JP5292606B2 - Liquid detergent composition for clothing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent the stiffening and resoiling generated upon the washing of clothes. <P>SOLUTION: Disclosed is a liquid detergent composition for clothes comprising: (A) a nonionic surfactant of 10 to 50 mass%; (B) long-length tertiary amine and/or the salt thereof and/or a cationic surfactant of 0.1 to 10 mass%; and (C) a water soluble polymer having (c1) an alkylene terephthalate unit and/or an alkylene isophthalate unit and (c2) an oxyalkylene unit and/or a polyoxyalkylene unit of 0.01 to 10 mass%. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a liquid detergent composition suitably used for washing clothes and the like.

Conventionally, many liquid cleaning compositions for clothing aimed at improving the texture such as flexibility in addition to washing dirt have been proposed. In the liquid detergent composition for clothes having the flexibility, the softener and the surfactant contained in the detergent composition adhere to the article to be washed with the dirt once removed from the article to be washed. Often cause recontamination.
Therefore, various techniques for preventing recontamination as well as a cleaning effect and an effect of imparting flexibility have been studied.
For example, in order to maintain the texture, a detergent composition (Patent Documents 1 and 2) containing a specific nonionic surfactant and a silicone compound, and a water-soluble polymer are contained to impart a recontamination preventing effect. A cleaning composition (Patent Documents 3 and 4) has been studied.

JP 2006-225635 A JP 2002-249799 A JP 2006-63304 A JP 2002-180092 A

However, even when the above technique is used, the following problems occur.
In recent years, a large-capacity washing machine represented by a drum-type washing machine has been widely used for the purpose of increasing the size of a washing machine and improving the water-saving effect. Such a large-capacity washing machine has a large capacity and can wash clothes together. On the other hand, there is a demerit that the clothes are likely to become stiff and re-contaminated after washing due to a decrease in the bath ratio due to collective washing and water saving effect.
Furthermore, with respect to the textile material of clothing, the above-mentioned problems have become more serious as the blend of polyester material and cotton has increased.
In the conventional detergent composition, it has been difficult to avoid the above problems when washing clothes made of various fiber materials with a large-capacity washing machine such as a drum-type washing machine.

  The present invention has been made in view of the above circumstances, and provides a liquid detergent composition for clothing that is particularly excellent in the anti-stiffness effect and the anti-recontamination effect among the textures of the items to be washed. Let it be an issue.

As a result of intensive studies by the present inventors, it has been found that the above-mentioned problems can be solved by setting the cleaning composition for clothing to a specific composition, and the present invention has been achieved.
That is, the present invention
(A) 10-50 mass% of nonionic surfactant,
(B) 0.1-10% by mass of a cationic surfactant which is a long-chain tertiary amine and / or a salt thereof, and / or a quaternary ammonium salt, and (C) an alkylene terephthalate unit and / or an alkylene isophthalate. The present invention relates to a liquid detergent composition for clothing comprising 0.01 to 10% by mass of a water-soluble polymer having units and oxyalkylene units and / or polyoxyalkylene units.

− − − （１）
（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は炭素数２〜４のアルキレン基であり、Ｘは０〜１０の数であり、ｙは１〜１００の数である。）

− − −（２）
（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は炭素数２〜４のアルキレン基であり、Ｘは０〜１０の数であり、ｙは１〜１００の数である。） In the present invention, (C) is a water-soluble polymer represented by the following general formula (1) and / or (2).

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

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

  In the present invention, as (D), maleic acid and a hydrocarbon monomer having 4 to 12 carbon atoms copolymerizable with maleic acid and / or a copolymer of maleic acid and acrylic acid, and / or More preferably, the salt is contained in an amount of 0.01 to 10% by mass.

  By using the liquid detergent composition of the present invention, even when washing clothes at a low bath ratio typified by a drum-type washing machine, for example, the amount of water with respect to the cloth is 5 to 15 times, While maintaining the performance required for liquid detergent compositions for clothing, it is possible to impart a texture such as flexibility to clothing and to prevent recontamination of the items to be washed. .

Liquid detergent composition for clothing of the present invention The liquid detergent composition of the present invention comprises the components (A), (B) and (C) described below, and if necessary, the component (D) and / or It is obtained by blending other components. In addition, by mix | blending (D) component, the effect which prevents the recontamination of the cleaning composition for clothing of this invention further improves by the synergistic effect with (C) component.
Below, each component used in this invention is demonstrated.

(A) Component In the present invention, the component (A) is a nonionic surfactant and is blended mainly for imparting a cleaning function to the liquid cleaning composition for clothing. The nonionic surfactant in this invention can use the nonionic surfactant generally used in the field | area of a detergent composition without a restriction | limiting especially, Even if it uses individually by 1 type, 2 or more types are used. You may use together.
Examples of these nonionic surfactants include polyoxyalkylene type nonionic surfactants.

As the nonionic surfactant used in the present invention, for example, the following general formula (3) can be particularly preferably used.
R ³ —Y — [(EO) _m (PO) _n ] —R ⁴ ------ (3)
[Wherein R ³ represents a linear or branched alkyl group or alkenyl group; —Y— represents —O— or —COO—. R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. EO represents ethylene oxide, PO represents propylene oxide; m and n represent the average number of moles added.
In the general formula (3), when -Y- is -O-, the component (A) is an alcohol alkoxylate. In this case, R ³ has 10 to 22 carbon atoms, preferably 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, which may be linear or branched, It may have an unsaturated bond. In this case, R ⁴ is preferably a hydrogen atom.
When -Y- is -COO-, the component (A) is a fatty acid ester type nonionic surfactant. In this case, R ³ has 9 to 21 carbon atoms, preferably 11 to 21, may be linear or branched, and may have an unsaturated bond. Good. In this case, R ⁴ is preferably a C ₁ -C ₃ alkyl group.
EO and PO may be added alone or as a mixture, and EO group and PO group may be added as a block. In addition, the addition order of EO and PO may be as shown in the above formula (3), 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 3 to 20, preferably 5 to 18, and more preferably an integer of 5 to 15. The average added mole number n of PO is 0-6, preferably 0-3.
By setting m to 20 or less, it is possible to suppress a decrease in cleaning function due to disadvantageous cleaning of sebum due to an excessively high HLB value. By setting m to 3 or more, deterioration of odor is prevented. By setting n to 6 or less, it is possible to suppress a decrease in storage stability of the cleaning composition at a high temperature.
The added mole number distribution of EO or PO varies depending on the reaction method during the production of the nonionic surfactant (A), 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. Then, metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ and Mn ²⁺ described in JP-B-615038 were added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a specific alkoxylation catalyst such as magnesium oxide, the distribution tends to be relatively narrow.

  As a specific example of the component (A), (hereinafter, “Cp” (p is an integer) indicates that the carbon number is p.) Manufactured by Sasol: trade name Safol 23 (C12 / C13 mixture) Synthetic alcohol obtained by the oxo method such as, or manufactured by P & G: trade name CO-1214 (C12 / C14 mixture), trade name CO-1270 (C12 / 14 mixture), Eco Green Oleo Chemical: trade name Ecorol ( C12 / C14 mixture) and other natural alcohols with 15 or 12 moles of ethylene oxide added, Shin Nippon Rika Co., Ltd .: natural alcohols such as the trade name Conol (C12) To one mole of C13 alcohol obtained by adding ethylene, C12 alkene obtained by triming butene to oxo method 7 mol (BASF, trade name: Lutensol TO7) or 10 mole equivalent of ethylene oxide added (BASF, trade name: Lutensol TO10), 15 moles of ethylene oxide equivalent to lauric acid methyl ester Addition, 10 moles of ethylene oxide added to 1 mole of C12 alcohol obtained by subjecting hexanol to garvet reaction (CONDEA: trade name ISOFOL12-10EO), C12-14 secondary 15 mole equivalent ethylene oxide added to alcohol (Nippon Shokubai Co., Ltd .: trade name Softanol 150), methyl laurate equivalent to 15 mole ethylene oxide and 3 mole equivalent using alkoxylation catalyst And those obtained by adding propylene oxide.

Among the exemplified above, because of excellent detergency, those obtained by adding ethylene oxide 12 or 15 mole equivalent to C ₁₃ or C _12/13 alcohol, the C ₁₂ or C _12/14 natural alcohol 9,12 or 15 Those obtained by adding a molar equivalent of ethylene oxide or those obtained by adding 15 mol of ethylene oxide to lauric acid methyl ester are preferred. Further, because of excellent appearance stability of the liquid detergent composition at low temperatures, obtained by adding ethylene oxide 7 molar equivalent to C ₁₃ branched synthetic alcohols (BASF Corp., trade name Lutensol TO7) are preferred.

(B) component (B) component of this invention is a cationic surfactant which is a long-chain tertiary amine and / or its salt, and / or a quaternary ammonium salt, By blending the component B), it is possible to prevent or reduce wrinkles that occur in clothing washed with the detergent composition. Here, the long-chain tertiary amine means one represented by the following general formula (4).

上記式（４）中、Ｒ⁵は炭素数７〜２７（ここでの炭素数には、置換基及び連結基中の炭素数は含まない）の炭化水素基であり、直鎖であっても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く、さらには置換基を含むものであっても良い。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く、連結基としてはアミド基、エステル基が好ましく用いられる。
中でも、Ｒ⁵としては「−Ｒ⁸−Ｗ」（但し、Ｒ⁸は炭素数１〜４の直鎖又は分岐したアルキレン基である。Ｗは、−ＮＨＣＯ−Ｒ⁹又は−ＯＯＣ−Ｒ¹⁰であり、Ｒ⁹は炭素数７〜２３、好ましくは７〜２１の炭化水素基であり、Ｒ¹⁰は炭素数１１〜２３、好ましくは１２〜２０の炭化水素基であり、Ｒ⁹およびＲ¹⁰は直鎖であっても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。）が好ましく用いられる。 As the component (B), a long-chain tertiary amine represented by the following general formula (4) is preferable.

In the above formula (4), R ⁵ is a hydrocarbon group having 7 to 27 carbon atoms (the number of carbon atoms here does not include the number of carbon atoms in the substituent and the linking group). It may be branched, may be saturated or unsaturated, and may further contain a substituent. R ⁵ may have a linking group such as an amide group, an ester group or an ether group in its chain, and an amide group or an ester group is preferably used as the linking group.
Among them, R ⁵ is “—R ⁸ —W” (where R ⁸ is a linear or branched alkylene group having 1 to 4 carbon atoms. W is —NHCO—R ⁹ or —OOC—R ¹⁰ . R ⁹ is a hydrocarbon group having 7 to 23 carbon atoms, preferably 7 to 21 carbon atoms, R ¹⁰ is a hydrocarbon group having 11 to 23 carbon atoms, preferably 12 to 20 carbon atoms, and R ⁹ and R ¹⁰ are It may be linear or branched, and may be saturated or unsaturated).

R ⁶ is a hydrocarbon group having 1 to 25 carbon atoms.
R ⁶ may be linear or branched, may be saturated or unsaturated, and may further contain a substituent. R ⁶ may have a linking group such as an amide group, an ester group or an ether group in the chain. Of these, a linear or branched alkyl group having 1 to 4 carbon atoms and a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms are preferably used.
R ⁷ is any one of a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, and a polyoxyethylene group having 1 to 25 moles of EO addition. A linear or branched alkyl group having 1 to 4 carbon atoms and a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms are preferably used.

但し、上記式（５）中、Ｒ¹¹、Ｒ¹²は、それぞれ炭素数１〜４の直鎖又は分岐したアルキル基、又は炭素数１〜４の直鎖又は分岐したヒドロキシアルキル基である。
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。 Among the above formulas (4), long chain tertiary amines represented by the following formula (5) are more preferable.

However, in the above formula ^{(5), R 11, R} 12 are each linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms.
R ¹³ is a linear or branched alkylene group having 1 to 4 carbon atoms.

但し、上記式（６）中、Ｒ¹⁴の炭素数は７〜２３、好ましくは７〜２１の炭化水素基であり、上記式（７）中、Ｒ¹⁵の炭素数は１１〜２３、好ましくは１２〜２０の炭化水素基であり、Ｒ¹⁴およびＲ¹⁵は直鎖であっても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。 Z is a group represented by the following formula (6) or (7).

However, in the above formula (6), R ^{14 has} a carbon number of 7 to 23, preferably 7 to 21, and in the above formula (7), R ^{15 has} a carbon number of 11 to 23, preferably 12 to 20 hydrocarbon groups, R ¹⁴ and R ¹⁵ may be linear or branched, and may be saturated or unsaturated.

Specific examples of the long-chain tertiary amine compound as component (B) include caprylic amidopropyl dimethylamine, capric amidopropyl dimethylamine, lauric amidopropyl dimethylamine, myristic amidopropyl dimethylamine, palmitic acid. Long chain aliphatic amide alkyl tertiary amines such as amidopropyl dimethylamine, amidopropyl dimethylamine stearate, amidopropyl dimethylamine behenate, amidopropyl dimethylamine oleate; palmitate ester propyldimethylamine, stearate ester propyldimethylamine Aliphatic ester alkyl tertiary amines such as: amidopropyl diethanolamine palmitate, amidopropyl diethanolamine stearate, etc. The possible alone or be used in combination of two or more.
Among them, caprylic amidopropyl dimethylamine, capric amidopropyl dimethylamine, lauric amidopropyl dimethylamine, myristic amidopropyl dimethylamine, palmitic amidopropyl dimethylamine, stearic acid amidopropyl dimethylamine, behenic acid amidopropyl dimethylamine It is particularly preferable to use amidopropyldimethylamine oleate alone or in combination of two or more. Among these, it is more preferable to use amidopropyldimethylamine palmitate and amidopropyldimethylamine stearate in combination. In this case, it is preferable that the ratio is amidopropyldimethylamine palmitate: amidopropyldimethylamine stearate = 10: 90 to 50:50, preferably 20:80 to 40:60. By using at such a ratio, a composition having excellent stability and high anti-stiffness performance can be obtained.

In addition, as a specific example in the case of producing the component (B), for example, when producing a “long-chain aliphatic amide alkyl tertiary amine”, fatty acids or fatty acid lower alkyl esters, animal / vegetable oils and fats, etc. A fatty acid derivative and a dialkyl (or alkanol) aminoalkylamine are subjected to a condensation reaction, and then unreacted dialkyl (or alkanol) aminoalkylamine is distilled off under reduced pressure or nitrogen blowing.
Here, as the fatty acid or fatty acid derivative, 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 oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, flaxseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oil or animal oil fatty acid, or their methyl ester, ethyl ester, glyceride, 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 alkanol) aminoalkylamine” include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, etc. Among them, dimethylaminopropylamine is particularly preferable.

In addition, the amount of dialkyl (or alkanol) aminoalkylamine used in the production of the long-chain aliphatic amidoalkyl tertiary amine is preferably 0.9 to 2.0 moles relative to the fatty acid or derivative thereof. 0 to 1.5 times mole is particularly preferable.
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 maintained moderately, and coloring of the tertiary amine compound obtained by setting the reaction temperature to 220 ° C. or lower can be prevented or reduced.
As for the usage-amount of the dialkylamino alcohol in esterification reaction at the time of manufacturing aliphatic ester alkyl tertiary amine, 0.1-5.0 times mole is preferable with respect to a fatty acid or its derivative (s), and 0.3-3. 0 times mole is more preferable, 0.9-2.0 times mole is further 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. If the reaction temperature is less than 100 ° C., the reaction is too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored, which is not preferable.

The production conditions other than those described above for the long-chain aliphatic amidoalkyl 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. It is also possible to introduce the active gas by blowing it.
Also, when using fatty acids, acid catalysts such as sulfuric acid and p-toluenesulfonic acid, and when using fatty acid derivatives, alkaline catalysts such as sodium methylate, caustic potash and caustic soda can be used for a short time at a low reaction temperature. The reaction can proceed 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 dissolve in a solvent to make it liquid.

Other suitable specific examples of component (B) include lauryl dimethylamine, myristyl dimethylamine, palm alkyl dimethylamine, palmityl dimethylamine, beef tallow alkyl dimethylamine, hardened beef tallow alkyl dimethylamine, stearyl dimethylamine, stearyl diethanolamine, Examples include polyoxyethylene-cured beef tallow alkylamine (product name: ETHOMEEN HT / 14 manufactured by Lion Akzo Co., Ltd.) and the like.
Specific examples of salts of long-chain tertiary amines include acid salts obtained by neutralizing the above amine compounds with acids.
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.

前記一般式（８）中、Ｒ¹⁸は、炭素数８〜２５の炭化水素基であり、直鎖であっても分岐鎖状であってもよく、飽和であっても不飽和であってもよく、さらにはヒドロキシ基等の置換基を含むものであってもよい。また、アミド基、エステル基［−Ｃ（Ｏ）−Ｏ−］又はエーテル基［−Ｏ−］等の連結基を、その鎖中に有するものであってもよい。
中でも、炭素数８〜２５、より好ましくは炭素数１６〜２２の炭化水素基（直鎖であっても分岐鎖状であってもよく、飽和であっても不飽和であってもよい。）が好ましく用いられる。また、エステル基［−Ｃ（Ｏ）−Ｏ−］を鎖中に有するものも好ましい。 Moreover, the cationic surfactant which is the quaternary ammonium salt, which is another component (B), is not particularly limited as the cationic surfactant. A quaternary ammonium salt represented by the following general formula (8) is preferably used because it is excellent in stability of the aggregate formed with the component (C) in the cleaning composition.

In the general formula (8), R ¹⁸ is a hydrocarbon group having 8 to 25 carbon atoms, which may be linear or branched, saturated or unsaturated. Moreover, it may further contain a substituent such as a hydroxy group. Moreover, you may have connecting groups, such as an amide group, ester group [-C (O) -O-], or ether group [-O-] in the chain | strand.
Among these, a hydrocarbon group having 8 to 25 carbon atoms, more preferably 16 to 22 carbon atoms (which may be linear or branched, may be saturated or unsaturated). Is preferably used. Also preferred are those having an ester group [—C (O) —O—] in the chain.

R ¹⁶ and R ¹⁷ are each independently a hydrocarbon group having 1 to 25 carbon atoms, may be linear or branched, may be saturated or unsaturated, Further, it may contain a substituent such as a hydroxy group. Further, it may have a linking group such as an amide group, an ester group [—C (O) —O—] or an ether group [—O—] in the chain, and the EO addition mole number is 1. It may be ˜25 polyoxyethylene groups. Especially, a C1-C4 linear or branched alkyl group and a C1-C4 linear or branched hydroxyalkyl group are preferable, and a hydrogen atom and a methyl group are used more preferably. Also preferred are those having an ester group [—C (O) —O—] in the chain.
R ¹⁹ is any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and a polyoxyethylene group having 1 to 25 moles of EO addition. Especially, a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 hydroxyalkyl group are preferable, and a hydrogen atom and a methyl group are used more preferably.

Z ⁻ represents an anion. Specifically, halogen atom ions such as chlorine ion, bromine ion and iodine ion, and general formula R ²⁰ SO ₄ ⁻ [wherein R ²⁰ is an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group) Group), and particularly preferably a methyl group. ] The ion etc. which are represented by] are mentioned. Of these, chlorine ions are preferred.

Specific examples of the cationic surfactant represented by the general formula (8) include cetyltrimethylammonium chloride, cetostearyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride; monoester ammonium salt, diester ammonium salt , Alkanolamine ester quaternary salts such as triester ammonium salts, and mixtures thereof. Among these, a mixture of stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, and alkanolamine ester quaternary salt is preferable.
As the component (B), the above-mentioned long-chain tertiary amine and / or a salt thereof, or a cationic surfactant can be used alone, or two or more can be used in combination. In particular, by using a long-chain tertiary amine and / or a salt thereof alone, it is possible to obtain a more excellent anti-sticking effect.

Component (C) The component (C) in the present invention is a water-soluble polymer having an alkylene terephthalate unit and / or an alkylene isophthalate unit (c1 unit) and an oxyalkylene unit and / or a polyoxyalkylene unit (c2 unit). . By mix | blending (C) component with the cleaning composition of this invention, the darkening which generate | occur | produces in the clothing during washing | cleaning can be prevented, and the recontamination prevention effect can be given.

式中、Ｒ²¹は低級アルキレン基を意味し、例えば炭素数４以下、特に２〜４であることが好ましい。
アルキレンテレフタレート単位としては、具体的には、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から１ 種又は２ 種以上を用いることができる。本発明においては、中でもイソプロピレンテレフタレート単位が好ましい。 (C1) Unit The unit (c1) is an alkylene terephthalate unit and / or an alkylene isophthalate unit. The alkylene terephthalate unit is represented by the following general formula.

In the formula, R ²¹ means a lower alkylene group, for example, preferably 4 or less, particularly 2 to 4 carbon atoms.
Specific examples of the alkylene terephthalate unit include ethylene terephthalate units, n-propylene terephthalate units, isopropylene terephthalate units, n-butylene terephthalate units, isobutylene terephthalate units, sec-butylene terephthalate units, tert-butylene terephthalate units, and the like. Species or two or more can be used. In the present invention, an isopropylene terephthalate unit is particularly preferable.

式中、Ｒ²²は低級アルキレン基を意味し、例えば炭素数４ 以下、特に２ 〜 ４ であることが好ましい。 The alkylene isophthalate unit is represented by the following general formula.

In the formula, R ²² represents a lower alkylene group, and for example, it is preferably 4 or less, particularly 2 to 4 carbon atoms.

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. These may be used alone or in combination. Can be used. In the present invention, a propylene isophthalate unit is particularly preferable.
As the unit (c1) in the present invention, those selected from the above-mentioned alkylene terephthalate units and alkylene isophthalate units can be used alone or in combination of two or more.

(C2) Unit The unit (c2) is an oxyalkylene unit and / or a polyoxyalkylene unit. Both the oxyalkylene unit and the polyoxyalkylene unit can be represented by the general formula — (R ²³ O) s—. That is, an oxyalkylene unit is a case where s is 1, and a polyoxyalkylene unit means a case where s is 2 or more. In the formula, R ²³ is a lower alkylene group, and its carbon number is preferably 4 or less, for example. s is an integer of 1 or more.
The oxyalkylene unit and / or polyoxyalkylene unit is preferably an oxyalkylene unit or polyoxyalkylene unit having s 1 of 1 or more, preferably 5 to 150, more preferably 10 to 100, such as oxyethylene unit or polyoxyethylene. Units: oxypropylene units or polyoxypropylene units; polyoxyethylene polyoxypropylene units and the like are mentioned, and oxyethylene units or polyoxyethylene units are more preferable.
(C) In a component, what is chosen from (c2) unit may be contained 1 type, or 2 or more types.

Details of Component C The component (C) in the present invention is preferably a polymer compound in which the above (c1) unit and (c2) unit are polymerized randomly or in blocks, particularly polymerized in blocks. Those are preferred.
The component (C) may contain units other than these (c1) units and (c2) units (for example, units derived from a polymerization initiator, a polymerization terminator, etc., and other copolymerizable units). In addition, it is preferable that 80 mol% or more, preferably 90 mol% or more is formed by the units (c1) and (c2).

−−−−−−−−−−−−−−−（１）
（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、炭素数２ 〜 ４ のアルキレン基、好ましくは炭素数２〜３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 、さらに好ましくは１０〜５０ 、特に好ましくは２０〜３０である）

−−−−−−−（２）
（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、炭素数２ 〜 ４ のアルキレン基、好ましくは炭素数２〜３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 、さらに好ましくは１０〜５０ 、特に好ましくは２０〜３０である） The specific structure of the component (C) that can be preferably used in the present invention is represented by the following general formula as an example. In addition, although the following general formula represents what was obtained using the terephthalate unit (Formula (1)) and what was obtained using the isophthalate unit (Formula (2)), this invention is the following. The structure is not limited to such a formula, and for example, a structure in which a terephthalate unit and an isophthalate unit are present as a mixed (c1) unit may be used. The C component in the present invention has, for example, the following formula (1) and / or formula (2).

--------------- (1)
Wherein A ¹ and B 2 are each independently a hydrogen atom or a methyl group, preferably a methyl group, and R ¹ and R ² are alkylene groups having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. 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 1 to 50. More preferably, it is 10-50, and particularly preferably 20-30)

------- (2)
Wherein A ¹ and B 2 are each independently a hydrogen atom or a methyl group, preferably a methyl group, and R ¹ and R ² are alkylene groups having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. 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 1 to 50. More preferably, it is 10-50, and particularly preferably 20-30)

  In the above formulas (1) and (2), the ratio of X and y is such that X: y is preferably 1: 5 to 1:20, and more preferably 1: 8 to 1:18. preferable. It is preferable for X 1 and y to be in such ranges since the soil release performance is sufficiently exhibited and the solubility in water is improved.

The component (C) preferably has a mass average molecular weight of 500 or more, more preferably 800 or more, particularly preferably 1000 or more from the viewpoint of the cleaning effect. On the other hand, the upper limit value of the mass average molecular weight is preferably 8000 or less from the viewpoint of dispersibility in water, more preferably 5000 or less, and particularly preferably 4000 or less from the viewpoint of maintaining performance during storage.
Here, the mass average molecular weight can be measured by conversion using PEG (polyethylene glycol) as a calibration curve when the solvent is measured by THF (tetrahydrofuran) by GPC (gel permeation chromatography).
For example, the component (C) in the present invention is 10 g of the component (C) added to 1000 g of water, and the temperature is set to 40 ° C., and the temperature is set to 40 ° C. with a stirrer (thickness 8 mm, length 50 mm, 1 liter beaker). What melt | dissolves after stirring for time can be used preferably.
(C) A commercial item can also be used for a component, and it can also synthesize | combine by the method disclosed in various literatures.

As a commercial item, trade name TexCareSRN-100 (manufactured by Clariant, mass-average molecular weight 3000) (hereinafter abbreviated as SRN-100), trade name Tex CareSRN-300 (manufactured by Clariant, mass-average molecular weight 7000) , Abbreviated as SRN-300.). Particularly preferred is Tex Care SRN-100 (manufactured by Clariant). The reason is that the solubility in water is high and the deterioration of the cleaning performance after storage is small.
Examples of methods disclosed in the literature include Journal of Polymer Science, Volume 3, pages 609-630 (1948), Journal of Polymer Science, Volume 8, pages 1-22 (1951), The method described in JP-A-61-218699 may be used, or other methods may be used.
In the present invention, the trade name TexCare SRN-170 (manufactured by Clariant, Inc .: 70% aqueous solution of the above SRN-100) can be used particularly preferably.

(D) Component (D) The maleic acid copolymer of the component is a copolymer of maleic acid and a hydrocarbon monomer having 4 to 12 carbon atoms copolymerizable with the maleic acid and / or acrylic acid, and / Or a salt thereof, and by containing the component (D) in the cleaning composition of the present invention, a synergistic effect with the component (C) is expressed, and an effect of preventing darkening during washing (an effect of preventing recontamination) ) Can be further improved.
In the maleic acid copolymer, the monomer copolymerized with maleic acid is not particularly limited as long as it is a hydrocarbon monomer having 4 to 12 carbon atoms copolymerizable with maleic acid and / or acrylic acid, The following are preferably used.
The hydrocarbon monomer copolymerizable with maleic acid has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms from the viewpoint of the handleability of the raw material. In addition, as a copolymer of maleic acid and a hydrocarbon monomer having 4 to 12 carbon atoms and / or a salt thereof, a salt in which a carboxyl group is neutralized with a normal alkali agent even in an unneutralized copolymer But you can. In particular, a copolymer salt of maleic acid and a hydrocarbon monomer is preferably used.

As the hydrocarbon monomer used in the present invention, an olefin monomer can be preferably used. When maleic acid and an olefin monomer are copolymerized, the olefin monomer that can be copolymerized with maleic acid is preferably an olefin monomer having 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms. When the carbon number is 4 or more, the effect of preventing recontamination is exhibited. On the other hand, when the number of carbon atoms is 12 or less, the handleability of the raw material is improved.
1000-100000 are preferable and, as for the mass mean molecular weight (measured value by the gel permeation chromatography of polystyrene conversion) of the copolymer of a maleic acid and a hydrocarbon type monomer, 3000-50000 are more preferable. When the mass average molecular weight is 1000 or more, the effect of preventing recontamination is improved, and when the mass average molecular weight is 100000 or less, the stability of the composition is improved.

When preparing a copolymer of maleic acid and acrylic acid (hereinafter referred to as “acrylic acid copolymer”), the molar ratio of maleic acid and acrylic acid is preferably 20:80 to 50:50, and 30: 70-50: 50 is more preferable, and 35: 65-45: 55 is still more preferable. About the ratio of acrylic acid, by making the molar ratio of maleic acid and acrylic acid 20:80 or less, the ability to decompose the complex of insolubilized modified starch and calcium is improved, and the detergency becomes sufficient. By making the molar ratio of maleic acid and acrylic acid 50:50 or more, the polymerizability increases and the production of the acrylic acid copolymer becomes easy.
Moreover, 5000-100000 are preferable and, as for the mass average molecular weight (measured value by the gel permeation chromatography of polystyrene conversion) of the copolymer of maleic acid and acrylic acid, 5000-50000 are more preferable. When the mass average molecular weight is 5000 or more, the effect of preventing re-contamination is improved, and when the mass average molecular weight is 100000 or less, the stability of the composition is improved.
In the present invention, it is more preferable to use a copolymer of maleic acid and a hydrocarbon-based monomer because the effect of preventing recontamination on a synthetic fiber (for example, polyester) and a natural fiber (for example, cotton) can be exhibited at the same time.

As the component (D) in the present invention, those described above can be used, and as these commercially available products, for example, Quinflow 540 (sodium salt) manufactured by Nippon Zeon Co., Ltd., which is a copolymer salt of maleic acid and olefin. , Molecular weight: 8000, pH: 10), 542 (Sodium salt, Molecular weight: 8000, pH: 8), 543 (Ammonium salt, pH: 6.8), 640 (Sodium salt, pH: 8), etc., or BASF Sokalan CP9 (sodium salt, molecular weight: 12000, pH: 11) (both are trade names) and the like can be used.
As the copolymer of maleic acid and acrylic acid and / or a salt thereof, Sokalan CP7 (sodium salt, molecular weight: 50000, pH: 8) manufactured by BASF Corporation, Aqualic TL- manufactured by Nippon Shokubai Co., Ltd. 400 (molecular weight: 50000), TL-500 (molecular weight: 10,000), TL-37 (molecular weight: 5000) (all are trade names) and the like can be used.

Other components For the cleaning composition of the present invention, in addition to the above components, for example, enzymes (proteases, lipases, cellulases, etc.), stabilizers (sodium benzoate, citric acid, sodium citrate, polyhydric alcohols) , Polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, paratoluenesulfonic acid, 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 adjusters (sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine, etc.), preservatives, hydrotropes, fluorescent agents, dye transfer inhibitors, pearl agents, acids General-purpose dyes and pigments such as acid red 138, direct blue 86, Polar Red RLS, acid yellow 203, acid blue 9, blue 1, blue 205, turquoise PGR (all trade names) Additives such as flavoring agents and emulsifying agents, and solvents such as water and alcohol can be incorporated, but are not limited thereto. In addition, the selection and blending amount of these components can be arbitrarily selected as long as the object of the present invention is not hindered.

Blending amount of each of the above components in the cleaning composition In the cleaning composition of the present invention, the blending amount of the component (A) is 10 to 50% by weight, preferably 15 to 40% by weight with respect to the entire cleaning composition. % Is preferred. When the blending amount of the component (A) is 10% by mass or more, the detergency is improved, and by setting it to 50% by mass or less, the viscosity of the composition is prevented from increasing excessively and the handling becomes easy.
The blending amount of the component (B) with respect to the cleaning composition of the present invention is preferably 0.1 to 10% by mass, particularly preferably 0.5 to 5% by mass, based on the entire cleaning composition. . When the blending amount of the component (B) is 0.1% by mass or more, the anti-sticking effect is improved, and when the blending amount is 10% by mass or less, the stability of the composition is improved and economically. It will be advantageous.
In this invention, (C) component is 0.01-10 mass% with respect to the whole cleaning composition of this invention, Preferably it is preferable to contain 0.05-5 mass%. By making the blending amount of component (C) 0.01% by mass or more, the effect of preventing recontamination of the cleaning composition of the present invention is improved, and by making the blending amount 10% by mass or less, the stability of the composition As well as an economic advantage.

Content of (D) component arbitrarily mix | blended in this invention is 0.01-10 mass% with respect to the whole cleaning composition of this invention, Preferably it contains 0.05-5 mass% Is preferred. When the content of the component (D) is 0.01% by mass or more, the effect of preventing recontamination can be exhibited, and when it is 10% by mass or less, the effect of preventing recontamination can be obtained sufficiently and economically. It is advantageous.

In addition, in the cleaning composition of the present invention, the component (D) is contained, and in order to have a synergistic effect with the component (C), the ratio of the component (C) :( D) is the component (C): It is preferable that the component D) has a mass ratio of 9: 1 to 1: 9, more preferably 7: 3 to 3: 7. By making the blending amount of the component (D) with respect to the component (C) within the above range, the recontamination preventing effect of the cleaning composition of the present invention can be further improved.
Moreover, in the cleaning composition in the present invention, when the component (C) and the component (D) are used in combination, the total amount of the component (C) and the component (D) is based on the total mass of the cleaning composition. The content is preferably 0.1 to 15% by mass, and more preferably 0.5 to 15% by mass. Even if the blending amount is more than 15% by mass, the effect more than expected is not exhibited, and conversely, the object to be washed tends to be stiff. On the other hand, if the blending amount is less than 0.1% by mass, the effect of adding these is hardly exhibited.

Specific preferred formulation examples of the cleaning composition of the present invention are, for example, the following combinations:
Component (A): Nonionic surfactant of formula (3) wherein R ³ is an alkyl group having 10 to 16 carbon atoms, Y = O, m = 5 to 15, n = 0 to 3, and R ⁴ = H: 15-40% by mass
Component (B): R ¹¹ and R ¹² are linear alkyl groups having 1 to 4 carbon atoms, R ¹³ is a linear alkylene group having 1 to 4 carbon atoms, and Z is a hydrocarbon chain R ¹⁴ having 7 to ²¹ carbon atoms. Long chain tertiary amine which is a group of formula (6): 0.5 to 5% by mass
(C) Component: A and B are both methyl groups, R ¹ and R ² are alkylene groups having 2 to 3 carbon atoms, X is 0.5 to 2.5, and y is 20 to 30 A water-soluble polymer of formula (1) and / or A and B are both methyl groups, R ¹ and R ² are alkylene groups having 2 to 3 carbon atoms, and X is 0.5 to 2.5. Y is 20 to 30 (2) water-soluble polymer: 0.05 to 5% by mass
Component (D): Copolymer of maleic acid and hydrocarbon monomer having a mass average molecular weight of 3000 to 50000: 0.05 to 5% by mass.

Manufacturing method of cleaning composition The cleaning composition of this invention can be manufactured using the method normally used when manufacturing a liquid detergent composition. For example, a 1-liter scale glass beaker is used, and a magnetic stirrer (MITAMURA RIKEN KOGYO INC.) Is used and blended in the following order. (A) The component is dissolved in ethanol, water is added thereto, the component (B) previously dissolved in ethanol at 40 ° C. is added, and after sufficient stirring, the components (C), (D) and any The ingredients are added, and the mixture is further thoroughly stirred, and the pH is adjusted to around 7 with a pH adjuster.

Physical properties of the cleaning composition The cleaning composition of the present invention preferably has a pH of 4 to 8, preferably 5 to 8 at a temperature of 25 ° C. By setting the pH within the above range, the storage stability of the cleaning composition is improved. In addition, in order to adjust pH of a cleaning composition, it is possible to adjust suitably using the said pH adjuster etc.
Moreover, it is preferable that the cleaning composition of this invention has a viscosity of 5-500 mPa * s in 25 degreeC temperature conditions. By setting the viscosity to 500 or less, the usability of the composition such as the remaining bottle, applicability to an object to be washed, and ease of measurement with a cap is improved.

  Hereinafter, the cleaning composition of the present invention will be described in more detail with reference to examples. The following examples do not limit the scope of the present invention. In addition, in the following description, “%” and “part” mean “% by mass” and “part by mass”, respectively.

Component (A) used in the Examples Component A-1: EO12 mol adduct of Sasol 23 alcohol manufactured by Sasol (R ³ = C12 / C13 alkyl group (mass ratio of C12 / C13 alcohol as raw material = 6/4), Y = O, branching ratio: 50% ^{* 1} , R ⁴ = H, m = 12, n = 0)
(Synthesis method of A-1)
224.4 g of Sasol 23 alcohol manufactured by Sasol and 2.0 g of 30% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 610.7 g of ethylene oxide (gaseous) was gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, and thus obtained.
* 1: Branching rate: The branching rate indicates a ratio to the total number of moles of alcohol in terms of the number of moles of alcohol having a branched alkyl group in the raw material alcohol.

A-2: EO15 molar adduct of Safol 23 alcohol manufactured by Sasol (R ³ = C12 / C13 alkyl group (mass ratio of C12 / C13 alcohol as raw material = 6/4), Y = O, branching ratio: 50% , R ⁴ = H, m = 15, n = 0)
(Synthesis method of A-2)
Product name manufactured by Sasol: Safol 23 alcohol was synthesized in the same manner as A-1 except that 224.4 g of alcohol and 763.4 g of ethylene oxide were used.

A-3: manufactured by P & G Co., Ltd. Trade name: EO15 mol adduct of CO-1214 alcohol (R ³ = C12 / C14 alkyl group (mass ratio of C12 / C14 alcohol as raw material = 71/29), Y = O, Branching rate 0%, R ⁴ = H, m = 15, n = 0)
(Synthesis method of A-3)
P & G CO-1214 alcohol 224.4g and ethylene oxide (gaseous) 759.5g were used, and others were synthesized in the same manner as A-1.

A-4: EO 7 mole adduct of C13 alcohol with 3 Ryokakarada synthesized by oxo process of butene (alkyl group ^{R 3 = C13, Y = O} , branched rate ^{100%, R 4 = H,} m = 7, n = 0) Product name: Lutensol TO7, manufactured by BASF

(B) Component B-1: C16C18 amidoamine: long chain fatty acid dimethylaminopropylamide (mass ratio of stearic acid (C18) / palmitic acid (C16) = 7/3), trade name: Katinaral MPAS-R (Toho Chemical Co., Ltd.) Made)

B-2: C16C18 amidoamine synthetic product: long chain fatty acid dimethylaminopropylamide (mass ratio of stearic acid / palmitic acid = 7/3)
(Synthesis method of B-2)
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: stearic acid dimethylaminopropylamide
(Synthesis method of B-3)
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 maintaining at 150 to 160 ° C. for 1 hour, the temperature was raised to 185 ° C. over 1 hour, and 45 g of dimethylaminopropylamine was 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 (synthesis method of B-4)
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 the mixed fatty 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 the mixed fatty acid calculated from the acid value was 97.2%.

  B-5: Stearyltrimethylammonium chloride, trade name: ARCARD T-800 (manufactured by Lion Akzo)

(C) Component C-1: Water-soluble polymer, manufactured by Clariant, trade name TEXCARE
SRN-170 (mass average molecular weight: 2000 to 3000, 70% aqueous solution of TEXCARE SRN-100)
C-2: Water-soluble polymer, manufactured by Clariant, trade name TEXCARE SRN-300 (mass average molecular weight: 7000)
(D) Component D-1: Sodium salt of copolymer of maleic acid / olefin monomer, manufactured by BASF, trade name Socaran CP9 (molecular weight 12000)
D-2: Sodium salt of acrylic acid / maleic acid copolymer, manufactured by BASF, trade name Socaran CP7 (molecular weight 50000, molar ratio of acrylic acid / maleic acid 60/40)

Common ingredient Sodium benzoate: manufactured by Toa Gosei Co., Ltd., trade name: Sodium benzoate citric acid: manufactured by Fuso Chemical Industry Co., Ltd., trade name: liquid citric acid 95% ethanol: Nippon Alcohol Sales Co., Ltd., trade name: Specific alcohol 95 degree synthetic p-toluenesulfonic acid: Kyowa Hakko Kogyo Co., Ltd.
Perfume: perfume composition A described in Tables 11 to 18 of JP-A-2002-146399

Preparation of liquid detergent composition for clothing
(1) Add ethanol and the component (A) in the following common component a into a 300 ml beaker and stir well with a magnetic stirrer (MITAMURA RIKEN KOGYO INC.).
(2) After the water in the common component a adjusted to 40 degrees is added to (1), the component (B) dissolved in ethanol in advance is added and sufficiently dissolved.
(3) Add components (C) and (D) to (2) and stir well.
(4) Add common ingredient a and stir well to obtain a liquid cleaning composition for clothing.

In addition, the common component a in a table | surface points out the following compositions.
<Common component a>
Sodium benzoate 0.5% by mass
Trisodium citrate 0.2% by mass
95% ethanol 5.0% by mass
Paratoluenesulfonic acid 2.0% by mass
Fragrance 0.3% by mass
pH adjuster appropriate amount (added until pH is adjusted to 7)
Water balance (100 parts of total cleaning composition)
Amount to do)

Evaluation method Evaluation of the liquid cleaning composition for clothes of the Examples , Reference Examples and Comparative Examples prepared above was performed by the following method. In addition, about the result of each evaluation, it describes in Table 1 and 2, respectively.
(1) Evaluation of the effect of suppressing wrinkles <Cleaning method>
Twelve commercially available cotton towels (100% cotton) and three cotton shirts to secure mass were put into a Toshiba drum washing machine (TW-130VB), and 25 mL of the composition prepared in each example was added. A cleaning operation was performed in which the mixture was added at a ratio, and washing, rinsing, and dehydration were sequentially performed in a standard course. The washing time, rinsing, dehydration, and water volume were not adjusted at all and the standard course setting of the washing machine was used.
<Evaluation method>
The cotton towel subjected to the above washing treatment was suspended for 12 hours and dried. Thereafter, the sample was left in a constant temperature and humidity room at 25 ° C. and 65% RH for 2 days, and this was used as a test cloth for evaluation of non-stickiness. As a control cloth for evaluation, a cloth washed in the same manner as described above using a 20% aqueous solution of a nonionic surfactant (alcohol ethoxylate added with an average of 15 moles of ethylene oxide per mole of lauryl alcohol) was similarly treated with cotton. It was used for the evaluation of the non-stickiness of the towel.
Each cloth was subjected to sensory evaluation by a specialized panelist, and a paired comparison was made with respect to the evaluation control cloth according to the following criteria to obtain the average value of the scores of the specialized panelists (n = 10). The higher the score, the less stiff.
(Evaluation criteria): 2 points or more are acceptable range 1 point: Equivalent or less than control cloth 2 points: Stiffness is suppressed slightly compared to control cloth 3 points: Stiffness is suppressed more than control cloth 4 points: Control It is much less stiff than cloth.

(2) Evaluation of recontamination prevention property In a washing bath of Terg-O-Tomter (UNITED STATED TESTING CO., INC. Model 7243S), 900 mL of tap water and 0.8 mL of cleaning solution were added and stirred at 120 rpm for 3 minutes. Put 10 pieces of red soil cloth (3 × 4cm), 5 pieces of oil stain cloth (5 × 5cm), 2 pieces of white polyester tropical cloth (5 × 5cm), 2 pieces of cotton skin shirt pieces (5 × 5cm) for 10 minutes Washed (25 ° C.). The washing solution was removed by emptying the colander, and the test cloth was dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine. Further, rinse for 3 minutes in a Terg-O-Tomometer bath containing 900 mL of tap water, dehydrate the test cloth for 1 minute in the dewatering tank of a 2-tank washing machine, repeat this twice, and then reflect the reflectance of the white cloth. And the difference from the reflectance before cleaning was calculated as the recontamination degree (ΔZ).
Reflectance: Color meter SE2000 (NIPPON DENSHOKU) used (evaluation criteria): Less than ΔZ6 is acceptable range

Evaluation Results Evaluation results are listed in Tables 1 and 2 below.

Component (C) and (D) and Example 3-12 in which the components were combined, by comparing the ratio Comparative Examples, darkening prevention effect with the liquid detergent composition in the scope of the present invention, component (C) It can be seen that the combination of the component (D) and the component (D) further improves the synergistic effect of the component (C) and the component (D).

  By using the liquid detergent composition of the present invention, in the case of washing clothes using a large washing machine represented by a drum-type washing machine, the clothes can be washed without causing the clothes to be washed. Can be maintained, and at the same time, recontamination such as darkening can be prevented.

Claims (4)

(A) 10-50 mass% of nonionic surfactant,
(B) 0.1-5% by mass of a cationic surfactant which is a long-chain tertiary amine represented by the following general formula (4) and / or a salt thereof, and / or a quaternary ammonium salt,

(Where
R ⁵ is a hydrocarbon group having 7 to 27 carbon atoms or —R ⁸ —W (wherein R ⁸ is a linear or branched alkylene group having 1 to 4 carbon atoms, and W is —NHCO—R. ⁹ (R ⁹ is a hydrocarbon group having 7 to 23 carbon atoms) or —OOC—R ¹⁰ (R ¹⁰ is a hydrocarbon group having 11 to 23 carbon atoms) ;
R ⁶ is a hydrocarbon group having 1 to 25 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms ,
R ⁷ is any one of a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, and a polyoxyethylene group having 1 to 25 moles of EO addition. It is the basis of. )
(C) 0.01 to 10% by mass of a water-soluble polymer having (c1) alkylene terephthalate unit and / or alkylene isophthalate unit and (c2) oxyalkylene unit and / or polyoxyalkylene unit, and (D) malee A copolymer of an acid and a hydrocarbon monomer having 4 to 12 carbon atoms copolymerizable with the maleic acid, and / or a copolymer of maleic acid and acrylic acid, and / or a salt thereof; 01-10% by mass
A liquid detergent composition for clothing comprising
(C) Component: The mass ratio of (D) component is 7: 3 to 3: 7, and the total amount of (C) component and (D) component is with respect to the total mass of this liquid detergent composition. The liquid detergent composition for clothes which exists in the range of 0.1-15 mass%. The liquid detergent composition according to claim 1, wherein (C) is a water-soluble polymer represented by the following general formula (1) and / or (2).

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

− − − − (2)
(In the formula, A 1 and B 2 are each independently a hydrogen atom or a methyl group, R ¹ and R ² are alkylene groups having 2 to 4 carbon atoms, X is 0 to 10 and y is 1; ~ 100) The liquid detergent composition according to claim 1 or 2, wherein the component (B) is a long-chain tertiary amine represented by the following formula (5) and / or a salt thereof, and / or a quaternary ammonium salt. .

(Where
R ¹¹ and R ¹² are each a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms,
R ¹³ is a linear or branched alkylene group having 1 to 4 carbon atoms,
Z is a group represented by the following formula (6) or (7).

(In the formula, R ¹⁴ is a hydrocarbon group having 7 to 23 carbon atoms.)

(In the formula, R ¹⁵ is a hydrocarbon group having 11 to 23 carbon atoms.))   The liquid detergent according to any one of claims 1 to 3, wherein the component (D) is a copolymer of maleic acid and a hydrocarbon monomer having 4 to 12 carbon atoms copolymerizable with the maleic acid. Composition.