined using high performance liquid chromatography-mass spectroscopy (hereinafter, the present invention uses the abbreviation HPLC-MS). In the present description, the content of each compound containing a sulfonate group at different positions should be determined as the mass ratio according to the peak areas of HPLC-MS of the compound containing a sulfonate group at each position of all forms of the HAS component (A). In the present invention, HAS means hydroxyalkane sulfonate, i.e. the hydroxy group-containing form of the internal olefin sulfonate in compounds obtained by sulfonation of internal olefin sulphonic acid.

[0014]

In the present invention, the content of an internal olefin sulfonate (IO-1S) containing 16 or more and 24 or less carbon atoms, containing a sulfonate group at position 2 or more and position 4 or closer, is represented by a typical value of numerical values based on peak areas in HPLC-MS of sulfonates containing 16 or more and 24 or less carbon atoms, containing a sulfonate group in position 2 or more and position 4 or closer, in HAS forms containing 16 or more and 24 or less carbon atoms.

In addition, the content of an internal olefinsulfonate (IO-2S) containing 16 or more and 24 or less carbon atoms, containing a sulfonate group at position 5 or further, is represented by a typical value of numerical values based on peak areas in HPLC-MS of sulfonates, containing 16 or more and 24 or less carbon atoms, containing a sulfonate group in position 5 or further in the forms of HAS containing 16 or more and 24 or less carbon atoms.

[0015]

Note that the internal olefin sulfonates of component (A) include an internal olefin sulfonate (IO-1S) having 16 or more and 24 or less carbon atoms, having a sulfonate group at the 2-position or further and a 4-position or closer, and an internal olefin sulfonate (IO-1S). 2S) containing 16 or more and 24 or less carbon atoms, containing a sulfonate group at position 5 or further. The maximum attachment position number of the sulfonate group in the internal olefinsulfonate (IO-2S) varies depending on the number of carbon atoms.

[0016]

Finally, the (IO-2S)/(IO-1S), mass ratio for component (A) based on component (A) is obtained. For example, even if the internal olefin sulfonate is produced by mixing internal olefin sulfonates for which the mass ratio (IO-2S)/(IO-1S) is outside the above range, the resulting internal olefin sulfonate is considered to be the internal olefin sulfonate of component (A) if its mass ratio is (IO-2S)/(IO-1S) is in the above range.

[0017]

The number of carbon atoms in the internal olefinsulfonate of component (A) is 16 or more and 24 or less, preferably 22 or less, more preferably 20 or less, and more preferably 18 or less. Component (A) is preferably an internal olefinsulfonate containing 16 carbon atoms. Thus, the textile detergent composition of the present invention preferably contains an internal olefinsulfonate having 16 carbon atoms as component (A). It should be noted that the number of carbon atoms in the salt moiety is not included in the number of carbon atoms in component (A). Thus, the number of carbon atoms in the olefin fragment means the number of carbon atoms in the component (A).

[0018]

Examples of the internal olefinsulfonate salt include an alkali metal salt, an alkaline earth metal salt (1/2 atom), an ammonium salt, or an organic ammonium salt. Examples of the alkali metal salt include sodium salt and potassium salt. Examples of the organic ammonium salt include an alkanolammonium salt containing 1 or more and 6 or less carbon atoms.

[0019]

Component (A) also includes components containing a trace amount of the so-called alpha-olefin sulfonate (hereinafter also referred to as α-olefin sulfonate), in which the sulfonate is in position 1 of the carbon chain. The content of α-olefin sulfonate in the internal olefin sulfonate imposes a certain limitation in terms of further improving the ability to wash dirt adhering to textiles containing chemical fibers, where the upper limit value of the content is 10 mass% or less, more preferably 7 mass% or less, more preferably 5 wt.% or less, and even more preferably 3 wt.% or less; and the content is preferably 0.01 wt% or more from the viewpoint of reducing the production cost and increasing productivity.

[0020]

Component (A) proposed in the present invention can be obtained by sulfonation of an olefin containing 16 or more and 24 or less carbon atoms, containing a double bond in the position 2 or higher, as the main component. If the internal olefin is sulfonated, a β-sultone is formed quantitatively and part of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are then converted to hydroxyalkane sulfonate and olefin sulfonate by the course of neutralization and hydrolysis (e.g., J. Am. Oil Chem. Soc. 69 , 39 (1992)). In this case, the hydroxy group of the resulting hydroxyalkane sulfonate is located inside the alkane chain and the double bond of the olefin sulfonate is located inside the olefin chain. Furthermore, although the resulting product is generally a mixture of the two, in some cases it may include a trace amount of a hydroxyalkane sulfonate containing a hydroxy group at the end of its carbon chain or an olefin sulfonate containing a hydroxy group at the end of its carbon chain.

[0021]

In the present description, each of these products and their mixture is collectively referred to as internal olefinsulfonate (component (A)). In addition, hydroxyalkane sulfonate is referred to as the hydroxy group-containing form (hereinafter also referred to as HAS) of the internal olefin sulfonate, and the olefin sulfonate is referred to as the olefin form (also referred to as IOS in the present invention) of the internal olefin sulfonate.

It should be noted that the mass ratio of compounds in component (A) can be determined using high resolution HPLC-MS. More precisely, the mass ratio can be determined from the peak area of the HPLC-MS component (A).

[0022]

<Component (B)>

Component (B) is a soil-repellent agent. The term "soil repellant" can also be used to refer to a dirt separating agent. Soil repellant agents are known as compounds that can be pre-applied to textiles prior to use of the textiles, such as wearing, and thereby, even if dirt has adhered to the textiles during use, promote desorption of the soil from the textiles when laundered after use. The soil repellant is used as one of the components included in the washing composition for textiles in the present invention, and thus the soil repellant can adhere to the textiles at the same time that the textile is washed and is effective.

[0023]

Examples of component (B) are not particularly limited if they can be adsorbed after washing on textiles in the presence of component (A). Examples of component (B) include, for example, one or more soil-repellent agents selected from among the following: as component (b1), one or two or more polysaccharide derivatives containing one or more groups selected from the group consisting of cationic a group and a hydrocarbon group containing 1 or more and 18 or less carbon atoms; as component (b2), one or two or more polymers containing one or two units selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit, and an oxyalkylene unit; and as component (b3), one or two or more polyalkylene imines containing a polyoxyalkylene group. Component (B) is preferably one or more soil-repellent agents selected from among components (b1).

[0024]

[Component (b1): one or two or more polysaccharide derivatives containing one or more groups selected from the group consisting of a hydrocarbon group containing 1 or more and 18 or less carbon atoms and a cationic group]

Component (b1) is one or two or more polysaccharide derivatives containing one or more groups selected from the group consisting of a hydrocarbon group containing 1 or more and 18 or less carbon atoms and a cationic group.

Component (b1) according to the present invention is characteristically a polysaccharide derivative in which one more group selected from the group consisting of a cationic group and a hydrocarbon group containing 1 or more and 18 or less carbon atoms are linked, directly or through a bridge a group with a group without a hydrogen atom of the hydroxy group of the polysaccharide or derivative thereof, which is the precursor compound of component (b). It should be noted that the above expression "one more groups selected from the group consisting of a cationic group and a hydrocarbon group containing 1 or more and 18 or fewer carbon atoms are linked, directly or via a bridge group, to a group without a hydrogen atom of the hydroxy group of the polysaccharide or its derivative" does not include the type of bonding in which a cationic atom of a cationic group, for example, a nitrogen cation, is directly bonded to a group without a hydrogen atom of the hydroxy group of the polysaccharide or its derivative, i.e. with an oxygen atom.

[0025]

Examples of the polysaccharide include, for example, one or more polysaccharides selected from the group consisting of cellulose, guar gum or starch. When component (b1) is a polysaccharide derivative, any polysaccharide derivative can be used as a precursor compound for its preparation. Thus, component (b1) may be a derivative of a polysaccharide derivative. Examples of the polysaccharide derivative which is the precursor compound of component (b1) include a polysaccharide derivative in which part or all of the hydrogen atoms of the hydroxy groups of the above polysaccharide are/are replaced by a hydroxyalkyl group containing 1 or more and 4 or less carbon atoms (below in the present invention, also called hydroxyalkyl substituted product). The hydroxyalkyl group containing 1 or more and 4 or less carbon atoms is preferably a hydroxyalkyl group containing preferably 2 or more and 4 or less carbon atoms. Examples of a hydroxyalkyl group having 2 or more and 4 or less carbon atoms include, for example, one or more groups selected from the group consisting of a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group, and it is preferably one or more groups selected from the group consisting of a hydroxyethyl group and a hydroxypropyl group. Component (b1) may be a compound in which one or more groups selected from the group consisting of a hydrocarbon group containing 1 or more and 18 or less carbon atoms and a cationic group are introduced into a polysaccharide or a polysaccharide derivative selected from the group, comprising: one or more polysaccharides selected from the group consisting of cellulose, guar gum or starch; or their hydroxyalkyl-substituted products.

[0026]

In component (b1), examples of a polysaccharide derivative containing a hydrocarbon group containing 1 or more and 18 or less carbon atoms include a polysaccharide derivative in which a hydrocarbon group containing 1 or more and 18 or less carbon atoms is linked, directly or through a bridging group [ hereinafter referred to as the bridging group (1) of the component], with a polysaccharide or derivative thereof which is the precursor compound of the component (b1).

[0027]

Examples of the above bridge group (1) include one or more groups selected from the group consisting of: an alkyleneoxy group containing 1 or more and 3 or less carbon atoms, which may contain a hydroxy group; a polyoxyalkylene group in which the alkylene group is an alkylene group containing 1 or more and 3 or less carbon atoms; a carbonyl group; a carbonyloxy group; and an oxycarbonyl group. One bridging group (1) may be one or a combination of the plurality of bridging groups mentioned above. In addition, the polysaccharide derivative may include one or more bridging groups.

In the present invention, if the above hydrocarbon group is bonded to the oxygen atom of the bridge group (1), the number of carbon atoms in the hydrocarbon group of component (b1) means the number of carbon atoms in the above hydrocarbon group bonded to the oxygen atom. If the above hydrocarbon group is linked through a carbonyl group, the acyl group is linked in its structure, and the number of carbon atoms in the hydrocarbon group of the component (b1) means the number of carbon atoms in the acyl group. Similarly, if the above hydrocarbon group is linked through a carbonyloxy group and an oxycarbonyl group, their carbon numbers are included. When 1,2-epoxyalkane is used to introduce a hydrocarbon group into a polysaccharide or a polysaccharide derivative, the number of carbon atoms in the hydrocarbon group of the component (b1) means the number of carbon atoms in the aliphatic hydrocarbon group associated with the ether group derived from the epoxy group. The epoxy moiety is a bridging group (1). For example, if 1,2-epoxytetradecane is used to introduce a hydrocarbon group into a polysaccharide or polysaccharide derivative, the number of carbon atoms in the hydrocarbon group is 12. Thus, the oxyethylene group, which is a bridge group (1), is linked to the hydroxy group of the polysaccharide or polysaccharide derivative , and an alkyl group containing 12 carbon atoms (dodecyl group) is linked via a bridging group. The same applies when an alkyl glycidyl ether is used.

[0028]

In component (b1), examples of the polysaccharide derivative containing a hydrocarbon group containing 1 or more and 18 or less carbon atoms further include a polysaccharide derivative in which a hydrocarbon group containing 1 or more and 18 or less carbon atoms is bonded, directly or through a bridging group (1), preferably via a bridging group (1), with oxygen atoms without hydrogen atoms of part or all of the hydroxy groups of the above hydroxyalkyl substituted product.

[0029]

A hydrocarbon group having 1 or more and 18 or less carbon atoms is preferred because it can impart hydrophobicity to the component (b1) and further improve the adsorption capacity on textiles, especially on textiles containing chemical fibers, thereby improving the ability of textiles products are easy to desorb dirt. From the viewpoint of ease of removal of dirt adhering to textiles, the number of carbon atoms in the hydrocarbon group containing 1 or more and 18 or less carbon atoms is preferably 2 or more, more preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, and even more preferably 12 or more, and preferably 16 or less, and more preferably 14 or less. In addition, if dirt is adhered during use of the textiles to which the component (b1) is attached, from the viewpoint of facilitating removal of the dirt together with the component (b1) from the textiles in a subsequent washing operation, it is preferable if the number of carbon atoms in the hydrocarbon group of the component (b1) is almost equal to the number of additional carbon atoms after the carbon atom to which the hydrophilic group of the component (A) is attached, in terms of removing the component (b1) from the textile along with dirt. The hydrocarbon group, from the viewpoint of ease of interaction with the component (A), is preferably an aliphatic hydrocarbon group.

[0030]

In the polysaccharide derivative of component (b1) containing a hydrocarbon group containing 1 or more and 18 or less carbon atoms, the degree of substitution of the hydrocarbon group containing 1 or more and 18 or less carbon atoms is preferably 0.0001 or more, more preferably 0.001 or more and more preferably 0.005 or more in terms of interaction with the hydrocarbon group of the component (A) and ease of desorption from textiles along with dirt; and preferably 0.4 or less, more preferably 0.2 or less, more preferably 0.1 or less, even more preferably 0.08 or less, and even more preferably 0.06 or less in terms of ease of desorption from textiles, especially from textiles containing chemical fibers.

[0031]

In component (b1), examples of the polysaccharide derivative containing one or more groups selected from the group consisting of cationic groups include a polysaccharide derivative in which the cationic group is bonded through an alkylene group containing 1 or more and 4 or less carbon atoms, which may include a hydroxy group which is a bridging group [hereinafter referred to as bridging group (2)] with a group without a hydrogen atom of the hydroxy group of the polysaccharide or derivative thereof, preferably the above hydroxyalkyl substituted product, which is the precursor compound of component (b1).

The cationic group, from the viewpoint of ease of desorption from textiles due to interaction with the component (A), is preferably a group including a nitrogen-containing cation and more preferably a quaternary ammonium group.

[0032]

The bridging group (2) is an alkylene group containing 1 or more and 4 or less carbon atoms, which may include a hydroxy group. Examples of an alkylene group having 1 or more and 4 or less carbon atoms include one or more alkylene groups selected from the group consisting of a linear alkylene group having 1 or more and 4 or less carbon atoms, which may include a hydroxy group, and a branched alkylene group. a group containing 3 or more and 4 or less carbon atoms, which may include a hydroxy group.

[0033]

When the cationic group is a quaternary ammonium group, examples of each of the three hydrocarbon groups bonded to the non-bridging quaternary ammonium group (2) independently include a linear hydrocarbon group containing 1 or more and 4 or less carbon atoms, or a branched hydrocarbon group, containing 3 or more and 4 or less carbon atoms. Examples of a linear hydrocarbon group containing 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Examples of the branched hydrocarbon group having 3 or more and 4 or less carbon atoms include an isopropyl group, a sec-butyl group, a tert-butyl group, and an isobutyl group. The linear hydrocarbon group containing 1 or more and 4 or less carbon atoms is preferably a methyl group or an ethyl group.

Examples of the counterion for the quaternary ammonium group include one or more counterions selected from the group consisting of an alkyl sulfate ion containing 1 or more and 3 or less carbon atoms, a sulfate ion, a phosphate ion, a fatty acid ion containing 1 or more and 3 or less carbon atoms, and a halide ion. Of these, in terms of ease of preparation and availability of raw materials, one or more selected from the group consisting of alkyl sulfate ion having 1 or more and 3 or less carbon atoms, sulfate ion and halide ion are preferred, and halide ion is more preferred. Examples of the halide ion include fluoride ion, chloride ion, bromide ion, and iodide ion. From the viewpoint of water solubility and chemical stability of the polysaccharide derivative of component (b1), one or more selected from the group consisting of chloride ion and bromide ion is preferred, and chloride ion is more preferred. It should be noted that there may be only one counterion, or there may be two or more.

[0034]

If the degree of substitution of the cationic group in the polysaccharide derivative of the cationic group-containing component (b1) is high, the anionic group-containing component (A) strongly interacts with the cationic group-containing component (b1) during washing, and thus the component (A) and the component (b1) containing the cationic group become more hydrophobic, resulting in greater hydrophobicity than in the case of water contained in the washing liquid, and it is poorly desorbed from textiles. On the other hand, since textiles tend to have a negative charge in the washing liquid and interact with the cationic group-containing component (b1), the larger the value of the degree of substitution of the cationic group of the cationic group-containing component (b1), the greater the adsorption on the textiles, and this is preferred. In addition, it is assumed that if the number of moles of the cationic group of the soil repellant of the cationic group-containing component (b1) attached to the textile is less than the number of moles of the anion group of the component (A), the soil repellant is easily desorbed from the textiles along with dirt. during washing due to interaction with the anionic group. In the present invention, it is preferable if the value of the degree of substitution of the cationic group is chosen taking into account these points of view. The degree of substitution of the cationic group of the polysaccharide derivative of the component (b1) containing the cationic group from the above points of view is preferably 0.001 or more, more preferably 0.005 or more, and more preferably 0.01 or more, and preferably 1 or less, more preferably 0.7 or less, more preferably 0.4 or less, even more preferably 0.35 or less, even more preferably 0.3 or less, even more preferably 0.25 or less, and even more preferably 0.2 or less.

[0035]

In the present invention, the degree of substitution of each of one or more groups selected from the group consisting of a hydrocarbon group containing 1 or more and 18 or less carbon atoms and a cationic group of the component (b1) means the number of substituent groups in terms of the monosaccharide unit of the component, those. average molar degree of substitution (MS). For example, if the polysaccharide is cellulose, the "degree of group substitution" means the average number of moles of groups introduced in 1 mole of the anhydroglucose unit. The degree of substitution by a cationic group and the degree of substitution by a hydrocarbon group containing 1 or more and 18 or less carbon atoms in the polysaccharide derivative are determined as described in the examples.

[0036]

Component (b1) may be a polysaccharide derivative containing both a hydrocarbon group containing 1 or more and 18 or less carbon atoms and a cationic group. The degree of substitution of each group in this case is as described above.

[0037]

If the component (b1) can also contain an anionic group, the ratio of the degree of substitution of the anionic group to the sum of the degree of substitution of the cationic group and the degree of substitution of the hydrocarbon group containing 1 or more and 18 or less carbon atoms in the component (b1), which is the degree of substitution anionic group/(degree of substitution of cationic group + degree of substitution of hydrocarbon group containing 1 or more and 18 or less carbon atoms), preferably 3 or less, more preferably 1.7 or less, more preferably 1.5 or less, even more preferably 1 or less, even more preferably 0.5 or less, and even more preferably 0.1 or less; and may be 0 or more, preferably 0 in terms of washing performance.

[0038]

The weight average molecular weight of the polysaccharide or derivative thereof which is the precursor compound of the component (b1) of the present invention is preferably 1000 or more, more preferably 10000 or more, more preferably 30000 or more, even more preferably 50000 or more, even more preferably 70,000 or more, even more preferably 100,000 or more, even more preferably 300,000 or more, and even more preferably 500,000 or more from the point of view of improving washing performance, and preferably 3 ppm or less, and more preferably 2.5 ppm or less from the point of view of lightness use. This weight average molecular weight of the precursor compound can be calculated in terms of polyethylene glycol using GPC (Gel Permeation Chromatography).

[0039]

Examples of component (b1) include a polysaccharide derivative in which one or more groups selected from the group consisting of a cationic group and a hydrocarbon group containing 1 or more and 18 or fewer carbon atoms are bonded, directly or through a bridging group, to a group without hydrogen atom of the hydroxy group of the polysaccharide or its derivative, which is a precursor compound, where:

if the cationic group is bonded to a group without a hydrogen atom of the hydroxy group, it is bonded to it directly or via a bridging group (2) and if the hydrocarbon group is bonded to a group without a hydrogen atom of the hydroxy group, it is bonded to it directly or via a bridging group (1); where

the bridging group (1) is one or more groups selected from the group consisting of: an alkyleneoxy group containing 1 or more and 3 or less carbon atoms, which may contain a hydroxy group; a polyoxyalkylene group in which the alkylene group is an alkylene group containing 1 or more and 3 or less carbon atoms; a carbonyl group; a carbonyloxy group; and an oxycarbonyl group; and

the bridging group (2) is an alkylene group containing 1 or more and 4 or less carbon atoms, which may include a hydroxy group.

[0040]

[Component (b2): polymer containing one or two units selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit, and an oxyalkylene unit]

Component (b2) of the present invention is a polymer containing one or two units selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit.

[0041]

Examples of the alkylene terephthalate unit include one or more selected from the group consisting of an ethylene terephthalate unit, a propylene terephthalate unit, and a butylene terephthalate unit, and of these, the ethylene terephthalate unit is preferred.

[0042]

Examples of the alkylene isophthalate unit include one or more selected from the group consisting of an ethylene isophthalate unit, a propylene isophthalate unit, and a butylene isophthalate unit, and of these, the ethylene isophthalate unit is preferred.

[0043]

Examples of the polyoxyalkylene unit include one or more selected from the group consisting of a polyoxyethylene unit, a polyoxypropylene unit, and a polyoxyethylene polyoxypropylene unit.

[0044]

The ratio of the number of moles of an oxyalkylene unit to the number of moles of one or more units, to the number of moles of one or more units selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit (number of moles of an oxyalkylene unit)/(number of moles of one or more units selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit) from the viewpoint of providing further improvement in washing performance, preferably 0.6 or less, more preferably 0.5 or less, and more preferably 0.4 or less, and preferably 0 or more, and more preferably 0.1 or more.

[0045]

The weight average molecular weight of the component (b2) from the point of view of further improving adsorbability on textiles, thereby further improving the ability to wash dirt adhering to textiles after use, is preferably 300 or more, more preferably 500 or more, and more preferably 1000 or more, and preferably 20,000 or less, and more preferably 15,000 or less. It should be noted that the weight average molecular weight of the component (b2) is a value obtained by converting based on the calibration curve in PEG (polyethylene glycol) value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent.

[0046]

[Component (b3): polyalkyleneimine containing a polyoxyalkylene group]

Component (b3) is a polyalkyleneimine containing a polyoxyalkylene group.

Examples of the oxyalkylene group of the polyoxyalkylene group include an oxyalkylene group having 2 or more and 3 or less carbon atoms, preferably one or more groups selected from the group consisting of an oxyethylene group and an oxypropylene group. Examples of the alkylene group of the polyalkyleneimine include an alkylene group having 2 or more and 6 or less carbon atoms. More preferred examples thereof include one or more selected from the group consisting of an ethylene group and a butylene group attached in various ways. Preferably, the number of polyoxyalkylene groups associated with the polyalkyleneimine is on average 3 or more and 100 or less polyoxyalkylene groups, based on the active hydrogen atom of the polyalkyleneimine. From the viewpoint of further enhancing the ability to wash dirt adhering to textiles, the weight average molecular weight of the polyalkyleneimine is preferably 300 or more, more preferably 500 or more, and more preferably 1000 or more, and preferably 1 million or less, more preferably 500,000 or less and more preferably 100,000 or less.

[0047]

<Fibres>

The fibers forming the textiles that are washed with the textile detergent composition of the present invention may be man-made fibers or natural fibers. Examples of the chemical fiber include, for example, polyamide-based fiber (such as nylon), polyester-based fiber (such as polyester), polyacrylonitrile-based fiber (such as acrylic), polyvinyl alcohol-based fiber (such as vinylon), polyvinyl chloride-based fiber (such as polyvinyl chloride), polyvinylidene chloride-based fiber (such as vinylidene), polyolefin-based fiber (such as polyethylene and polypropylene), polyurethane-based fiber (such as polyurethane), and polyvinyl chloride/polyvinyl alcohol copolymer fiber (such as polychlal). Examples of natural fiber include seed fiber (such as cotton, tree cotton and kapok), bast fiber (such as flax, ramie, hemp and jute), vein fiber (such as manila hemp and sisal hemp), coconut fiber, cane fiber straw, animal hair fiber (such as wool, mohair, cashmere, camel hair, alpaca wool, vicuña and angora wool), silk fiber (domesticated silkworm and wild silkworm), feather and down and cellulose fiber ( such as viscose, polynose, copper ammonium and acetate). The fibers that are used in the present invention are preferably man-made fibers.

[0048]

<Textile products>

In the present invention, textile products means fabrics such as woven fabric, knitted fabric or non-woven fabric obtained using the above chemical fibers or natural fibers, and products obtained using fabrics such as T-shirt, T-shirt, business shirt, blouse, pants, hat, neckerchief, towel, knitwear, socks, underwear and tights. Since it is easier to improve the washing ability of the soil repellant used with the component (A) of the present invention, the textiles are preferably textiles including chemical fibers. From the point of view of further improving the washing ability of the soil-repellent agent when used together with the component (A) of the present invention, the content of chemical fibers in textiles is preferably 5 mass% or more, more preferably 10 mass% or more, more preferably 20 wt.% or more, even more preferably 30 wt.% or more, and even more preferably 50 wt.% or more, and even more preferably 100 wt.% or less. The content of chemical fibers in textiles can be 100 wt.%.

[0049]

<Composition and others>

The laundry detergent composition of the present invention may be (1) a laundry detergent composition for use by dilution in water, i. e. detergent composition for textiles used by dilution in water [hereinafter referred to as detergent composition (1) for textiles], or may be (2) a detergent composition for textiles intended to be used unchanged as a detergent composition for washing textiles, i.e. a washing composition for textiles used unchanged as a washing liquid without dilution [hereinafter referred to as washing composition (2) for textiles]. In the present specification, when the term "textile detergent composition" or "textile detergent composition of the present invention" is indicated, it includes these textile detergent compositions (1) and (2).

[0050]

The content of the component (A) in the detergent composition (1) for textiles is 5 wt.% or more, preferably 7 wt.% or more, and more preferably 10 wt.% or more from the point of view of further improving the washing power in terms of the weight of detergent composition (1) for textiles when washing fibers and preferably 60 wt.% or less, more preferably 50 wt.% or less, and more preferably 40 wt.% or less from the viewpoint of suppressing settling or separating solids in the composition (1) in a low temperature environment.

In addition, the content of the component (A) in the detergent composition (2) for textiles is preferably 0.005 wt.% or more, more preferably 0.01 wt.% or more, and preferably 0.1 wt.% or more in terms of additional improve the washing ability when washing fibers and preferably 1 wt.% or less and more preferably 0.8 wt.% or less from the point of view of economic efficiency.

It should be noted that the content of the component (A) contained in the washing composition for textiles of the present invention, such as the washing composition (1) for textiles or the washing composition (2) for textiles, is based on the value calculated by converting counterion to sodium ion. Thus, it represents the content in terms of the sodium salt.

[0051]

In the present invention, the content of the internal olefinsulfonate of component (A) in the total amount of anionic surfactants contained in the textile detergent composition is preferably 50 wt.% or more, more preferably 60 wt.% or more, more preferably 70 wt. % or more and more preferably 80 wt.% or more and 100 wt.% or less.

[0052]

The content of the component (B) in the washing composition (1) for textiles of the present invention, in terms of further enhancing the washing power, in terms of the weight of the washing composition (1) for textiles, for dirt adhering to the fibers, is preferably 0 1 wt% or more, and more preferably 0.2 wt% or more, and preferably 10 wt% or less, more preferably 5 wt% or less, more preferably 3 wt% or less, and even more preferably 1 wt. .% or less.

In addition, the content of the component (B) in the detergent composition (2) for textiles is preferably 0.1 mg/kg or more, more preferably 0.5 mg/kg or more, more preferably 1.0 mg/kg or more, and even more preferably 3.0 mg/kg or more from the point of view of improving the washing ability when washing fibers, and preferably equal to 800 mg/kg or less, more preferably 500 mg/kg or less, more preferably 100 mg/kg or less, even more preferably 50 mg/kg or less, even more preferably 30 mg/kg or less, even more preferably 10 mg/kg or less, and even more preferably 5 mg/kg or less from the point of view of economic efficiency.

[0053]

Washing composition for textiles proposed in the present invention may contain water. For example, to ensure the characteristics of the composition proposed in the present invention, at 4°C or higher and 40°C or lower in the liquid state, it may contain water. Deionized water (which can also be called ion-exchanged water) or ion-exchanged water to which sodium hypochlorite is added in an amount of 1 mg/kg or more and 5 mg/kg or less can be used as the water. You can also use tap water. The water content of the composition is preferably 10% by mass or more, and more preferably 20% by mass or more, and preferably 90% by mass or less, and more preferably 80% by mass or less.

[0054]

<Optional component>

The detergent composition for textiles of the present invention preferably contains a nonionic surfactant as component (C). From the point of view of combining with the above component (B) to improve the ability to wash dirt adhering to textiles, the detergent composition for textiles of the present invention preferably contains component (C). From the point of view of combining with component (B) to further enhance the ability to wash dirt adhering to textiles, component (C) is preferably a nonionic surfactant containing one or more groups selected from the group consisting of a hydroxy group and a polyoxyalkylene group . Component (C) is preferably a nonionic surfactant containing a polyoxyalkylene group and having an HLB index of 7 or more and 20 or less. From the viewpoint of further enhancing the ability to wash dirt adhering to textiles by combining with component (B), the HLB value is preferably 8 or more, more preferably 9 or more, and more preferably 10 or more, and preferably 20 or less, and more preferably 19 or less.

[0055]

The Griffin HLB value is used for the HLB value of the component (C) containing the polyoxyethylene group and is given by the following formula:

HLB (Griffin) = [(molecular weight of polyoxyethylene group)/(molecular weight of component (C))]×20

[0056]

In addition, the HLB value calculated by the Davis method is used for the HLB value of the component (C) not containing the polyoxyethylene group.

[0057]

More preferred examples of component (C) include a nonionic surfactant which has an HLB index of preferably 7 or more, more preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more, and preferably 20 or less or more preferably 19 or less and which is described by the following general formula (C):

R ¹ (CO) _m O-(A ¹ O) _n -R ² (C)

in which R ¹ means an aliphatic hydrocarbon group containing 9 or more and 16 or less carbon atoms; R ² means a hydrogen atom or a methyl group; CO is a carbonyl group; m is a number equal to 0 or 1; the A ¹ O group is one or more groups selected from the group consisting of an ethyleneoxy group and a propyleneoxy group; and n means the average number of added moles and is a number equal to 3 or more and 50 or less.

[0058]

In the general formula (C), R ¹ means an aliphatic hydrocarbon group containing 9 or more and 16 or less carbon atoms. The greater the number of carbon atoms in R ¹ , the lower the value of the HLB index, and the smaller the number of carbon atoms in R ¹ , the greater the value of the HLB index if all other structures are the same. From the viewpoint of facilitating the removal of dirt adhering to textiles, the number of carbon atoms in R ¹ is 9 or more, preferably 10 or more, and more preferably 11 or more, and preferably 18 or less, more preferably 16 or less, more preferably 15 or less and even more preferably 14 or less. Examples of the aliphatic hydrocarbon group R ¹ include a group selected from the group consisting of an alkyl group and an alkenyl group.

[0059]

In the general formula (C), the A ¹ O group represents one or more groups selected from the group consisting of an ethyleneoxy group and a propyleneoxy group. If an ethyleneoxy group and a propyleneoxy group are contained, the ethyleneoxy group and the propyleneoxy group may be bonded in a block type or random type. From the viewpoint of further enhancing the dirt repellency of the component (B), the A ¹ O group is preferably a group including an ethyleneoxy group. The value of the HLB index of the ethyleneoxy group is greater than that of the propyleneoxy group.

[0060]

In the general formula (C), n is the average number of added moles, and is a number equal to 3 or more and 50 or less. The larger the value of n, the larger the value of the HLB score, and the smaller the value of n, the smaller the value of the HLB score, if all other structures are the same. From the point of view of further enhancing the ability to wash dirt adhering to products, especially containing chemical fibers, by combining with the component (A) and component (B) of the present invention, n is preferably 4 or more, more preferably 5 or more, and more preferably 6 or more.

[0061]

If the washing composition for textiles of the present invention contains the component (C), the content of the component (C) in the composition is preferably 1 wt% or more, more preferably 3 wt% or more, more preferably 5 wt% or more and more preferably 10 wt.% or more, and preferably 60 wt.% or less, more preferably 50 wt.% or less, and more preferably 45 wt.% or less.

[0062]

If the washing composition for textiles of the present invention contains a component (C) in which the mass ratio (C)/(B) of the content of the component (C) to the content of the component is preferably 2 or more, more preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more, and preferably 100 or less, more preferably 90 or less, and more preferably 80 or less from the viewpoint of further enhancing the ability to wash dirt adhering to textiles when combined with component (B).

[0063]

The detergent composition for textiles of the present invention may contain, as component (D), other anionic surfactants than component (A), to the extent that the effect of the present invention is not suppressed.

Examples of component (D) include one or more anionic surfactants selected from the following component (d1), component (d2), component (d3), and component (d4):

component (d1): alkyl or alkenyl sulfate;

component (d2): polyoxyalkylene alkyl ether sulfate or polyoxyalkylene alkenyl ether sulfate;

component (d3): an anionic surfactant containing a sulfonate group (except for component (A)); and

component (d4): fatty acid or salt thereof.

[0064]

More preferred examples of component (d1) include one or more anionic surfactants selected from the group consisting of an alkyl sulfate in which the number of carbon atoms in the alkyl group is 10 or more and 18 or less, and an alkenyl sulfate in which the number of carbon atoms in the alkenyl group is 10 or more and 18 or less. From the viewpoint of improving the washing power, the component (d1) is preferably one or more anionic surfactants selected from the group consisting of an alkyl sulfate in which the number of carbon atoms in the alkyl group is 12 or more and 14 or less, and more preferably is is one or more anionic surfactants selected from the group consisting of sodium alkyl sulfate, in which the number of carbon atoms in the alkyl group is 12 or more and 14 or less.

[0065]

More preferred examples of component (d2) include one or more anionic surfactants selected from the group consisting of polyoxyalkylene alkyl sulfate, in which the number of carbon atoms in the alkyl group is 10 or more and 18 or less, and the average number of moles of alkylene oxide added is 1 or more and 3 or less; and a polyoxyalkylene alkenyl ether sulfate in which the number of carbon atoms in the alkenyl group is 10 or more and 18 or less and the average number of moles of added alkylene oxide is 1 or more and 3 or less. From the viewpoint of improving the washing ability, the component (d2) is preferably a polyoxyethylene alkyl sulfate in which and the average mole of added ethylene oxide is 1 or more and 2.2 or less, more preferably a polyoxyethylene alkyl sulfate in which the number of carbon atoms in the alkyl group is 12 or more and 14 or less and the average number of moles of ethylene oxide added is 1 or more and 2.2 or less, and more preferably its sodium salt.

[0066]

Anionic surfactant of component (d3) containing a sulfonate group means an anionic surfactant containing a sulfonate group as a hydrophilic group (wherein component (A) is excluded).

More preferred examples of component (d3) include one or more anionic surfactants selected from the group consisting of alkylbenzenesulfonate in which the number of carbon atoms in the alkyl group is 10 or more and 18 or less, alkenylbenzenesulfonate in which the number of carbon atoms in alkenyl group is 10 or more and 18 or less, an alkane sulfonate in which the number of carbon atoms in the alkyl group is 10 or more and 18 or less, an α-olefin sulfonate in which the number of carbon atoms in the α-olefin moiety is 10 or more and 14 or less, a fatty α-sulfonic acid salt in which the number of carbon atoms in the fatty acid moiety is 10 or more and 18 or less, and a lower alkyl ester salt of fatty α-sulfonic acid in which the number of carbon atoms in the fatty acid moiety is 10 or more, and 18 or less and the number of carbon atoms in the ester moiety is 1 or more and 5 or less. From the viewpoint of improving the washing ability, the component (d3) is preferably an alkylbenzenesulfonate in which the number of carbon atoms in the alkyl group is 11 or more and 14 or less, and more preferably a sodium alkylbenzenesulfonate in which the number of carbon atoms in the alkyl group is 11 or more and 14 or less.

[0067]

Examples of the fatty acid or salt thereof which is the component (d4) include a fatty acid having 10 or more and 20 or less carbon atoms or a salt thereof. From the point of view of less deterioration in washability, the number of carbon atoms in the component (d4) is 10 or more, preferably 12 or more, and more preferably 14 or more, and 20 or less, and preferably 18 or less.

[0068]

The salt of the anionic surfactants of components (d1) to (d4) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and more preferably a sodium salt.

[0069]

If the washing composition for textiles of the present invention contains the component (D), the content of the component (D) in the composition is preferably 0.5 mass% or more and 15 mass% or less.

[0070]

The detergent composition for textiles of the present invention, in addition to those mentioned above, can be prepared with the following components (e1) - (e7):

(e1) an anti-redeposition agent and a dispersing agent such as polyacrylic acid, polymaleic acid or carboxymethyl cellulose in an amount of 0.01 wt.% or more and 10 wt.% or less in the composition;

(e2) a bleaching agent such as hydrogen peroxide, sodium percarbonate or sodium perborate in an amount of 0.01 wt.% or more and 10 wt.% or less in the composition;

(e3) a bleach activator such as tetraacetylethylenediamine, or bleach activators having the general formulas (I-2) to (I-7) in JP-A H6-316700 in an amount of 0.01 mass% or more and 10 mass .% or less in the composition;

(e4) 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 including amylase and protease in an amount equal to 0.001% by weight or more, preferably 0.01 wt.% or more, more preferably 0.1 wt.% or more, and more preferably 0.3 wt.% or more, and 2 wt.% or less, and preferably 1 wt.% or less in the composition;

(e5) a fluorescent dye such as the fluorescent dye sold under the name Tinopal CBS (trade name, manufactured by Ciba Specialty Chemicals Inc.) or Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) in the composition in an amount, equal to 0.001 wt.% or more and 1 wt.% or less;

(e6) an antioxidant such as butylhydroxytoluene, distyrene-substituted cresol, sodium sulfite and sodium hydrosulfite in the composition in an amount of 0.01 wt.% or more and 2 wt.% or less; and

(e7) a pigment, fragrance, antiseptic or defoamer such as silicone in a suitable amount.

[0071]

The textile detergent composition of the present invention may be a textile detergent composition prepared with component (A) and component (B), as well as an optional component such as component (C).

[0072]

The detergent composition for textiles according to the present invention is preferably a liquid. If the laundry detergent composition of the present invention is a liquid, its pH at 20°C is preferably 3 or more, and more preferably 4 or more, and preferably 10 or less, more preferably 9 or less, and more preferably 8.5 or less in terms of suppressing settling or separation of a solid in the composition in a low temperature environment. The pH value is measured by the pH measurement procedure described below.

<Method of measuring pH>

A compound pH electrode (manufactured by HORIBA, Ltd., glass sleeve type) is connected to a pH meter (manufactured by HORIBA, Ltd., pH/ion meter F-23) and the power is turned on. A saturated aqueous solution of potassium chloride (3.33 mol/L) was used as the internal liquid for the pH electrode. Then, pH 4.01 standard solution (phthalate standard solution), pH 6.86 standard solution (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) were placed into 100 ml beakers, respectively, and 30 min was immersed in a thermostatic bath at 25°C. The pH electrode was immersed in constant temperature standard solutions for 3 minutes and calibrated in the following order: pH 6.86, pH 9.18 and pH 4.01. The above pH meter electrode was immersed in the test sample, the temperature of which was set to 25°C, and its pH was measured after 1 minute.

[0073]

The present invention relates to a method for washing textiles, including washing textiles with a washing liquid containing a washing composition for textiles according to the present invention and water. The objects noted for the detergent composition for textiles of the present invention can be appropriately applied to this washing method. The content of component (A) in the above washing liquid is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and more preferably 0.1 mass% or more, and preferably 1 mass% or less and more preferably 0.8 mass% or less. In addition, the content of the component (B) in the above washing liquid is preferably 0.1 mg/kg or more, more preferably 0.5 mg/kg or more, more preferably 1.0 mg/kg or more, and even more preferably 3 .0 mg/kg or more from the point of view of further enhancing the ability to wash dirt adhering to the fibers when washing the fibers, and preferably 800 mg/kg or less, more preferably 500 mg/kg or less, more preferably 100 mg/kg or less, still more preferably 50 mg/kg or less, even more preferably 30 mg/kg or less, even more preferably 10 mg/kg or less, and even more preferably 5 mg/kg or less from the point of view of economic efficiency. The above washing liquid may be a washing composition (2) for textiles proposed in the present invention. In addition, the above washing liquid can be obtained by diluting the washing composition (1) for textiles proposed in the present invention.

[0074]

In the method of washing textiles according to the present invention, water of high hardness is preferably used. From the viewpoint of further improving the texturing effect of textiles, the water hardness is preferably 1°dH (German hardness) or more, more preferably 2°dH or more, more preferably 3.5°dH or more, even more preferably 5°dH or more. more and more preferably 7°dH or more, and preferably 20°dH or less, more preferably 18°dH or less, and more preferably 15°dH or less. As used herein, German hardness (°dH) means the concentration of calcium and magnesium in water expressed as CaCO ₃ in units of 1 mg/l (ppm) = about 0.056°dH (1°dH=17.8 ppm). /mln).

The concentration of calcium and magnesium for this German hardness can be determined by chelate titration using ethylenediaminetetraacetic acid disodium salt.

The specific technique for measuring German hardness used in the present invention is described below.

<Procedure for measuring German water hardness>

[Reagent]

0.01 mol/L EDTA⋅2Na solution: 0.01 mol/L aqueous ethylenediaminetetraacetic acid disodium salt solution (Titration solution, 0.01 M EDTA-Na2, available from Sigma-Aldrich Co. LLC.)

Universal BT indicator (product name: Universal BT, manufactured by Dojindo Laboratories)

ammonia buffer solution for measuring hardness (solution prepared by dissolving 67.5 g of ammonium chloride in 570 ml of 28 wt./vol.% aqueous ammonia solution and adding ion-exchanged water to a total volume of 1000 ml)

[Hardness measurement]

(1) A 20 ml sample of water is collected with a whole pipette into a conical beaker.

(2) add 2 ml of ammonia buffer solution to measure the hardness.

(3) add 0.5 ml of Universal BT indicator to it. Check if the solution has turned reddish-violet after addition.

(4) A 0.01 mol/L EDTA⋅2Na solution is added dropwise from the buret to the water sample, while the conical beaker is vigorously shaken, and the position at which the color of the water sample turns blue is determined as the end point of the titration.

(5) Total stiffness is determined by the following calculation formula:

Hardness (°dH) = T×0.01×F×56.0774×100/A

wherein,

T: Amount of 0.01 mol/l EDTA⋅2Na solution used for titration (ml);

A: Sample volume (20 ml, water sample volume); and

F: Multiplier for 0.01 mol/l EDTA⋅2Na solution.

[0075]

The washing liquid used in the present invention is preferably a washing liquid obtained by mixing the component (A), the component (B) and water with a German hardness of 1°dH or more and 20°dH or less. In addition, the above washing liquid may be a washing liquid obtained by mixing the washing composition (1) for textiles of the present invention and water with a German hardness of 1°dH or more and 20°dH or less.

[0076]

In the method for washing textiles of the present invention, the value of the washing ratio described by the ratio of the amount of washing liquid (L) to the mass of textiles (kg), i.e., the value of the quantity of washing liquid (L)/weight of textiles (kg) (below in the present invention, this ratio can also be used as the washing ratio) is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more, and preferably 400 or less, and more preferably 300 or less.

[0077]

In the method of washing textiles of the present invention, from the viewpoint of further improving the effect of imparting texture to textiles, the washing time of textiles is preferably 1 minute or more, more preferably 2 minutes or more, and more preferably 3 minutes or more, and preferably 12 hours or more. less, more preferably 8 hours or less, more preferably 6 hours or less, even more preferably 3 hours or less, and even more preferably 1 hour or less.

[0078]

The clothes washing method of the present invention is also suitable for the drum washing method. The drum washing method means a washing method in which textiles not fixed in a rotary machine are rotated along with the washing liquid about a rotation axis. The drum washing process can be carried out in a rotary type washing machine. Specific examples of the rotary type washing machine include a drum type washing machine, an impulse type washing machine, or an activator type washing machine. For each of these rotary type washing machines, a commercially available household machine can be used. From the point of view of further reducing the amount of water used per wash, drum type washing machines, which have become widespread recently, can achieve a significant reduction in the amount of water during washing.

[0079]

<Objects of the present invention>

The objects of the present invention are illustrated below. The objects noted for the detergent composition for textiles and the method for washing textiles of the present invention can be appropriately applied to these objects.

[0080]

<1> Detergent composition for textiles, containing the following component (A) and the following component (B):

component (A): an internal olefin sulfonate containing 16 or more and 24 or less carbon atoms, where the ratio of the mass of an internal olefin sulfonate (IO-1S) containing 16 or more and 24 or less carbon atoms containing a sulfonate group at position 2 or further and position 4 or closer, to the mass of internal olefinsulfonate (IO-2S) containing 16 or more and 24 or less carbon atoms, containing a sulfonate group in position 5 or more, which has the form (IO-2S)/(IO-1S), equal to 0.30 or more and 5 or less; and

component (B): soil-repellent agent.

[0081]

<2> The detergent composition for textiles according to paragraph <1>, in which (IO-2S)/(IO-1S), which is the ratio of the mass of (IO-2S) contained to the mass of (IO-1S) contained (IO- 1S) in component (A) is 0.35 or more, preferably 0.40 or more, more preferably 0.50 or more, more preferably 0.60 or more, even more preferably 0.70 or more, even more preferably 0.80 or more, even more preferably 0.90 or more, and even more preferably 1.0 or more, and 4 or less, and preferably 3 or less.

[0082]

<3> The textile detergent composition of <1> or <2>, wherein the number of carbon atoms in the internal olefinsulfonate of component (A) is 16 or more and 22 or less, preferably 20 or less, and more preferably 18 or less .

[0083]

<4> The detergent composition for textiles according to any one of <1> to <3>, wherein the content of α-olefin sulfonate in the internal olefin sulfonate of component (A) is 10 mass% or less, preferably 7 mass% or less, more preferably 5 wt% or less, and more preferably 3 wt% or less, and 0.01 wt% or more.

[0084]

<5> The textile detergent composition according to any one of <1> to <4>, wherein the content of the component (A) in the total amount of anionic surfactants contained in the textile detergent composition is 50% by mass, or more and 100 wt.% or less.

[0085]

<6> The textile detergent composition according to any one of <1> to <5>, wherein the content of the component (A) in the total amount of anionic surfactants contained in the textile detergent composition is 60% by mass, or more, preferably 70 wt.% or more, and more preferably 80 wt.% or more, and 100 wt.% or less.

[0086]

<7> The washing composition for textiles according to any one of paragraphs <1> to <6>, wherein the component (B) is one or more soil-repellent agents selected from among the following: as component (b1), one or two, or more polysaccharide derivatives containing one or more groups selected from the group consisting of a cationic group and a hydrocarbon group containing 1 or more and 18 or less carbon atoms; as component (b2), one or two or more polymers containing one or two units selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit, and an oxyalkylene unit; and as component (b3), one or two or more polyalkylene imines containing a polyoxyalkylene group.

[0087]

<8> Washing composition for textiles according to paragraph <7>, in which

component (b1) is a polysaccharide derivative in which one or more groups selected from the group consisting of a cationic group and a hydrocarbon group containing 1 or more and 18 or fewer carbon atoms are linked, directly or through a bridging group, to a group without an atom hydrogen of the hydroxy group of the polysaccharide or its derivative, which is a precursor compound; and

if the cationic group is bonded to a group without a hydrogen atom of the hydroxy group, it is bonded to it directly or through a bridging group (2) and if the hydrocarbon group is bonded to a group without a hydrogen atom of the hydroxy group, it is bonded to it directly or through a bridging group (1), in which

the bridging group (1) is one or more groups selected from the group consisting of: an alkyleneoxy group containing 1 or more and 3 or less carbon atoms, which may contain a hydroxy group; a polyoxyalkylene group in which the alkylene group is an alkylene group containing 1 or more and 3 or less carbon atoms; a carbonyl group; a carbonyloxy group; and an oxycarbonyl group; and

the bridging group (2) is an alkylene group containing 1 or more and 4 or less carbon atoms, which may include a hydroxy group.

[0088]

<9> The textile detergent composition of <8>, wherein the polysaccharide derivative that is the precursor compound of component (b1) is a hydroxyalkyl-substituted product in which part or all of the hydrogen atoms of the hydroxy groups of the polysaccharide are/are replaced by a hydroxyalkyl group containing 1 or more and 4 or less carbon atoms.

[0089]

<10> The textile detergent composition of <9>, 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 one or more groups selected from the group consisting of a hydroxyethyl group, a hydroxypropyl group and a hydroxybutyl group, and more preferably one or more groups selected from the group consisting of a hydroxyethyl group and a hydroxypropyl group.

[0090]

<11> The textile detergent composition of any one of <7> to <10>, wherein the polysaccharide is one or more polysaccharides selected from the group consisting of cellulose, guar gum, or starch.

[0091]

<12> The laundry detergent composition according to any one of <7> to <11>, wherein the number of carbon atoms in a hydrocarbon group containing 1 or more and 18 or less carbon atoms is 2 or more, preferably 4 or more, more preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and even more preferably 12 or more, and 16 or less, and preferably 14 or less.

[0092]

<13> The textile detergent composition of any one of <7> to <12>, wherein the hydrocarbon group is an aliphatic hydrocarbon group.

[0093]

<14> The detergent composition for textiles according to any one of paragraphs <7> to <13>, wherein in the polysaccharide derivative of component (b1) containing a hydrocarbon group containing 1 or more and 18 or less carbon atoms, the degree of substitution of the hydrocarbon group, containing 1 or more and 18 or less carbon atoms is 0.0001 or more, preferably 0.001 or more, and more preferably 0.005 or more, and 0.4 or less, preferably 0.2 or less, more preferably 0.1 or less , more preferably 0.08 or less, and even more preferably 0.06 or less.

[0094]

<15> The textile detergent composition of any one of <7> to <14>, wherein the polysaccharide derivative containing one or more groups selected from the group consisting of cationic groups is a polysaccharide derivative in which the cationic group is bonded through the alkylene group of the bridge group (2) containing 1 or more and 4 or less carbon atoms, which may include a hydroxy group, with a group without a hydrogen atom of the hydroxy group of the polysaccharide or derivative thereof, which is the precursor compound of component (b1), preferably a hydroxyalkyl substituted product.

[0095]

<16> The textile detergent composition of any one of <7> to <15>, wherein the cationic group is a nitrogen-containing cation-containing group and preferably a quaternary ammonium group.

[0096]

<17> The textile detergent composition of any one of <7> to <16>, wherein the cationic group is a quaternary ammonium group, and three hydrocarbon groups bonded to the non-bridged quaternary ammonium group (2), all independently are a linear hydrocarbon group containing 1 or more and 4 or less carbon atoms, or a branched hydrocarbon group containing 3 or more and 4 or less carbon atoms, where a linear hydrocarbon group containing 1 or more and 4 or less carbon atoms is preferably is a group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group and an n-butyl group and a branched hydrocarbon group containing 3 or more and 4 or less carbon atoms, preferably is a group selected from the group consisting of an isopropyl group, a sec-butyl group, a t-butyl group and an isobutyl group.

[0097]

<18> The detergent composition for textiles according to any one of paragraphs <8> to <17>, in which the alkylene group of the bridge group (2) containing 1 or more and 4 or less carbon atoms, which may include a hydroxy group, an alkylene group containing 1 or more and 4 or less carbon atoms is one or more alkylene groups selected from the group consisting of a linear alkylene group containing 1 or more and 4 or less carbon atoms, which may include a hydroxy group, and a branched alkylene group containing 3 or more and 4 or less carbon atoms, which may include a hydroxy group.

[0098]

<19> The textile detergent composition according to any one of <7> to <18>, wherein in the polysaccharide derivative of component (b1) containing a cationic group, the degree of substitution of the cationic group is 0.001 or more, preferably 0.005 or more, and more preferably 0.01 or more, and 1 or less, preferably 0.7 or less, more preferably 0.4 or less, more preferably 0.35 or less, even more preferably 0.3 or less, even more preferably 0.25 or less and even more preferably 0.2 or less.

[0099]

<20> The textile detergent composition according to any one of <7> to <19>, wherein the weight average molecular weight of the polysaccharide or its derivative which is the precursor compound of component (b1) is 1000 or more, preferably 10000 or more, more preferably 30,000 or more, more preferably 50,000 or more, even more preferably 70,000 or more, even more preferably 100,000 or more, even more preferably 300,000 or more, and even more preferably 500,000 or more, and 3 ppm or less, and preferably 2, 5 million or less.

[0100]

<21> The textile detergent composition of any one of <7> to <20>, wherein the alkylene terephthalate unit is one or more selected from the group consisting of an ethylene terephthalate unit, a propylene terephthalate unit, and a butylene terephthalate unit; the alkylene isophthalate unit is one or more selected from the group consisting of an ethylene isophthalate unit, a propylene isophthalate unit, and a butylene isophthalate unit; and the polyoxyalkylene unit is one or more selected from the group consisting of a polyoxyethylene unit, a polyoxypropylene unit, and a polyoxyethylene polyoxypropylene unit.

[0101]

<22> The textile detergent composition of any one of <7> to <21>, wherein (number of moles of an oxyalkylene unit)/((number of moles of one or more units selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit) The ratio of the number of moles of the oxyalkylene unit to the number of moles of one or more units to the number of moles of one or more units selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit is 0.6 or less, preferably 0.5 or less, and more preferably 0.4 or less, and 0 or more, and preferably 0.1 or more.

[0102]

<23> The textile detergent composition according to any one of <7> to <22>, wherein the weight average molecular weight of component (b2) is 300 or more, preferably 500 or more, and more preferably 1,000 or more, and 20,000 or less, and preferably 15000 or less.

[0103]

<24> The textile detergent composition of any one of <7> to <23>, wherein component (b3) is a polyalkylene imine containing a polyoxyalkylene group, wherein the oxyalkylene group of the polyoxyalkylene group is an oxyalkylene group containing 2 or more and 3 or less carbon atoms, preferably one or more groups selected from the group consisting of an oxyethylene group and an oxypropylene group; the alkylene group of the polyalkyleneimine is an alkylene group having 2 or more and 6 or less carbon atoms, more preferably one or more groups selected from the group consisting of an ethylene group and a butylene group attached in various ways; the number of polyoxyalkylene groups associated with the polyalkyleneimine is on average 3 or more and 100 or less, based on the active hydrogen atom of the polyalkyleneimine; and the weight average molecular weight of the polyalkyleneimine is 300 or more, preferably 500 or more, and more preferably 1000 or more, and 1 million or less, preferably 500,000 or less, and more preferably 100,000 or less.

[0104]

<25> The textile detergent composition according to any one of <7> to <24>, wherein component (B) is one or two or more polysaccharide derivatives containing one or more groups selected from the group consisting of hydrocarbon a group containing 1 or more and 18 or less carbon atoms, and a cationic group.

[0105]

<26> The textile detergent composition according to any one of <1> to <25>, wherein the textile detergent composition is a textile detergent composition (1) used by dilution in water, wherein the content of component (A) in detergent composition (1) for textiles is 5 wt.% or more, preferably 7 wt.% or more, and more preferably 10 wt.% or more, and 60 wt.% or less, preferably 50 wt.% or less and more preferably 40 mass% or less, and the content of component (B) is 0.1 mass% or more, and preferably 0.2 mass% or more, and 10 mass% or less, preferably 5 mass% or less, more preferably 3 wt% or less, and more preferably 1 wt% or less.

[0106]

<27> The textile detergent composition according to any one of <1> to <25>, wherein the textile detergent composition is the textile detergent composition (2) used as a washing liquid unchanged without dilution, where the content the component (A) in the detergent composition (2) for textiles is 0.005 mass% or more, preferably 0.01 mass% or more, and more preferably 0.1 mass% or more, and 1 mass% or less, and preferably 0.8 mass% or less, and the content of component (B) is 0.1 mg/kg or more, preferably 0.5 mg/kg or more, more preferably 1.0 mg/kg or more, and more preferably 3 0 mg/kg or more, and 800 mg/kg or less, preferably 500 mg/kg or less, more preferably 100 mg/kg or less, more preferably 50 mg/kg or less, even more preferably 30 mg/kg or less, even more preferably 10 mg/kg or less, and even more preferably 5 mg/kg or less.

[0107]

<28> Washing composition for textiles according to any one of paragraphs <1> to <27>, containing water.

[0108]

<29> The textile detergent composition of any one of <1> to <28>, further comprising a nonionic surfactant as component (C).

[0109]

<30> The textile detergent composition of <29>, wherein component (C) is a nonionic surfactant containing one or more groups selected from the group consisting of a hydroxy group and a polyoxyalkylene group.

[0110]

<31> The textile detergent composition of <29> or <30>, wherein component (C) is a nonionic surfactant containing a polyoxyalkylene group and having an HLB index of 7 or more, preferably 8 or more, more preferably 9 or more and more preferably 10 or more and 20 or less and preferably 19 or less.

[0111]

<32> The textile detergent composition according to any one of <29> to <31>, wherein the component (C) is a nonionic surfactant having an HLB index of 7 or more, preferably 8 or more, more preferably 9 or more and more preferably 10 or more and 20 or less and preferably 19 or less and is represented by the following general formula (C):

R ¹ (CO) _m O-(A ¹ O) _n -R ² (C)

in which R ¹ means an aliphatic hydrocarbon group containing 9 or more and 16 or less carbon atoms; R ² means a hydrogen atom or a methyl group; CO is a carbonyl group; m is a number equal to 0 or 1; the A ¹ O group is one or more groups selected from the group consisting of an ethyleneoxy group and a propyleneoxy group; and n means the average number of added moles and is a number equal to 3 or more and 50 or less.

[0112]

<33> The textile detergent composition of <32>, wherein in the general formula (C), the number of carbon atoms in R ¹ is 10 or more, and more preferably 11 or more, and preferably 15 or less, and more preferably 14 or less; aliphatic hydrocarbon group R ¹ means a group selected from the group consisting of an alkyl group and an alkenyl group; the A ¹ O group is a group containing an ethyleneoxy group; and n is 4 or more, more preferably 5 or more, and more preferably 6 or more.

[0113]

<34> The textile detergent composition according to any one of <29> to <33>, wherein the content of the component (C) in the textile detergent composition is 1 mass% or more, preferably 3 mass% or more, more preferably 5 wt% or more and more preferably 10 wt% or more and 60 wt% or less, preferably 50 wt% or less, and more preferably 45 wt% or less.

[0114]

<35> The detergent composition for textiles according to any one of <29> to <34>, wherein the mass ratio (C)/(B) of component (C) content to component (B) content is 2 or more, preferably 10 or more, more preferably 20 or more, and more preferably 30 or more, and 100 or less, preferably 90 or less, and more preferably 80 or less.

[0115]

<36> A method for washing textiles, including washing textiles with a washing liquid containing a washing composition for textiles according to any one of paragraphs <1> to <35> and water, wherein the content of component (A) in the washing liquid is 0.005 mass% or more, preferably 0.01 mass% or more, and more preferably 0.1 mass% or more, and 1 mass% or less, and preferably 0.8 mass% or less, and the content of the component (B) in the washing liquid equal to 0.1 mg/kg or more, preferably 0.5 mg/kg or more, more preferably 1.0 mg/kg or more, and more preferably 3.0 mg/kg or more, and 800 mg/kg or less, preferably 500 mg/kg or less, more preferably 100 mg/kg or less, more preferably 50 mg/kg or less, even more preferably 30 mg/kg or less, even more preferably 10 mg/kg or less, and even more preferably 5 mg/kg or less.

Examples

[0116]

<Composition Components>

[Component (A) or component (A')]

Component (A) or component (A') is an internal olefinsulfonate. Table 1 shows the distribution of the related sulfonate groups of the internal olefin sulfonates used in the Examples, Comparative Examples, Composition Examples, and Comparative Composition Examples. If component (A') is also component (D) then, for convenience, it is designated as component (A') because it is a comparative compound for component (A).

Component (A) or component (A') listed in Table 1 was obtained by sulfonation of internal olefins containing double bonds in different positions. Sodium hydroxide was used for neutralization after sulfonation. The relative contents of internal olefinsulfonates to which a sulfonate group is attached were determined by high performance liquid chromatography/mass spectroscopy (HPLC-MS). In particular, hydroxy-containing forms to which a sulfonate group is attached were separated by high performance liquid chromatography (HPLC) and each was examined by mass spectroscopy (MS) for identification. Each content was determined by the resulting peak area in HPLC-MS. In the present description, each content, determined by the area of the peak, was calculated as a mass.

It should be noted that the devices and conditions used for research were as follows: HPLC device “LD20ASXR” (manufactured by Shimadzu Corporation); column: "ODS Hypersil (R)" (4.6×250 mm, particle size: 3 μm, manufactured by Thermo Fisher Scientific K.K.); sample preparation (1000 times diluted with methanol); eluent A (10 mM ammonium acetate with addition of water); eluent B (10 mM ammonium acetate solution with addition of methacrylonitrile/water = 95/5 (v/v)); gradient mode (0 min (A/B=60/40) → from 15.1 to 20 min (30/70) → from 20.1 to 30 min (60/40); MS instrument “LCMS-2020” (manufactured by Shimadzu Corporation); ESI detection (negative ion detection, m/z: 321.10 (component (A) containing 16 carbon atoms); column temperature (40°C); flow rate (0.5 ml/min ); and injection volume (5 μl).

[0117]

[Component (B)]

Synthesis (b-1)

90 g of Hydroxyethylcellulose (Ashland, Natrosol 250 GR, weight average molecular weight: 300,000, degree of substitution of hydroxyethyl group (MS): 2.5) were placed in a 1 L separating flask and nitrogen was bubbled through. 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 48% aqueous sodium hydroxide solution was added and further mixed in within 15 min. Then, 5.6 g of lauryl glycidyl ether (Yokkaichi Chemical Co., Ltd., LA-EP) was added and alkylated at 80° C. for 13 hours. , SY-GTA80) and cationized at 50° C. for 1.5 hours. Then, 10.9 g of 90% aqueous acetic acid was added and stirred for 30 minutes, and thus a neutralization reaction was carried out.

The resulting suspension was placed in two equal portions of 500 ml into centrifuge bottles and centrifuged in a high speed refrigerated centrifuge (Hitachi Koki Co., Ltd., CR21G III). The supernatant was discarded and an 85% aqueous IPA solution was added in the same amount as that removed and redispersed. The operations of centrifugation and redispersion were repeated once more, and after the third centrifugation, the precipitate was collected. The resulting precipitate was dried under reduced pressure using a vacuum dryer (ADVANTEC CO., LTD., VR-420) at 80° C. overnight and ground in a high efficiency mill (WARING COMMERCIAL, MX-1200XTM) to give (b-1) in in the form of a powdered composition of a cellulose derivative. In the resulting (b-1), the degree of substitution with the lauryl group was 0.030 and the degree of substitution with the cationic group was 0.023.

[0118]

Synthesis of (b-2) and (b-3)

To obtain (b-2) and (b-3) in the above synthesis (b-1), the weight average molecular weight of the raw material - hydroxyethylcellulose (the degree of substitution of the hydroxyethyl group remained the same), the amount of loaded lauryl glycidyl ether, glycidyltrimethylammonium chloride, reaction conditions, etc. .P. changed accordingly.

(b-2)

The weight average molecular weight of the raw material hydroxyethyl cellulose for component (b-2) was 150,000, the degree of substitution of the lauryl group was 0.019, and the degree of substitution of the cationic group was 0.10.

(b-3)

The weight average molecular weight of the raw material hydroxyethyl cellulose for component (b-3) was 2.1 million, the degree of substitution of the lauryl group was 0.016, and the degree of substitution of the cationic group was 0.092.

[0119]

Synthesis (b-4)

90 g of Hydroxyethylcellulose (Dow Inc., QP-100MH, weight average molecular weight: 2.1 million, degree of substitution of hydroxyethyl group (MS): 2.5) were placed in a 1 L separating flask and nitrogen was bubbled through. 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 48% aqueous sodium hydroxide solution was added and further mixed in within 15 min. Then 10.1 g of 1,2-epoxyoctane (Wako Pure Chemical Industries, Ltd.) was added and alkylated at 80°C for 13 hours. Then 10.9 g of 90% aqueous acetic acid was added and stirred for 30 minutes and thus, a neutralization reaction was carried out.

The resulting suspension was placed in two equal portions of 500 ml into centrifuge bottles and centrifuged in a high speed refrigerated centrifuge (Hitachi Koki Co., Ltd., CR21G III). The supernatant was discarded and an 85% aqueous IPA solution was added in the same amount as that removed and redispersed. The operations of centrifugation and redispersion were repeated once more, and after the third centrifugation, the precipitate was collected. The resulting precipitate was dried under reduced pressure using a vacuum dryer (ADVANTEC CO., LTD., VR-420) at 80° C. overnight and ground in a high performance mill (WARING COMMERCIAL, MX-1200XTM) to give (b-4) in in the form of a powdered composition of a cellulose derivative. In the resulting (b-4), the degree of substitution of the hexyl group was 0.053.

[0120]

Synthesis (b-5) - (b-9)

To obtain (b-5) - (b-7) in the above synthesis (b-4), the weight average molecular weight of the raw material - hydroxyethyl cellulose was appropriately changed; instead of 1,2-epoxyoctane, other 1,2-epoxyalkanes were used, having hydrocarbon groups of a different length (the number of carbon atoms in the hydrocarbon group corresponded to the number in the hydrocarbon group of each compound); and loading amounts, reaction conditions, and the like. changed accordingly. In addition, stearyl glycidyl ether was used in place of 1,2-epoxyoctane, and loading amounts, reaction conditions, etc. were changed accordingly in the above synthesis (b-4) to obtain (b-8). In addition, lauryl glycidyl ether was used in place of 1,2-epoxyoctane, and loading amounts, reaction conditions, and the like were changed accordingly in the above synthesis (b-4) to obtain (b-9).

(b-5)

The weight average molecular weight of the raw material hydroxyethyl cellulose for component (b-5) (hydroxyethyl group substitution degree: 2.5) was 2.1 ppm and the decyl group substitution degree was 0.013.

(b-6)

The weight average molecular weight of the raw material hydroxyethyl cellulose for (b-6) (hydroxyethyl group substitution degree: 2.5) was 2.1 ppm and the lauryl group substitution degree was 0.015.

(b-7)

The weight average molecular weight of the raw material hydroxyethyl cellulose for (b-7) (degree of substitution of hydroxyethyl group: 2.5) was 2.1 ppm and the degree of substitution of palmityl group was 0.0059.

(b-8)

The weight average molecular weight of the raw material hydroxyethyl cellulose for (b-8 (hydroxyethyl substitution degree: 2.5)) was 2.1 million and the stearyl group substitution degree was 0.010.

(b-9)

The weight average molecular weight of the raw material hydroxyethyl cellulose for (b-9) (degree of substitution of hydroxyethyl group: 2.5) was 300,000 and the degree of substitution of lauryl group was 0.0096.

[0121]

Synthesis (b-10)

The same operations as in the synthesis of (b-1) were carried out and (b-10) was obtained with the difference that the amount of glycidyltrimethylammonium chloride was 18.2 g and no reaction with lauryl glycidyl ether was carried out.

(b-10)

The weight average molecular weight of the raw material hydroxyethyl cellulose for (b-10) (hydroxyethyl group substitution degree: 2.5) was 300,000 and the cationic group substitution degree was 0.14.

[0122]

Synthesis (b-11) and (b-12)

The same operations as in the synthesis of (b-1) were carried out and (b-11) and (b-12) were obtained, with the difference that the amount of glycidyltrimethylammonium chloride was changed accordingly and the reaction with lauryl glycidyl ether was not carried out.

(b-11)

The weight average molecular weight of hydroxyethyl cellulose feedstock for (b-11)n (degree of substitution by hydroxyethyl group: 2.5) was 300,000 and the degree of substitution by cationic group was 0.04.

[0123]

(b-12)

Polyoxyethylene terephthalate (Repel-O-Tex-SRP4 from Rhodia)

[0124]

The degree of substitution of component (B) and the weight average molecular weight of the precursor compound of component (B) were determined as follows.

(1) Determination of the degree of substitution

Pretreatment of the polysaccharide derivative

After dissolving 1 g of the polysaccharide derivative of component (B) in 100 g of water, the aqueous solution was sent to a dialysis membrane (Spectra/Por, threshold molecular weight: 1000) and subjected to dialysis for 2 days. The resulting aqueous solution was freeze dried in a freeze dryer (eyela, FDU-1100) to obtain a pretreated polysaccharide derivative.

[0125]

Calculation of the mass of the cationic group according to the Kjeldahl method

200 mg of the polysaccharide derivative pretreated as above was accurately weighed, and 10 ml of concentrated sulfuric acid and one Kjeldahl tablet (Merck) were added, and thermal decomposition was carried out in a Kjeldahl digester (manufactured by BUCHI Labortechnik AG, K-432). After completion of decomposition, 30 ml of ion-exchanged water was added to the sample, and the nitrogen content (wt %) of the sample was determined using a Kjeldahl automatic distillation apparatus (manufactured by BUCHI Labortechnik AG, K-370), and thus the mass of the cationic group was calculated.

[0126]

Calculation of the mass of the hydrocarbon group (alkyl group) according to the Zeisel method

200 mg of the Polysaccharide Derivative pretreated as above and 220 mg of adipic acid were accurately weighed into a 10 ml vial (mighty vial No. 3) and 3 ml of an internal standard solution (tetradecane/o-xylene=1/25 (vol. /v)) and 3 ml of hydrochloric acid, and the vial was sealed. In addition, a standard curve sample was prepared by adding 2.4 mg or 9 mg of 1-ioddecane in place of the polysaccharide derivative. Each sample was heated while stirring with a stirrer head using a heating block (manufactured by PIERCE, Reacti-Therm III Heating/Stirring module) at 160°C for 2 hours. After the sample was cooled to room temperature, the top layer (o-xylene layer) collected and analyzed by gas chromatography (GC) (Shimadzu Corporation, QD2010 plus) under the following conditions:

Analysis conditions with GC

Column: Agilent HP-1 (length: 30 m, liquid film thickness: 0.25 µm, internal diameter: 32 mm)

Sample division 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 amount: 2 µl.

The amount of detected 1-iododecane obtained by GC was used to determine the mass of the alkyl group in the sample.

[0127]

Determination of the mass of the hydroxyalkyl group

The mass of the hydroxyalkyl group was determined by quantifying the alkyl iodide formed using the hydroxyalkyl group in the same manner as in the above determination of the mass of the alkyl group.

[0128]

Calculation of the degrees of substitution of the cationic group and the alkyl group

The degrees of substitution of the cationic group and the alkyl group were calculated as molar averages by calculating the mass of the backbone of the polysaccharide derivative using the above masses of the cationic group and the alkyl group and the total mass of the sample and converting them all to the amount of substance (in moles).

[0129]

Weight Average Molecular Weight Measurement

The weight average molecular weight of hydroxyethyl cellulose (HEC), which is the precursor compound of component (B), was calculated as polyethylene glycol by GPC (Gel Permeation Chromatography).

The measurement conditions were as follows:

Column: TSKgel α-M

Eluent: 50 mmol/l LiBr, 1% CH ₃ COOH, ethanol/water=3/7

Temperature: 40°C

Flow rate: 0.6 ml/min.

[0130]

[Component (C)]

(c-1): polyoxyalkylene lauryl ether (compound obtained by adding an average of 9 moles of an ethyleneoxy group to 1 mole of lauryl alcohol, followed by an average of 2 moles of a propyleneoxy group, and followed by an average of 9 moles of an ethyleneoxy group; HLB=14.5)

(c-2): polyoxyethylene lauryl ether (compound obtained by adding an average of 14 moles of ethyleneoxy group to 1 mole of lauryl alcohol; HLB=15.4)

(c-3): polyoxyethylene alkyl ether (the alkyl group is a mixed alkyl group consisting of a lauryl group/myristyl group=8/2 (mass ratio); the average mole of added oxyethylene groups is 10 moles; and HLB=13.9 )

[Component (D)]

(d-1): sodium α-olefinsulfonate containing from 12 to 14 carbon atoms

[Water]

Ion exchanged water

[0131]

<Production of detergent composition (1) for textiles>

Using the above component contents, the textile detergent compositions (1) shown in Table 2 and Table 3 were obtained, and the textile detergent compositions (1) shown in Table 2 were tested for the following characteristics. The results are shown in table 2.

Washing compositions (1) for textiles shown in table 2 and table 3, in particular, were obtained as follows. A magnetic stir bar made of Teflon (R) 5 cm long was placed in a 200 ml glass beaker and weighed. Then 80 g of ion-exchanged water at 20°C, component (A) or component (A'), component (B), optional component (C), and the like. was placed in a beaker and the beaker was sealed on top with Saran Wrap (R).

The contents of the beaker were placed in a water bath at 60°C, placed on a magnetic stirrer and stirred at 100 rpm for 30 minutes, while the temperature of the water in the water bath was maintained in the range of 60±2°C. The water in the water bath was then replaced with tap water at 5°C and the composition in the beaker was cooled until the temperature was 20°C. Then, Saran Wrap (R) was removed and ion-exchanged water was added until the mass of the contents became 100 g, and re-stirred at 100 rpm for 30 seconds, and the washing compositions (1) for textiles shown in Table 2 were obtained. and table 3.

[0132]

<Production of detergent composition (2) for textiles>

Using the above contents of the components was obtained washing compositions (2) for textiles, shown in table 4.

Washing compositions (2) for textiles, shown in table 4, in particular, was obtained as follows. A magnetic stir bar made of Teflon (R), 8 cm long, was placed in a 1000 ml glass beaker and weighed. Then 800 g of water, the hardness of which was adjusted to 4°dH by adding calcium chloride and magnesium chloride in a mass ratio of 8:2 to ion-exchanged water at 20°C, component (A) or component (A'), component (B) , an optional component (C) and the like at the contents indicated in Table 4 were placed in a beaker and the beaker was sealed on top with Saran Wrap (R).

The contents of the beaker were placed in a water bath at 60°C, placed on a magnetic stirrer and stirred at 200 rpm for 30 minutes, while the temperature of the water in the water bath was maintained in the range of 60±2°C. The water in the water bath was then replaced with tap water at 5°C and the composition in the beaker was cooled until the temperature was 20°C. The Saran Wrap (R) was then removed and water, the hardness of which was adjusted to 4°dH by adding calcium chloride and magnesium chloride in a weight ratio of 8:2, to the ion-exchanged water at 20°C, was added until the weight of the content was 100 g , and re-mixed at 200 rpm for 30 s to obtain detergent compositions (2) for textiles shown in Table 4.

In Table 4, for example, 150 mg/kg, the concentration of component (A), corresponds to 0.015 wt.%.

In addition, in Table 4, the remainder of the washing composition (2) for textiles is water with a hardness of 4°dH added in an amount to bring the total weight of the composition to 1 kg.

[0133]

<Washing ability test>

???Using the washing composition (1) for textiles shown in Table 2, a washing ability study was carried out. The results are shown in Table 2. In addition, the washing power of the detergent composition (1) for textiles shown in Table 3 can also be examined as follows. In addition, the washing ability of the washing composition (2) for textiles shown in Table 4 can be examined by replacing the washing liquid indicated below with the washing composition (2) for textiles shown in Table 4.

(1) Pre-treatment of textiles containing chemical fibers

18 AIRism crew neck short sleeve T-shirts (fibre composition: polyester 89%, polyurethane 11%; manufactured by FAST RETAILING CO., LTD.; item # 182496; and size 4XL) were washed on a standard cycle using a fully automatic washing machine (manufactured by Panasonic Corporation, NA-F70PB1) five times in a row using for washing (4.8 g of EMULGEN 108 (manufactured by Kao Corporation); water amount: 48 L; washed for 12 minutes; rinsed twice; and spun for 3 min). Then, they were washed once with water only (amount of water: 48 L; washed for 12 minutes; rinsed twice; and wrung out for 3 minutes), further rinsed with running water using a two-chamber type washing machine (manufactured by Hitachi, Ltd., model : PS-H45L) until bubbles completely disappeared and dried at 24°C for 24 hours at 55% RH. Then they were cut into pieces measuring 6 cm × 6 cm.

[0134]

(2) Preparation of textiles for washing ability research

(2-1) Obtaining garments treated to impart stain repellency

The soil-repellent treatment was carried out with a shaker (Yamato Scientific Co., Ltd., Model No.: SA300). The water used for the treatment was wash water, the hardness of which was adjusted to 4°dH by adding calcium chloride and magnesium chloride in a weight ratio of 8:2 to the ion-exchanged water. Washing liquid was obtained by mixing component (A), component (B) and component (C) with washing water, so that the total amounts of components in the washing composition (1) for textiles shown in Table 2 were in the washing liquid at a concentration, equal to 150 mg/kg. 50 ml of washing liquid (24°C) and 5 pieces of textiles obtained in (1) above were placed in a 100 ml screw cap bottle (Maruemu Corporation, No. 8, 40 mm × 120 mm). The wash ratio was 20. The textiles were shaken in a horizontal plane with reciprocating motion in a shaker at 300 rpm for 10 minutes. After treatment, they were wrung out for 1 minute in a double chamber type washing machine (manufactured by Hitachi, Ltd., model: PS-H45L). Then, 50 ml of washing water (24° C.) and the resulting textiles were placed in a 100 ml screw cap vial. The textiles were rinsed in a shaker at 340 rpm for 3 minutes. After rinsing, they were wrung out for 1 minute in a double-chamber type washing machine and dried at 24°C for 24 hours at 55% RH to obtain textiles for washing ability testing.

[0135]

(2-2) Obtaining Stain Repellency Treated Garments Artificially Contaminated with Model Skin Oil

0.1 ml of Model Sebum Solution for Artificial Pollution obtained by mixing 0.02% Sudan III (manufactured by Tokyo Chemical Industry Co., Ltd.) as a pigment with Model Sebum having the following composition was applied to the middle of each textile the product obtained in (2-1) above, in the form of a circle with a diameter of 4 cm, and the textiles were dried for 1 hour by blowing air at a constant temperature in a drying chamber (manufactured by ADVANTEC CO., LTD., DRM420DA) at a temperature of 60° C. The textiles were then dried in a 20° C., 70% RH environment for 24 hours to obtain a stain-repellent treated garment artificially contaminated with model sebum. * Model sebum composition: lauric acid: 0.54 wt.%, myristic acid: 1.78 wt.%, pentadecanoic acid: 0.91 wt.%, palmitic acid: 3.53 wt.%, heptadecanoic acid: 0 .30 wt.%, linoleic acid: 1.40 wt.%, oleic acid: 19.74 wt.%, triolein: 46.00 wt.%, squalene: 13.80 wt.%, cholesterol: 2.90 wt. .%, sterol ester: 3.00 wt.%, and n-hexadecyl palmitate: 6.10 wt.% (total: 100 wt.%).

[0136]

(2-3) Washing study

The washing operation was carried out using a tergotometer (manufactured by Ueshima Seisakusho Co., Ltd., MS-8212). The treatment water was wash water, the hardness of which was adjusted to 4°dH by adding calcium chloride and magnesium chloride in a weight ratio of 8:2 to the ion-exchanged water. Washing liquid was obtained by mixing component (A), component (B) and component (C) with washing water, so that the total amounts of components in the washing composition (1) for textiles shown in Table 2 were in the washing liquid at a concentration, equal to 600 ml of washing liquid and 5 pieces of textiles artificially soiled with model sebum obtained in (2-2) above were placed in a 1 L stainless steel beaker for washing research (washing ratio: 300). The temperature of the washing liquid was 20°C. Clothes artificially soiled with model sebum were washed using a tergotometer at 85 rpm for 10 minutes. After washing, it was rinsed in 5 liters of stored water. After rinsing, it was wrung out and dried at 24° C. for 24 h at 55% RH.

[0137]

(2-4) Examination of the washing degree

The washing rates obtained above in the washing study in (2-3) clothes artificially soiled with model sebum were set as follows and an average value was determined for 5 pieces. The results are shown in Table 2. The reflectance at 460 nm of the original garment before soiling and the garment before and after washing was measured with a differential colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., SE-2000), and the wash rate (%) was determined according to the formula below. Calibration was performed using a standard reflector (white, X: 94.03, Y: 95.96, Z: 113.16). It should be noted that the values shown in Table 2 are the average values of the degrees of washing for 5 pieces. The larger the value of the degree of washing, the better the washing ability.

Wash rate (%) = 100×[(reflectivity after washing - reflectivity before washing)/(reflectivity of the original garment - reflectivity before washing)]

[0138]

[0139]

[Table 2 ]

[0140]

[Table 3]

[0141]

[Table 4]

Claims (25)

1. Washing composition for textiles containing the following component (A), the following component (B) and the following component (C): component (A): an internal olefinsulfonate containing 16 or more and 24 or less carbon atoms, where the ratio of the mass of an internal olefinsulfonate (IO-1S) containing 16 or more and 24 or less carbon atoms containing a sulfonate group at position 2 or further and position 4 or closer, to the mass of internal olefinsulfonate (IO-2S) containing 16 or more and 24 or less carbon atoms, containing a sulfonate group in position 5 or more, which has the form (IO-2S)/(IO-1S), equal to 0.30 or more and 3 or less; and component (B): one or more soil-repellent agents selected from: as component (b1), one or two or more polysaccharide derivatives containing one or more groups selected from the group consisting of a cationic group and a hydrocarbon group containing 1 or more and 18 or less carbon atoms, where in the polysaccharide derivative of component (b1) containing a hydrocarbon group containing 1 or more and 18 or less carbon atoms, the degree of substitution of the hydrocarbon group containing 1 or more and 18 or less carbon atoms is 0.0001 or more and 0.4 or less; and in the polysaccharide derivative of component (b1) containing a cationic group, the degree of substitution of the cationic group is 0.001 or more and 0.4 or less; component (C): a nonionic surfactant having an HLB index of 7 or more and 20 or less, and having the following general formula (C): R ¹ (CO) _m O-(A ¹ O) _n -R ² , (C) in which R ¹ means an aliphatic hydrocarbon group containing 9 or more and 16 or less carbon atoms; R ² means a hydrogen atom or a methyl group; CO is a carbonyl group; m is a number equal to 0 or 1; the A ¹ O group is one or more groups selected from the group consisting of an ethyleneoxy group and a propyleneoxy group; and n means the average number of added moles and is a number equal to 3 or more and 50 or less, where mass ratio. (C)/(B) the content of component (C) to the content of component (B) is 2 or more and 100 or less. 2. The textile detergent composition according to claim 1, wherein the content of α-olefin sulfonate in the internal olefin sulfonate of component (A) is 10% by mass or less and 0.01% by mass or more. 3. The detergent composition for textiles according to claim 1 or 2, wherein the content of component (A) in the total amount of anionic surfactants contained in the detergent composition for textiles is 50 wt.% or more and 100 wt.% or less. 4. Washing composition for textiles according to any one of paragraphs. 1-3, in which component (b1) is a polysaccharide derivative in which one or more groups selected from the group consisting of a cationic group and a hydrocarbon group containing 1 or more and 18 or fewer carbon atoms are linked, directly or through a bridging group, to a group without an atom hydrogen of the hydroxy group of the polysaccharide or its derivative, which is a precursor compound; and if the cationic group is bonded to a group without a hydrogen atom of the hydroxy group, it is bonded to it directly or through a bridging group (2), and if the hydrocarbon group is bonded to a group without a hydrogen atom of the hydroxy group, it is bonded to it directly or through a bridging group (1), where the bridging group (1) is one or more groups selected from the group consisting of: an alkyleneoxy group containing 1 or more and 3 or less carbon atoms, which may contain a hydroxy group; a polyoxyalkylene group in which the alkylene group is an alkylene group containing 1 or more and 3 or less carbon atoms; a carbonyl group; a carbonyloxy group; and an oxycarbonyl group; and the bridging group (2) is an alkylene group containing 1 or more and 4 or less carbon atoms, which may include a hydroxy group. 5. A laundry detergent composition according to claim 4, wherein the polysaccharide is one or more polysaccharides selected from the group consisting of cellulose, guar gum, or starch. 6. Washing composition for textiles according to any one of paragraphs. 1-5, in which the weight average molecular weight of the polysaccharide or its derivative, which is the precursor compound of component (b1), is 1000 or more and 3 ppm or less. 7. Washing composition for textiles according to any one of paragraphs. 1-6, in which component (B) is one or two or more polysaccharide derivatives containing one or more groups selected from the group including a hydrocarbon group containing 1 or more and 18 or less carbon atoms, and a cationic group . 8. Washing composition for textiles according to any one of paragraphs. 1-7, where the detergent composition for textiles is a detergent composition (1) for textiles, used by dilution in water; and the content of the component (A) in the detergent composition (1) for textiles is 5 wt.% or more and 50 wt.% or less, and the content of the component (B) is 0.1 wt.% or more and 10 wt. % or less. 9. Washing composition for textiles according to any one of paragraphs. 1-7, where the washing composition for textiles is a washing composition (2) for textiles, used as a washing liquid in unchanged form without dilution; and the content of the component (A) in the detergent composition (2) for textiles is 0.005 wt% or more and 1 wt% or less, and the content of the component (B) is 0.1 mg/kg or more and 800 mg/ kg or less. 10. Washing composition for textiles according to any one of paragraphs. 1-9 containing water. 11. Washing composition for textiles according to any one of paragraphs. 1-10, wherein the content of the component (C) in the detergent composition for textiles is 1% by mass or more and 60% by mass or less. 12. A method of washing textiles, including washing textiles with a washing liquid containing a washing composition for textiles according to any one of paragraphs. 1-11 and water, wherein the content of the component (A) in the washing liquid is 0.005 mass% or more and 1 mass% or less, and the content of the component (B) in the washing liquid is 0.1 mg/kg or more and 800 mg /kg or less.