JP2009161622A - Liquid detergent composition for clothes - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition suitable for washing clothes, especially polyester clothes. <P>SOLUTION: The liquid detergent composition is prepared by blending the following components A-D: the component A is a nonionic surfactant; the component B is a tertiary amine compound; the component C is a water-soluble polymer having an alkylene terephthalate unit and/or an alkylene isophthalate unit and an oxyalkylene unit and/or a polyoxyalkylene unit; and the component D is an anionic surfactant. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid cleaning composition for clothing. In particular, the present invention relates to a liquid detergent composition suitable for clothing made of polyester fibers.

Polyester fibers such as polyethylene terephthalate have great elasticity and are excellent in rigidity and heat resistance. Clothing using this polyester fiber (polyester clothing) does not lose its shape, does not easily wrinkle, and has excellent wash and wear properties. Accordingly, polyester garments are used in various applications such as T-shirts, shirts, underwear and sportswear, and occupy a high share among the synthetic garments.
Various liquid detergent compositions for clothing including polyester clothing are known (Patent Documents 1 and 2).

JP 2005-179529 A JP 2007-169514 A

As mentioned above, polyester garments have various advantages. However, polyester clothing is inferior in water absorption because it is made of polyester which is a hydrophobic fiber. In particular, in polyester clothing that is worn directly on the skin, the stuffiness caused by its low water absorption may cause discomfort to the wearer. In addition, as with clothing made of other fibers, there is a drawback that wrinkles occur by repeated washing.
Under such circumstances, development of a technique capable of overcoming the above-described drawbacks is demanded.

（式中、Ａ及びＢはそれぞれ独立して、水素原子又はメチル基であり、Ｒ¹及びＲ²はそれぞれ独立して、炭素数２〜４のアルキレン基であり、Ｘは０〜１０であり、ｙは１〜１００である。）

（式中、Ａ及びＢはそれぞれ独立して、水素原子又はメチル基であり、Ｒ¹及びＲ²はそれぞれ独立して、炭素数２〜４のアルキレン基であり、Ｘは０〜１０であり、ｙは１〜１００である。）、並びに
（３）ポリエステル衣料用である、前記（１）に記載の衣料用液体洗浄剤組成物に関するものである。 In order to solve the above-mentioned problems, the present inventors have made extensive studies and have found that polyester garments using a liquid detergent composition comprising a predetermined surfactant, a tertiary amine compound and a water-soluble polymer are blended. It was found that there is no problem of stuffiness or stuffiness after washing. The present invention has been made based on this finding.
That is, the present invention
(1) The following components A to D:
A: nonionic surfactant,
B: tertiary amine compound,
C: a water-soluble polymer having an alkylene terephthalate unit and / or an alkylene isophthalate unit and an oxyalkylene unit and / or a polyoxyalkylene unit, and
D: A liquid detergent composition for clothing, comprising an anionic surfactant;
(2) The liquid cleaning composition according to the above (1), wherein the component C is a water-soluble polymer represented by the formula (9) and / or the formula (10):

(In the formula, A and B are each independently a hydrogen atom or a methyl group, R ¹ and R ² are each independently an alkylene group having 2 to 4 carbon atoms, and X is 0 to 10) , Y is 1 to 100.)

(In the formula, A and B are each independently a hydrogen atom or a methyl group, R ¹ and R ² are each independently an alkylene group having 2 to 4 carbon atoms, and X is 0 to 10) , Y is 1 to 100), and (3) the liquid cleaning composition for clothing according to (1), which is for polyester clothing.

  The liquid detergent composition for clothing of the present invention can suppress the disadvantages of polyester clothing, that is, the occurrence of wrinkles due to repeated washing and the occurrence of stuffiness due to low water absorption, as shown in the examples described later. . Therefore, the present invention can be advantageously used for cleaning polyester garments.

Hereinafter, the present invention will be described in detail.
Component A: Nonionic surfactant Any nonionic surfactant can be used without particular limitation as long as it is usually used in a liquid detergent composition for clothing. For example, it is described as “nonionic surfactant” in “Patent Office Gazette 10 (1998) -25 [7159] Collection of Well-known and Conventional Techniques (powder detergent for clothing), issued on March 26, 1998”. You can use what you have.
Nonionic surfactants are known substances and can be easily obtained in the market.

Specific examples thereof include compounds represented by the following formula (1).
R ³ —Y — [(EO) _m (PO) _n ] —R ⁴ (1)
(In the formula, R ³ is a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, preferably 10 to 16 carbon atoms. —Y— is —O— or —COO—. R ⁴ Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO is ethylene oxide, m is an average added mole number of EO, and is an integer of 3 to 20. PO is propylene oxide, n is PO The average number of moles added is an integer of 0 to 6.)
EO and PO may be added alone or as a mixture. EO and PO may be added as blocks. The addition order of EO and PO may be as shown in the above formula (1), or may be reversed.
When EO and PO are mixed and added, the total amount of EO groups is preferably 60% by mass or more in terms of mass ratio in all alkylene oxide groups.
The average added mole number m of EO is an integer of 3-20, preferably 5-18, more preferably 5-15. When m is 20 or less, the deterioration of the cleaning function (due to the disadvantage that the sebum cleaning is disadvantageous because the HLB value of the nonionic surfactant becomes too high) can be suppressed, and when m is 3 or more, the odor Can be prevented.
The average added mole number n of PO is 0-6, preferably 0-3. When n is 6 or less, a decrease in storage stability of the liquid detergent composition at high temperatures can be suppressed.
The added mole number distribution of EO or PO varies depending on the reaction method during the production of the nonionic surfactant, and is not particularly limited. For example, the addition mole number distribution of EO or PO is relatively wide when ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. Tend to be. Magnesium oxide added with metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in JP-B-615038 When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a specific alkoxylation catalyst such as the above, the distribution tends to be relatively narrow.

In the formula (1), when -Y- is -O-, the component A is an alcohol alkoxylate. In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R ³ is 10 to 22, preferably 10 to 20, and more preferably 10 to 16. R ³ may have an unsaturated bond. In this case, R ⁴ is preferably a hydrogen atom.
In the formula (1), when -Y- is -COO-, the component A is a fatty acid ester type nonionic surfactant. In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R ³ is 9 to 21, preferably 11 to 21. R ³ may have an unsaturated bond. In this case, R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms.

Among the compounds represented by the formula (1), a polyoxyalkylene type nonionic surfactant is preferable. Specific examples include the following.
1: Synthetic alcohol obtained by the oxo method (for example, manufactured by Sasol: trade name Safol 23 (C ₁₂ / C ₁₃ mixture)) or natural alcohol (for example, manufactured by P & G: trade name CO-1214 (C ₁₂ / C ₁₄ Mixture), Eco Green, manufactured by Oleo Chemicals Co., Ltd .: Trade name Ecolol (C ₁₂ / C ₁₄ mixture)) 1 mol of ethylene oxide equivalent to 15 or 12 mol 2: Natural alcohol (for example, Shin Nippon Rika) Company: Trade name Conol (C ₁₂ )) 1 mol of ethylene oxide equivalent to 9 mol 3: C ₁₃ obtained by subjecting C ₁₂ alkene obtained by trimerization of butene to oxo method 7 mol or 10 mol equivalent of ethylene oxide added to 1 mol of alcohol (for example, BASF Corporation: trade name Lutensol TO7, ASF Co., Ltd .: trade name Lutensol TO10)
4: hexanol against C ₁₂ alcohol 1 mole obtained was subjected to Guerbet reaction, and adding ethylene oxide 10 molar equivalent (e.g., CONDEA Ltd.: trade name ISOFOL12-10EO)
5: the second alcohol of C _{12 to 14,} obtained by adding ethylene oxide 15 molar equivalent (e.g., manufactured by Nippon Shokubai Co., Ltd.: trade name Softanol 150)
6: A compound obtained by adding 15 moles of ethylene oxide and 3 moles of propylene oxide to methyl laurate using an alkoxylation catalyst Among the nonionic surfactants 1 to 6 described above, From the viewpoint of superiority, 1 is preferable. 3 is preferable in that the liquid detergent composition for clothing is excellent in appearance stability at low temperatures.

  As the component A, a single type of nonionic surfactant may be used alone, or a plurality of types of nonionic surfactants may be used in combination.

  The nonionic surfactant which is A component is mix | blended mainly for providing the cleaning power to the liquid cleaning composition for clothes of this invention. The compounding quantity of A component is 10-50 mass% with respect to the total mass of the liquid cleaning composition for garments, Preferably it is 10-40 mass%, Most preferably, it is 15-30 mass%. When it is 10% by mass or more, a high cleaning power can be imparted to the liquid cleaning composition for clothing. High stability can be provided to the liquid cleaning composition for clothes as it is 50 mass% or less.

（式中、Ｒ⁵は置換基及び／又は連結基を有していても良い炭素数７〜２７の炭化水素基ある（置換基及び／又は連結基を有する場合、置換基及び／又は連結基中の炭素数はここでの炭素数に含まれない）。Ｒ⁶及びＲ⁷はそれぞれ独立して炭素数１〜４の直鎖又は分岐したアルキル基、炭素数１〜４の直鎖若しくは分岐したヒドロキシアルキル基又はＥＯ付加モル数１〜２５のポリオキシエチレン基である。）
Ｒ⁵の炭化水素基の炭素数（置換基及び／又は連結基を有する場合、置換基及び／又は連結基中の炭素数はここでの炭素数に含まれない）は、７〜２７、好ましくは炭素数７〜２５である。Ｒ⁵は直鎖又は分岐鎖であってもよく、飽和であっても不飽和であっても良い。また、Ｒ⁵はアミド基、エステル基又はエーテル基等の連結基をその鎖中に有するものであっても良い。 Component B: tertiary amine compound The tertiary amine compound is a compound represented by the following formula (2).

(In the formula, R ⁵ is a hydrocarbon group having 7 to 27 carbon atoms which may have a substituent and / or a linking group (when it has a substituent and / or a linking group, the substituent and / or the linking group). R ⁶ and R ⁷ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched group having 1 to 4 carbon atoms. Or a polyoxyethylene group having 1 to 25 moles of added EO.)
The carbon number of the hydrocarbon group of R ⁵ (when having a substituent and / or linking group, the carbon number in the substituent and / or linking group is not included in the carbon number here) is 7 to 27, preferably Has 7 to 25 carbon atoms. R ⁵ may be linear or branched and may be saturated or unsaturated. R ⁵ may have a linking group such as an amide group, an ester group or an ether group in the chain.

（式中、Ｒ⁸は、直鎖又は分岐鎖であっても良く、飽和であっても不飽和であっても良い炭素数７〜２３、好ましくは７〜２１の炭化水素基である。Ｒ⁹は、炭素数１〜４の直鎖又は分岐したアルキレン基である。Ｒ¹⁰及びＲ¹¹はそれぞれ独立して炭素数１〜４の直鎖又は分岐したアルキル基、炭素数１〜４の直鎖若しくは分岐したヒドロキシアルキル基又はＥＯ付加モル数１〜２５のポリオキシエチレン基である。）

（式中、Ｒ¹²は、直鎖又は分岐鎖であっても良く、飽和であっても不飽和であっても良い炭素数１１〜２３、好ましくは１２〜２０の炭化水素基である。Ｒ¹³は、炭素数１〜４の直鎖又は分岐したアルキレン基である。Ｒ¹⁴及びＲ¹⁵はそれぞれ独立して炭素数１〜４の直鎖又は分岐したアルキル基、炭素数１〜４の直鎖若しくは分岐したヒドロキシアルキル基又はＥＯ付加モル数１〜２５のポリオキシエチレン基である。） Among the compounds represented by the formula (2), tertiary amine compounds represented by the following formula (3) or the following formula (4) are preferable.

(In the formula, R ⁸ may be linear or branched, and may be a saturated or unsaturated hydrocarbon group having 7 to 23 carbon atoms, preferably 7 to 21 carbon atoms. ⁹ is a linear or branched alkylene group having 1 to 4 carbon atoms, R ¹⁰ and R ¹¹ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and a straight chain having 1 to 4 carbon atoms. A chain or branched hydroxyalkyl group or a polyoxyethylene group having 1 to 25 moles of EO addition.)

(In the formula, R ¹² may be linear or branched, and may be a saturated or unsaturated hydrocarbon group having 11 to 23 carbon atoms, preferably 12 to 20 carbon atoms. ¹³ is a linear or branched alkylene group having 1 to 4 carbon atoms, R ¹⁴ and R ¹⁵ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and a straight chain having 1 to 4 carbon atoms. A chain or branched hydroxyalkyl group or a polyoxyethylene group having 1 to 25 moles of EO addition.)

Specific examples of the tertiary amine compound include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropyl. Long-chain aliphatic amide dialkyl tertiary amines such as amide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide (compound represented by formula (3)); palmitate ester propyldimethylamine, stearate ester propyldimethylamine Long chain aliphatic ester dialkyl tertiary amine (compound represented by formula (4)); palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopro Such as it is possible to increase the Ruamido.
Among them, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide Oleic acid dimethylaminopropylamide is preferred.

  Tertiary amine compounds are known substances and can be easily obtained on the market. Moreover, it can also manufacture according to the following method.

For example, a long-chain aliphatic amidodialkyl tertiary amine is obtained by subjecting a fatty acid or a derivative thereof (fatty acid lower alkyl ester, animal / vegetable oil or fat) to a condensation reaction with a dialkyl (or dialkanol) aminoalkylamine, It can be obtained by distilling off the dialkyl (or dialkanol) aminoalkylamine of the reaction under reduced pressure or nitrogen blowing.
Examples of the “fatty acid or derivative thereof” include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid, corn Specific examples include oil fatty acids, beef tallow fatty acids, palm kernel oil fatty acids, soybean oil fatty acids, linseed oil fatty acids, castor oil fatty acids, olive oil fatty acids and other vegetable oils or animal oil fatty acids, or methyl esters, ethyl esters, glycerides, etc. Among them, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are particularly preferable.
These fatty acids or fatty acid derivatives may be used alone or in combination of two or more. Specific examples of the “dialkyl (or dialkanol) aminoalkylamine” include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine and the like, and among them, dimethylaminopropylamine is particularly preferable.
The amount of dialkyl (or dialkanol) aminoalkylamine used in the production of the long-chain aliphatic amidodialkyl tertiary amine is preferably 0.9 to 2.0 times the moles of the fatty acid or derivative thereof, 1.0 -1.5 times mole is particularly preferred.
The reaction temperature is usually 100 to 220 ° C, preferably 150 to 200 ° C. By setting the reaction temperature to 100 ° C. or higher, the reaction rate can be kept moderate, and by setting the reaction temperature to 220 ° C. or lower, the coloring of the tertiary amine compound obtained can be prevented or reduced.

The production conditions other than those described above for the long-chain aliphatic amidodialkyl tertiary amine can be appropriately changed depending on the type of raw material used. For example, the pressure during the reaction may be normal pressure or reduced pressure, and an inert gas such as nitrogen may be blown during the reaction.
In addition, when using a fatty acid, an acid catalyst such as sulfuric acid or p-toluenesulfonic acid is used. When using a fatty acid derivative, an alkali catalyst such as sodium methylate, caustic potash or caustic soda is used for a short time at a low reaction temperature. The reaction can proceed more efficiently.
In addition, when the obtained tertiary amine compound is a long chain amine having a high melting point, it is preferably formed into a flake shape or a pellet shape after the reaction in order to improve handling properties, or an organic material such as ethanol. It is preferable to make it liquid by dissolving in a solvent.

When producing a long-chain aliphatic ester dialkyl tertiary amine, the amount of dialkylamino alcohol used in the esterification reaction is preferably 0.1 to 5.0 moles relative to the fatty acid or derivative thereof, 0.3 to 3.0 times mole is more preferable, 0.9-2.0 times mole is still more preferable, and 1.0-1.5 times mole is especially preferable.
The reaction temperature is usually 100 to 220 ° C, preferably 120 to 180 ° C. When the reaction temperature is 100 ° C. or higher, the reaction rate can be kept moderate, and when the reaction temperature is 220 ° C. or lower, the coloration of the tertiary amine compound obtained can be prevented or reduced.

  Other specific examples of the tertiary amine compound that can be used as the component B include lauryl dimethylamine, myristyl dimethylamine, palm alkyl dimethyl amine, palmityl dimethyl amine, beef tallow alkyl dimethyl amine, cured beef tallow alkyl dimethyl amine, stearyl dimethyl amine, Stearyl diethanolamine, polyoxyethylene hydrogenated beef tallow alkylamine (trade name: ETHOMEEN HT / 14 manufactured by Lion Akzo Co., Ltd.), and the like.

  In the present invention, an acid salt obtained by neutralizing the above-mentioned tertiary amine compound with an acid can also be used. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid, cumenesulfonic acid, and the like. Two or more types may be used in combination.

  In the present invention, a single type of tertiary amine compound may be used alone, or a plurality of types of tertiary amine compounds may be used in combination.

  The tertiary amine compound as the component B is blended mainly for the purpose of imparting to the liquid cleaning composition for clothing of the present invention the effect of suppressing the wrinkle of clothing generated by washing. The compounding quantity of B component is 0.1-10 mass% with respect to the total mass of the liquid cleaning composition for garments, Preferably it is 0.5-5 mass%. If it is 0.1% by mass or more, it is possible to obtain an anti-stiffness effect on clothing. When the content is 10% by mass or less, the liquidity of the liquid cleaning composition for clothing can be favorably maintained.

（式中、Ｒ²¹は低級アルキレン基である。）
Ｒ²¹の炭素数は１〜４、好ましくは２〜４である。
アルキレンテレフタレート単位の具体的としては、例えばエチレンテレフタレート単位、ｎ−プロピレンテレフタレート単位、イソプロピレンテレフタレート単位、ｎ−ブチレンテレフタレート単位、イソブチレンテレフタレート単位、ｓｅｃ−ブチレンテレフタレート単位、ｔｅｒｔ−ブチレンテレフタレート単位等があげられる。これらの中ではイソプロピレンテレフタレート単位が好ましい。
ｃ１単位として、単一種類のアルキレンテレフタレート単位を単独で用いてもよく、複数種類のアルキレンテレフタレート単位を組み合わせて使用してもよい。 Component C: Water-soluble polymer having an alkylene terephthalate unit and / or an alkylene isophthalate unit and an oxyalkylene unit and / or a polyoxyalkylene unit. “An alkylene terephthalate unit and / or an alkylene isophthalate unit constituting a water-soluble polymer of component C” ”(Hereinafter also referred to as c1 unit), the alkylene terephthalate unit is a unit represented by the following formula (6).

(In the formula, R ²¹ is a lower alkylene group.)
R ²¹ has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
Specific examples of the alkylene terephthalate unit include an ethylene terephthalate unit, an n-propylene terephthalate unit, an isopropylene terephthalate unit, an n-butylene terephthalate unit, an isobutylene terephthalate unit, a sec-butylene terephthalate unit, and a tert-butylene terephthalate unit. . Of these, isopropylene terephthalate units are preferred.
As the c1 unit, a single type of alkylene terephthalate unit may be used alone, or a plurality of types of alkylene terephthalate units may be used in combination.

（式中、Ｒ²²は低級アルキレン基である。）
Ｒ²²の炭素数は１〜４、好ましくは２〜４である。
アルキレンイソフタレート単位の具体例としては、例えば、エチレンイソフタレート単位、プロピレンイソフタレート単位、ｎ−ブチレンイソフタレート単位、ｓｅｃ−ブチレンイソフタレート単位、ｔｅｒｔ−ブチレンイソフタレート単位等が挙げられる。これらの中ではプロピレンイソフタレート単位が好ましい。
ｃ１単位として、単一種類のアルキレンイソフタレート単位を単独で用いてもよく、複数種類のアルキレンイソフタレート単位を組み合わせて使用してもよい。 Among the c1 units constituting the water-soluble polymer, the alkylene isophthalate unit is a unit represented by the following formula (7).

(In the formula, R ²² is a lower alkylene group.)
R ²² has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
Specific examples of the alkylene isophthalate unit include an ethylene isophthalate unit, a propylene isophthalate unit, an n-butylene isophthalate unit, a sec-butylene isophthalate unit, and a tert-butylene isophthalate unit. Of these, propylene isophthalate units are preferred.
As the c1 unit, a single type of alkylene isophthalate unit may be used alone, or a plurality of types of alkylene isophthalate units may be used in combination.

  As the c1 unit, one selected from the above-mentioned alkylene terephthalate units and alkylene isophthalate units can be used alone or in combination of two or more. That is, the c1 unit may be composed only of an alkylene terephthalate unit, may be composed only of an alkylene isophthalate unit, or may be composed of a mixture of an alkylene terephthalate unit and an alkylene isophthalate unit. Good.

The “oxyalkylene unit and polyoxyalkylene unit” (hereinafter also referred to as c2 unit) constituting the water-soluble polymer of component C is a unit represented by the following formula (8).
− (R ²³ O) _s − (8)
(In the formula, R ²³ is a lower alkylene group, and s is an integer of 1 to 100.)
R ²³ has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
In Formula (8), when S is 1, it becomes an oxyalkylene unit, and when S is 2 or more, it becomes a polyoxyalkylene unit. S is an integer of 1 to 100, preferably 1 to 80, particularly preferably 1 to 50.
Specific examples of the c2 unit include an oxyethylene unit and a polyoxyethylene unit; an oxypropylene unit and a polyoxypropylene unit; a polyoxyethylene polyoxypropylene unit. An oxyethylene unit and a polyoxyethylene unit are preferred.
As the c2 unit, those selected from the above oxyalkylene units and polyoxyalkylene units can be used alone or in combination of two or more. That is, the c2 unit may be composed only of an oxyalkylene unit, may be composed only of a polyoxyalkylene unit, or may be composed of a mixture of an oxyalkylene unit and a polyoxyalkylene unit. Good.

The component C is preferably a polymer compound in which the above-mentioned c1 unit and c2 unit are polymerized randomly or in a block, and in particular, those polymerized in a block are preferred.
The component C may contain units other than the above-mentioned c1 unit and c2 unit (for example, a unit derived from a polymerization initiator, a polymerization terminator, and the like, and other copolymerizable units). In that case, it is preferable that 80 mol% or more, preferably 90 mol% or more of the component C is composed of c1 units and c2 units.

  The “water-soluble polymer” in component C is 10 g of the polymer added to 1000 g of water at 40 ° C. and stirred for 12 hours (200 rpm with a stirrer (thickness 8 mm, length 50 mm, 1 liter beaker)). ) That completely dissolves.

（式中、Ａ及びＢはそれぞれ独立して、水素原子又はメチル基、好ましくは共にメチル基であり、Ｒ¹及びＲ²はそれぞれ独立して、炭素数２〜４のアルキレン基、好ましくは炭素数２〜３のアルキレン基であり、Ｘは０〜１０、好ましくは０．５〜５、特に好ましくは０．５〜２．５であり、ｙは１〜１００、好ましくは1〜８０、より好ましくは1〜５０、更に好ましくは１０〜５０、特に好ましくは２０〜３０である。）

（式中、Ａ及びＢはそれぞれ独立して、水素原子又はメチル基、好ましくは共にメチル基であり、Ｒ¹及びＲ²はそれぞれ独立して、炭素数２〜４のアルキレン基、好ましくは炭素数２〜３のアルキレン基であり、Ｘは０〜１０、好ましくは０．５〜５、特に好ましくは０．５〜２．５であり、ｙは、１〜１００、好ましくは１〜８０、より好ましくは1〜５０、更に好ましくは１０〜５０、特に好ましくは２０〜３０である。） Specific examples of suitable component C include compounds represented by the following formula (9) or (10).

(In the formula, A and B are each independently a hydrogen atom or a methyl group, preferably a methyl group, and R ¹ and R ² are each independently an alkylene group having 2 to 4 carbon atoms, preferably carbon. An alkylene group having a number of 2 to 3, X is 0 to 10, preferably 0.5 to 5, particularly preferably 0.5 to 2.5, and y is 1 to 100, preferably 1 to 80. Preferably it is 1-50, More preferably, it is 10-50, Most preferably, it is 20-30.)

(In the formula, A and B are each independently a hydrogen atom or a methyl group, preferably a methyl group, and R ¹ and R ² are each independently an alkylene group having 2 to 4 carbon atoms, preferably carbon. An alkylene group having a number of 2 to 3, X is 0 to 10, preferably 0.5 to 5, particularly preferably 0.5 to 2.5, and y is 1 to 100, preferably 1 to 80, More preferably, it is 1-50, More preferably, it is 10-50, Most preferably, it is 20-30.)

  In the formulas (9) and (10), the ratio of X and y is preferably such that X: y is 1: 5 to 1:20, and more preferably 1: 8 to 1:18. When X: y is within such a range, the soil release performance is sufficiently exhibited and the solubility in water is improved, which is preferable.

The component C preferably has a weight average molecular weight of 500 to 8000. When the component C in this weight average molecular weight range is used, the dispersibility in water can be improved, and the effect of improving the water absorption of hydrophobic fibers (especially polyester) can be sufficiently exhibited. The liquid appearance is improved.
The weight average molecular weight refers to a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent and using PEG (polyethylene glycol) as a calibration curve. The lower limit of the weight average molecular weight is more preferably 800 or more, and particularly preferably 1000 or more. The upper limit of the weight average molecular weight is preferably 7000 or less, and particularly preferably 6000 or less. Therefore, the weight average molecular weight is preferably 800 to 7000, and particularly preferably 1000 to 6000.

The pH of component C (5% aqueous solution at 20 ° C.) is preferably 3-7.
The melting point of component C is preferably 25 ° C to 60 ° C.
It is preferable that the viscosity (50 degreeC) of C component is 100-1000 mPa * s. The viscosity is a value measured using a No. 2 rotor with a Brookfield viscometer.

  Component C is a known substance and can be easily obtained in the market. Further, synthesis methods disclosed in literatures: for example, Journal of Polymer Science, Vol. 3, pages 609 to 630 (1948), Journal of Polymer Science, Vol. 8, pages 1 to 22 (1951), JP It can be produced by the method described in JP-A-61-218699.

  Specific examples of the component C are commercially available as trade name: TexCare SRN-100 (Clariant, weight average molecular weight: 2000 to 3000) and trade name: TexCare SRN-300 (Clariant, weight average molecular weight: 7000). What is being done is mentioned. Among these, TexCare SRN-100 is preferable because of its high solubility in water and little reduction in cleaning performance after storage. Particularly preferred is a 70% aqueous solution of TexCare SRN-100, which is commercially available as trade name: TexCare SRN-170 (manufactured by Clariant).

  The C component is blended mainly for the purpose of imparting the water absorption improving action of the polyester garment to the liquid detergent composition for garment of the present invention, in combination with the D component described later. The compounding quantity of C component is 0.1-10 mass% with respect to the total mass of the liquid cleaning composition for garments, Preferably it is 0.1-5 mass%, Most preferably, it is 0.5-3 mass%. When the content is 0.1% by mass or more, the water absorption improvement effect of the polyester garment can be obtained. When the content is 10% by mass or less, the stability of the liquid detergent composition for clothing can be favorably maintained.

Component D: Anionic surfactant Anionic surfactants can be used without particular limitation as long as they are commonly used in liquid detergent compositions for clothing. For example, it is described as "anionic surfactant" in "Patent Office Gazette 10 (1998) -25 [7159] Collection of Known and Conventional Techniques (powder detergent for clothing), issued on March 26, 1998". You can use what you have.
Anionic surfactants are known substances and can be easily obtained on the market.

Specific examples include a linear alkylbenzene sulfonic acid or a salt thereof; an α-olefin sulfonate; a linear or branched alkyl sulfate ester salt; an alkyl ether sulfate ester salt or an alkenyl ether sulfate ester salt; an alkanesulfone having an alkyl group. Acid salts, α-sulfo fatty acid ester salts; higher fatty acid salts and the like.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
In the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide added (ie, , Polyoxyethylene alkyl ether sulfates or polyoxyethylene alkenyl ether sulfates) are preferred. Carbon number of the alkyl group which comprises polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt is 10-20, Preferably it is 10-16. The average added mole number of ethylene oxide is 1 to 10, preferably 0.5 to 8.
The carbon number of the alkane sulfonate is 10 to 20, preferably 14 to 17. Secondary alkane sulfonates are particularly preferred.
The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.
As higher fatty acid salts, those having 10 to 20 carbon atoms are preferred.

  Among the specific examples described above, linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, and polyoxyethylene alkyl ether sulfate are preferable.

  As D component, a single kind of anionic surfactant may be used alone, or a plurality of kinds of anionic surfactants may be used in combination.

  The anionic surfactant which is the D component is blended mainly for the purpose of imparting the water absorption improving action of the polyester garment to the liquid detergent composition for garment of the present invention in combination with the above-mentioned C component. The compounding amount of the anionic surfactant is preferably 0.1 to 5% by mass, particularly preferably 0.5 to 3% by mass, based on the total mass of the liquid detergent composition for clothing. When the content is 0.1% by mass or more, the water absorption improvement effect of the polyester garment can be obtained. When the content is 5% by mass or less, the B component is adsorbed to the polyester clothing, and an effect of inhibiting the clothing from being stiffened is obtained.

In addition to the components A to D, optional components can be blended with the garment cleaning composition of the present invention. Specific examples include enzymes (proteases, lipases, cellulases, etc.), stabilizers (sodium benzoate, citric acid, sodium citrate, p-toluenesulfonic acid, polyhydric alcohol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, polyethylene Polypropylene glycol alkyl ether, polyethylene (propylene) glycol phenyl ether, polypropylene glycol phenyl ether, polyethylene polypropylene glycol phenyl ether, etc.), texture improver such as silicone, pH adjuster (sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine, etc.) ), Preservatives, hydrotropes, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, colorants (Acid Red 138, Direct) Luo 86, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Turquoise PGR (both trade names) and other general-purpose dyes and pigments), flavoring agents and emulsifying agents, etc. Additives and solvents such as water and alcohol (eg, ethanol) are included, but are not limited thereto.
The selection and blending amount of the optional component can be arbitrarily selected as long as the object of the present invention is not impaired.
In addition, the liquid cleaning composition for clothes which does not contain the cationic polymer described in JP 2005-179529 A, or the liquid cleaning composition for clothes which does not contain the silicone compound described in JP 2007-169514 A Is one embodiment of the present invention.

The pH (25 degreeC) of the liquid cleaning composition for clothes of this invention is 4-8, Preferably it is 5-8. When the pH is 4 to 8, high storage stability of the liquid detergent composition can be obtained.
The liquid detergent composition for clothing of the present invention has a viscosity (25 ° C.) of 5 to 500 mPa · s, preferably 10 to 300 mPa · s. When the viscosity is 5 mPa · s or more, measurement with a cap is easy, and when the viscosity is 500 mPa · s or less, the usability of the liquid detergent composition (bottle remaining, applicability to an object to be washed, measurement with a cap) The ease of such as) is improved. The viscosity is a value measured with a BL type viscometer and No. 1 rotor at 25 ° C. using a 300 ml tall beaker.

  The liquid detergent composition for clothing of the present invention can be prepared based on a conventional method. For example, ethanol is charged into a reaction vessel, and component A is added and dissolved therein. Further, water is added, component B previously dissolved in ethanol at 40 ° C. is added and stirred sufficiently, and component C is then added. And D component and an arbitrary component are added, it stirs fully, and it can manufacture by adjusting pH with a pH adjuster.

  The liquid cleaning composition for clothing of the present invention can be used in the same manner as a liquid cleaning composition for clothing. For example, washing can be performed by immersing clothing that is an object to be washed in a liquid detergent composition for clothing dissolved in water.

The article to be washed which is the object of the liquid cleaning composition for clothing of the present invention is clothing. Among the garments, polyester garments (garments including polyester fibers) are preferable in that the occurrence of stuffiness and wrinkle can be suppressed. The polyester apparel may be an apparel made of 100% polyester fiber, or may be a blended apparel made of polyester fiber and other fibers.
In addition, since the liquid detergent composition for clothes of the present invention has excellent cleaning power for clothes other than polyester clothes (other clothes), the polyester clothes and other clothes can be washed simultaneously, It can also be used for washing clothes only.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples.

Production of liquid detergent composition for clothing A liquid detergent composition for clothing having the composition shown in Table 1 was produced according to the following steps. Add ethanol to a 1 liter scale glass beaker placed in a magnetic stirrer (MITAMURA RIKEN KOGYO INC.), Add component A to it, dissolve in ethanol, add water, and then add ethanol at 40 ° C in advance. The B component dissolved in was added and stirred sufficiently, then the C component, D component and optional component were added, and after further sufficient stirring, the pH was adjusted with a pH adjuster.
The compounding amount unit of each component in Table 1 is mass% based on the total mass of the liquid detergent composition.

As the component A (nonionic surfactant), substances shown in the following A-1 to A-4 were used.
A-1
Product name: 12 mol of ethylene oxide (EO) added to 1 mol of alcohol of Safol 23 (manufactured by Sasol) (compound of formula (1) (wherein R ³ = C ₁₂ or C ₁₃ linear or Branched alkyl group or alkenyl group (C ₁₂ / C ₁₃ mass ratio = 6/4), R ³ branching ratio: 50%, Y = —O—, R ⁴ = H, m = 12, n = 0) Equivalent to

A-2
Product name: A compound obtained by adding 15 mol of ethylene oxide (EO) to 1 mol of alcohol of Safol 23 (manufactured by Sasol) (a compound of formula (1) (wherein R ³ = C ₁₂ or C ₁₃ linear) Or branched alkyl group or alkenyl group (C ₁₂ / C ₁₃ mass ratio = 6/4), R ³ branching ratio: 50%, Y = —O—, R ⁴ = H, m = 15, n = 0 Equivalent to

A-3
Product name: CO-1214 (manufactured by P & G) with 12 moles of ethylene oxide added to 1 mole of natural alcohol (compound of formula (1) (wherein R ³ = C ₁₂ or C ₁₄ linear) Alkyl group or alkenyl group (C ₁₂ / C ₁₄ mass ratio = 7/3), R ³ branching ratio: 0%, Y = —O—, R ⁴ = H, m = 12, n = 0) Equivalent)

A-4
A product obtained by adding 7 moles of ethylene oxide to 1 mole of C ₁₃ alcohol synthesized by subjecting a trimer of butene to the oxo method (trade name: Lutensol TO7 (manufactured by BASF)) (compound of formula (1) (In the formula, R ³ = C ₁₃ branched alkyl group or alkenyl group, R ³ branching ratio: 100%, Y = —O—, R ⁴ = H, m = 7, n = 0))

As B component (tertiary amine compound), the substances shown in the following B-1 to B-4 were used.
B-1
Long chain fatty acid (C ₁₆ / C ₁₈ ) dimethylaminopropylamide (mass ratio of stearic acid (C ₁₈ ) / palmitic acid (C ₁₆ ) = 7/3), trade name Katchinal MPAS-R (manufactured by Toho Chemical Co., Ltd.) (Corresponding to the compound of formula (3))

B-2
Long chain fatty acid (C ₁₆ / C ₁₈ ) dimethylaminopropylamide (mass ratio of stearic acid / palmitic acid = 7/3) (corresponding to the compound of formula (3))
B-2 was produced according to the following steps. A 1-liter four-necked flask equipped with a reflux condenser was charged with 252 g of stearic acid (molecular weight 284) and 108 g of palmitic acid (molecular weight 256), and heated to 80 ° C. to melt the stearic acid. After carrying out nitrogen substitution twice, the temperature was raised to 150 ° C., and 127 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to the mixed fatty acid: 0.95) was added dropwise over 1 hour. Next, after maintaining at 150 to 160 ° C. for 1 hour, the temperature was raised to 185 ° C. over 1 hour, and 47 g of dimethylaminopropylamine was further added dropwise over 1 hour. After completion of the dropping, the temperature was maintained at 185 to 190 ° C. and aged for 7 hours to distill off by-product water out of the system. Further, while maintaining the temperature at 170 to 190 ° C., the pressure was reduced (4.0 kPa) and the mixture was allowed to stand for 1 hour to distill off unreacted dimethylaminopropylamine.

B-3
C18 amidoamine synthetic product: dimethylaminopropylamide stearate (corresponding to the compound of formula (3))
B-3 was produced according to the following procedure. A 1 liter four-necked flask equipped with a reflux condenser was charged with 360 g of stearic acid (molecular weight 284) and heated to 80 ° C. to melt the stearic acid. After performing nitrogen substitution twice, the temperature was raised to 150 ° C., and 123 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to stearic acid: 0.95) was added dropwise over 1 hour. Next, after holding at 150 to 160 ° C. for 1 hour, the temperature was raised to 185 ° C. over 1 hour, and 45 g of dimethylaminopropylamine was further added dropwise over 1 hour. After completion of the dropping, the temperature was maintained at 185 to 190 ° C. and aged for 7 hours to distill off by-product water out of the system. Further, while maintaining the temperature at 170 to 190 ° C., the pressure was reduced (4.0 kPa) and the mixture was allowed to stand for 1 hour to distill off unreacted dimethylaminopropylamine.

B-4
C10 amidoamine synthetic product: capric acid dimethylaminopropylamide (corresponding to the compound of formula (3))
B-4 was produced according to the following procedure. A 1-liter four-necked flask equipped with a reflux condenser was charged with 260.9 g of methyl caprate (manufactured by Lion Chemical Co., Ltd., pastel M-10, molecular weight 186) and subjected to nitrogen substitution twice at 60 ° C. The temperature was raised to 150 ° C., and 186 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to capric acid: 1.30) was added dropwise over 1.5 hours. After completion of dropping, the mixture was kept at 185 to 190 ° C. and aged for 7 hours. The conversion rate of capric acid calculated from the acid value was 97.2%.

As the component C (water-soluble polymer having an alkylene terephthalate unit and / or an alkylene isophthalate unit and an oxyalkylene unit and / or a polyoxyalkylene unit), substances shown in the following C-1 to C-2 were used.
C-1
Product name: TexCare SRN-170 (manufactured by Clariant) (weight average molecular weight: 2000 to 3000, pH (5% aqueous solution at 20 ° C.): 4. Viscosity (20 ° C.): 300 mPa · s). TexCare SRN-170 is trade name: TexCare SRN-100 (manufactured by Clariant) (weight average molecular weight: 2000-3000, pH (5% aqueous solution at 20 ° C.): 4. Melting point: 31-37 ° C. Viscosity (50 ° C. ): 340 mPa · s) (70% aqueous solution of the compound of formula (9).

C-2
Product name: TexCare SRN-300 (manufactured by Clariant) (weight average molecular weight: 7000). pH (5% aqueous solution at 20 ° C.): 5. Melting point: 35-55 ° C. (Corresponding to the compound of formula (9))

C-1 and C-2 were both water-soluble polymer conditions described above (10 g of polymer was added to 1000 g of water at 40 ° C., and a stirrer (thickness 8 mm, length 50 mm, 1 liter beaker). ) For 12 hours with stirring (200 rpm).

As the D component D component (anionic surfactant), the substances shown in the following D-1 to D-4 were used.

D-1
Linear alkylbenzene sulfonate Na (manufactured by Lion) (alkyl group carbon chain length 10-14)

D-2
Polyoxyethylene C _12-13 mixed alkyl ether sulfate Na (average added mole number of ethylene oxide 2). Product name: Neodol 23 (manufactured by Shell) (C ₁₂ / C ₁₃ mass ratio = 4/6, branching rate 30%) was used as the raw material alcohol.

D-3
Secondary Alkanesulfonate Na (trade name: HOSTAPUR SAS 93 (manufactured by Clariant)) Alkyl group having 14 to 17 carbon atoms

D-4
C _12-13 sodium alkylethoxysulfate (average addition mole number of ethylene oxide 2). The product name: Saffol 23 (manufactured by Sasol) (mass ratio of C ₁₂ / C ₁₃ = 6/4, branching rate 50%) was used as the raw alcohol.

^*衣料用洗浄剤組成物全体の量を100部（Ａ〜Ｄをはじめとする各成分の質量％の計算の基準となる衣料用洗浄剤組成物の総質量）とするための量。 Common component The liquid cleaning composition for clothing contained the following components in common (common components in Table 1).

^* Amount for setting the total amount of the cleaning composition for clothing to 100 parts (the total weight of the cleaning composition for clothing as a basis for calculating the mass% of each component including A to D).

Evaluation of liquid detergent composition for clothing Polyester garments were washed with the various liquid detergent compositions produced above, and the polyester clothes after washing were evaluated for stiffness and water absorption.

Washing procedure (1) Preparation of test cloth Non-ionized commercially available polyester jersey (dyeing material manufactured by Tanigami Shoten Co., Ltd.) in a two-tank washing machine (CW-C30A1-H, manufactured by Mitsubishi Electric, the same applies hereinafter) Washing for 10 minutes (bath ratio 30 times) using a 20% aqueous solution of a surfactant (alcohol ethoxylate added with an average of 15 moles of ethylene oxide per mole of lauryl alcohol) and tap water at 40-50 ° C Then, rinsing with tap water of any temperature was performed for 15 minutes. These procedures were repeated twice. Then, what was dried at room temperature was used as a test cloth.
(2) Cleaning of test cloth Fully automatic washing of test cloth for 0.4 kg of polyester jersey (a part of the jersey was cut out) and four cotton shirts (600 kg) to secure the mass of the item to be washed Machine (model name: AW-80VC, manufactured by Toshiba), add 25mL of the liquid detergent composition for clothing shown in Table 1 to 30L of water (20% bath ratio, use tap water at 25 ° C) ) After that, those that were dried at room temperature for 24 hours were evaluated for inhibition of sticking and water absorption.

Evaluation of Stiffness Control The evaluation of stiffness control was conducted using “20% aqueous solution of nonionic surfactant described in“ (1) Preparation of test cloth ”as a cleaning agent, and“ (2) Cleaning test cloth ”. The test cloth washed and dried in accordance with the described procedure was used as a control cloth, and was subjected to a paired comparative evaluation by ten professional panelists. The evaluation criteria were as follows. Two points or more were regarded as passing (having an effect of suppressing the stickiness). The evaluation results are shown in the column of “Stabilization control” in Table 1.

(Evaluation criteria)
1 point: Stiffness is equal to or more than that of the control cloth 2 points: Stiffness is suppressed slightly compared to the control cloth 3 points: Stiffness is suppressed more than the control cloth 4 points: Stiffness is suppressed much more than the control cloth Have

Evaluation of water absorption It evaluated according to JISL1096 (Bairec method). Specifically, the test cloth was cut into 2.0 cm × 20 cm, immersed in pure water (25 ° C.) colored with a blue pigment for 5 mm, and the height (mm) of colored water rising for 10 minutes was measured. The case where the height of the colored water is 10 mm or more, which reflects the state of feeling sensuously if there is no discomfort due to stuffiness due to low water absorption, was regarded as acceptable. The evaluation results are shown in the column of “Water absorption” in Table 1.

Comparative Examples 1 and 2 in which the C component and the D component of the present invention were not blended did not satisfy the acceptance criteria in water absorption. Moreover, the comparative example 3 which does not mix | blend D component of this invention and the comparative example 4 which does not mix | blend C component of this invention also did not satisfy the acceptance criteria in water absorption.
Moreover, the comparative example 5 which does not mix | blend B component of this invention did not satisfy | fill the acceptance | permission standard in suppression of wobbling.
On the other hand, Examples 1-16 which comprise the requirements of this invention satisfy | filled the acceptance standard in any of stickiness suppression and water absorption. Moreover, it is understood from the comparison between Example 4 and Comparative Examples 3 and 4 that the combined use of Component C and Component D dramatically improves the water absorption of the polyester garment.

  The present invention can be used as a liquid cleaning composition for clothing.

Claims (3)

The following components A to D:
A: nonionic surfactant,
B: tertiary amine compound,
C: a water-soluble polymer having an alkylene terephthalate unit and / or an alkylene isophthalate unit and an oxyalkylene unit and / or a polyoxyalkylene unit, and
D: A liquid detergent composition for clothing, comprising an anionic surfactant. The liquid cleaning composition according to claim 1, wherein the component C is a water-soluble polymer represented by formula (9) and / or formula (10).

(In the formula, A and B are each independently a hydrogen atom or a methyl group, R ¹ and R ² are each independently an alkylene group having 2 to 4 carbon atoms, and X is 0 to 10) , Y is 1 to 100.)

(In the formula, A and B are each independently a hydrogen atom or a methyl group, R ¹ and R ² are each independently an alkylene group having 2 to 4 carbon atoms, and X is 0 to 10) , Y is 1 to 100.)   The liquid detergent composition for clothing according to claim 1, which is for polyester clothing.