JP2021120423A - Liquid detergent composition for drum-type washing machine - Google Patents

Abstract

To provide a liquid detergent composition for drum-type washing machines capable of finishing fiber products that could not be achieved into soft feeling only with a detergent even when water used for washing is at low temperature, in the cleaning by the drum-type washing machine.SOLUTION: A liquid detergent composition for drum-type cleaning machines containing (A) an internal olefinic sulphonate of 1 mass% or larger and 50 mass% or smaller, and (B) an anionic surfactant other than an internal olefin sulfonate of 0.1 mass% or larger and 20 mass% or smaller, (C) nonionic surfactant of 0.1 mass or larger and 20 mass% or smaller, (D) silicone of 0.02 mass or larger and 5 mass% or smaller, and water, in which the ratio of (A1) the internal olefin sulfonate having carbon number 18 in (A) is 80 mass% or larger.SELECTED DRAWING: None

Description

The present invention relates to a liquid detergent composition for a drum-type washing machine.

In recent years, the performance that consumers demand from liquid detergents for textile products has diversified, and it is also required that not only the cleaning performance but also the cleaning performance such as flexibility is not impaired.

Conventionally, an anionic surfactant, particularly an alkylbenzene sulfonate, an olefin sulfonate, or an internal olefin sulfonate obtained by using an internal olefin having a double bond inside instead of the end of the olefin chain as a raw material, has 2 carbon atoms. Nonionic surfactants containing ~ 3 oxyalkylene groups are widely used as cleaning components for household and industrial use.

Patent Documents 1 to 3 describe an internal olefin sulfonate having a specific carbon number and a detergent composition containing the same. Patent Documents 1 and 2 describe that the hair is excellent in foaming property and foam quality at the time of washing hair. Patent Document 3 describes that the fiber is softened when used in combination with a specific nonionic surfactant. Patent Document 4 describes that a texture such as flexibility can be imparted to a textile product by using a predetermined internal olefin sulfonate in a predetermined washing method. Patent Document 5 describes that the water absorption of a textile product can be maintained by using a predetermined internal olefin sulfonate in a predetermined washing method. Patent Document 6 discloses that a predetermined internal olefin sulfonate is used as a modifier for softening a textile product. Patent Document 7 discloses an amphoteric aqueous liquid detergent composition containing a surfactant system containing alkylethoxysulfate, a nonionic surfactant, and soap, a predetermined defoaming agent, and a structural agent. Since these surfactants have relatively high water solubility at low temperatures and foaming at low temperatures is relatively gentle, there are few problems during use in winter.

Japanese Unexamined Patent Publication No. 2014-077126 Japanese Unexamined Patent Publication No. 2014-076988 JP-A-2017-214567 Japanese Unexamined Patent Publication No. 2017-214678 JP-A-2018-104880 JP-A-2018-66102 Special Table 2013-521377

The foaming property and foam quality of the internal olefin sulfonate can be a problem in cleaning textile products depending on the situation. In general, as a household fully automatic washing machine, in addition to the vertical type (for example, pulsator type) that has been conventionally used, there is a fully automatic washing machine called a drum type that has become widely used in recent years. Drum-type washing machines tend to foam more depending on how they are washed by tapping textile products. If there is a lot of foaming, the cleanability by tapping with the foam as a cushion is lowered, and the rinsing process is strengthened by the sensor, so that the amount of water used increases. In addition, this tendency is particularly remarkable in washing at low temperature, but in the social situation where energy saving is desired, it is permissible to increase the amount of water used and wash at a high temperature such as washing water. It is difficult to wash and can be a particular problem in winter. The present inventors have an internal olefin sulfonate having a specific carbon number, which tends to have strong foaming in washing such as a drum type washing machine, and has a property of softening a textile product, but at a low temperature. It was found that the drum-type cleaning in Japan did not fully demonstrate its ability and could be further enhanced.

The present invention is a liquid for a drum-type washing machine that can finish a textile product with a soft texture that could not be achieved by a detergent alone, even if the water used for washing is low temperature in washing with a drum-type washing machine. A detergent composition is provided.

In the present invention, (A) internal olefin sulfonate [hereinafter referred to as (A) component] is 1% by mass or more and 50% by mass or less, and (B) an anionic surfactant other than internal olefin sulfonate [hereinafter, (B). ) Component] is 0.1% by mass or more and 20% by mass or less, (C) Nonionic surfactant [hereinafter referred to as (C) component] is 0.1% by mass or more and 20% by mass or less, (D) Silicone [ Hereinafter referred to as component (D)] 0.02% by mass or more and 5% by mass or less, and a liquid detergent composition for a drum-type washing machine containing water.
The ratio of the internal olefin sulfonate having 18 carbon atoms (A1) in the component (A) [hereinafter referred to as the component (A1)] is 80% by mass or more.
The present invention relates to a liquid detergent composition for a drum-type washing machine.

The present invention also relates to a method for washing a textile product, in which the textile product is washed by the drum type washing machine using the liquid detergent composition for a drum type washing machine of the present invention.

According to the present invention, with respect to washing using a drum-type washing machine, it is possible to obtain a liquid detergent composition for textile products that can impart flexibility that cannot be obtained with conventional detergent compositions to textile products regardless of the season. .. Further, according to the present invention, in the case of a washing method in which the detergent composition is used in a drum-type washing machine to carry out the steps of washing, dehydrating and drying without taking out the object to be washed from the tub, finally. A washing method is provided that can give the textile a texture with a very preferred softness.

In the present invention, as a method for evaluating the flexibility, a method for evaluating the flexibility of the textile product after dehydration is also used. This evaluation method not only has the conventional flexibility after drying, but also has less entanglement between the objects to be washed after dehydration, can be an index for gently finishing the textile product without damaging it, and softens the texture of the finished textile product. It has been found to be an indicator of detergent compositions for smooth finishes. The difference in the flexibility of the textile product after dehydration can be perceived by touch, and the difference in the present invention is so clear that it facilitates the comparison of favorable textures.

[Liquid detergent composition for drum-type washing machines]
<Ingredient (A)>
The component (A) of the present invention is an internal olefin sulfonate. The internal olefin sulfonate of the component (A) may be an internal olefin sulfonate having 12 or more carbon atoms and 16 or more and 24 or less carbon atoms.
The ratio of the internal olefin sulfonate [(A1) component] having 18 carbon atoms in the component (A) is 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and preferably. It is 100% by mass or less, and may be 100% by mass. The internal olefin sulfonate having a carbon number other than 18 has a carbon number of preferably 12 or more, more preferably 14 or more, still more preferably 16 or more, and preferably 24 or less, more preferably 22 or less, still more preferably. 20 or less internal olefin sulfonates.
The carbon number of the component (A) and the component (A1) represents the carbon number of the internal olefin covalently bonded to the sulfonate.
In the present invention, by using a predetermined amount of the component (A1) as the component (A), excellent flexibility can be imparted to the textile product by washing with a drum type washing machine.
The liquid detergent composition for a drum-type washing machine of the present invention preferably contains an internal olefin sulfonate having 12 or more carbon atoms and 16 to 24 carbon atoms as a component (A), and (A) in this carbon number range. Among the components, it contains an internal olefin sulfonate in which the proportion of the component (A1) is 80% by mass or more.
In the present invention, the contents of the component (A) and the component (A1) are the amounts converted into sodium salts unless otherwise specified. That is, the mass% or mass ratio of the component (A) and the component (A1) is calculated in terms of sodium. Further, the description described below as the component (A) can also be applied to the component (A1).

The internal olefin sulfonate of the component (A) contains 80% by mass or more, preferably 90% by mass or more, more preferably an internal olefin having 18 carbon atoms (an olefin having a double bond inside the olefin chain) as a raw material. A sulfonate obtained by sulfonated, neutralized and hydrolyzed an internal olefin containing 95% by mass or more.

Such internal olefins also include those containing a trace amount of so-called alpha olefin (hereinafter, also referred to as α-olefin) in which the position of the double bond exists at the 1st position of the carbon chain. Further, when the internal olefin is sulfonated, β-saltone is quantitatively generated, and a part of β-saltone is changed to γ-saltone and olefin sulfonic acid, which are hydroxy in the neutralization / hydrolysis step. Conversion to alkane sulfonates and olefin sulfonates (eg, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxy group of the obtained hydroxyalkane sulfonate is inside the alkane chain, and the double bond of the olefin sulfonate is inside the olefin chain. Further, the obtained product is mainly a mixture of these, and a part thereof is a hydroxyalkane sulfonate having a hydroxy group at the end of the carbon chain, or an olefin having a double bond at the end of the carbon chain. It may contain trace amounts of sulfonate.
In the present specification, each of these products and a mixture thereof are collectively referred to as an internal olefin sulfonate (component (A)). Further, the hydroxyalkane sulfonate is referred to as a hydroxy form of an internal olefin sulfonate (hereinafter, also referred to as a HAS form), and an olefin sulfonate is referred to as an olefin form of an internal olefin sulfonate (hereinafter, also referred to as an IOS form).
The mass ratio of the HAS form and the IOS form of the compound in the component (A) can be measured by a high performance liquid chromatography mass spectrometer (hereinafter abbreviated as HPLC-MS). Specifically, the mass ratio can be obtained from the HPLC-MS peak area of the component (A).

Examples of the salt of the internal olefin sulfonate include an alkali metal salt, an alkaline earth metal (1/2 atom) salt, 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 alkanol ammonium salt having 2 or more and 6 or less carbon atoms, which will be described later. Organic ammonium salts also include amine salts. From the viewpoint of versatility, the salt of the internal olefin sulfonate is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt.

As is clear from the above production method, the sulfonic acid group of the internal olefin sulfonate of the component (A) is present inside the carbon chain of the internal olefin sulfonate, that is, the olefin chain or the alkane chain, and is a part thereof. In some cases, a trace amount of a sulfonic acid group present at the end of the carbon chain may be contained.

The content of the internal olefin sulfonate having a sulfonic acid group at the 5-position or higher, preferably the 5-position or higher and the 9-position or lower in the component (A) is preferably 5% by mass from the viewpoint of improving the flexibility of the fiber. More preferably 10% by mass or more, further preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 45% by mass. Below, it is more preferably 40% by mass or less. The content of the internal olefin sulfonate having a sulfonic acid group at the 5-position or higher, preferably the 5-position or higher and the 9-position or lower in the component (A1) is also preferably in this range.

The content of the internal olefin sulfonate [hereinafter sometimes referred to as (IO-1S)] in which the sulfonic acid group is present at the 2-position or higher and 4-position or lower in the component (A), and the sulfonic acid group at the 5-position or higher. (IO-1S) / (IO-2S) is a mass ratio with the content of the internal olefin sulfonate [hereinafter sometimes referred to as (IO-2S)] present at the 5-position or higher and 9-position or lower. From the viewpoint of improving the flexibility of the fiber, it is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and more preferably 10 or less, more preferably 6 or less, still more preferably. It is 4 or less. The mass ratio of (IO-1S) / (IO-2S) in the component (A1) is also preferably in this range.

The content of each compound having a different position of the sulfonic acid group in the component (A) can be measured by HPLC-MS. The content of each compound having a different sulfonic acid group position in the present specification is determined as a mass ratio based on the HPLC-MS peak area of the compound having the sulfonic acid group at each position in the total HAS form of the component (A). And.

The content of the olefin sulfonate having a sulfonic acid group at the 1-position in the component (A) is good flexibility for the fiber even when the temperature of the water used for washing is as low as 0 ° C. or higher and 15 ° C. or lower. From the viewpoint of imparting properties, preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, and the production cost in the component (A). From the viewpoint of reduction and improvement of productivity, it is preferably 0.01% by mass or more. The content of the olefin sulfonate having a sulfonic acid group at the 1-position in the component (A1) is also preferably in this range.
The position of the sulfonic acid group of these compounds is the position in the olefin chain or the alkane chain.

The internal olefin sulfonate can be a mixture of hydroxy and olefinic compounds. The mass ratio (olefin / hydroxy) of the olefin content of the internal olefin sulfonate and the hydroxy content of the internal olefin sulfonate in the component (A) is 0/100 or more, and further 5 /. It can be 95 or more, 50/50 or less, 40/60 or less, 30/70 or less, and 25/75 or less.

The mass ratio of the hydroxy form content of the internal olefin sulfonate to the olefin content of the internal olefin sulfonate in the component (A) is determined from the component (A) by the method described in Examples by HPLC-MS. Can be measured with.

The component (A) can be produced, for example, by sulfonated, neutralized and hydrolyzed an internal olefin containing a predetermined amount of an internal olefin having 18 carbon atoms, preferably an internal olefin having 18 carbon atoms, as a raw material. .. The sulfonate reaction can be carried out by reacting 1 mol of the internal olefin with 1.0 to 1.2 mol of sulfur trioxide gas. The reaction temperature can be 20 to 40 ° C.
Neutralization is carried out by reacting an alkaline aqueous solution such as sodium hydroxide, ammonia, or 2-aminoethanol in an amount of 1.0 to 1.5 mol times the theoretical value of the sulfonic acid group. The hydrolysis reaction may be carried out at 90 to 200 ° C. for 30 minutes to 3 hours in the presence of water. These reactions can be carried out continuously. After the reaction is completed, it can be purified by extraction, washing or the like.
In producing the internal olefin sulfonate (A), sulfonate, neutralization, and hydrolysis may be performed using the raw material internal olefin mainly containing the internal olefin having 18 carbon atoms, and the internal olefin has 18 carbon atoms. It is also possible to mix sulfonated, neutralized, and hydrolyzed raw material internal olefins composed of the above, and if necessary, multiple types of internal olefin sulfonates having different carbon numbers prepared in advance. good.

In the present invention, the internal olefin means an olefin having a double bond inside the olefin chain as described above. The internal olefin used for the component (A) may be used alone with only 18 carbon atoms, or may be used in combination of two or more olefins having a carbon number other than 18.

When the internal olefin of the raw material is sulfonated, neutralized, and hydrolyzed to obtain the internal olefin sulfonate of the component (A) containing a specific amount of the component (A1), the double bond in the internal olefin of the raw material is at the 2-position. From the viewpoint of improving the flexibility of the fiber, the total content of the existing internal olefins is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more. , More preferably 30% by mass or more, even more preferably 35% by mass or more, even more preferably 40% by mass or more, and preferably 60% by mass or less.

The total content of the so-called alpha olefin, which has a double bond at the 1st position in the raw material internal olefin, is good flexibility for the fiber even when the temperature of the water used for washing is as low as 0 ° C. or higher and 15 ° C. or lower. From the viewpoint of imparting properties, it is preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, still more preferably 3% by mass or less, and reducing production costs and improving productivity. From the viewpoint of the above, it is preferably 0.01% by mass or more.

From the viewpoint of solution stability, the content of the olefin having a double bond at the 6th position or higher in the raw material internal olefin is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less. , More preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably. It is 10% by mass or less. The maximum value of the position of the double bond in the olefin inside the raw material differs depending on the number of carbon atoms.

The distribution of double bonds in the raw material internal olefin can be measured by, for example, a gas chromatograph mass spectrometer (hereinafter abbreviated as GC-MS). Specifically, each component having a different carbon chain length and double bond position is accurately separated by a gas chromatograph analyzer (hereinafter abbreviated as GC), and each component is subjected to a mass spectrometer (hereinafter abbreviated as MS). Then, the double bond position can be identified, and the ratio of each can be obtained from the GC peak area.

The component (A) is an important base that not only cleans textile products but also gives a soft finish to textile products, but its effect is insufficient especially in low temperature treatment in a drum type washing machine. The present inventors have found. Further, this tendency becomes stronger as the amount of the component (A1) effective for imparting flexibility is increased, and in the present invention, in order to solve the problem, the following components (B) to (D) are blended and therefore. We propose the compounding conditions of.

<Ingredient (B)>
The component (B) of the present invention is an anionic surfactant other than the internal olefin sulfonate. The component (B) can increase the flexibility of the component (A).

The component (B) includes a compound (B1) represented by the following general formula (b1) [hereinafter referred to as a component (B1)] and a compound represented by the general formula (b2) (B2) [hereinafter referred to as a component (B2)). ] And the compound (B3) represented by the general formula (b3) [hereinafter, referred to as the component (B3)], one or more compounds are preferable.
R ^1b- O- (PO) _m (EO) _n- SO ₃ M (b1)
(In the formula (b1), R ^1b represents an alkyl group having 8 or more carbon atoms and 22 or less carbon atoms, the carbon atom bonded to the oxygen atom is the first carbon atom, PO represents a propyleneoxy group, and EO is an ethyleneoxy group. EO and PO may be block or random bond, m and n are average addition moles, m is 0 or more and 5 or less, n is 0 or more and 16 or less, and M is hydrogen. Atomic, alkali metal, alkaline earth metal (1/2 atom), ammonium or organic ammonium.)
R ^2b- B-SO ₃ M (b2)
(In the formula (b2), R ^2b represents an alkyl group having 9 or more and 21 or less carbon atoms, B represents a benzene ring, and the carbon atom of R ^2b bonded to the carbon atom of B is a secondary carbon atom. M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), ammonium or organic ammonium. The sulfonic acid group is bonded to the para position with respect ^{to R 2b bonded to B.)}
R ^3b- CH (SO ₃ M) COOR ^4b (b3)
(In the formula (b3), R ^3b represents an alkyl group having 6 or more and 20 or less ^{carbon atoms, R 4b} represents an alkyl group having 1 or more and 6 or less carbon atoms, and M represents a hydrogen atom, an alkali metal, or an alkaline earth metal (alkali earth metal). 1/2 atom), indicating ammonium or organic ammonium.)

In the general formula (b1), R ^1b is preferably an alkyl having 9 or more carbon atoms, more preferably 10 or more, still more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, still more preferably 14 or less. Is the basis. R1 is preferably a linear alkyl group.
In the general formula (b1), m is preferably 4 or less, more preferably 3 or less.
In the general formula (b1), n is preferably 0.5 or more, more preferably 1 or more, and preferably 10 or less, more preferably 5 or less, still more preferably 4 or less.
In the general formula (b1), M is preferably a hydrogen atom, an alkali metal such as sodium and potassium, an alkaline earth metal (1/2 atom) such as magnesium and calcium, or an organic ammonium. The organic ammonium salt may be a salt of the amine component (D) described later. M is more preferably an alkali metal such as sodium or potassium, alkanolammonium such as monoethanolammonium or diethanolammonium, and even more preferably sodium.

As the component (B1), the number of carbon atoms of the alkyl group is 12 or more and 14 or less, the average number of added moles of propioxy group is 0 or more and 4 or less, and the average number of added moles of ethyleneoxy group is 1 or more and 4 or less (poly). Oxypropylene) polyoxyethylene alkyl ether sulfate sodium salt is preferable. That is, the component (B1) is preferably a compound in the general formula (b1) in which R ^1b is an alkyl group having 12 or more and 14 or less carbon atoms, m is 0 or more and 4 or less, n is 1 or more and 4 or less, and M is sodium. ..

In the general formula (b2), R ^2b is an alkyl group having 9 or more carbon atoms, preferably 10 or more, more preferably 11 or more, and preferably 18 or less, more preferably 16 or less, still more preferably 14 or less. ..
In the general formula (b2), M is preferably a hydrogen atom, an alkali metal such as sodium and potassium, an alkaline earth metal (1/2 atom) such as magnesium and calcium, or an organic ammonium. The organic ammonium salt may be a salt of the amine component (D) described later. M is more preferably an alkali metal such as sodium or potassium, alkanolammonium such as monoethanolammonium or diethanolammonium, and even more preferably sodium.

As the component (B2), a p-alkylbenzene sulfonate having an alkyl group having 11 or more and 14 or less carbon atoms is preferable, and a p-alkylbenzene sulfonic acid sodium salt having an alkyl group having 11 or more and 14 or less carbon atoms is more preferable. That is, as the component (B2), in the general formula (b2) ^{, a compound in which R 2b} is an alkyl group having 11 or more and 14 or less carbon atoms and M is sodium is preferable.

In the general formula (b3), R ^3b preferably represents an alkyl group having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and preferably 18 or less, more preferably 16 or less carbon atoms.
In the general formula (b3), R ^4b represents an alkyl group having 1 or more carbon atoms, preferably 5 or less carbon atoms, and more preferably 4 or less carbon atoms.
In the general formula (b3), M is preferably a hydrogen atom, an alkali metal such as sodium and potassium, an alkaline earth metal (1/2 atom) such as magnesium and calcium, or an organic ammonium salt. The organic ammonium salt may be an amine salt. M is more preferably an alkali metal such as sodium or potassium, alkanolammonium such as monoethanolammonium or diethanolammonium, and even more preferably sodium.

As the component (B3), in the general formula (b3), a compound in which R ^3b has an alkyl group having 11 or more and 14 or less ^{carbon atoms, R 4b} has an alkyl group having 1 or more carbon atoms and 5 or less carbon atoms, and M is sodium is preferable.

As the component (B) of the present invention, one or more anionic surfactants selected from the components (B1) and (B2) are preferable from the viewpoint of increasing the flexibility of the component (A), and the component (B2). One or more anionic surfactants selected from the above are more preferable. That is, from this viewpoint, the liquid detergent composition for a drum-type washing machine of the present invention preferably contains the component (B2) as the component (B).

As the component (B) of the present invention, from the viewpoint of increasing the flexibility of the component (A), it is preferable to use two or more of the components (B1), (B2) and (B3) in combination, and further, cleaning. From the viewpoint of enhancing the properties, it is more preferable to use the component (B1) and the component (B2) in combination. That is, from this point of view, the liquid detergent composition for a drum-type washing machine of the present invention has two or more kinds selected from the component (B1), the component (B2) and the component (B3) as the component (B), and further (B1). ) And (B2) are preferably contained.

When the liquid detergent composition for a drum-type washing machine of the present invention contains the component (B1) and the component (B2) as the component (B), the content of the component (B1) and the mass of the content of the component (B2) The ratio (B1) / (B2) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 10 or less, more preferably 10 or less, from the viewpoint of enhancing detergency. It is 7 or less, more preferably 5 or less.

<Ingredient (C)>
The component (C) of the present invention is a nonionic surfactant. Examples of the nonionic surfactant of the component (C) include a nonionic surfactant represented by the following general formula (c1).
R ^1c (CO) _m1 O- (AO) _n1- R ^2c (c1)
[In the formula, R ^1c is an aliphatic hydrocarbon group having 9 or more carbon atoms and 18 or less carbon atoms, R ^2c is a hydrogen atom or a methyl group, CO is a carbonyl group, and m1 is a number of 0 or 1. The AO group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group, and n1 is the average number of added moles, which is 3 or more and 50 or less. ]

In the general formula (c1), R ^1c is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms. ^{The carbon number of R c1} is 9 or more, preferably 10 or more, more preferably 11 or more in terms of making it easier to remove stains attached to the fibers, and 18 or less in terms of further enhancing the softening effect of the fibers. It is preferably 16 or less, more preferably 15 or less, and even more preferably 14 or less.
As ^{the aliphatic hydrocarbon group of R c1} , a group selected from an alkyl group and an alkenyl group is preferable.
In the general formula (c1), m1 is preferably 0.
In the general formula (c1), R ^2c is preferably a hydrogen atom.

In the general formula (c1), the AO group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group. When the ethyleneoxy group and the propyleneoxy group are contained, the ethyleneoxy group and the propyleneoxy group may be a block type bond or a random type bond. The AO group is preferably a group containing an ethyleneoxy group from the viewpoint of not inhibiting the softening effect of the fiber by the component (A).

In the general formula (c1), n1 is the average number of moles added, which is 3 or more and 50 or less. The larger the number of n1, the higher the HLB value, and the smaller the number, the lower the HLB value. n1 is 3 or more, preferably 5 or more, more preferably 7 or more, still more preferably 8 or more, still more preferably 9 or more, still more preferably 10 or more, and more, from the viewpoint of stably blending the component (A). More preferably 12 or more, and from the viewpoint of detergency of stains adhering to the fibers, 50 or less, preferably 45 or less, more preferably 40 or less, still more preferably 35 or less, still more preferably 26 or less, and more. More preferably, it is 24 or less.

A more preferable compound as the nonionic surfactant of the component (C) of the present invention has an ethyleneoxy group (hereinafter sometimes referred to as an EO group) having an average degree of polymerization (or an average number of added moles) of 3 or more. It is preferably 5 or more, and 50 or less, preferably 25 or less, and the average degree of polymerization (or the average number of added moles) of the propyleneoxy group (hereinafter sometimes referred to as PO group) is 0 or more and 5 or less, preferably 0 or more. Is 3 or less, and the EO group and the PO group may be a random bond or a block bond, preferably a block bond, and more preferably, from the viewpoint of stability, EOPOEO with respect to the alkyl ether. Polys that are sequential or POEO-ordered block bonds and are derived from linear primary or secondary alcohols having an alkyl group having 12 or more and 18 or less carbon atoms, more preferably 12 or 14, and even more preferably 12. It is an oxyethylene (polyoxypropylene) alkyl ether.

<Ingredient (D)>
The component (D) of the present invention is silicone. Examples of the component (D) include unmodified silicone and silicone selected from modified silicone. Examples of the unmodified silicone include polyorganosiloxane and further polydimethylsiloxane. As the modified silicone, a silicone modified with a hydrophilic group, for example, a modified silicone compound such as a polyether modification, a carboxy modification, an amino modification, an amide modification, an amino polyether modification, or an amide polyether modification can be used. In the present invention, in order to sufficiently exhibit the flexibility of the component (A), the component (D) is an alkyl group such as a propyl group, an ethyl group or a methyl group, preferably an ethyl group or a methyl group, and more preferably a methyl group. An unmodified polysiloxane-based silicone having substantially no organic groups other than those at both ends is preferable, and an unmodified polydimethylsiloxane is further preferable.

In the present invention, as the silicone of the component (D), a silicone-based defoaming agent can be used from the viewpoint of its use in detergents and the fact that many of them contain polydimethylsiloxane as a main component. The silicone-based defoaming agent is, for example, a silicone-based defoaming agent selected from an oil type, an oil compound type, a solution type, an emulsion type, and a self-emulsifying type, and further selected from an oil type, an oil compound type, and an emulsion type. Examples include silicone-based defoamers. The oil compound type silicone defoaming agent is, for example, a mixture of silicone oil and water-insoluble particles such as fine powder silica. The solution-type silicone defoaming agent is, for example, a silicone oil dissolved in a solvent such as isoparaffin. The emulsion-type silicone defoaming agent is, for example, a silicone oil emulsified with a nonionic surfactant.

The silicone-based defoaming agent is preferably a silicone-based defoaming agent composed of substantially unmodified polydimethylsiloxane.
Examples of commercially available products include SH200 (Toray Dow Corning Co., Ltd.) as an oil-type silicone defoaming agent.
As an oil compound type silicone defoaming agent, 8590 Adaptive (Toray Dow Corning Co., Ltd.), AF-8014 Antifoam (Toray Dow Corning Co., Ltd.), AC-8066 Antifoam (Toray Dow Corning Co., Ltd.), ACP -3073 Antifoam (Toray Dow Corning Co., Ltd.), KS-66 (Shin-Etsu Chemical Co., Ltd.), etc.
Examples of the solution type silicone defoamer include KS-602A (Shin-Etsu Chemical Co., Ltd.).
As emulsion type defoamers, FS Antifoam 93 (Toray Dow Corning Co., Ltd.), KM-73 (Shin-Etsu Chemical Co., Ltd.), KM-7750 (Shin-Etsu Chemical Co., Ltd.), KM-7752 (Shin-Etsu Chemical Co., Ltd.) Co., Ltd.) etc.

In the present invention, as the silicone of the component (D), an oil compound type silicone defoamer containing a silicone oil containing polydimethylsiloxane and fine particle silica is used in order to sufficiently exhibit the flexibility of the component (A). Is preferable.

The weight average molecular weight of the component (D) is preferably 1000 or more, more preferably 2000 or more, and preferably 500,000 or less, more preferably 300,000 or less. The weight average molecular weight of the component (D) can be measured by gel permeation chromatography (GPC) using chloroform as a solvent and polystyrene as a standard.

<Composition>
The content of the component (A) in the liquid detergent composition of the present invention is 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably, from the viewpoint of giving flexibility to the textile product. Is 15% by mass or more, and 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.

The content of the component (B) in the liquid detergent composition of the present invention is 0.1% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass from the viewpoint of increasing the flexibility of the component (A). The above is more preferably 3% by mass or more, and 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less.

The total content of the component (A) and the component (B) in the liquid detergent composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass, from the viewpoint of increasing the flexibility of the component (A). Above, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, still more preferably 35% by mass. % Or less.

The content of the component (C) in the liquid detergent composition of the present invention is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and ( A) From the viewpoint of increasing the flexibility of the components, it is 20% by mass or less, preferably 18% by mass or less, and more preferably 15% by mass or less.

The content of the component (D) in the liquid detergent composition of the present invention is 0.02% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass from the viewpoint of enhancing foam compatibility. Above, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and from the viewpoint of improving detergency, 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass. It is as follows.
The mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) in the liquid detergent composition of the present invention is preferably from the viewpoint of increasing the flexibility of the component (A). 0.2 or more, more preferably 0.5 or more, still more preferably 1 or more, still more preferably 1.5 or more, still more preferably 2 or more, and preferably 15 or less, more preferably 10 or less, still more preferable. Is 8 or less.

The mass ratio (A) / (C) of the content of the component (A) to the content of the component (C) in the liquid detergent composition of the present invention is preferably from the viewpoint of increasing the flexibility of the component (A). It is 0.1 or more, more preferably 1 or more, still more preferably 2 or more, still more preferably 5 or more, and preferably 200 or less, more preferably 100 or less, still more preferably 50 or less.

The liquid detergent composition for a drum-type washing machine of the present invention is a mass ratio of the total content of the component (A), the component (B), and the component (C) to the content of the component (D). [(A) + (B) + (C)] / (D) is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, and foam suitability, from the viewpoint of increasing the flexibility of the component (A). From this point of view, it is preferably 600 or less, more preferably 500 or less, still more preferably 400 or less, still more preferably 300 or less.

The mass ratio (A) / (D) of the content of the component (A) to the content of the component (D) in the liquid detergent composition of the present invention is preferably 1 or more, more preferably 1 or more from the viewpoint of improving the feel performance. Is 5 or more, more preferably 20 or more, and from the viewpoint of preventing an increase in the number of rinses due to foaming, it is preferably 400 or less, more preferably 300 or less, still more preferably 200 or less.

<Water>
The rest of the liquid detergent composition for drum-type washing machines of the present invention is water. Water that is generally used for liquid detergents is used, but deionized water (sometimes also called ion-exchanged water) or sodium hypochlorite is added to ion-exchanged water at 1 mg / kg or more and 5 mg / kg or less. The added water can be used. You can also use tap water. The water content is preferably 4% by mass or more, more preferably 5% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less.

<Arbitrary components, pH, etc.>
The liquid detergent composition for a drum-type washing machine of the present invention can contain the following components as long as the effects of the present invention are not impaired.

<Ingredient (E)>
The liquid detergent composition for a drum-type washing machine of the present invention can contain an organic solvent having a hydroxyl group as the component (E). Organic solvents are generally used as solubilizers. However, in the present invention, by using the component (E) in combination with the component (A) and (B), the effect of imparting flexibility to the textile product when washing at a low temperature is further improved. Can be done.

From the viewpoint of further improving the effect of imparting flexibility to the textile product when used in combination with the components (A) and (B) of the liquid detergent composition for a drum-type washing machine of the present invention, the component (E) is used. It is preferable that the CLogP is an organic solvent of −1.5 or more and 2 or less. In the present invention, CRogP is used in ChemBioDrow Ultra ver. The calculated value calculated using the Chem Property of 14.0 is used. The larger the ClogP value, the higher the hydrophobicity.

As the component (E), CRogP is preferably-from the viewpoint that the effect of imparting texture to the textile product can be further improved even when the liquid detergent composition for a drum-type washing machine of the present invention is used for washing at a low temperature. 1.4 or more, more preferably -1.2 or more, still more preferably -1 or more, still more preferably -0.8 or more, still more preferably -0.5 or more, still more preferably -0.1 or more. , More preferably 0 or more, even more preferably 0.2 or more, even more preferably 0.4 or more, even more preferably 0.6 or more, and preferably 2 or less, more preferably 1.8 or less. It is an organic solvent having a hydroxyl group, more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less.

As the component (E), CRogP is preferable from the viewpoint that even if the liquid detergent composition for a drum-type washing machine of the present invention is directly adhered to the textile product and washed, the effect of imparting texture to the textile product can be further improved. Is -1.4 or more, more preferably -1.2 or more, still more preferably -1 or more, still more preferably -0.8 or more, still more preferably -0.5 or more, still more preferably -0. 1 or more, more preferably 0 or more, even more preferably 0.2 or more, even more preferably 0.4 or more, even more preferably 0.6 or more, and preferably 2 or less, more preferably 1.8. Hereinafter, it is an organic solvent having a hydroxyl group, more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less.

The component (E) is selected from the following components (E1) to (E4) 1 in that the effect of imparting flexibility to the textile product by the combined use of the component (A) and the component (B) can be further enhanced. More than a seed organic solvent is preferred.
(E1) Component: Monovalent alcohol having 2 or more and 6 or less carbon atoms (E2) Component: Alcohol having 2 or more and 12 or less carbon atoms and divalent or more and 12 or less valent alcohol (E3) Component: Hydrocarbon having 1 or more and 8 or less carbon atoms Organic solvent having hydrogen group, ether group and hydroxyl group (However, hydrocarbon group excludes aromatic group)
Component (E4): Organic solvent having an aromatic group, an ether group and a hydroxyl group which may be partially substituted The following are specific examples of the components (E1) to (E4). The numbers in parentheses are from PerkinElmer's Chem Bio DrawUltra ver. It is a calculated value (CLogP) of each component calculated by using Chemproperty of 14.0.

Examples of the monohydric alcohol having 2 or more and 6 or less carbon atoms, which is the component (E1), include ethanol (−0.24), 1-propanol (0.29), 2-propanol (0.07), and phenol (1). .48) can be mentioned.

Examples of alcohols having 2 or more and 12 or less carbon atoms and divalent or more and 12-valent or less, which are components (E2), include ethylene glycol (-1.4), propylene glycol (-1.1), and butylene glycol (-0. 73), hexylene glycol (-0.02), diethylene glycol (-1.3), triethylene glycol (-1.5), tetraethylene glycol (-1.66), dipropylene glycol (-0.69). , Tripropylene glycol (-0.55), 3-methyl-1,3-butanediol (-0.56), glycerin (-1.5).

Examples of the organic solvent having a hydrocarbon group having 1 to 8 carbon atoms, an ether group and a hydroxyl group as the component (E3) include diethylene glycol monomethyl ether (-0.78), diethylene glycol dimethyl ether (-0.26) and triethylene. Glycol monomethyl ether (-0.96), diethylene glycol monoethyl ether (-0.39), diethylene glycol diethyl ether (0.52), diethylene glycol monobutyl ether (0.67), dipropylene glycol monomethyl ether (-0.16) , Dipropylene glycol monoethyl ether (0.23), Tripropylene glycol monomethyl ether (-0.03), 1-methoxy-2-propanol (-0.30), 1-ethoxy-2-propanol (0.09) ), 3-methoxy-3-methyl-1-butanol (0.18), 1-methylglycerin ether (-1.43), 2-methylglycerin ether (-0.73), 1,3-dimethylglycerin ether (-0.67), 1-ethyl glycerin ether (-1.04), 1,3-diethyl glycerin ether (0.11), triethyl glycerin ether (0.83), 1-pentyl glyceryl ether (0.54) ), 2-Pentyl glyceryl ether (1.25), 1-octyl glyceryl ether (2.1), 2-ethylhexyl glyceryl ether (2.0).

Examples of the organic solvent having a partially substituted aromatic group, ether group and hydroxyl group as the component (E4) include 2-phenoxyethanol (1.2) and diethylene glycol monophenyl ether (1.25). Examples thereof include triethylene glycol monophenyl ether (1.08), polyethylene glycol monophenyl ether having an average molecular weight of about 480 (cannot be calculated), 2-benzyloxyethanol (1.1), and diethylene glycol monobenzyl ether (0.96). ..

The component (E) is an organic solvent having a hydroxyl group selected from the components (E3) and (E4), and the organic solvent having a ClogP of 0.6 or more and 1.5 or less is preferable.

The liquid detergent of the present invention is an organic solvent selected from the above-mentioned (E3) component and (E4) component from the viewpoint of imparting more excellent flexibility to the textile product even if it adheres directly to the textile product. The content ratio of the organic solvent having a ClogP of 0.6 or more and 1.5 or less is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass, among all the components (E). % Or more, and preferably 100% by mass or less.

The content of the component (E) in the liquid detergent composition of the present invention is preferably 0.1% by mass or more, more preferably 3% by mass, from the viewpoint of further increasing the flexibility of the component (A) during washing at a low temperature. % Or more, more preferably 5% by mass or more, still more preferably 6% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20. It is mass% or less.

The mass ratio (A) / (E) of the content of the component (A) to the content of the component (E) in the liquid detergent composition of the present invention increases the flexibility of the component (A) during washing at a low temperature. From the viewpoint of enhancing, it is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, and preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.

<(F) component>
The liquid detergent composition for a drum-type washing machine of the present invention can contain a fatty acid glyceride having a hydroxyl group in an aliphatic acyl group as the component (F). The component (F) is preferably a fatty acid glyceride having an aliphatic acyl group having 14 or more carbon atoms and 18 or less carbon atoms in which one or more hydrogen atoms are substituted with hydroxyl groups, because it has a high effect of imparting thixotropy. By having a hydroxyl group in the aliphatic acyl group, the crystal growth of the component (F) is promoted by the intermolecular hydrogen bond between the components (F). Further, the fatty acid glyceride having a hydroxyl group in the aliphatic acyl group can have up to three aliphatic acyl groups having a hydroxyl group in the aliphatic acyl group. The average number of acyl groups of a fatty acid glyceride having a hydroxyl group in an aliphatic acyl group is 1 or more, preferably 2 or more, and more preferably 2.5 or more from the viewpoint of promoting crystal formation. From the viewpoint of storage stability of crystals, the average number is preferably 3. Further, the iodine value such as fatty acid glyceride having a hydroxyl group in the aliphatic acyl group is preferably 5 or less in that the viscosity of the liquid detergent composition at low shear is further increased by producing more uniform crystals. 4 or less is more preferable, 3 or less is further preferable, and 2 or less is further preferable. The iodine value can be determined according to the method described in JIS K 0070: 1992 (Test method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products). As the component (F), it is preferable to use hardened castor oil or hydrogenated castor oil. At least one kind of component (F) may be used, and two or more kinds may be used in combination.

The content of the component (F) in the liquid detergent composition for a drum-type washing machine of the present invention is preferably 0.01% by mass or more, more preferably 0, from the viewpoint of stably dispersing the component (A) at a low temperature. It is 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less.

<Other ingredients>
In addition to the above components, the following components (G1) to (G9) may be added to the liquid detergent composition for a drum-type washing machine of the present invention.
(G1) To adjust pH, alkaline agents such as ammonia, monoethanolamine, diethanolamine, triethanolamine, N-methylpropanolamine, 2-amino-2-methyl-1-propanol, hydrochloric acid, sulfuric acid, citric acid, etc. Add an appropriate amount of (G2) polyacrylic acid, polymaleic acid, carboxymethyl cellulose and other anti-contamination agents and dispersants in the composition of 0.01% by mass or more and 10% by mass or less (G3) hydrogen peroxide, sodium percarbonate. Alternatively, bleach such as sodium hydrogen peroxide is added to the composition in an amount of 0.01% by mass or more and 10% by mass or less (G4) tetraacetylethylenediamine, according to the general formulas (I-2) to (I-7) of JP-A-6-316700. A bleaching activator such as the represented bleaching activator is contained in the composition in an amount of 0.01% by mass or more and 10% by mass or less.
(G5) One or more enzymes selected from cellulase, amylases, pectinase, protease and lipase, preferably one or more enzymes selected from amylases and proteases in an amount of 0.001% by mass or more, preferably 0.01. Mass% or more, more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, and 2% by mass or less, preferably 1% by mass or less (G6) fluorescent dye, for example, Tinopearl CBS (trade name, trade name, Fluorescent dyes commercially available as Ciba Speciality Chemicals) or Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) are used in the composition in an amount of 0.001% by mass or more and 1% by mass or less (G7) butyl hydroxytoluene, disstyrene cresol, Antioxidants such as sodium sulfite and sodium hydrogen sulfite in the composition 0.01% by mass or more and 2% by mass or less (G8) Perfume Microcapsules in an appropriate amount 0.01% by mass or more and 2% by mass or less (G9) Dye, fragrance (G9) Non-capsule type), appropriate amount of antibacterial preservative.

The pH of the liquid detergent composition for a drum-type washing machine of the present invention at 20 ° C. is preferably 3 or more, more preferably 3 or more, from the viewpoint of suppressing precipitation or separation of solids in the composition in a low temperature environment. It is 4 or more, more preferably 5 or more, and preferably 10 or less, more preferably 9.5 or less, still more preferably 9 or less. The pH is measured according to the pH measuring method described below. The pH of the liquid detergent composition for a drum-type washing machine of the present invention at 20 ° C. is an alkaline agent selected from the group consisting of monoethalamine, diethanolamine, triethanolamine, N-methylpropanol, and ammonia, as well as hydrochloric acid, sulfuric acid, and the like. Methylsulfate, ethylsulfate, p-toluenesulfonic acid, (o-, m-, p-) xylene sulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, ethylenediamine tetraacetic acid, citric acid, benzoic acid, and salicylic acid It can be adjusted by an acid agent selected from the group consisting of.

<Measurement method of pH>
Connect the pH measurement composite electrode (HORIBA glass sliding sleeve type) to the pH meter (HORIBA pH / ion meter F-23) and turn on the power. A saturated aqueous potassium chloride solution (3.33 mol / L) is used as the pH electrode internal solution. Next, pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) were each filled in a 100 mL beaker, and 20 Immerse in a constant temperature bath at ° C for 30 minutes. The electrode for pH measurement is immersed in a standard solution adjusted to a constant temperature for 3 minutes, and the calibration operation is performed in the order of pH 6.86 → pH 9.18 → pH 4.01. The sample to be measured is adjusted to 20 ° C., the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.

The viscosity of the liquid detergent composition for a drum-type washing machine of the present invention at 20 ° C. is preferably 10 mPa · s or more, more preferably 30 mPa · s or more, still more preferably 50 mPa · s or more, from the viewpoint of ease of handling. Then, it is preferably 400 mPa · s or less, more preferably 300 mPa · s or less, and further preferably 200 mPa · s or less. For these viscosities, a B-type viscometer (VISCOMETER MODEL DVM-B, manufactured by Tokyo Keiki Co., Ltd.) was used to determine the rotor number. It was measured at 3 or 4, the rotation speed of 60 r / min, and the measurement time of 60 seconds.

The liquid detergent composition for a drum-type washing machine of the present invention is suitable for washing textile products in water containing a hardness component. The above-mentioned "suitable for washing textile products in water containing a hardness component" means that the textile products are washed in water containing a hardness component using the liquid detergent composition for a drum-type washing machine of the present invention. This means that the textile product is soft, has good foaming suitability, and can clean stains adhering to the textile product.

In water containing a hardness component used for cleaning, the hardness of water is German hardness, preferably 1 ° dH or more, more preferably 2 ° dH or more, from the viewpoint of further improving the effect of imparting flexibility to textile products. It is more preferably 3 ° dH or more, preferably 20 ° dH or less, more preferably 18 ° dH or less, still more preferably 15 ° dH or less. Here, the German hardness (° dH) in the present specification, the calcium and magnesium concentration in water, 1mg / L (ppm) in terms of CaCO ₃ concentration = about 0.056 ° dH (1 ° dH = 17. Refers to the one expressed in 8 ppm).
The concentrations of calcium and magnesium for this German hardness are determined by chelatometric titration using ethylenediaminetetraacetic acid disodium salt.
A specific method for measuring the German hardness of water in the present specification is shown below.
<Measurement method of German hardness of water>
〔reagent〕
-0.01 mol / l EDTA / 2Na solution: 0.01 mol / l aqueous solution of ethylenediaminetetraacetic acid disodium (titration solution, 0.01 M EDTA-Na2, manufactured by SIGMA-ALDRICH)
-Universal BT indicator (Product name: Universal BT, manufactured by Dojin Chemical Laboratory Co., Ltd.)
-Ammonia buffer solution for hardness measurement (a solution in which 67.5 g of ammonium chloride is dissolved in 570 ml of 28 w / v% ammonia water and the total volume is 1000 ml with ion-exchanged water).
[Measurement of hardness]
(1) Collect 20 ml of water as a sample in a conical beaker with a whole pipette.
(2) Add 2 ml of ammonia buffer for hardness measurement.
(3) Add 0.5 ml of Universal BT indicator. Confirm that the solution after addition is purplish red.
(4) While shaking the conical beaker well, a 0.01 mol / l EDTA · 2Na solution is added dropwise from the burette, and the point at which the sample water turns blue is defined as the end point of the titration.
(5) The total hardness is calculated by the following formula.
Hardness (° dH) = T × 0.01 × F × 56.0774 × 100 / A
T: 0.01 mol / l EDTA · 2Na solution titration (mL)
A: Sample volume (20 mL, volume of sample water)
F: Factor of 0.01 mol / l EDTA / 2Na solution

<Fiber>
The fibers to be washed with the liquid detergent composition for a drum-type washing machine of the present invention may be either hydrophobic fibers or hydrophilic fibers. Examples of hydrophobic fibers include protein fibers (milk protein gazein fibers, promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol-based fibers. Fiber (vinylon, etc.), Polyvinyl chloride fiber (polyvinyl chloride, etc.), Polyvinylidene chloride fiber (vinylidene, etc.), Polyethylene fiber (polyethylene, polypropylene, etc.), Polyurethane fiber (polyurethane, etc.), Polyvinyl chloride / Polyvinyl alcohol copolymer fiber (polycleral etc.), polyalkylene paraoxybenzoate fiber (benzoate etc.), polyfluoroethylene fiber (polytetrafluoroethylene etc.), glass fiber, carbon fiber, alumina fiber, silicone carbide fiber, rock Examples thereof include fibers (rock fibers), slag fibers (slug fibers), and metal fibers (gold thread, silver thread, steel fiber). Examples of hydrophilic fibers include seed hair fibers (cotton, momen, capoc, etc.), bast fibers (hemp, flax, linseed, cannabis, yellow hemp, etc.), leaf vein fibers (manila hemp, sisal hemp, etc.), palm fibers, and the like. Igusa, straw, animal hair fiber (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fiber (household silk, wild silk), feather, cellulose fiber (rayon, polynosic, cupra, acetate, etc.) Etc. are exemplified.

<Textile products>
Textile products include fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics using the above-mentioned hydrophobic fibers and hydrophilic fibers, and undershirts, T-shirts, shirts, blouses, slacks, hats, handkerchiefs, and towels obtained by using them. , Knits, socks, underwear, tights and other products.

[How to wash textiles]
The drum-type washing machine liquid detergent composition of the present invention is used for washing using a drum-type washing machine. INDUSTRIAL APPLICABILITY The present invention provides a method for washing a textile product, in which the textile product is washed by the drum-type washing machine using the liquid detergent composition for a drum-type washing machine of the present invention. The matters described in the liquid detergent composition of the present invention can be appropriately applied to the method for washing textile products of the present invention.

A drum-type washing machine is a washing machine that uses a drum-type washing tub that is rotatably supported by a horizontal or inclined rotating shaft. The washing tub (drum) rotates and lifts the laundry upward. It is a washing method in which the washing is done by knocking it down. In addition, most of the commercially available drum-type washing machines have a drying function, and depending on the course setting, it is possible to continuously perform from washing to drying.

In washing using the drum-type washing machine liquid detergent composition of the present invention, even if washing, for example, low-temperature washing, rinsing, dehydration, and then drying is performed by general indoor drying or outdoor drying, a sufficient softening effect is obtained. However, by drying using the drying process, which is a feature of the drum-type washing machine, a remarkably excellent softening effect can be obtained. The drying is preferably heat drying.

The components (A) to (D) are as described above, and by using a liquid detergent composition containing these components in a drum-type washing machine, it exhibits more excellent flexibility than ever for textile products. be able to. In a drum-type washing machine, since a series of operations are performed in the same washing drum, preferably a horizontal drum-type washing tub, the burden on the textile products to be washed is small, and further, it cannot be obtained with conventional detergents. It is possible to finish the textile product to be washed with a texture that is softer than that.

In the present invention, each treatment of washing, rinsing, dehydrating, and drying the textile product is performed in the same washing tub of the drum type washing machine, and the treatment is performed from the start of washing to the end of drying without removing the textile product from the washing tub. Is preferable. It is preferable that these processes are continuously performed in this order. Moreover, another process may be performed between each process.

The washing method of the present invention may include washing (hereinafter referred to as a washing step), rinsing (hereinafter referred to as a rinsing step), dehydration (hereinafter referred to as a dehydration step), and drying (hereinafter referred to as a drying step) of a textile product. preferable. Hereinafter, each step will be described.

<Washing process>
In the washing step, the washing liquid containing the drum-type washing machine liquid detergent composition of the present invention and water is brought into contact with the textile product in the washing tub of the drum-type washing machine. The cleaning liquid is a detergent composition of the present invention diluted with water. The cleaning liquid has a component concentration (A) of preferably 0.001% by mass or more, more preferably 0.002% by mass or more, still more preferably 0.003% by mass or more, and preferably 1.0% by mass or less. It is more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less, still more preferably 0.02% by mass or less. It is preferable to dilute the drum-type washing machine liquid detergent composition of the present invention with water so as to have this concentration.

The temperature of the cleaning liquid is preferably 0 ° C. or higher, more preferably 3 ° C. or higher, further preferably 5 ° C. or higher, and the fibers themselves constituting the clothing, from the viewpoint of further improving the cleanability of stains adhering to the textile products. The temperature is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, from the viewpoint that the contained oil agent can be not dropped too much and the textile product can be finished with a softer and lasting scent.

The pH of the cleaning liquid at 20 ° C. is preferably 3 or more, more preferably 4 or more from the viewpoint of further improving the detergency of stains adhering to the textile product, and preferably from the viewpoint of being able to finish the textile product softer. Is 10 or less, more preferably 9 or less. The pH of the cleaning liquid can be measured in the same manner as the pH of the liquid detergent composition.

In recent years, washing machines have become larger, and the value of the bath ratio expressed by the ratio of the mass of clothes (kg) and the amount of water in the washing liquid (liter), that is, the amount of water in the washing liquid (liter) / the mass of the clothes (kg) (hereinafter, this) The ratio may be the bath ratio), which tends to be smaller. The bath ratio is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, even more preferably 5 or more, and preferably 45 from the viewpoint of maintaining the detergency, from the viewpoint of finishing the textile product softer. Below, it is more preferably 40 or less, still more preferably 30 or less, still more preferably 20 or less.

The method for washing textile products of the present invention can finish textile products softer even if the washing time is short. The cleaning time is preferably 1 minute or more, more preferably 2 minutes or more, still more preferably 3 minutes or more, from the viewpoint of making it easier to remove stains adhering to the textile product or making the textile product softer. From the viewpoint of being able to finish the product softer, it is preferably 1 hour or less, more preferably 30 minutes or less, still more preferably 20 minutes or less, still more preferably 15 minutes or less.

<Rinse process>
After the washing step, the washing liquid is discharged from the washing tub and a rinsing step is performed. Preferably, the rinsing process is carried out in the same washing tub without removing the textile products from the washing tub of the drum type washing machine. In some washing machines, dehydration is done before rinsing. The dehydration time is preferably 10 minutes or less. After dehydration, water for rinsing is introduced into the washing tub, preferably within the range of the previous bath ratio. The time of the rinsing process is preferably 1 minute or more, more preferably 2 minutes or more, still more preferably 3 minutes or more from the viewpoint of being able to finish the textile product softer, and from the viewpoint of being able to finish the textile product softer. It is preferably 30 minutes or less, more preferably 25 minutes or less, still more preferably 20 minutes or less, and even more preferably 15 minutes or less. The temperature of water used in the rinsing step is, for example, 0 ° C. or higher and 40 ° C. or lower.

<Dehydration process>
After the rinsing process, a dehydration process is performed. Preferably, the dehydration step is performed in the same washing tub without removing the textile product from the washing tub of the drum type washing machine. The dehydration time is preferably 1 minute or more, more preferably 2 minutes or more, still more preferably 3 minutes or more, from the viewpoint of making it easier to remove stains adhering to the textile product or making the textile product softer. From the viewpoint of being able to finish the product softer, it is preferably 1 hour or less, more preferably 30 minutes or less, still more preferably 20 minutes or less, still more preferably 15 minutes or less.

<Drying process>
After the dehydration process, a drying process is performed. Preferably, the textile products are dried in the same washing tub without removing the textile products from the washing tub of the drum type washing machine. After dehydration, for example, the drying process is started by blowing air while rotating the drum. Recent drum-type washing machines can be dried at a relatively low temperature by a dehumidifying and drying function equipped with a compressor from the viewpoint of suppressing damage to textile products or from the viewpoint of ease of removing and discharging moisture. In order to obtain a textile product having more preferable softness, it is preferable to perform a drying step by heating to some extent. In the drying step, it is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, further preferably 20 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. to avoid heat damage. Dry below ° C. The drying time is preferably 10 minutes or longer, more preferably 20 minutes or longer, further preferably 30 minutes or longer, and to avoid heat damage in order to complete the drying and obtain a textile product having more preferable softness. In addition, it is preferably 5 hours or less, more preferably 4 hours or less, and further preferably 2 hours or less.

In the present invention, the washing step, the rinsing step, the dehydration step and the drying step are performed in the same washing tub by using a drum type washing machine, so that the finished object to be washed is a softener without using a finishing agent. It has a softness equal to or higher than that of the softener, but its texture is different from that of the softener, and it shows a finish with a new softness.

<Ingredients>
In the examples and comparative examples, the following components were used.
[(A) component]
(A-1): The mass ratio of the olefin (sodium olefin sulfonate) / hydroxy (sodium hydroxyalkane sulfonate) in the internal sodium olefin sulfonic acid salt (a-1) having 18 carbon atoms is 16/84. .. The mass ratio of the position distribution of the sulfonic acid group of the HAS form in (a-1) is as follows. 1st place / 2nd place / 3rd place / 4th place / 5th place / 6th to 9th place = 1.5 / 22.1 / 17.2 / 21.8 / 13.5 / 23.9. Further, (IO-1S) / (IO-2S) = 1.6 (mass ratio).

(A-2): The mass ratio of the olefin (sodium olefin sulfonate) / hydroxy (sodium hydroxyalkane sulfonate) in the internal sodium olefin sulfonic acid salt (a-2) having 16 carbon atoms is 15/85. .. The mass ratio of the position distribution of the sulfonic acid group of the HAS form in (a-2) is as follows. 1st place / 2nd place / 3rd place / 4th place / 5th place / 6th to 8th place = 1.5 / 24.1 / 19.9 / 24.6 / 14.1 / 15.8. Further, (IO-1S) / (IO-2S) = 2.3 (mass ratio).
The position distribution of the sulfonic acid group of the HAS form and the mass ratio of the olefin form and the hydroxy form (HAS form) contained in each internal olefin sulfonate were measured by a high performance liquid chromatograph mass spectrometer. The internal olefin sulfonate having a double bond at the 6-position or higher had overlapping peaks and could not be clearly fractionated. The equipment and analysis conditions used for the measurement are as follows.
〔measuring equipment〕
LC device: "LC-20ASXR" (manufactured by Shimadzu Corporation)
LC-MS device: "LCMS-2020" (manufactured by Shimadzu Corporation)
Column: ODS Hypersil (length: 250 mm, inner diameter: 4.6 mm, particle size: 3 μm, manufactured by Thermo Fisher Scientific) Detector: ESI (-), m / z = 349.15 (C18), 321. 10 (C16), 293.05 (C14)
〔solvent〕
Solvent A: 10 mM ammonium acetate aqueous solution Solvent B: Acetonitrile / water = 95/5 solution to which 10 mM ammonium acetate was added [Elution conditions]
Gradient: Solvent A 60% Solvent B 40% (0 to 15 minutes) → Solvent A 30% Solvent B 70% (15.1 to 20 minutes) → Solvent A 60% Solvent B 40% (20 to 30 minutes)
-Flow velocity: 0.5 ml / min
-Column temperature: 40 ° C
・ Injection amount: 5 μl

[Component (B)]
(B-1): Poly (polyoxypropylene) poly in which the number of carbon atoms of the alkyl group is derived from lauryl alcohol, the average number of added moles of the propyleneoxy group is 2 mol, and the average number of added moles of the ethyleneoxy group is 2 mol. Oxyethylene lauryl ether sulfate sodium salt.
(B-2): Sodium alkylbenzene sulfonate (alkyl composition: C10 / C11 / C12 / C13 = 11/29/34/26 (mass ratio, the number next to C means carbon number), mass average carbon number = 17.75)

[Component (C)]
(C-1): Polyoxyalkylene lauryl ether (with respect to 1 mol of lauryl alcohol, 9 mol of ethyleneoxy groups were added on average, 2 mol of propyleneoxy groups were added on average, and then 9 ethyleneoxy groups were added on average. Molly added compound, HLB = 14.5, in general formula (c1), R ^1c : lauryl group, m1: 0, AO: ethyleneoxy group and propyleneoxy group, n1: 20, R ^2c : compound of hydrogen atom)
(C-2): Polyoxyethylene lauryl ether (average number of moles of oxyethylene group added is 10 mol, HLB = 14.0, in general formula (c1), R ^1c : lauryl group, m1: 0, AO: ethylene. Oxy group, n1:10, R ^2c : compound of hydrogen atom)

[Component (D)]
(D-1): Compound type silicone containing polydimethylsiloxane and fine particle silica (mass% in the table is mass% in terms of polydimethylsiloxane).

[(E) component]
(E-1): Ethanol (e-2): Propylene Glycol (e-3): Diethylene Glycol Monobutyl Ether (e-4): 2-Phenoxyethanol

[(F) component]
(F-1): hydrogenated castor oil (iodine value _1.5g-I 2 / 100g)

〔water〕
Ion-exchanged water

<Preparation of liquid detergent composition for drum-type washing machines>
The liquid detergent composition for a drum-type washing machine shown in Table 1 was prepared using the above-mentioned compounding ingredients, and the following items were evaluated. The results are shown in Table 1. Specifically, the method for preparing the liquid detergent composition for a drum-type washing machine shown in Table 1 was as follows.
A 5 cm long Teflon (registered trademark) stirrer piece was placed in a 200 mL glass beaker and the mass was measured. Next, 50 g of ion-exchanged water at 20 ° C., (E) component, (A) component, (B) component, and (C) component are added in this order, and then the upper surface of the beaker is sealed with Saran Wrap (registered trademark). bottom. A beaker containing the contents was placed in a water bath at 60 ° C. installed in a magnetic stirrer, and the water in the water bath was stirred at 100 r / min for 30 minutes within a temperature range of 60 ± 2 ° C. Next, the water in the water bath was replaced with tap water at 5 ° C., and the composition was cooled in the beaker until the temperature reached 20 ° C. Next, Saran Wrap (registered trademark) was removed, and the pH was adjusted to pH 7 with an alkaline agent (monoethanolamine) or an acid agent (citric acid). Add the components (D) and (F), add ion-exchanged water so that the mass of the contents becomes 100 g, and stir again at 100 r / min for 30 minutes for the drum-type washing machine shown in Table 1. A liquid detergent composition was obtained.

<Evaluation method of flexibility>
(1) Pretreatment of evaluation fiber (cotton towel) A commercially available towel (manufactured by Takei Towel, 100% cotton, made by Takei Towel, 100% cotton, using a nonionic surfactant (ethylene oxide adduct of lauryl alcohol (average addition mole number 8)) is used in advance. The washing process of Hitachi automatic washing machine NW-6CY was repeated 5 times (34 cm x 86 cm x 12 sheets) about 1.6 kg (nonionic surfactant usage 4.5 g, standard course, water volume 45 L, water temperature 20 ° C., Washing time 10 minutes, rinsing twice). Then, it was dried under the condition of 25 ° C. and 45% RH for 1 day. The towel after pretreatment is hereinafter referred to as cotton towel.

(2) Washing of evaluation fibers 40 g of each of the liquid detergent compositions for drum-type washing machines shown in Table 1 was put into a fully automatic drum-type washing machine (manufactured by PANASONIC (NA-VX9300L)) by the above method. Twenty-four pretreated cotton towels (about 4 kg) were placed. After that, using Wakayama City water at 5 ° C., the washing process was performed with the setting of washing for 12 minutes, water injection rinsing once, trial rinsing once, and dehydration for 4 minutes. The cotton towel was taken out of the washing tub without using the drying process of the drum type washing machine. After evaluating the dehydrated wet cotton towel by the following evaluation method, hang it on a towel dryer so that it folds at half of the cotton towel, and in a room kept at 25 ° C and 45% RH. The washing of the evaluation fiber was completed by leaving it to stand for 12 hours and drying it.

(3) Evaluation of flexibility The softness of the cotton towel before washing, rinsing, dehydrating, and drying using the liquid detergent composition for a drum-type washing machine shown in Table 1 by the above method is evaluated for the texture of the fibers. The average score of 6 people was calculated by scoring with the following criteria by 6 skilled workers. At that time, the score of the cotton towel was obtained from one evaluator for one composition, and the average value was used as the evaluation score for the composition. The evaluation points were totaled for 6 people, and the average score was calculated. The results are shown in Table 1. As for the average score, 0.5 points or more pass, and it is preferable that the numerical value is high. The evaluation of the flexibility of the textile products after dehydration is not only an index of the finish in which the textile products are less entangled with each other and the damage of the textile products is suppressed, but also the difference in the soft and smooth texture of the textile products. It is easy to know.
The present inventors have confirmed that the texture after drying does not conflict with the evaluation when wet. In addition, the evaluation time can be shortened by evaluating when wet.
-1 ... It is softer than the cotton towel treated with the composition of Comparative Example 1 and does not finish.
0 ... Finished to be as soft as a cotton towel treated with the composition of Comparative Example 1.
1 ... The finished product was slightly softer than the cotton towel treated with the composition of Comparative Example 1.
2 ... The finished product was softer than the cotton towel treated with the composition of Comparative Example 1.
3 ... It was finished very softly as compared with the cotton towel treated with the composition of Comparative Example 1.

In Table 1, the liquid detergent composition for a drum-type washing machine of the present invention can finish the fibers softly during low-temperature washing. Further, the liquid detergent composition for a drum-type washing machine of the present invention can clean stains adhering to fibers.

(4) Evaluation when the drying process is performed using a drum-type washing machine The drums shown in Example 1 and Comparative Example 1 in Table 1 are applied to a fully automatic drum-type washing machine (manufactured by PANASONIC (NA-VX9300L)). 40 g of each of the liquid detergent compositions for a washing machine was added, and 24 cotton towels (about 4 kg) pretreated by the above method were placed therein. Then, using Wakayama City water at 5 ° C., the washing process was carried out at a setting of 12 minutes for washing, 1 rinsing with water, 1 rinsing for trial, 4 minutes for dehydration, and 120 minutes for drying. These treatments were performed without removing the cotton towel from the washing tub. After the washing process was completed, when the temperature of the object to be washed reached about 30 ° C., it was taken out from the washing machine and the softness of the towel to be washed was confirmed by touching it. As a result, the object to be washed washed with the composition of Example 1 was finished softer than the object to be washed washed with the composition of Comparative Example 1. Further, in the composition of Example 1, a high-finished object to be washed with overwhelmingly excellent softness, which cannot be obtained by a conventional washing method, was obtained.

Claims (7)

(A) Internal olefin sulfonate [hereinafter referred to as component (A)] is 1% by mass or more and 50% by mass or less, (B) Anionic surfactant other than internal olefin sulfonate [hereinafter referred to as component (B)] 0.1% by mass or more and 20% by mass or less, (C) nonionic surfactant [hereinafter referred to as (C) component] by 0.1% by mass or more and 20% by mass or less, (D) silicone [hereinafter, (D) ) Ingredients] A liquid detergent composition for a drum-type washing machine containing 0.02% by mass or more and 5% by mass or less and water.
The ratio of the internal olefin sulfonate having 18 carbon atoms (A1) in the component (A) [hereinafter referred to as the component (A1)] is 80% by mass or more.
Liquid detergent composition for drum-type washing machines. The components (A1) are an internal olefin sulfonate (IO-1S) having 18 carbon atoms in which a sulfonic acid group is present at the 2-position or higher and 4-position or lower, and an internal olefin having 18 carbon atoms in which a sulfonic acid group is present at the 5-position or higher. It contains sulfonate (IO-2S) and is the mass ratio of the content of (IO-1S) to the content of (IO-2S) in the component (A1) (IO-1S) / (IO-). The liquid detergent composition for a drum-type washing machine according to claim 1, wherein 2S) is 0.5 or more and 10 or less. [(A) + (B) + (C)] / which is the mass ratio of the total content of the component (A), the component (B), and the component (C) to the content of the component (D). The liquid detergent composition for a drum-type washing machine according to claim 1 or 2, wherein (D) is 10 or more and 600 or less. (E) The liquid detergent composition for a drum-type washing machine according to any one of claims 1 to 3, further containing (E) an organic solvent having a hydroxyl group in an amount of 0.1% by mass or more and 40% by mass or less. A method for washing a textile product, wherein the textile product is washed by the drum type washing machine using the liquid detergent composition for a drum type washing machine according to any one of claims 1 to 4. Washing, rinsing, dehydrating, and drying the textiles are performed in the same washing tub of the drum-type washing machine, and the above treatments are performed from the start of washing to the end of drying without removing the textiles from the washing tub. Item 5. The method for washing textile products according to Item 5. The method for washing a textile product according to claim 6, wherein the drying is performed by heating and drying.