JP2007314701A - Liquid detergent composition for clothes - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition with excellent detergent performance in hard water and excellent preservation stability at low temperature. <P>SOLUTION: The invention relates to the liquid detergent composition for clothes comprising 15-60%.mass of a nonionic surfactant, 2-15%.mass of a solubilizing agent and/or phase regulator, and 5-75%.mass of water, wherein the nonionic surfactant comprises a higher secondary alcohol alkoxylate composition represented by formula (1):[the higher secondary alcohol alkoxylate of the formula, (in the formula, R<SP>1</SP>and R<SP>2</SP>are each an alkyl group and the sum of number of carbon atoms of the R<SP>1</SP>and R<SP>2</SP>is 7-29, A is a lower alkylene group, n is an average of 1-50), the molar ration of (X)/(Y) is 30/70-90/10, wherein the (X) represents a compound in which the R<SP>1</SP>is a methyl group and the (Y) represents a compound in which the R<SP>1</SP>is an alkyl group with at least two carbon atoms.]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  Higher secondary alcohol ethoxylates are widely used as nonionic surfactants because of their low pour point and ease of handling.

For example, Patent Document 1 discloses a nonionic surfactant containing a higher secondary alcohol alkoxylate adduct represented by a specific chemical formula, and a primary alcohol alkoxylate, an anionic surfactant or a cationic surfactant. A cleaning composition is disclosed. According to such a detergent composition, it has excellent detergency, and further has the effects of less skin irritation and less odor. Furthermore, it has the effect that it is easy to handle with low viscosity and has excellent solubility in water at low temperatures.
Japanese Patent Laid-Open No. 11-349984

  Although this cleaning composition was quite useful for having the effects of skin irritation and less odor, development of a more useful cleaning composition was desired.

  Then, the objective of this invention is providing the cleaning composition which has the favorable washing | cleaning performance in hard water, and was excellent in the storage stability in low temperature.

  The present invention relates to a higher secondary alcohol alkoxylate composition represented by the following chemical formula 1:

[In the formula, R ¹ and R ² each independently represents an alkyl group, the total number of carbon atoms of R ¹ and R ² is 7 to 29, and the number of carbon atoms of R ² Is at least the number of carbon atoms of R ¹ , A represents a lower alkylene group, n is 1 to 50 on average, provided that n is 2 or more, the type of oxyalkylene group represented by AO May be one type or two or more types, and when there are two or more oxyalkylene groups, it means that there are an average of n types of oxyalkylene groups in total.) of rate, the molar ratio of R ¹ is a methyl group higher secondary alcohol alkoxylate (X) and a higher secondary alcohol alkoxylate R ¹ is an alkyl group containing two or more carbon atoms (Y) (X ) / (Y) is 30/70 ~ 90/10. 15 to 60% by mass of a nonionic surfactant containing as an essential component; 2 to 15% by mass of a solubilizer and / or a phase modifier; and 5 to 75% by mass of water as an essential component The present invention relates to a liquid detergent composition for clothing.

  The liquid detergent composition for clothing of the present invention has good cleaning performance in hard water and has excellent storage stability at low temperatures.

  Hereinafter, the liquid cleaning composition for clothes of the present invention will be described in detail.

(Liquid detergent composition for clothing)
The liquid detergent composition for clothing of the present invention comprises 15 to 60% by mass of a nonionic surfactant containing a higher secondary alcohol alkoxylate composition represented by Chemical Formula 1 as an essential component; a solubilizer and / or a phase It contains 2 to 15% by mass of an adjusting agent and 5 to 75% by mass of water as essential components.

  The solubilizer is not particularly limited as long as it dissolves a component that is difficult to dissolve in water or makes the dissolved component appear transparent without turbidity. Specifically, alcohols such as ethanol, ethylene glycol And glycols such as propylene glycol, p-toluenesulfonic acid, benzoate and the like.

  Examples of the phase adjusting agent include polyoxyalkylene benzyl ether, polyoxyalkylene phenyl ether, and polyoxyalkylene alkyl ether.

  The liquid detergent composition for clothing of the present invention has good cleaning performance in hard water and has excellent storage stability at low temperatures.

  In addition, the liquid detergent composition for clothing of the present invention contains, as non-ionic surfactants, a composition represented by Chemical Formula 1 and a primary alcohol alkoxylate represented by Chemical Formula 2 as essential components, and a chemical formula The mass ratio of the composition represented by 1 and the compound represented by Chemical Formula 2 is preferably 90/10 to 10/90. The liquid detergent composition for clothes of the present invention exhibits excellent detergency against specific dirt (sebum dirt).

Furthermore, the liquid detergent composition for clothing of the present invention is a higher secondary alcohol alkoxylate composition represented by Chemical Formula 1, wherein the sum of the number of carbon atoms of R ^{1 and} the number of carbon atoms of R ² is 11, 13 or It is preferable that the mass ratio of the higher secondary alcohol alkoxylate composition which is 15 is 80% or more of the whole higher secondary alcohol alkoxylate composition.

Further, the liquid detergent composition for clothing of the present invention is a higher secondary alcohol alkoxylate composition represented by Chemical Formula 1, wherein the sum of the number of carbon atoms of R ^{1 and} the number of carbon atoms of R ² is 11. It is preferable that the mass ratio of the secondary alcohol alkoxylate composition is 50% or more of the whole of the higher secondary alcohol alkoxylate composition.

Furthermore, the liquid detergent composition for clothing of the present invention is a higher secondary alcohol alkoxylate composition represented by the chemical formula 1, wherein the sum of the number of carbon atoms of R ^{1 and} the number of carbon atoms of R ² is 13. It is preferable that the mass ratio of the secondary alcohol alkoxylate composition is 50% or more of the whole of the higher secondary alcohol alkoxylate composition.

Further, the liquid detergent composition for clothing of the present invention is a higher secondary alcohol alkoxylate composition represented by Chemical Formula 1, wherein the sum of the number of carbon atoms of R ^{1 and} the number of carbon atoms of R ² is 15. It is preferable that the mass ratio of the secondary alcohol alkoxylate composition is 50% or more of the whole of the higher secondary alcohol alkoxylate composition.

(Nonionic surfactant)
The nonionic surfactant used in the present invention contains a higher secondary alcohol alkoxylate composition represented by Chemical Formula 1 as an essential component.

  The higher secondary alcohol alkoxylate composition is represented as follows: Secondary alcohol alkoxylate represented by Chemical Formula 1

(However, in the formula, R ¹ and R ² each independently represent an alkyl group, the total number of carbon atoms of R ¹ and R ² is 7 to 29, and the number of carbon atoms of R ² is R ^{1 is} the number of carbon atoms or more, A represents a lower alkylene group, n is 1 to 50 on average, but when n is 2 or more, the type of oxyalkylene group represented by AO is 1 Or two or more types, and when there are two or more types of oxyalkylene groups, it means that the total number of various oxyalkylene groups is n in total).
The molar ratio of the secondary alcohol alkoxylate R ¹ is secondary alcohol alkoxylate (X) and the alkyl group R ¹ is 2 or more carbon atoms is a methyl group (Y) (X) / ( Y) is It is in the range of 30/70 to 90/10. The ratio between (X) and (Y) is determined by NRM analysis. Here, “lower” means that the number of carbon atoms is in the range of 1 to 7, while “higher” means that the number of carbon atoms is in the range of 8 to 30.

(Production of higher secondary alcohol alkoxylate)
The higher secondary alcohol alkoxylate used in the present invention is obtained by adding a higher secondary alcohol alkoxylate obtained by addition reaction of an olefin having 8 to 30 carbon atoms and (poly) alkylene glycol to 2 to 2 carbon atoms. It is obtained by reacting with 8 alkylene oxide.

  The olefin having 8 to 30 carbon atoms is an aliphatic hydrocarbon having 8 to 30 carbon atoms, preferably 10 to 20 carbon atoms, having one double bond. The olefin is linear or branched. The position of the double bond is not particularly limited and may be in the α position or the inner position. Specific examples of the olefin include octene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene and the like. You may use these individually or in mixture of 2 or more types.

  The (poly) alkylene glycol is not particularly limited as long as it is an alcohol having two —OH atom groups in one molecule. Specific examples thereof include mono-, di-, tri-ethylene glycol, Examples include polyethylene glycol, mono-, di-, tri-propylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,6-hexanediol, and the like. You may use these individually or in mixture of 2 or more types. Of these, monoalkylene glycols such as monoethylene glycol and monopropylene glycol are preferably used.

  A method for producing a corresponding higher secondary alcohol alkoxylate by addition reaction of the olefin and (poly) alkylene glycol is carried out by a known method (for example, JP-B-61-51570, JP-A-3-148233). And JP-A-9-52856).

  Next, the obtained alcohol alkoxylate is further reacted with an alkylene oxide having 2 to 8 carbon atoms to obtain a higher secondary alcohol alkoxylate adduct.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. You may use these individually or in mixture of 2 or more types.

  The reaction between the alcohol alkoxylate and the alkylene oxide can be performed using an alkali catalyst. The molar ratio of the alkylene oxide to the alcohol alkoxylate is usually in the range of 1/1 to 30/1, preferably 4/1 to 20/1.

  Examples of the alkali catalyst include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. The usage-amount of an alkali catalyst is 0.01-2 mass% normally with respect to this alcohol alkoxylate, Preferably it exists in the range of 0.02-0.5 mass%. The alkali catalyst may be added in the form of powder, granules, or an aqueous solution.

The reaction temperature is usually in the range of 50 to 250 ° C, preferably 100 to 200 ° C. The reaction pressure may be normal pressure or increased pressure, and can usually be appropriately selected from the range of normal pressure to 20 kg / cm ² . In addition, it is preferable to perform reaction in inert gas atmosphere, such as nitrogen. The reaction is usually performed in the absence of a solvent, but may be performed in the presence of a solvent, if necessary.

  The reaction between the alcohol alkoxylate and the alkylene oxide is carried out by a commonly used method such as a batch reaction or a continuous reaction, as in the production of the alcohol alkoxylate.

  The reaction mixture after completion of the reaction can be used as it is. The alkali catalyst in the adduct may be neutralized with an acid such as acetic acid.

(Other nonionic surfactants)
A primary alcohol alkoxylate will be described as another nonionic surfactant used in the liquid detergent composition for clothing of the present invention.

The primary alcohol alkoxylate is represented by the following chemical formula 2:
R ³ —CH ₂ —O— (BO) p—H (2)
(In the formula, R ³ represents a linear or branched alkyl group having 7 to 29 carbon atoms, B represents a lower alkylene group, p is an average value of 1 to 50, and p is 2 or more. In this case, the oxyalkylene group represented by BO may be one type or two or more types. When the number of the oxyalkylene groups is two or more, the average number of the various oxyalkylene groups is p. Show.)

  In addition to the nonionic surfactants described above, nonionic surfactants such as fatty acid alkanolamides and polyoxyethylene alkylamine oxides can be added to the liquid detergent for clothing of the present invention.

  The primary alcohol alkoxylate can be produced by a known method.

(Anionic surfactant)
As the anionic surfactant used in the liquid detergent composition for clothing of the present invention, generally known anionic surfactants can be used. For example, an alkyl sulfate having 10 to 18 carbon atoms, an alkanesulfonate having 10 to 18 carbon atoms, an alkylbenzene sulfonic acid having 10 to 18 carbon atoms in an alkyl group, and the number of carbon atoms in an alkyl group or alkenyl group May be an alkyl (or alkenyl) polyethoxy sulfate (average added mole number of ethylene oxide: 2 to 7). Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolamine salts, and the like. These may be used alone or in combination of two or more.

(builder)
Examples of the builder used in the liquid detergent composition for clothing of the present invention include organic builder or at least one inorganic builder selected from the group consisting of aluminosilicate, carbonate, and sulfate. Specific examples include carriers such as crystalline aluminosilicate, amorphous aluminosilicate, and crystalline silicate, and inorganic salts such as alkali metal silicate, alkali metal carbonate, and sulfate.

  A chelating agent such as sodium tripolyphosphate, sodium citrate, sodium polyacrylate, and acrylic acid / maleic acid copolymer (salt) may be added.

  First, a method for testing the performance of the liquid detergent composition will be described.

<Low temperature stability test>
A 50 mL sample bottle (No. 6 wide-mouth standard bottle, glass, cylindrical shape with a diameter of 40 mm and a height of 80 mm) was filled with 40 mL of the liquid detergent composition, capped, and then kept in a thermostatic chamber at 5 ° C. for 30 days. Left to stand. The stability of the liquid was visually determined based on the following criteria.

Judgment standard (circle): It is a uniform liquid phase and is excellent in liquid stability.

    Δ: Somewhat separated or precipitated, but not to worry.

    X: Separation or precipitation is observed.

<Detergency test>
1 g of the detergent composition shown in Table 1 is dissolved in 1 L of artificial hardness water adjusted to a hardness of 70 ppm (calcium carbonate equivalent) by adding calcium chloride to ion-exchanged water to prepare a cleaning solution. About each of these washing | cleaning liquids, after adding 10 sheets of contaminated cloth and adjusting the bath ratio to 1:30 and washing | cleaning for 10 minutes at 120 rpm with a targot meter (TM-4, the product made from Daiei Kagaku), it is made into ion-exchange water. Rinsing is carried out for 10 minutes using 1 L of artificial hard water prepared by adding calcium chloride to a hardness of 70 ppm (calcium carbonate equivalent). After drying with a dryer at 80 ° C. for 1 hour, the reflectance of the washed contaminated cloth is measured with a surface reflectometer (TC-8600A, manufactured by Tokyo Denshoku). From the reflectance of the base fabric and the contaminated fabric before and after cleaning, the cleaning rate is calculated by the following formula (Kubelka-Munk formula).

Detergency (%) = 100 × (Rw−Rs) / (Ro−Rs)
However, in the formula, Ro is the reflectance of the raw cloth, Rs is the reflectance of the artificially contaminated cloth, and Rw is the reflectance of the cleaning cloth.

  In addition, the used contaminated cloth is WFK-10D, WFK-20D, WFK-10C (manufactured by Waschereiforshuns Krefeld e.V., 5 cm × 5 cm), WFK-10D and 20D are free fatty acids 13.00%, Tallow 23.85%, triglyceride 2.62%, lanolin 13.31%, cholesterol 2.69%, hydrocarbon 8.73%, cutin 8.43%, kaolin 23.45%, carbon black 2.18%, It was prepared using artificial soil mainly composed of inorganic soil having a composition of ferric oxide 1.09% and ferrous oxide 0.55%. WFK-10C is lanolin: 84.20% , Sheep oil composed of kaolin: 13.58%, carbon black: 1.26%, ferric oxide: 0.63%, ferrous oxide: 0.32% It was prepared using.

  Hereinafter, the present invention will be described in detail based on examples.

(Synthesis Example 1: Synthesis of alcohol alkoxylate (1))
1-dodecene was reacted in the liquid phase at 150 ° C. for 10 hours with 5 mass% of BEA zeolite (trade name: VALFOR CP811 BL-25) manufactured by PQ, and 25 mol% of 1-dodecene and inner dodecene 75 were reacted. A dodecene isomer mixture consisting of mol% was obtained.

  810 g of the obtained dodecene isomer mixture, 900 g of monoethylene glycol and 100 g of BEA type zeolite (trade name: VALFOR CP811 BL-25, manufactured by PQ) were charged into a 3000 mL glass reactor equipped with a stirrer and a reflux condenser. The mixture was reacted at 150 ° C. for 3 hours in a nitrogen atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, and the upper dodecene phase separated was separated and distilled. After distilling unreacted dodecene, 155 g of secondary dodecanol monoethoxylate was obtained in a boiling point range of 129 to 131 ° C. under a reduced pressure of 2 mmHg.

In the obtained secondary dodecanol ethoxylate, the proportion of ethoxylate in which R ¹ is a methyl group was 71 mol%, and the remainder was an ethoxylate in which R ¹ was an ethyl group or higher. This ratio was determined by NMR analysis.

(Synthesis Example 2: Synthesis of alcohol polyalkoxylate (1))
155 g (0.67 mol) of the secondary dodecanol ethoxylate obtained in Synthesis Example 1 and 0.2 g of sodium hydroxide were charged into a stainless steel autoclave, purged with nitrogen, heated to 150 ° C., and ethylene oxide 209 0.7 g (4.76 mol) was introduced in 3 hours, and then maintained at 150 ° C. for an additional hour, followed by cooling and purging of the internal gas, and then secondary dodecanol polyethoxylate was added as a reaction product. Obtained. The added mole number of ethylene oxide in this polyethoxylate was 7.1 moles.

(Synthesis Example 3: Preparation of alcohol alkoxylate (2))
Secondary tetradecanol ethoxylate was obtained in the same manner as in Synthesis Example 1 except that 1-tetradecene was used instead of 1-dodecene.

In the obtained secondary tetradecanol ethoxylate, the proportion of ethoxylate in which R ¹ is a methyl group was 66 mol%, and the remainder was an ethoxylate in which R ¹ was an ethyl group or higher. This ratio was determined by NMR analysis.

(Synthesis Example 4: Synthesis of alcohol polyalkoxylate (2))
A secondary tetradecanol polyethoxylate was obtained in the same manner as in Synthesis Example 2 except that the secondary tetradecanol ethoxylate obtained in Synthesis Example 3 was used instead of the secondary dodecanol ethoxylate. . The number of moles of ethylene oxide added in the obtained polyethoxylate was 7.2 moles.

(Synthesis Example 5: Preparation of alcohol alkoxylate (3))
Secondary hexadecanol ethoxylate was obtained in the same manner as in Synthesis Example 1 except that 1-hexadecene was used instead of 1-dodecene.

In the obtained secondary hexadecanol ethoxylate, the proportion of ethoxylate in which R ¹ is a methyl group was 62 mol%, and the remainder was an ethoxylate in which R ¹ was an ethyl group or higher. This ratio was determined by NMR analysis.

(Synthesis Example 6: Synthesis of alcohol polyalkoxylate (3))
A secondary hexadecanol polyethoxylate was obtained in the same manner as in Synthesis Example 2 except that the secondary hexadecanol ethoxylate obtained in Synthesis Example 5 was used instead of the secondary dodecanol ethoxylate. It was. The number of moles of ethylene oxide added in the obtained polyethoxylate was 9.0 moles.

(Synthesis Example 7: Preparation of alcohol alkoxylate (4))
Secondary decanol ethoxylate was obtained in the same manner as in Synthesis Example 1 except that 1-decene was used instead of 1-dodecene.

In this secondary decanol ethoxylate, the proportion of ethoxylate in which R ¹ is a methyl group was 75 mol%, and the balance was an ethoxylate in which R ¹ was an ethyl group or higher. This ratio was determined by NMR analysis.

(Synthesis Example 8: Synthesis of alcohol polyalkoxylate (4))
Secondary decanol ethoxylate was obtained in the same manner as in Synthetic Example 2, except that the secondary decanol obtained in Synthesis Example 7 was used instead of the secondary decanol ethoxylate. The added mole number of ethylene oxide in this polyethoxylate was 8.9 moles.

(Examples 1-9)
Using the higher secondary alcohol polyalkoxylate synthesized in Synthesis Examples 2, 4, 6 and 8, liquid detergent compositions having the compositions of Examples 1 to 9 shown in Table 1 were produced.

(Comparative Examples 1-3)
As comparative examples for performance evaluation, liquid detergent compositions having the compositions of Comparative Examples 1 to 3 shown in Table 1 were produced by a spray drying method.

(Performance evaluation)
About the liquid detergent composition manufactured in Examples 1-9 and Comparative Examples 1-3, a low temperature stability test and a detergency test were done, and the result is shown in Table 2.

  In Table 1, the meanings of the following symbols are shown.

AE1: Alcohol ethoxylate obtained by adding an average of 7.1 moles of EO to the secondary alcohol having 12 carbon atoms synthesized in Synthesis Example 2 AE2: EO to the secondary alcohol having 14 carbon atoms synthesized in Synthesis Example 4 Ethoxylate added with an average of 7.2 mol of alcohol AE3: alcohol ethoxylate added with an average of 9.0 mol of EO to the secondary alcohol having 16 carbon atoms synthesized in Synthesis Example 6 AE4: synthesized in Synthesis Example 8 Alcohol ethoxylate obtained by adding an average of 8.9 moles of EO to the secondary alcohol having 10 carbon atoms Prim-012-7EO: alcohol ethoxylate obtained by adding an average of 7 moles of EO to the primary alcohol having 12 carbon atoms SFT-30S: Addition of 3 moles of EO on average to secondary alcohols with 12 to 14 carbon atoms Sulfuric esters of alcohol ethoxylates, which was (manufactured by Nippon Shokubai Co., Softanol 30S)
Prim-012-2EO: Alcohol ethoxylate obtained by adding an average of 2 moles of EO to a primary alcohol having 12 carbon atoms LAS: Sodium dodecylbenzenesulfonate * 1: Monolauryltrimethylammonium chloride * 2: Amidopropyl betaine laurate AA : Acrylic acid MA: Maleic acid B: Balance.

Claims (6)

A higher secondary alcohol alkoxylate composition represented by the following chemical formula 1:

[In the formula, R ¹ and R ² each independently represents an alkyl group, the total number of carbon atoms of R ¹ and R ² is 7 to 29, and the number of carbon atoms of R ² Is at least the number of carbon atoms of R ¹ , A represents a lower alkylene group, n is 1 to 50 on average, provided that n is 2 or more, the type of oxyalkylene group represented by AO May be one type or two or more types, and when there are two or more oxyalkylene groups, it means that there are an average of n types of oxyalkylene groups in total.) of rate, the molar ratio of R ¹ is a methyl group higher secondary alcohol alkoxylate (X) and a higher secondary alcohol alkoxylate R ¹ is an alkyl group containing two or more carbon atoms (Y) (X ) / (Y) is 30/70 ~ 90/10. And 15 to 60% by mass of a nonionic surfactant containing as an essential component;
2-15% by weight of solubilizer and / or phase modifier;
A liquid detergent composition for clothing comprising 5 to 75% by mass of water as an essential component. As the nonionic surfactant, a composition represented by Chemical Formula 1 and a primary alcohol alkoxylate represented by Chemical Formula 2 below:
R ³ —CH ₂ —O— (BO) p—H (2)
(In the formula, R ³ represents a linear or branched alkyl group having 7 to 29 carbon atoms, B represents a lower alkylene group, p is an average value of 1 to 50, and p is 2 or more. In this case, the oxyalkylene group represented by BO may be one type or two or more types. When the number of the oxyalkylene groups is two or more, the average number of the various oxyalkylene groups is p. The composition according to claim 1, wherein the mass ratio of the composition represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 is 90/10 to 10/90. object. A higher secondary alcohol alkoxylate composition represented by the above chemical formula 1, wherein the sum of the number of carbon atoms of R ^{1 and} the number of carbon atoms of R ² is 11, 13 or 15. The composition according to claim 1 or 2, wherein a mass ratio is 80% or more of the whole secondary alcohol alkoxylate composition. In the higher secondary alcohol alkoxylate composition represented by Chemical Formula 1, the mass ratio of the higher secondary alcohol alkoxylate composition in which the sum of the number of carbon atoms of R ^{1 and} the number of carbon atoms of R ² is 11 is: 3. The composition according to claim 1, wherein the composition is 50% or more of the total composition of the secondary alcohol alkoxylate. In the higher secondary alcohol alkoxylate composition represented by the chemical formula 1, the mass ratio of the higher secondary alcohol alkoxylate composition in which the sum of the number of carbon atoms of R ^{1 and} the number of carbon atoms of R ² is 13, 3. The composition according to claim 1, wherein the composition is 50% or more of the total composition of the secondary alcohol alkoxylate. In the higher secondary alcohol alkoxylate composition represented by the chemical formula 1, the mass ratio of the higher secondary alcohol alkoxylate composition in which the sum of the number of carbon atoms of R ^{1 and} the number of carbon atoms of R ² is 15, 3. The composition according to claim 1, wherein the composition is 50% or more of the total composition of the secondary alcohol alkoxylate.