JP2009013336A - Color tone change inhibitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color tone change inhibitor exhibiting excellent effect in the color tone change inhibitor of a colored fiber product. <P>SOLUTION: The color tone change inhibitor for the colored fiber product contains carboxymethyl cellulose and further contains (A) a nonionic surfactant and (B) a long chain aliphatic alkyl amine and/or amide amine and is added into a liquid detergent composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a color tone change inhibitor for colored fiber products.

Colored fiber products such as fashionable clothes colored with dyes and pigments may change the color tone in normal washing and impair the appearance. This is known to be due to the browning of the colorant due to the action of residual free chlorine in tap water.
Various studies have been made to prevent such color change of clothes during washing. For example, Japanese Unexamined Patent Application Publication No. 2003-206495 discloses a laundry detergent composition containing an amidoamine compound having a supplementary effect of residual free chlorine in tap water. However, the laundry detergent composition described in the above publication is not sufficient in preventing color change.

JP 2003-206495 A

  An object of the present invention is to provide a color tone change inhibitor having an excellent effect.

The present inventors have found that by adding carboxymethyl cellulose to a liquid detergent composition together with a long-chain aliphatic alkylamine and / or amidoamine, a further excellent color change prevention effect of a colored fiber product can be obtained. It came to complete.
That is, the present invention is a color fiber product color-change preventing agent containing carboxymethylcellulose, which is a liquid containing (A) a nonionic surfactant and (B) a long-chain aliphatic alkylamine and / or amidoamine. Provided is a color change inhibitor for addition to a cleaning composition.
The present invention also provides:
(A) nonionic surfactant,
(B) a long chain aliphatic alkylamine and / or amidoamine, and
(C) Provided is a liquid detergent composition containing the color change inhibitor.

  By using the color tone change preventing agent of the present invention, an excellent color tone change preventing effect can be obtained together with a yellow color change preventing effect when washing a colored fiber product.

The color change preventive agent of the color fiber product of the present invention contains carboxymethylcellulose, and (A) a nonionic surfactant, and (B) a liquid detergent composition containing a long-chain aliphatic alkylamine and / or amidoamine. Added to the product.
In the present invention, “colored textile product” means a textile product having a color other than white, and examples thereof include clothing such as fashionable clothes. The chromatic color is not particularly limited, and examples thereof include red, blue, yellow, green, and mixed colors thereof. Of these colorings, blue is preferable. The fiber used in the textile product may be either a natural fiber or a synthetic fiber. Examples of the natural fiber include cotton, wool, hemp, and examples of the synthetic fiber include nylon, polyester, and acrylic fiber. Further, it may be a regenerated fiber such as cupra or rayon, or may be a mixture of the above fibers. Of the above fibers, natural fibers, particularly cotton, are preferred.

(A) Nonionic surfactant The liquid detergent composition to which the color tone change preventing agent of the present invention is added contains (A) a nonionic surfactant and (B) a long-chain aliphatic alkylamine and / or an amidoamine. .
The nonionic surfactant (A) is a component mainly responsible for the cleaning function of the liquid detergent composition, and may be used alone or in combination of two or more.
The nonionic surfactant (A) used in the present invention is not particularly limited. For example, a polyoxyalkylene type nonionic surfactant represented by the following formula (III) is preferably used.

In the above formula (III), R ² is a hydrocarbon group having 8 to 22 carbon atoms, preferably 10 to 16 carbon atoms.
Preferred examples of the hydrocarbon group include an alkyl group and an alkenyl group, which may be linear or branched. Examples of the raw material used for introducing the hydrophobic group include primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.
R ³ is a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably a hydrogen atom.
-Y- is a linking group, preferably -O-, -COO-, or -CONH-, more preferably -O-.
EO is ethylene oxide and PO is propylene oxide. s and t represent the average number of moles added. s is 3-20, Preferably it is 5-18, More preferably, it is an integer of 5-15. t is 0-6, preferably 0-3.
By setting the average added mole number s of EO 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, and an average added mole number s of EO of 3 By making the average addition mole number t of PO 6 or less as described above, it is possible to suppress a decrease in storage stability of the composition at 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 nonionic surfactant (A) represented by the above formula (III), (i) Mitsubishi Chemical Co., Ltd. product name: Diadol (C13 (showing carbon number 13; hereinafter, “Cn "(N is an integer) indicates that the number of carbon atoms is n.)), A synthetic alcohol obtained by an oxo method such as a product name Safol 23 (C12 / C13 mixture) manufactured by Sasol, or P & G (stock) Product name: CO-1214 (C12 / C14 mixture), Eco Green Oreo Chemicals: Product name Ecolol (C12 / C14 mixture), etc. ii) Shin Nippon Rika Co., Ltd .: A product obtained by adding 9 moles of ethylene oxide to natural alcohol such as Conol (C12), (iii) 7 mol or 10 mol equivalent of ethylene oxide is added to 1 mol of C13 alkene obtained by subjecting C12 alkene obtained by trimerization to oxo method (BASF: trade name Lutensol TO7, Lutensol) TO10), (iv) 15 mol equivalent of ethylene oxide added to lauric acid methyl ester, (v) 10 mol equivalent of oxidation to 1 mol of C12 alcohol obtained by subjecting hexanol to garvet reaction Ethylene added (CONDEA: trade name ISOFOL12-10EO), (vi) 15 mole equivalent ethylene oxide added to C12-14 secondary alcohol (Nippon Shokubai Co., Ltd. product: Commodity Name softener 150), (vii) alkoxy against methyl laurate And those obtained by adding ethylene oxide with 3 moles equivalent of propylene oxide 15 molar equivalent with Le of catalyst.

Further, as the nonionic surfactant (A), nonionic surfactants other than the nonionic surfactant represented by the above formula (III) can also be used.
Other suitable nonionic surfactants include, for example, polyoxyethylene (EO addition mole number 1 to 20) sorbitan fatty acid (C10-22) ester, polyoxyethylene (EO addition mole number 1 to 20) sorbite 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 and the like.

These nonionic surfactants may be used alone or in combination of two or more.
In the present invention, the blend amount of the nonionic surfactant (A) (when two or more types are used in combination, it means the total amount. The same applies to other components described later). 10-50 mass% is preferable in the cleaning composition after addition of an inhibitor, and 10-40 mass% is especially preferable from the point of the color tone change prevention of a colored fiber product. When the blending amount of the nonionic surfactant (A) is 10% by mass or more, the detergency is improved, and when it is 50% by mass or less, the viscosity of the composition is prevented from being excessively increased and the handling becomes easy.

(B) Long-Chain Aliphatic Alkylamine and Amidoamine The long-chain aliphatic alkylamine and amidoamine contained in the detergent composition to which the color tone change preventing agent of the present invention is added may be linear or branched. It may be saturated or unsaturated, may further have a substituent, and may have a linking group in the chain. Is mixed with a tertiary amine containing 1 to 3 hydrocarbon groups and / or a salt thereof. In particular, a tertiary amine containing 1 to 3, preferably 1 or 2 hydrocarbon groups having 7 to 25 carbon atoms and / or a salt thereof is blended.
Here, the “substituent” specifically includes a hydroxy group, an amino group, and the like. Specific examples of the “linking group” include an amide group, an ester group, and an ether group.
Specific examples of tertiary amines and / or salts thereof include those using tertiary amines as they are, and acid salts obtained by neutralizing tertiary amines 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.

  As the long-chain aliphatic alkylamine and amidoamine, a tertiary amine represented by the following formula (IV) and / or a salt thereof is particularly suitable.

In the above formula (IV), R ⁴ is a hydrocarbon group having 7 to 27 carbon atoms (the carbon number here does not include the carbon number in the substituent and the linking group), It may be branched, may be saturated or unsaturated, and may further contain a substituent. R ⁴ 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 ⁴ is “—R ⁷ —W” (where R ⁷ is a linear or branched alkylene group having 1 to 4 carbon atoms. W is —NHCO—R ⁸ or —OOC—R ⁹ . R ⁸ is a hydrocarbon group having 7 to 23 carbon atoms, preferably 7 to 21 carbon atoms, R ⁹ is a hydrocarbon group having 11 to 23 carbon atoms, preferably 12 to 20 carbon atoms, and R ⁸ and R ⁹ are It may be linear or branched, and may be saturated or unsaturated).

R ⁵ is a hydrocarbon group having 1 to 25 carbon atoms. R ⁵ may be linear or 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 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 ⁶ 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 3 moles of EO addition. And 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 is preferably used.

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

However, in the above formula ^{(V), R 10, R} 11 are each a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms.
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 the above formula (VI), R ^{13 has} a carbon number of 7 to 23, preferably 7 to 21, and in the above formula (VII), R ^{14 has} a carbon number of 11 to 23, preferably 12 to 20 hydrocarbon groups, R ¹³ and R ¹⁴ may be linear or branched, and may be saturated or unsaturated.

Preferred examples of the long-chain aliphatic alkylamine or amidoamine (B) include caprylic amidopropyl dimethylamine, capric amidopropyl dimethylamine, lauric amidopropyl dimethylamine, myristic amidopropyl dimethylamine, palmitic acid amide. Long chain aliphatic amide alkyl tertiary amines such as propyldimethylamine, amidopropyl dimethylamine stearate, amidopropyl dimethylamine behenate, amidopropyl dimethylamine oleate or salts thereof; palmitate ester propyldimethylamine, stearate ester propyl Aliphatic ester alkyl tertiary amines such as dimethylamine or salts thereof; amidopropyl diethanolamine palmitate, amidopropyl diethanolamine stearate Emissions, and the like.
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 Particularly preferred is amidepropyldimethylamine oleate or a salt thereof.

The “long-chain aliphatic amidoalkyl tertiary amine” in the above examples is a condensation of a fatty acid or a fatty acid derivative such as a fatty acid lower alkyl ester or animal / vegetable oil and fat with a dialkyl (or alkanol) aminoalkylamine. After the reaction, unreacted dialkyl (or alkanol) aminoalkylamine is obtained by distilling off under reduced pressure or nitrogen blowing.
On the other hand, the “aliphatic ester alkyl tertiary amine” is obtained, for example, by an esterification reaction in which a fatty acid or a fatty acid lower alkyl ester, a fatty acid derivative such as animal or vegetable oil and fat, and a dialkylamino alcohol are condensed.

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, Specific examples include corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oils or animal oil fatty acids, or methyl esters, ethyl esters, glycerides, etc. Among them, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are particularly preferable.
These fatty acids or fatty acid derivatives may be used alone or in combination of two or more.

Specific examples of the “dialkyl (or alkanol) aminoalkylamine” include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, etc. Among them, dimethylaminopropylamine is particularly preferable.
Examples of “dialkylamino alcohol” include dimethylaminoethanol, diethylaminoalcohol and the like. As the diethylamino alcohol, diethylaminoethanol is preferable. Among these, dimethylaminoethanol 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. 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.

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. In this range, an appropriate reaction rate can be maintained, and excessive coloration of the resulting tertiary amine can be prevented.

The production conditions of the long-chain aliphatic amidoalkyl tertiary amine and aliphatic ester alkyl tertiary amine other than those described above are the same, and the pressure during the reaction may be normal pressure or reduced pressure, and an inert gas such as nitrogen is blown during the reaction. It is also possible to introduce 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.
Further, when the obtained tertiary amine is a long-chain amine having a high melting point, it is preferably molded into a flake shape or a pellet shape after the reaction in order to improve handling properties, or in an organic solvent such as ethanol. It is preferable to dissolve and make it liquid.

  Other suitable specific examples of the long-chain aliphatic alkylamine or amidoamine (B) include lauryl dimethylamine, myristyl dimethylamine, palm alkyl dimethyl amine, palmityl dimethyl amine, beef tallow alkyl dimethyl amine, cured tallow alkyl dimethyl amine, Examples include stearyldimethylamine, stearyldiethanolamine, polyoxyethylene-cured tallow alkylamine (trade name: ETHOMEEN HT / 14 manufactured by Lion Akzo Co., Ltd.), and salts thereof.

The long-chain aliphatic alkylamine and amidoamine (B) may be used alone or in combination of two or more.
In the present invention, the blending amount of the long-chain aliphatic alkylamine and / or amidoamine (B) is preferably from 0.1 to 10% by mass, and preferably from 0.5 to 5% by mass in the detergent composition after the addition of the color tone inhibitor. Is particularly preferred. By controlling the blending amount of the component (B) to 0.1% by mass or more, it is possible to obtain a good color tone change preventing effect. On the other hand, when the blending amount of the component (B) is 10% by mass or less, a good whitening prevention effect for white clothing is obtained, the stability of the composition is improved, and it is economically advantageous.

(C) Color tone change inhibitor The color tone change inhibitor of this invention contains carboxymethylcellulose. The carboxymethyl cellulose is not particularly limited, and is generally produced by making caustic soda act on cellulose to produce alkali cellulose, which reacts with monochloroacetic acid, and introduces a carboxymethyl group into the hydroxyl group of cellulose. is there. There are three hydroxyl groups per unit cellulose, and when a carboxymethyl group is introduced into all of them, an etherification degree of 3 is obtained. What is used in the present invention is one having an etherification degree of 0.5 to 1.5, which is easy to produce and has good liquid stability.
Normally prepared carboxymethylcellulose has a weight average molecular weight of tens of thousands Mw to several million Mw. In the present invention, from the viewpoint of the effect of preventing color change of the colored fiber product, it is 1,000,000 Mw or less, preferably 600,000 Mw / It is preferable to use carboxymethyl cellulose of 10,000 Mw or less.
Specifically, for example, Daicel Chemical Industries, Ltd. CMC Daicel 1105 (weight average molecular weight 60,000 Mw), 1110 (weight average molecular weight 250,000 Mw), 1130 (weight average molecular weight 300,000 Mw), 1140 (weight average) Molecular weight 620,000 Mw), 1170 (weight average molecular weight 680,000 Mw), 1190 (weight average molecular weight 820,000 Mw), 1205 (weight average molecular weight 90,000 Mw), 1210 (weight average molecular weight 160,000 Mw), 1240 (weight average) Molecular weight 380,000 Mw), 1250 (weight average molecular weight 440,000 Mw), 1270 (weight average molecular weight 620,000 Mw), 1290 (weight average molecular weight 990,000 Mw), 1330 (weight average molecular weight 520,000 Mw), 1350 (weight average) Molecular weight 760,000 Mw), 1380 (weight average molecular weight 1.11 million Mw) and the like. The weight average molecular weight is measured by GPC (gel permeation chromatography) using polyethylene glycol having a high polymerization degree as a reference substance.
The color tone change preventing agent of the present invention may be carboxymethylcellulose alone, or may contain other optional components as necessary within a range not impairing the effects of the present invention, as will be described later.

(D) pH
In the detergent composition after the addition of the color change preventing agent of the present invention, a pH of 4 or more is preferable from the viewpoint of maintaining a good color change preventing effect and maintaining a good stability when the composition is stored for a long period of time. It is preferable to set it to 8 or less from the viewpoint of keeping the color tone change preventing effect satisfactorily.
What is necessary is just to mix | blend a pH adjuster suitably in order to adjust pH to 8 or less. As a pH adjuster, as long as the effect of the present invention is not impaired, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of blending stability.

The present invention also relates to a liquid detergent composition comprising (A) a nonionic surfactant, (B) a long-chain aliphatic alkylamine and / or amidoamine, and (C) a color change inhibitor.
The cleaning composition of the present invention may contain other optional components as necessary within a range not impairing the effects of the present invention. The optional component may be contained in the liquid detergent composition after the color change inhibitor is finally added, that is, may be contained in the color change inhibitor together with carboxymethyl cellulose. The liquid detergent composition containing (A) a nonionic surfactant and (B) a long-chain aliphatic alkylamine and / or an amidoamine prior to the addition of the color change inhibitor may be contained from the beginning.
Other ingredients that can be blended include, for example, enzymes (proteases, lipases, cellulases, etc.), stabilizers (sodium benzoate, citric acid, sodium citrate, Hydric alcohol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, polyethylene polypropylene glycol alkyl ether, polyethylene (propylene) glycol phenyl ether, polypropylene glycol phenyl ether, polyethylene polypropylene glycol phenyl ether, etc.), texture improver, pH adjuster, preservative , Hydrotropes, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, soil release agents and the like can be blended.

In addition, coloring agents, flavoring agents, emulsifying agents, and the like can be blended for the purpose of improving the added value of the product. As the colorant, general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, and Turquoise P-GR (both trade names) can be used. A preferable blending amount is about 0.00005 to 0.0005 mass%.
As the flavoring agent, for example, the fragrance compositions A, B, C, and D described in Tables 11 to 18 of JP-A-2002-146399 can be used, and the preferred blending amount is 0.1 to 1% by mass. .
Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (Saiden Chemical Co., Ltd. (trade name) Cybinol RPX-196 PE-3, solid content: 40% by mass) and the like. A preferable blending amount is 0.01 to 0.5% by mass. It is.

The preparation method of the liquid detergent composition to which the color tone change preventing agent of the present invention is added is not particularly limited, and the components (A) to ( It can be prepared by blending C), the above-mentioned optional components, and further water appropriately.
Moreover, the liquid detergent composition to which the color tone change preventing agent of the present invention is added can be used after being filled in a resin-made container. The method for using the liquid detergent composition is not particularly limited, and may be washing by hand or washing by a washing machine. For example, in the case of washing with a normal washing machine, after the article to be washed is put into the washing machine, the washing machine tub is filled with water, and the composition of the present invention is added to an appropriate concentration and dissolved. Thus, the washing liquid can be obtained, and thereby the washing object can be washed.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
As shown in Tables 1 to 3 below, components such as a color tone change inhibitor are mixed to prepare Examples 1 to 19 and Comparative Examples 1 to 5 as liquid detergent compositions, and color clothing and white clothing. The color change was evaluated. The evaluation criteria and results of the test are as follows.

● Method of cleaning treatment 1kg of commercial color (blue) clothing (100% cotton, manufactured by Big John Co., Ltd.) and white clothing (100% cotton, Gunze Sangyo Co., Ltd.) manufactured by Toshiba, fully automatic washing machine ( AW-F80HVP), each liquid detergent composition is used at a rate of 40ml in 30L of tap water, washed with weak water for 6 minutes, dehydrated for 1 minute, then rinsed (repeated twice, 4 minutes each), dehydrated The washing operation was performed with 1 minute as one step. The tap water used was adjusted to a temperature of 25 ° C.
● Evaluation of color tone change After shade-washing clothing that had been subjected to 10 washing treatments, it was dried at 25 ° C for 24 hours, and the degree of color tone change was compared with clothing before washing by visual observation by 10 professional panelists. Evaluation was made according to the following evaluation criteria, and the total score of 10 people was used as the score.
<Evaluation criteria for colored clothing>
It had almost the same color as the pre-cleaning garment: Slight change in color tone was observed compared to the 5-point pre-cleaning garment, but there was virtually no problem: slight change in color tone was observed compared to the 4-point pre-cleaning garment However, there was virtually no problem: color change was observed compared to 3 point pre-wash clothing: color change was significantly different from 2 point pre-wash clothing: 1 point
When the total score of 10 people is 45 or more, ◎◎, when it is 44-40, ◎ when 39-30, and when it is 29 or less, △. ○ If it is above, it shall have an effect of preventing color change.
<Evaluation criteria for white clothing>
Yellowing was not observed: Slight yellowing change was observed compared to 5 point pre-wash clothing, but virtually no problem: Slight yellowing change was observed compared to 4 point pre-wash clothing, but substantially No problem: Change in yellowing was observed compared to apparel before 3-point cleaning: Significant change in yellowing was observed compared to apparel before 2-point cleaning: 1 point
When the total score of 10 people is 45 or more, ◎◎, when it is 44-40, ◎ when 39-30, and when it is 29 or less, △. ○ If it is above, it shall have the effect of preventing yellowing change.
In addition, the number in a table | surface represents content of each component in the mass%.

In the table, as component (A),
(A-1): C _n H _{2n + 1} O (EO) ₁₅ H (n = 12/13 mixture (mass ratio 55/45)), synthetic product.
(A-2): C ₁₃ H ₂₇ O (EO) ₇ H (C chain length: branched type), manufactured by BASF (trade name) Lutensol TO7
It was used.

In addition, the manufacturing method of (a-1) is as follows.
Sasol (trade name) Safol 23 alcohol (branch rate 50%) 224.4 g and 30% by mass NaOH aqueous solution 2.0 g 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, 763.6 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid. At this time, it added, adjusting the addition rate so that reaction temperature might not exceed 180 degreeC using the 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 less, 70% by mass p-toluenesulfonic acid is added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product becomes about 7, (a-1) Got.

In the table, as component (B),
(B-1): 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. (trade name) Kachinar MPAS-R
(B-2): C ₁₆ H ₃₃ N (CH ₃ ) ₂ , Lion Akzo (trade name) Armin DM16D.
(B-3): C ₁₁ H ₂₃ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , synthetic product.
It was used.
In addition, the manufacturing method of (b-3) is as follows.
In a 1 liter four-necked flask, 261 g of lauric acid was charged, and nitrogen substitution was performed twice at 80 ° C. The temperature was raised to 170 ° C., and 173 g of dimethylaminopropylamine was added dropwise over 2 hours while distilling off by-product water.
After completion of dropping, the mixture was kept at 170 to 180 ° C. and aged for 7 hours. The conversion rate of lauric acid calculated from the acid value was 98%. After aging, the pressure was reduced to remove unreacted amine and water to obtain (b-3).

In the table, as component (C),
(C-1): Daicel Chemical Industries, Ltd., CMC Daicel 1330 Weight average molecular weight 520,000 Mw
(C-2): Daicel Chemical Industries, Ltd., CMC Daicel 1105 Weight average molecular weight 60,000 Mw
(C-3): Daicel Chemical Industries, Ltd., CMC Daicel 1290 Weight average molecular weight 990,000 Mw
(C-4): Daicel Chemical Industries, Ltd., CMC Daicel 1190 Weight average molecular weight 820,000 Mw
It was used.

In the common component, details of each component are as follows.
POE-modified silicone: polyether-modified silicone, manufactured by Toray Dow Corning Silicone Co., Ltd. (trade name) SH3775M.
Sokaran CP9: olefin / maleic acid copolymer sodium salt, manufactured by BASF (trade name) Sokalan CP9.
Sodium benzoate: Toagosei (trade name) sodium benzoate.
Trisodium citrate: Made by Miles (USA) (trade name) sodium citrate.
Para-toluenesulfonic acid: Kyowa Hakko Kogyo Co., Ltd. (trade name) PTS acid.
Dibutylhydroxytoluene: Sumitomo Chemical Co., Ltd. (trade name) SUMILIZER BHT-R.
Isothiazolone solution: Rohm and Haas (trade name) Caisson CG (5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water mixture liquid).
Dye (acid red 138): Sumitomo Chemical Co., Ltd. (trade name) Suminol Milling Brilliant Red BS
Fragrance | flavor: The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.

Claims (8)

  An agent for preventing color change of a colored fiber product containing carboxymethylcellulose, which is added to a liquid detergent composition comprising (A) a nonionic surfactant and (B) a long-chain aliphatic alkylamine and / or amidoamine. To prevent color change.   The color change inhibitor according to claim 1, wherein the pH of the liquid detergent composition after addition of the color change inhibitor is 4 to 8.   The color change prevention agent of Claim 1 or 2 whose weight average molecular weights of carboxymethylcellulose are 1 million Mw or less. (A) nonionic surfactant,
(B) a long chain aliphatic alkylamine and / or amidoamine, and
(C) A liquid detergent composition comprising the color change inhibitor according to any one of claims 1 to 3.   Furthermore, (D) The liquid cleaning composition of Claim 4 which is pH 4-8.   The liquid detergent composition according to claim 4 or 5, comprising 10 to 50% by mass of a nonionic surfactant.   The liquid detergent composition according to any one of claims 4 to 6, comprising 0.1 to 10% by mass of alkylamine and / or amidoamine.   The liquid detergent composition according to any one of claims 4 to 7, comprising 0.1 to 2% by mass of carboxymethylcellulose.