KR101125803B1 - Liquid detergent composition for textiles - Google Patents

Abstract

It is to provide a liquid detergent composition for clothes which imparts excellent slipperiness to clothes of polyester material.

The liquid detergent composition for garments of the present invention is a nonionic surfactant (A) and a nitrogen-containing tertiary amine having a hydrocarbon group having 7 to 28 carbon atoms which may have a substituent and may have a linking group in the chain and / or a salt thereof. It is characterized by containing a compound (B) and specific polyether modified silicone (C). Moreover, it is preferable to contain the maleic acid-type copolymer (D) of the copolymer of a maleic acid and the C4-C12 hydrocarbon-type monomer and / or acrylic acid which can be copolymerized with the said maleic acid, and / or its salt. Moreover, it is preferable to contain 10-50 mass% of said (A), 0.1-10 mass% of (B), and 0.01-10 mass% of (C), and also contain 0.1-10 mass% of (D). desirable.

Description

Liquid detergent composition for textiles

The present invention relates to a liquid detergent composition for clothing.

Background Art Conventionally, various kinds of liquid detergent compositions for clothes aimed at improving the feel of slipperiness of clothes and the like have been proposed.

For example, as a liquid detergent composition for imparting slipperiness to clothing, Japanese Patent Application Laid-Open No. 11-293297 includes a specific nonionic surfactant and a water-soluble polyether-type modified silicone having a specific cloud point. A composition is disclosed.

Japanese Unexamined Patent Application Publication No. 2000-144199 discloses a composition containing a nonionic surfactant, a specific cationic surfactant, and a specific amino modified silicone derivative.

In addition, Japanese Patent Application Laid-Open No. 7-242897 discloses a specific nonionic surfactant, a specific dialkyl type cationic surfactant, A composition containing a water soluble silicone derivative is disclosed.

However, in the washing of clothes at home, as the size of washing machines has become larger recently, opportunities for collecting and washing many clothes at once are increasing.

Clothing to be washed is mixed with clothes of various materials such as chemical fibers such as cotton and polyester, and in particular, clothing of polyester material is increasing every year.

Among the garments, polyester material is accompanied by a rough touch when the laundry is repeatedly washed at home and the smoothness (slipperiness) is lost.

For this reason, in addition to the cleaning function which removes time, the function which gives comfortable slipperiness to the garment which wash | cleaned is required for the improvement of comfort at the time of wearing is calculated | required.

However, the conventional liquid liquid detergent composition for clothes has insufficient effect of imparting slipperiness to clothes of polyester material.

This invention is made | formed in view of the said situation, and makes it a subject to provide the liquid detergent composition for garments which provides the outstanding slipperiness | lubricacy with respect to the garment of polyester material.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject can be solved by mix | blending a specific nitrogen compound and specific polyether modified silicone together, and came to complete this invention.

That is, the liquid detergent composition for garments of this invention is a tertiary amine which has a C7-C28 hydrocarbon group which may have a nonionic surfactant (A), a substituent, and may have a coupling group in a chain, and / or its salt It is characterized by containing a nitrogen-containing compound (B) and the 1 or more types of polyether modified silicone (C) chosen from following formula (I)-(II).

(Note that the formula (I), (II), R is any one of straight-chain or branched alkyl or alkenyl groups, hydrogen atoms having from 1 to 4 carbon atoms, each R may be different may be the same. R ¹ is, As a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms, each R ¹ may be the same or different X represents a polyoxyalkylene group The order of each structural unit to which l, m, n is attached may be different , l is 0 to 50, m is 10 to 10000, n is 1 to 1000, and an integer of m> n is represented, a is 5 to 10000, and b is an integer of 2 to 10000.)

Moreover, it is preferable to contain the maleic acid copolymer (D) which is a copolymer of maleic acid and a C4-C12 hydrocarbon-type monomer and / or acrylic acid copolymerizable with the said maleic acid, and / or its salt.

Moreover, the liquid detergent composition for garments of this invention contains 10-50 mass% of said nonionic surfactants (A), 0.1-10 mass% of said nitrogen-containing compounds (B), The said polyether modified silicone ( It is preferable to contain 0.01-10 mass% of C).

Moreover, it is preferable to contain 0.1-10 mass% of said maleic acid type copolymers (D).

Hereinafter, the present invention will be described in detail.

"Nonionic Surfactant (A)"

Nonionic surfactant (A) is a component mainly responsible for a washing function, and may be used individually by 1 type, or may use two or more types together.

Although it does not specifically limit as a nonionic surfactant (A) used by this invention, For example, the polyoxyalkylene type nonionic surfactant represented by following formula (III) is used preferably.

R ² -Y- (EO) _s (PO) _t -R ³ . (III)

However, in said formula (III), R <^2> is C8-22, Preferably it is a hydrophobic group of 10-16.

The hydrophobic group is preferably an alkyl group or an alkenyl group, and these may be linear or branched. As a raw material used for introduction of this hydrophobic group, primary or secondary higher alcohol, higher fatty acid, higher fatty acid amide, etc. are mentioned, for example.

R ³ is a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 6, preferably 1 to 3, carbon atoms, and more preferably, a hydrogen atom.

-Y- is a linking group, -O-, -COO, and -CONH- are preferable, and -O- is more preferable.

EO is ethylene oxide and PO is propylene oxide. s and t represent the average added moles. s is 3-20, Preferably it is 5-18, More preferably, it is an integer of 5-15. t is 0-6, Preferably it is 0-3.

By setting the average added mole number s of EO to 20 or less, the HLB value becomes too high and the deterioration of the cleaning function due to the disadvantage of sebum washing becomes disadvantageous, and the average added mole number s of EO is 3 or more, By making average addition mole number t into 6 or less, the fall of the storage stability under high temperature of a composition can be suppressed.

The added mole number distribution of EO or PO is fluctuated by the reaction method at the time of manufacturing a nonionic surfactant (A), and is not specifically limited.

For example, the added mole number distribution of EO or PO is relatively wide when ethylene oxide or propylene oxide is added to the hydrophobic raw material using an alkali catalyst such as general sodium hydroxide or potassium hydroxide, and Japanese Unexamined Patent Publication No. 6-15038 Al ^{3 +} described in ^{JP, Ga 3 +, in 3 +} , Tl 3 +, Co 3 +, Sc 3 +, La 3 +, Mn 2 + particular alkoxylation catalyst such as a magnesium oxide is added to metal ions such as When ethylene oxide or propylene oxide is added to the hydrophobic raw material using the polymer, it tends to be relatively narrow in distribution.

As a specific example of the nonionic surfactant (A) represented by the said Formula (III),

(i) Mitsubishi Chemical Co., Ltd. make: Brand name Diadol (C13 (C13 is shown. Hereafter, when "Cn" (n is an integer), the carbon number is n.))), manufactured by Sasol. Synthetic alcohol obtained by oxo method, such as a brand name Safol23 (C12 / C13 mixture), or P & G Co., Ltd. brand name: CO-1214 (C12 / C14 mixture), Ecogreen Oreo Chemicals make: Brand name Ecorol (C12 / C14 mixture) 15 mol equivalent of ethylene oxide is added to natural alcohols such as

(ii) New Nippon Chemical Co., Ltd. product: The addition of 9 mol of ethylene oxide to natural alcohols, such as a brand name Conol (C12),

(iii) adding 7 mol or 10 mol of ethylene oxide to 1 mol of C13 alcohol obtained by providing C12 alkene obtained by trimerizing butene to oxo method (manufactured by BASF: trade names Lutensol TO7, Lutensol TO10),

(iv) 15 mol of ethylene oxide is added to lauric acid methyl ester,

(v) 10 moles of ethylene oxide is added to 1 mole of C12 alcohol obtained by providing hexanol to a Guerbet reaction (manufactured by CONDEA: trade name ISOFOL12-10EO),

(vi) 15 mol of ethylene oxide is added to the C12-14 secondary alcohol (Japanese Catalyst Co., Ltd. product name: Sotananol 150),

(vii) The addition of 15 mol of ethylene oxide and 3 mol of propylene oxide using the alkoxylation catalyst with respect to methyl laurate is mentioned.

As component (A), although said nonionic surfactant represented by the said Formula (III) is suitable, other nonionic surfactant can also be used.

Other nonionic surfactants suitable for use include, for example, polyoxyethylene (EO addition mole number 1-20) sorbitan fatty acid (C10-22) ester, polyoxyethylene (EO mole number 1-20) sorbitan fatty acid. (C10-22) ester, polyoxyethylene (EO addition mole number 1-20) glycol fatty acid (C10-22) ester, glycerin fatty acid (C10-22) ester, alkyl (C10-22) glycoside, etc. are mentioned.

These components (A) may be used individually by 1 type, or may use 2 or more types together.

In the present invention, the compounding amount of component (A) (when two or more types are used in combination) means the total amount. The same applies to the other components described below. 15-40 mass% is especially preferable. By making the compounding quantity of a component (A) into 10 mass% or more, washing power improves, and by setting it as 50 mass% or less, the viscosity of a composition increases too much and handling becomes easy.

"Nitrogen-containing compound (B)"

In the composition of the present invention, the nitrogen compound (B) may be linear or branched, may be saturated or unsaturated, and may have a substituent or a linking group in the chain. The tertiary amine and / or its salt which contains 1-3 hydrocarbon groups of the substituent) and the carbon number in a coupling group are not contained in this, are mix | blended. In particular, the tertiary amine containing 1 to 3, preferably 1 to 2, hydrocarbon groups having 7 to 25 carbon atoms is compounded.

Here, as a "substituent", a hydroxyl group, an amino group, etc. are mentioned concretely.

Moreover, an amide group, an ester group, an ether group, etc. are mentioned specifically as an "connection group".

As tertiary amine and / or its salt, what uses a tertiary amine as it is, the acid salt which neutralized the tertiary amine with an acid, etc. are mentioned concretely.

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. You may use together a species or more.

Especially as a nitrogen-containing compound (B), the tertiary amine represented by following formula (IV) and / or its salt is suitable.

In said Formula (IV), R <^4> is a hydrocarbon group of 7-27 carbon atoms (The carbon number here does not contain a carbon number in a substituent and a coupling group), and may be linear, branched, saturated, or unsaturated. And a substituent may be included. R ⁴ may have a linking group such as an amide group, an ester group or an ether group in the chain, and an amide group or an ester group is preferably used as the linking group.

Among them, R ^{4 is} "? R ⁷ -W" (wherein R ⁷ is a linear or branched alkylene group having 1 to 4 carbon atoms. W is NHCO-R ⁸ or? OOC-R ⁹ and R ⁸ is carbon number). It is a 7-23, preferably 7-21 hydrocarbon group, R <^9> is a C11-23, preferably 12-20 hydrocarbon group, R <^8> and R <^9> may be linear, branched, or saturated. Good or unsaturated.) Is preferably used.

R <^5> is a C1-C25 hydrocarbon group. R ⁵ may be linear or branched, may be saturated or unsaturated, or may contain a substituent. R ⁵ may have a linking group such as an amide group, an ester group or an ether group in the chain.

Especially, a C1-C4 linear or branched alkyl group and a C1-C4 linear or branched hydroxyalkyl group are used preferably.

R ⁶ is any one of a straight or branched alkyl group having 1 to 4 carbon atoms, a straight or branched hydroxyalkyl group having 1 to 4 carbon atoms, a polyoxyethylene group having 1 to 25 moles of EO addition, and a straight chain having 1 to 4 carbon atoms Or a branched alkyl group, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms is preferably used.

Among the above formulas (IV), tertiary amines represented by the following formula (V) and / or salts thereof are more suitable.

However, in said Formula (V), R <^10> , R <^11> is a C1-C4 linear or branched alkyl group or a C1-C4 linear or branched hydroxyalkyl group, respectively.

R ¹² is a linear or branched alkylene group having 1 to 4 carbon atoms.

Z is a group represented by the following formula (VI) or (VII).

However, in said formula (VI), carbon number of R <^13> is 7-23, Preferably it is a hydrocarbon group of 7-21, In said formula (VII), carbon number of R <^14> is 11-23, Preferably it is 12- It is a hydrocarbon group of 20, R <^13> and R <^14> may be linear, branched chain, saturated, or unsaturated may be sufficient as it.

Suitable specific examples of component (B) include caprylic acid amide dimethylamine, capric acid propyl dimethylamine, lauric acid propyl dimethylamine, millic acid amide propyl dimethylamine, palmitic acid propyl dimethyl amine, stearic acid Long-chain aliphatic amidealkyl tertiary amines or salts thereof such as acid amide propyl dimethylamine, behenic acid propyl dimethyl amine and oleic acid propyl dimethyl amine; Aliphatic ester alkyl tertiary amines or salts thereof such as palmitate ester propyl dimethylamine and stearate ester propyl dimethyl amine; Palmitic acid amide propyl diethanolamine, a stearic acid amide propyl diethanolamine, etc. are mentioned.

Among them, caprylate amide dimethylamine, capric amide propyl dimethylamine, lauric amide propyl dimethylamine, milist amide propyl dimethylamine, palmitic acid propyl dimethyl amine, stearic acid amide dimethyl amine, Especially preferred are behenamideamide dimethylamine, oleateamidepropyl dimethylamine or salts thereof.

Moreover, "long-chain aliphatic amide alkyl tertiary amine" in the said example is condensation reaction of dialkyl (or alkanol) aminoalkylamine, and fatty acid derivatives, such as a fatty acid or fatty acid lower alkyl ester, a vegetable and vegetable fat, and the like, for example. After that, unreacted dialkyl (or alkanol) aminoalkyl amine can be obtained by releasing the mixture under reduced pressure or nitrogen blow.

On the other hand, "aliphatic ester alkyl tertiary amine" is obtained by esterification reaction of condensation of fatty acid derivatives, such as fatty acid or fatty acid lower alkyl ester, animal and vegetable fats and oils, and dialkylamino alcohol, for example.

Fatty acids or fatty acid derivatives include caprylic acid, capric acid, lauric acid, millic acid, palmitic acid, stearic acid, oleic acid, behenic acid, elcaic acid, 12-hydroxystearic acid, palm oil fatty acid, and cottonseed oil. Vegetable or animal oil fatty acids such as fatty acids, corn oil fatty acids, tallow fatty acids, palm kernel fatty acids, soybean oil fatty acids, linseed oil fatty acids, castor oil fatty acids, olive oil fatty acids, and the like, methyl esters and ethyl esters thereof Specific examples thereof include glyceride and the like, and caprylic acid, capric acid, lauric acid, millic acid, palmitic acid, stearic acid, oleic acid and behenic acid are particularly preferable.

These fatty acids or fatty acid derivatives may be used individually by 1 type, or may use 2 or more types together.

Examples of the "dialkyl (or alkanol) aminoalkylamine" include dimethylamino propylamine, dimethylamino ethylamine, diethylamino propylamine, diethylamino ethylamine, and the like. Among them, dimethylamino propyl Amines are particularly preferred.

As "dialkylamino alcohol", dimethylamino ethanol, diethylamino alcohol, etc. are mentioned, for example. As diethylamino alcohol, diethylamino ethanol is preferable. Among these, dimethylamino ethanol is particularly preferable.

Moreover, as for the usage-amount of the dialkyl (or alkanol) aminoalkylamine at the time of manufacturing long chain aliphatic amide alkyl tertiary amine, 0.9-2.0 times mole is preferable with respect to a fatty acid or its derivative, 1.0-1.5 times mole is especially preferable.

Reaction temperature is 100-220 degreeC normally, Preferably it is 150-200 degreeC. When reaction temperature is less than 100 degreeC, reaction will become slow too much and when it exceeds 220 degreeC, coloring of the tertiary amine obtained may become remarkable, and it is unpreferable.

As for the usage-amount of the dialkylamino alcohol in esterification at the time of manufacturing an aliphatic ester alkyl tertiary amine, 0.1-5.0 times mole is preferable with respect to a fatty acid or its derivative, 0.3-3.0 times mole is more preferable, 0.9-2.0 Pear moles are even more preferred, and 1.0-1.5 moles are particularly preferred.

Reaction temperature is 100-220 degreeC normally, Preferably it is 120-180 degreeC. If the reaction temperature is less than 100 ° C, the reaction may be too late and the coloring of the tertiary amine obtained may be remarkable, which is not preferable.

The conditions other than the above-mentioned preparation of long-chain aliphatic amide alkyl tertiary amine and aliphatic ester alkyl tertiary amine are the same, and the pressure at the time of reaction may be normal pressure or reduced pressure, and it introduces by blowing inert gas, such as nitrogen, at the time of reaction. It is possible.

In the case of using fatty acids, acid catalysts such as sulfuric acid and p-toluenesulfonic acid, and in the case of using fatty acid derivatives, alkali catalysts such as sodium methylate, caustic caustic and caustic soda can be used to react more efficiently in a short time at a lower reaction temperature. You can proceed.

In addition, when the tertiary amine obtained is a long chain amine having a high melting point, it is preferable to be molded into a flake or pellet form after the reaction in order to improve handling properties, or to dissolve in an organic solvent such as ethanol to make the liquid phase. Do.

Other suitable embodiments of component (B) include lauryl dimethylamine, millystil dimethylamine, palmalkyl dimethylamine, palmityl dimethylamine, ujialkyl dimethylamine, hardened uji alkyl dimethylamine, stearyl dimethylamine, stearyl diethanol Amines, polyoxyethylene cured tallow alkylamine (trade name of Lion Akzo Co., Ltd. make: ETHOMEEN HT / 14 etc.), these salts, etc. are mentioned.

These components (B) may be used individually by 1 type, or may use 2 or more types together.

In this invention, 0.1-10 mass% is preferable in a composition, and, as for the compounding quantity of a component (B), 0.5-5 mass% is especially preferable. By making the compounding quantity of a component (B) into 0.1 mass% or more, the compounding effect of a component (B) improves, and the tactile effect by the component (C) is fully expressed. On the other hand, when the compounding quantity of a component (B) is 10 mass% or less, stability of a composition improves and it is also advantageous economically.

[Polyether Modified Silicone (C)]

Polyether modified silicone (C) used for this invention is polyether modified silicone represented by said Formula (I)-(II).

However, in said Formula (I), (II), R is either a C1-C4 linear or branched alkyl group, an alkenyl group, or a hydrogen atom, and each R may be same or different.

R <^1> is a C1-C4 linear or branched alkyl group or alkenyl group, and each R <^1> may be same or different.

X represents a polyoxyalkylene group. Polyoxyalkylene group, Preferably it is C2-C5 of an alkylene group, The repeating number is 1-50.

l is an integer of 0-50, although there may be no structural unit to which l was attached, Preferably l is 0-10. m is 10-10000, n is 1-1000, and the integer of m> n is shown. In addition, the order of each structural unit to which l, m, and n are attached may differ.

Here, "the order of each structural unit to which l, m, n is attached may be different" means that SiO (H) (CH ₃ )-(structural unit to which l is attached) and? SiO (CH ₃ ) _2- (m The attached structural unit) and? Si (CH ₃ ) (R ¹ -XOR)-(structural unit to which n is attached) may be arranged in any order.

Moreover, a block copolymer may be sufficient as a component (C), and a random copolymer may be sufficient as it. For example, the l unit, the m unit, and the n unit may be arranged in a block form, and the l unit, n unit, and m unit may be used. The blocks may be arranged in order. In addition, one structural unit may be randomly arranged, such as a l unit, a n unit, a unit m, a unit m, and a unit n. .

A represents 5 to 10,000 and b represents an integer of 2 to 10,000;

Among the polyether-modified silicones (C) represented by the formulas (I) and (II), a copolymer of alkyl (C1-3) siloxane and polyoxyalkylene (C2-5 of alkylene group) is preferable. Moreover, the copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, random or block copolymer of ethylene oxide and propylene oxide, etc.) is especially preferable.

The manufacturing method of the polyether modified silicone represented by Formula (I) generally has organohydrogen polysiloxane which has Si-H group, and carbon-carbon double bonds, such as polyoxyalkylene allyl ether, at the terminal, for example. It can manufacture by addition-reacting polyoxyalkylene alkyl ether.

The manufacturing method of the polysiloxane-polyoxyalkylene block copolymer represented by Formula (II) is a dihydrocarbyl which has the polyoxyalkylene compound which has a reactive terminal group, and the terminal group which reacts with the reactive terminal group of the said compound. It can be prepared by reacting siloxanes.

As a specific example of the polyether modified silicone oil used by this invention, CF1188HV, SH3748, SH3749, SH3772M, SH3775M, SF8410, SH8700, BY22-008, BY22-012 by Toray Dow Corning Silicone Co., Ltd. make. , SILWET L-7001, SILWET L-7002, SILWET L-7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-2171 , ABN SILWET FZ-F1-009-01, ABN SILWET FZ-F1-009-02, ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-009-09 , ABN SILWET FZ-F1-009-11, ABN SILWET FZ-F1-009-13, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-2222, X-made by Shin-Etsu Chemical Co., Ltd. 20-8010B, KF352A, KF6008, KF615A, KF6012, KF6016, KF6017, TSF4450, TSF4452, TSF4445 (above, brand names) by GE Toshiba Silicon Corporation, etc. are mentioned. These polyether modified silicone oils may be used individually by 1 type, or may mix and use 2 or more types.

The component (C) using the said oil may be used individually by 1 type, or may use 2 or more types together. In this invention, 0.01-10 mass% is preferable in a composition, and, as for the compounding quantity of a component (C), 0.1-5 mass% is especially preferable. By making the compounding quantity of a component (C) into 0.01 mass% or more, the compounding effect of a component (C) is fully expressed, and favorable slipperiness | lubricacy is expressed with respect to the clothing of a polyester material. On the other hand, stability of a composition improves by making compounding quantity of a component (C) into 10 mass% or less.

Polyether modified silicone (C) expresses the slipperiness | lubricacy provision effect excellent with respect to the clothing of polyester material by mix | blending with a nitrogen-containing compound (B).

The reason for the manifestation of this effect is not clear, but as the nitrogen-containing compound (B) and the polyether-modified silicone (C) form a complex, the polyether-modified silicone (C) for the garment of polyester material is irrespective of the cleaning process. ) Is assumed to be due to high adsorption.

And the slipperiness | lubricacy provision effect of a polyether modified silicone is better than an amino modified silicone, and yellowing of the composition which was a subject in an amino modified silicone addition system does not generate | occur | produce, and is also excellent in stability with time.

`` Maleic acid copolymer (D) ''

In the present invention, as the maleic acid copolymer (D), it is preferable to mix maleic acid with a hydrocarbon monomer having 4 to 12 carbon atoms and copolymerizable with maleic acid and / or acrylic acid, and / or a salt thereof.

Cotton clothing, which is a representative material other than polyester, is inherently weakened by repetitive washing, and becomes thick. The maleic acid copolymer (D) exhibits the effect of suppressing the twisting of the cotton garment and providing the elasticity.

Therefore, the opportunity to collect a lot of clothing at a time is increasing, and when washing clothes of polyester material and cotton material together, the component (A), (B), (C) further contains component (D) By doing so, the slipperiness of the polyester material and the elasticity of the cotton material can be imparted at the same time.

In the maleic acid copolymer (D), the monomer copolymerized with maleic acid is not particularly limited as long as it is a C4-C12 hydrocarbon monomer and / or acrylic acid copolymerizable with maleic acid, but the following may be suitably used.

As carbon number of the hydrocarbon-type monomer copolymerizable with maleic acid, it is C4-C12 and C4-C8 is more preferable at the handling property of a raw material.

Further, the copolymer of maleic acid and a hydrocarbon monomer having 4 to 12 carbon atoms and / or a salt thereof may be a copolymer which has not been neutralized yet, or may be a salt in which the carboxyl group is neutralized with a common alkaline agent.

As a specific example, the copolymer salt of a maleic acid and an olefin is used suitably, The quinflow 540 (sodium salt), 542 (sodium salt), 543 (ammonium salt), 640 (sodium salt), etc. made from Nippon Zeon Co., Ltd., or BASF Corporation make Sokalan CP9 (sodium salt) (all are brand names), etc. are mentioned.

Moreover, as a copolymer of maleic acid and acrylic acid, and / or its salt, Sokalan CP7 (sodium salt) by BASF Corporation, Aquaric TL-400, TL-500, TL-37 (all brand names) by Japan Catalyst Co., Ltd., etc. are mentioned. Can be mentioned.

In the case of maleic acid, a hydrocarbon monomer having 4 to 12 carbon atoms and / or a salt thereof, the copolymer mass average molecular weight (measured by gel permeation chromatography in terms of polystyrene) is preferably 1000 to 100000, and 3000 to 50000 is More preferred.

By setting the mass average molecular weight to 1000 or more, the elasticity imparting effect to the cotton apparel is sufficiently expressed, and the stability of the composition is improved by setting the mass average molecular weight to 100000 or less.

Here, in the case of the copolymer of maleic acid and acrylic acid and / or its salt, the molar ratio of maleic acid and acrylic acid is preferably 20:80 to 50:50, more preferably 30:70 to 50:50, and 35:65 to 45 : 55 is more preferable.

Regarding the ratio of acrylic acid, the molar ratio of maleic acid and acrylic acid to 20:80 or less improves the ability to decompose the complex of insoluble modified starch and calcium, resulting in sufficient cleaning power and a molar ratio of maleic acid and acrylic acid of 50:50 or more. By setting it as such, the polymerizability rises and the production of the polymer becomes easy.

Moreover, as for the mass mean molecular weight (measured value by the gel permeation chromatography of polystyrene conversion) of the said copolymer, 5000-100000 are preferable, and 5000-50000 are more preferable.

By setting the mass average molecular weight to 5000 or more, the elasticity imparting effect to the cotton garments is sufficiently expressed, and the stability of the composition is improved by setting the mass average molecular weight to 100000 or less.

These components (D) may be used individually by 1 type, or may use 2 or more types together.

In this invention, 0.1-10 mass% is preferable in a composition, and, as for the compounding quantity of a component (D), 0.5-5 mass% is especially preferable. When the blending amount of the component (D) is 0.1% by mass or more, the elasticity imparting effect on the cotton garment is sufficiently expressed. On the other hand, when the component (D) is 10% by mass or less, a sufficient elasticity imparting effect can be obtained on the cotton garment. It is also economically advantageous.

The composition of this invention becomes more preferable by making the said components (A)-(C) essential and mix | blending a component (D), In addition to these components, if necessary, other arbitrary components do not impair the effect of this invention as needed. It can mix.

As another component which can be mix | blended, it is an enzyme (protease, a lipase, a cellulase, etc.), a stabilizer (sodium benzoate, citric acid, sodium citrate, polyhydric alcohol, polyethyleneglycol alkylether, for example, for the purpose of improving cleaning performance, a compounding stability, etc.). , Polypropylene glycol alkyl ether, polyethylene polypropylene glycol alkyl ether, polyethylene (propylene) glycol phenyl ether, polypropylene glycol phenyl ether, polyethylene polypropylene glycol phenyl ether, etc.), tactile enhancer, pH adjusting agent, preservative, hydrotroping agent, fluorescence Agent, anti-foaming agent, pearl agent, antioxidant, oil release agent and the like.

In addition, a coloring agent, a flavoring agent, an emulsifying agent, etc. can also be mix | blended for the purpose of the value added improvement of a product, etc.

As a coloring agent, general-purpose pigment | dyes and pigments, such as acid red 138, Polar Red RLS, acid yellow 203, acid blue 9, blue No. 1, blue No. 205, Turquoise P-GR (all brand name), can be used, and it is a preferable compounding quantity Is about 0.00005 to 0.0005 mass%.

As a representative example, a flavoring agent (A), (B), (C) and (D) of Table 11-18 of Unexamined-Japanese-Patent No. 2002-146399 can be used, As a preferable compounding quantity, it is 0.1-1 mass. %to be.

Examples of the emulsifying agent include polystyrene emulsion, polyvinyl acetate emulsion, and the like, and an emulsion having a solid content of 30 to 50% by mass is suitably used. As a specific example, a polystyrene emulsion (trade name: Cybinol RPX-196 PE-3 manufactured by Siden Chemical Co., Ltd., 40 mass% of solid content) etc. can be used, It is 0.01-0.5 mass% as a preferable compounding quantity.

In the composition of this invention, it is preferable to set it as pH4-9 from the point which maintains the favorable stability at the time of long-term storage of a composition, and pH 4-8 are more preferable.

What is necessary is just to mix | blend a pH adjuster suitably in order to adjust pH to 9 or less. Although there is no restriction | limiting in the pH regulator as long as it does not impair the effect of this invention, A sulfuric acid, sodium hydroxide, potassium hydroxide, an alkanolamine, etc. are preferable at the point of formulation stability.

The preparation method of the liquid detergent composition for clothes of the present invention is not particularly limited, and the essential ingredients (A) to (C) and the components ( D) and, if necessary, the above-mentioned optional components, and an appropriate amount of water may be blended to prepare them by mixing them.

Moreover, the composition of this invention can be filled into containers, such as resin, and can be used for use.

The method of using the composition of the present invention is not particularly limited, and may be hand washing or washing with a washing machine. For example, in the case of washing by a conventional washing machine, after washing the laundry into the washing machine, the washing tank is filled with water and the composition of the present invention is added and dissolved to obtain a suitable concentration to obtain a washing liquid, thereby washing the laundry. Can be.

According to the present invention, since the composition which mixes a nonionic surfactant (A), a nitrogen-containing compound (B), and a polyether modified silicone (C) is employ | adopted, it is excellent with respect to the garment of the polyester material which can be washed at home. Slipperiness can be provided. Moreover, the washing | cleaning function which removes time can also be obtained. In addition, by blending the maleic acid-based copolymer (D) it can provide a liquid detergent composition for clothes having an effect that can give elasticity to the clothing of the cotton material washed in a washing tank such as polyester-based clothing.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by the Example described below.

(Examples 1-68, Comparative Examples 1-7)

In each case, the clothing liquid detergent composition was prepared and evaluated similarly except having changed the compounding composition. The compounding composition of each example is shown to Tables 1-8.

In addition, the compounding quantity unit in a table | surface shows mass%. In addition, in the following description, "%" regarding a compounding quantity and concentration is "mass%" unless there is a notice in particular.

The table described only the component (A), the component (B), its comparative component (E), the component (C) and its comparative component (F), the component (D), and the comparative component (G). And the common component was mix | blended according to these components, the quantity of water was adjusted suitably so that the sum total of all components might be 100 mass%, and the clothing liquid cleaning composition was obtained. Moreover, any one of sulfuric acid, sodium hydroxide, monoethanolamine, and oxalic acid (all from Kanto Chemical) was adjusted as a pH adjuster so that pH of a composition might be shown in the same table | surface.

In addition, in a common component, the compounding quantity of each component shows the compounding quantity as it is (whole quantity), and the compounding quantity of components other than a common component shows the pure part conversion amount. The compounding quantity of "c-7 *" in Table 6, 7 shows the net part conversion amount of polyether modified silicone.

<Common Ingredients>

0.5 mass% of sodium benzoate

0.2 mass% of trisodium citrate

2.0% by mass of paratoluenesulfonic acid

Dibutylhydroxytoluene 0.03 mass%

0.2 mass% of fragrances

0.01% by mass of isothiazolone solution

Pigment (acid red 138) 0.0003 mass%

pH adjuster

Water balance

In addition, in the common component, the detail of each component is as follows.

Sodium benzoate: Kyo-synthetic (trade name) Sodium benzoate.

Trisodium citrate: It is a citric acid (brand name) product made by Miles Corporation (the United States).

Paratoluene sulfonic acid: PTS acid manufactured by Kyowa Fermentation Industry Co., Ltd. (brand name).

Dibutyl hydroxytoluene: Sumitomo Chemical Co., Ltd. (brand name) SUMILIZER BHT-R.

Isothiazolone liquid: (brand name) caisson CG (5-chloro- 2-methyl- 4-isothiazolin- 3-one / 2-methyl- 4-isothiazolin- 3-one / magnesium salt / water made by Rohm & Haas Corporation Mixed liquor).

Pigment (acid red 138): Sumitomo Chemical Co., Ltd. (trade name) Suminol milling brilliant red BS.

Fragrance | flavor: The fragrance composition A of Unexamined-Japanese-Patent No. 2002-146399, Table 11-18.

In addition, the following compounds were used as component (A).

(a-1): C ₁₃ H ₂₇ O (EO) ₁₅ H, average EO 15 mol adduct of Mitsubishi Chemical Corporation (trade name) Diadol alcohol (branching rate 50%).

(a-2): C _n H _{2n +1} O (EO) ₁₅ H (n = 12/13 mixture (mass ratio 55/45)), a synthetic product.

(a-3): C _n H _{2n +1} O (EO) ₁₂ H (n = 12/13 mixture (mass ratio 55/45)), a synthetic product.

(a-4): C _n H _{2n +1} O (EO) ₁₅ H (n = 12/14 mixture (mass ratio 71/29)), a synthetic product.

(a-5): C _n H _{2n +1} CH C _m H _{2m +1} O (EO) ₁₅ H (n + m = 11 to 13), manufactured by Nippon Catalyst Co., Ltd. (trade name) Sotanan 150.

(a-6): C _n H _{2n +1} O (EO) ₁₅ H (n = 12/13 mixture (mass ratio 45/55)), a synthetic product.

(a-7): C _n H _{2n +1} O (EO) ₁₂ H (n = 12/13 mixture (mass ratio 45/55)), a synthetic product.

(a-8): C ₁₁ H ₂₃ COO (EO) ₁₅ CH ₃ , synthetic.

(a-9): C ₁₃ H ₂₇ O (EO) ₁₂ (PO) ₂ H, synthetic.

(a-10): C ₁₃ H ₂₇ O (EO) ₁₀ H (C chain length: branched), manufactured by BASF (trade name) Lutensol TO10.

(a-11): C ₁₃ H ₂₇ O (EO) ₇ H (C chain length: branched), manufactured by BASF (trade name) Lutensol TO7.

(a-12): C ₁₃ H ₂₇ O (EO) ₁₅ H, synthetic.

As the component (B), the following compounds were used.

(b-1): C ₉ H ₁₉ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , synthetic.

(b-2): C ₁₁ H ₂₃ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , synthetic.

(b-3): C ₁₅ H ₃₁ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , synthetic.

(b-4): C ₁₇ H ₃₅ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , synthetic.

(b-5): C ₂₁ H ₄₃ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , synthetic.

(b-6): C ₁₇ H ₃₃ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , synthetic.

(b-7): C ₁₇ H ₃₅ COO (CH ₂ ) ₃ N (CH ₃ ) ₂ , synthetic.

(b-8): C ₁₆ H ₃₃ N (CH ₃ ) ₂ , Lion Akzo Co., Ltd. (trade name) amine DM16D.

(b-9): C ₁₈ H ₃₇ N (CH ₃ ) ₂ , Lion Akzo Co., Ltd. (trade name) amine DM18D.

(b-10): C _n H _2n + ₁ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ (n = 15/17 mixture (mass ratio 3/7)), manufactured by Toho Chemical Co., Ltd. ) Cardinal MPAS-R.

(b-11): C _n H _{2n +1} CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ (n = 15/17 mixture (mass ratio 3/7)), a synthetic product.

(b-12): C _n H _{2n +1} CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ (n = 7/9 mixture (mass ratio 6/4)), a synthetic product.

In addition, the following component (E) was used as a comparison of component (B).

(e-1): (C 2 H 5) 3 N, Kanto Chemical Co., the triethylamine

As the component (C), the following compounds were used.

(c-1): Polyether modified silicone, Toray Dow Corning Silicone Co., Ltd. product (brand name) SH3775M.

(c-2): polyether modified silicone, the above-described general formula (I), m = 210, n = 9, l = 0, R ¹ = C ₃ H ₆ , X =? (OC ₂ H ₄ ) _10- , A silicone compound having R = CH ₃ , a synthetic product.

(c-3): Polyether modified silicone, the Shin-Etsu Chemical Co., Ltd. make (brand name) KF6016.

(c-4): Polyether modified silicone, Toray Dow Corning Silicone Co., Ltd. product (brand name) F1-009-02.

(c-5): polyether modified silicone, the above-described general formula (I), m = 210, n = 9, l = 0, R ¹ = C ₃ H ₆ , X = (OC ₂ H ₄ ) ₁₁ , R = CH ₃ Silicone compound, synthetic.

(c-6): polyether modified silicone, the above-described general formula (I), m = 210, n = 9, l = 0, R ¹ = C ₃ H ₆ , X = (OC ₂ H ₄ ) ₉ , R = H compound, synthetic.

(c-7): a mixture of (c-6) and butylcarbitol. The mixing ratio is (c-6) / butyl carbitol = 9/1 by mass ratio.

(c-8): polyether modified silicone, the above-described general formula (I), m = 70, n = 3, l = 0, R ¹ = C ₃ H ₆ , X = (OC ₂ H ₄ ) ₁₁ , R Silicone compound composite with = CH ₃ .

In addition, the following component (F) was used as a comparison of component (C).

(f-1): amino modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd. (brand name) KF877.

(f-2): Amino polyether modified silicone, Toray Dow Corning Silicone Co., Ltd. (brand name) BY16-893.

(f-3): Amide polyether modified silicone, Toray Dow Corning Silicone Co., Ltd. (brand name) BY16-878.

(f-4): Dimethyl silicone, Doe Dow Corning Silicone Co., Ltd. (brand name) SH200-1000.

As the component (D), the following compounds were used.

(d-1):? C 5 olefin-maleic acid copolymer sodium salt, Japan Zeon Co., Ltd. The (trade name) 542 Queen flow.

(d-2):? C 5 olefin-maleic acid copolymer sodium salt, Japan Zeon Co., Ltd. The (trade name) 540 Queen flow.

(d-3):? C 5 olefin maleic acid copolymer ammonium salt, Japan Zeon Co., Ltd. The (trade name) 543 Queen flow.

(d-4): Olefin maleic acid copolymer sodium salt, BASF make (brand name) Sokalan CP9.

(d-5): Acrylic acid maleic acid copolymer (molar ratio 60:40), the copolymer sodium salt of the mass mean molecular weight 50000, the BASF Corporation make (brand name) Sokalan CP7.

(d-6): Acrylic acid-maleic acid copolymer (molar ratio 60:40), the copolymer sodium salt of the mass mean molecular weight 50000, Nippon-Catalog Co., Ltd. (brand name) Aquaric TL-400.

In addition, the following component (G) was used as a comparison of component (D).

(g-1): Polyvinylpyrrolidone, ISP Japan product (brand name) polyvinylpyrrolidone K-30

Next, the manufacturing method of a synthetic product is shown below.

(a-2):

Sasol (brand name) Safol23 alcohol (branching ratio 50%) 224.4g and 30 mass% NaOH aqueous solution 2.0g were extract | collected in the pressure-resistant reaction container, and the inside of the container was nitrogen-substituted.

Next, after dehydrating for 30 minutes at the temperature of 100 degreeC and the pressure of 2.0 kPa or less, temperature was heated up to 160 degreeC. 763.6 g of ethylene oxide (gas phase) was slowly added into the alcohol liquid while stirring the alcohol. At this time, using a blown pipe was added while adjusting the rate of addition so that the reaction temperature does not exceed 180 ℃.

After the addition of ethylene oxide was completed, the mixture was aged at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was leached for 10 minutes at a temperature of 180 ° C. and a pressure of 6.0 kPa or less.

Then, after cooling temperature to 100 degrees C or less, 70 mass% p-toluenesulfonic acid was added and neutralized so that pH of the 1 mass% aqueous solution of a reaction material might be about 7, and (a-2) was obtained.

(a-3):

It was synthesize | combined as (a-2) using 265.5 g of Safol23 alcohol (brand name) by Sasol, 2.5 g of 30 mass% aqueous NaOH, and 723,4 g of ethylene oxide.

(a-4):

It was synthesize | combined as (a-2) using 224.4 g of C12-14 alcohols (0% of branch ratio) by P & G.

(a-6):

It was synthesize | combined as (a-2) using 224.4g of Neodol23 alcohol (brand name) (20% of branch ratio) made from Shell Chemicals.

(a--7):

It was synthesize | combined as (a-2) using 265.5 g of Neodol23 alcohol (brand name) made from shell chemicals (20% of branch ratios), 2.5 g of 30 mass% aqueous NaOH, and 723.4 g of ethylene oxide.

(a-8):

It synthesize | combined like the manufacture example 3 of Unexamined-Japanese-Patent No. 2000-186296.

(a-9):

As solution S1, 68.03 g (0.265 mol) of magnesium nitrate hexahydrate, 47.69 g (0.127 mol) of aluminum nitrate hexahydrate, and 24.33 g (0.085 mol) of manganese nitrate hexahydrate were dissolved in 450 g of deionized water.

On the other hand, 13.47 g (0.127 mol) of sodium carbonate was dissolved in 450 g of deionized water as solution S2.

The pH was adjusted to 9 by 2N NaOH in the catalyst control tank which put 1800 g of deionized water previously, and solution S1 and solution S2 were dripped for 1 hour, maintaining temperature at 40 degreeC.

Aged 1 hour after the end of dropping. The mother liquor was removed by filtration, and the precipitate was washed with 6 L of deionized water and spray dried to obtain 30 g of a composite hydroxide.

This composite hydroxide was calcined at 800 ° C. under nitrogen atmosphere for 3 hours to obtain 19 g of a composite oxide catalyst (Mg: Al: Mn (atomic ratio) = 0.56: 0.26: 0.18) of Mg, Al, Mn. The following synthesis was carried out using this catalyst.

186 g of lauryl alcohol was placed in a pressure resistant reactor, 0.8 g of the catalyst produced by the above method was added, and stirred at 180 MPa at 180 MPa for 1 hour at a rotation speed of 500 rpm.

Thereafter, 528 g of ethylene oxide was first introduced over 2 hours, and fully introduced, and then aged for 1 hour. Thereafter, the mixture was heated to 180 ° C, 116 g of propylene oxide was introduced over 1 hour, aged for 1 hour, and cooled to obtain (a-9).

(a-12):

It synthesize | combined by the method as described in Unexamined-Japanese-Patent No. 1-164437, Unexamined-Japanese-Patent No. 10-7620, and Unexamined-Japanese-Patent No. 2000-61304.

In addition, the narrow ratio defined in Unexamined-Japanese-Patent No. 2001-164298 was 55% or more about the obtained compound.

(b-1):

224 g of capric acid was placed in a 1 liter four-necked flask, and nitrogen substitution was performed twice at 80 ° C. 173 g of dimethylamino propylamines were dripped for 2 hours, heating up by 170 degreeC and distilling the byproduct water.

After completion of dropping, the mixture was kept at 170 to 180 ° C and aged for 7 hours. The conversion rate of capric acid calculated from the acid value was 98%.

After aging, the reaction mixture was dried under reduced pressure to remove unreacted amine and water to obtain (b-1).

(b-2):

Synthesis was carried out as in (b-1) except that 261 g of lauric acid was used instead of capric acid. The conversion rate of lauric acid calculated from the acid value was 98%.

(b-3):

Synthesis was carried out as in (b-1), except that 334 g of palmitic acid was used instead of capric acid. The conversion rate of palmitic acid calculated from the acid value was 98%.

(b-4):

Synthesis was carried out as in (b-1), except that 370 g of stearic acid was used instead of capric acid. The conversion rate of stearic acid calculated from the acid value was 98%.

(b-5):

Synthesis was carried out as in (b-1), except that 444 g of behenic acid was used instead of capric acid. The conversion rate of Behenic acid, calculated from the acid value, was 98%.

(b-6):

Synthesis was carried out as in (b-1), except that 368 g of oleic acid was used instead of capric acid. The conversion rate of oleic acid calculated from the acid value was 98%.

(b-7):

Into a one-liter four-necked flask, 386 g of methyl palmitic acid, 200 g of dimethylamino ethanol, and 2 g of p-toluenesulfonic acid were used as a catalyst, and nitrogen replacement was performed twice. The dehydration condensation reaction was carried out for 10 hours while distilling off byproduct methanol at a reaction temperature of 140 to 150 ° C. The conversion rate of methyl palmitate calculated from the saponification value was 99%.

Thereafter, the mixture was depressurized to flow unreacted dimethylamino ethanol and methanol to obtain (b-7).

(b-11):

252 g of stearic acid (molecular weight 284) and 108 g of palmitic acid (molecular weight 256) were put into a 1-liter four-necked flask equipped with a reflux condenser, and the stearic acid and palmitic acid were melted by heating to 80 ° C. After nitrogen substitution was performed twice, 127 g of dimethylamino propylamine (molecular weight 102) (molar ratio to mixed fatty acid: 0.95) was added dropwise over 1 hour by raising the temperature to 150 ° C.

Next, after hold | maintaining at 150-160 degreeC for 1 hour, it heated up at 185 degreeC over 1 hour, and 47 g of dimethylamino propylamine was dripped over 1 hour. After completion of the dropping, the mixture was kept at 185 to 190 ° C, aged for 7 hours, and the by-product water was distilled out of the system. Furthermore, unreacted dimethylamino propylamine was distilled off (b-11) by depressurizing (4.0 kPa) and leaving it to stand for 1 hour, keeping 170-190 degreeC.

The conversion rate of the mixed fatty acid calculated from the acid value was 99.2%.

(b-12):

In a 1-liter four-necked flask equipped with a reflux condenser, 133 g of methyl caprylate (manufactured by Lion Chemical Co., Ltd., product name: Pastel M-08, molecular weight 158), and methyl capricate (manufactured by Lion Chemical Company, brand name: Pastel M- 10, molecular weight 186) 104 g of nitrogen substitution was performed twice at 60 ° C., and then heated to 180 ° C., and 186 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to mixed fatty acid methyl ester: 1.30) was added over 3 hours. Dropped. Thereafter, the mixture was maintained at 180 to 190 ° C for 2 hours to prepare a reactant. Methanol by-produced by the reaction was taken out of the system by flowing hot water at 80 ° C. in a cooler. Furthermore, unreacted dimethylamino propylamine was distilled off (b-12) by depressurizing (4.0 kPa) and leaving to stand for 1 hour, maintaining 170-190 degreeC.

The conversion rate of the mixed fatty acid calculated from the acid value was 99.2%.

(c-2):

In a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet, 100 g of organohydrogen polysiloxane (α = 210, β = 9) represented by the following formula (VIII), 50 g of isopropyl alcohol, and the following formula 29 g of the polyoxyalkylene compound represented by (IX) (d = 10, G = CH ₃ ), 0.2 g of an addition reaction catalyst, and 0.3 g of an isopropyl alcohol solution of 2 mass% sodium acetate were added thereto, and these were added under a nitrogen atmosphere. It was made to react at 90 degreeC for 3 hours.

(C-2) was obtained by sending a solvent under reduced pressure after completion | finish of reaction.

CH ₂ = CHCH ₂ O- (C ₂ H ₄ O) _d -G ‥‥ (IX)

(c-5):

31 g of polyoxyalkylene compound (d = 11, G = CH ₃ ) represented by the same formula instead of 29 g of polyoxyalkylene compound (d = 10, G = CH ₃ ) represented by the formula (IX) Other than the synthesis under the same reaction conditions as in (c-2) to obtain (C-5).

(c-6):

Instead of using 29 g of polyoxyalkylene compound (d = 10, G = CH ₃ ) represented by the formula (IX) except that 26 g of polyoxyalkylene compound (d = 9, G = H) represented by the same formula was used. Synthesis was carried out under the same reaction conditions as in (c-2), to obtain (c-6).

(c-8):

Instead of 100 g of organohydrogen polysiloxane (α = 210, β = 9) represented by the formula (VIII), 100 g of organohydrogen polysiloxane (α = 70, β = 3) represented by the same formula is used, and 31 g of polyoxyalkylene compounds (d = 11, G = CH ₃ ) represented by the same formula instead of 29 g of polyoxyalkylene compounds (d = 10, G = CH ₃ ) represented by the formula (IX) Other than this was synthesize | combined on the same reaction conditions as (c-2), and it obtained (c-8).

(Assessment Methods)

Hereinafter, an evaluation method is demonstrated and the obtained evaluation result is shown to Tables 1-6.

<Evaluation of washing power>

1.washing treatment

10 sheets of polyester cloth (polyester faille) cut to the size of the sebum rubbed on the face's sebum, and 4 pieces of commercially available T-shirts (100% cotton, made by BVD) are manufactured by Mitsubishi Electric Corporation It put into the electric washing machine (CW-C30A1 type).

The composition prepared in each example was added at a rate of 40 mL to about 30 L of tap water at 25 ° C., washed with standard water flow (10 minutes), dehydrated (1 minute), and rinsed with standard water flow (2 repetitions / 5 times each). Min) and dewatering (1 min) were performed sequentially.

2. Evaluation of cleaning power

Color difference meter (SE200 type) made by Nippon Color Co., Ltd. for micro-fouling springs, contaminated cloth (before cleaning treatment), and cleaning cloth (after washing treatment) ), And the washing rate (%) was calculated based on the following formula.

Washing rate (%) = (K / S of dirty cloth K / S-clean cloth) / (K / S of dirty cloth K / S-dirty cloth) × 100

Furthermore, in the formula, K / S represents (1-R / 100) ² / (2R / 100), where R represents reflectance (%).

Judgment criteria are shown below.

1 point: The washing | cleaning rate is less than 60%.

2 points | pieces: The washing | cleaning rate is 60% or more and less than 65%.

3 points | pieces: The washing | cleaning rate is 65% or more and less than 70%.

4 points | pieces: The washing | cleaning rate is 70% or more.

<Evaluation of slipperiness of polyester>

The polyester payu cloth treated with the above washing treatment was dried for 12 hours. Then, it was left to stand in a constant temperature and humidity room of 25 degreeC / 65% RH for 2 days, and this was made into the test cloth and used for slip evaluation.

As the evaluation control cloth, polyester payucheon washed as described above using a 20% by mass aqueous solution of a nonionic surfactant (an alcohol ethoxylate added with an average of 15 moles of ethylene oxide per mole of lauryl alcohol) was similarly polyester. Provided for evaluation of slipperiness.

About each polyester fat-and-oil fabric, ten professional panels evaluated the slipperiness | lubricacy of polyester for sensory performance.

The evaluation was made by comparing a pair of comparison fabrics, and the average value of the scores of 10 professional panels was obtained based on the following criteria. Higher scores indicate better slipperiness of the polyester.

1 point: The slipperiness | lubricacy of a control cloth and polyester is equal or less.

2 points | pieces: Slipperiness | lubricacy of polyester is slightly better than a control cloth.

3 points | pieces: The slipperiness | lubricacy of polyester is better than a control cloth.

4 points | pieces: The slipperiness | lubricacy of polyester is much better than a control cloth.

<Cotton elasticity evaluation>

A commercial T-shirt (100% cotton, manufactured by B.V.D.) subjected to the above washing treatment was hanged on a hanger for 12 hours and dried.

Then, it was left to stand in a constant temperature and humidity room of 25 degreeC / 65% RH for 2 days. This operation was repeated 10 times and used for evaluation of cotton elasticity as a test garment.

Evaluation As a control garment, a cotton t-shirt was treated 10 times as in the test garment using a 20 mass% aqueous solution of a nonionic surfactant (an alcohol ethoxylate added with an average of 15 mol of ethylene oxide per mol of lauryl alcohol). Provided for resilience assessment.

In evaluation of cotton elasticity, ten professional panelists wore each garment, and the sensory evaluation at that time was carried out.

Evaluation evaluated a pair of comparison garments, and calculated | required the average value of ten professional panelists by the following reference | standard. Higher scores indicate better cotton elasticity.

1 point: Comparing clothing with cotton elasticity is equal or less.

2 points | pieces: There is a little elasticity of cotton compared with a control garment.

3 points | pieces: It is cotton elasticity more than control clothing.

4 points | pieces: It has more cotton elasticity than a control garment.

(Evaluation results)

As shown in each table, each containing a nonionic surfactant (A), a nitrogen-containing compound (B) which is a tertiary amine having a C7-C28 hydrocarbon group and / or a salt thereof, and a polyether-modified silicone (C) The composition of the Example had the effect of providing the outstanding slipper property with respect to a polyester raw material. Moreover, the washing | cleaning function which pulled out time was also favorable.

In addition, the composition of the Example which further mix | blended maleic acid and the copolymer of a C4-C12 hydrocarbon-type monomer and / or acrylic acid which can copolymerize with said maleic acid, and / or its salt is a non-blended composition (execution) Compared with Examples 40, 41, 43, 45, and 51), the surface elasticity was excellent.

On the other hand, it does not contain the comparative example 6 which does not contain the component (B) among the components (A), (B), and (C), and the comparative example 1 and the component (C) which mix | blended the component (E) instead of the component (B). In Comparative Examples 2-5 which mix | blended component (F) instead of the comparative example 7 and component (C) which were not, the slipperiness | lubricacy evaluation with respect to a polyester raw material was low.

It was confirmed from the above result that the effect of this invention is exhibited by containing a component (A), (B), (C).

According to this invention, the liquid detergent composition for garments which provides the outstanding slipperiness with respect to the garment of polyester material can be provided.

Claims (5)

Non-ionic surfactant (A), the nitrogen-containing compound (B) which is a tertiary amine which has a C7-C28 hydrocarbon group which may have a substituent, and may have a coupling group in a chain, and / or its salt, and following formula (I) A liquid detergent composition for clothes comprising at least one polyether-modified silicone (C) selected from) to (II). [Formula 1]

[Formula 2]

(Note that the formula (I), (II), R is any one of straight-chain or branched alkyl or alkenyl groups, hydrogen atoms having from 1 to 4 carbon atoms, each R may be different may be the same. R ¹ is, As a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms, each R ¹ may be the same or different X represents a polyoxyalkylene group The order of each structural unit to which l, m, n is attached may be different , l is 0 to 50, m is 10 to 10000, n is 1 to 1000, and an integer of m> n is represented, a is 5 to 10000, and b is an integer of 2 to 10000.) The liquid detergent composition for clothes according to claim 1, wherein the maleic acid copolymer (D) is a copolymer of maleic acid and a hydrocarbon monomer and / or acrylic acid having 4 to 12 carbon atoms copolymerizable with the maleic acid, and / or a salt thereof. The said polyether modified silicone (C) of Claim 1 or 2 containing 10-50 mass% of said nonionic surfactants (A), 0.1-10 mass% of said nitrogen-containing compounds (B), ) 0.01 to 10% by mass of a liquid detergent composition for clothes. The liquid detergent composition for clothes according to claim 2, wherein the maleic acid copolymer (D) is contained in an amount of 0.1 to 10% by mass. The liquid detergent composition for clothes according to claim 3, wherein the maleic acid copolymer (D) is contained in an amount of 0.1 to 10% by mass.