JP2019001837A - Liquid detergent composition for fiber products - Google Patents

Abstract

To provide a liquid detergent composition for fiber products having excellent detergency of solid fat.SOLUTION: A liquid detergent composition for fiber products contains (A) component: sorbitan fatty acid ester represented by general formula (a) (where Ris a C6-20 monovalent aliphatic hydrocarbon group), and (B) component: a compound represented by R-X-[(EO)/(PO)]-R(Ris a C8-18 monovalent hydrocarbon group, X is O, COO or CONH, Ris a hydrogen atom, a C1-6 alkyl group or a C2-6 alkenyl group, EO is an oxyethylene group, s is an average repetition number of EO to represent a number of 2-20, PO is an oxypropylene group, t is an average repetition number of PO to represent a number of 0-6), with a mass ratio represented by (A) component/(B) component of 3 or less, and water content being 30 mass% or more.SELECTED DRAWING: None

Description

  The present invention relates to a liquid detergent composition for textile products.

Among the stains on clothes, residual sebum that causes a foul odor on towels and sebum stains on collar sleeves are among the top stains consumers want to remove.
For example, in Examples of Patent Document 1, a polyoxyalkylene type nonionic surfactant having a short EO chain length obtained by adding 2 to 5 moles of ethylene oxide (also referred to as EO) to a higher alcohol is effective in cleaning sebum soil. It has been shown.

JP 2002-167600 A

However, the method described in Patent Document 1 is not always sufficient. For example, solid fat (fatty oil that is solid at normal temperature) among human-derived sebum is less likely to be removed by conventional methods than liquid fat, and improvement in cleaning performance for solid fat is desired.
An object of this invention is to provide the liquid cleaning composition for textiles which is excellent in the detergency with respect to solid fat.

The present invention has the following aspects.
[1] Component (A): a sorbitan fatty acid ester represented by the following general formula (a), and (B) component: a compound represented by the following general formula (b), the component (A) / (B) The liquid detergent composition for textiles whose mass ratio represented by a component is 3 or less, and contains 30 mass% or more of water.
In the general formula (a), R ¹ is a monovalent aliphatic hydrocarbon group having 6 to 20 carbon atoms.
In the general formula (b), R ² is a monovalent hydrocarbon group having 8 to 18 carbon atoms, X is O, COO or CONH, R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or An alkenyl group having 2 to 6 carbon atoms, EO is an oxyethylene group, s represents an average number of repetitions of EO, is a number of 2 to 20, PO is an oxypropylene group, and t is an average repetition of PO It represents a number and is a number from 0 to 6.

  [2] The liquid detergent composition for textiles according to [1], containing 0.05 to 10% by mass of the component (A).

[3] The liquid detergent composition for textiles according to [1] or [2], wherein the content of the component (B) is 1 to 30% by mass with respect to the total mass of the liquid detergent composition for textiles. object.
[4] The liquid detergent for textiles according to [1] or [2], wherein the total content of the surfactant is 1.5 to 50% by mass relative to the total mass of the liquid detergent composition for textiles Composition.
[5] The fiber according to [1] or [2], which contains a solvent other than water and has a total solvent content of 0.5 to 30% by mass relative to the total mass of the liquid detergent composition for textiles Liquid detergent composition for products.

  The liquid detergent composition for textiles of the present invention (hereinafter also simply referred to as a liquid detergent) is excellent in detergency against solid fat.

(Liquid cleaning agent)
The liquid detergent of the present invention contains (A) component: specific sorbitan fatty acid ester, and (B) component: specific polyoxyalkylene type nonionic surfactant.
<(A) component>
The component (A) is a sorbitan fatty acid ester represented by the following general formula (a).

In the general formula (a), R ¹ is a monovalent aliphatic hydrocarbon group having 6 to 20 carbon atoms. R ¹ may be an alkyl group and may have an unsaturated bond. The number of carbon atoms in R ¹ is preferably 7 to 17, 9 to 15 is more preferable. R ¹ is preferably an alkyl group.
Examples of the sorbitan fatty acid ester represented by the general formula (a) include sorbitan laurate, sorbitan caprylate, sorbitan caprate and the like, and sorbitan laurate is preferable. Commercially available products include SPAN 20, SPAN 40, SPAN 60, SPAN 80 (all product names, manufactured by Croda Japan), Nonion LP-20R, Nonion OP-80R (all product names, manufactured by NOF Corporation), Sorbon S-10E (product name, manufactured by Toho Chemical Co., Ltd.) and the like.

  The content of the component (A) is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, and further preferably 0.3 to 5% by mass with respect to the total mass of the liquid detergent. It is excellent in the detergency with respect to solid fat as it is more than the lower limit of the said range, and it is excellent in liquid stability as it is below an upper limit.

<(B) component>
(B) A component is a compound represented by the following general formula (b), and is a nonionic surfactant. (B) A component may be manufactured by a conventional method and a commercial item may be used for it.

In the general formula (b), R ² is a monovalent hydrocarbon group having 8 to 18 carbon atoms. The number of carbon atoms in R ² is preferably 10 to 18.
R ² may be linear or branched, and may include a cyclic structure. R ² may be saturated or may have an unsaturated bond.
R ² is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group or a linear or branched alkenyl group.
In the component (B), the carbon number of R ² may be uniform (single chain length), and the component (B) is a mixture of compounds having different carbon numbers of R ² (multiple chain lengths). May be.

X is O, COO or CONH, preferably O or COO.
R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. The carbon number of the alkyl group as R ³ is 1 to 3 are preferred. The alkenyl group as R ³ preferably has 2 or 3 carbon atoms.
EO is an oxyethylene group, and s represents the average number of repetitions of EO (that is, the average number of moles of ethylene oxide added). s is the number of 2-20, the number of 2-9 is preferable, and the number of 3-7 is more preferable. When the value of s is within the above range, the cleaning power and liquid stability are excellent.
PO is an oxypropylene group, and t represents the average number of repetitions of PO (that is, the average number of moles of propylene oxide added). t is a number from 0 to 6, and a number from 0 to 3 is preferred. When the value of t is within the above range, the cleaning power and liquid stability are excellent.

When t is more than 0, that is, when an adduct in which both ethylene oxide and propylene oxide are added is included, the addition method of ethylene oxide and propylene oxide in the adduct is not particularly limited, and for example, random addition or block addition But you can.
Examples of the block addition method include a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, and the like.
The addition mole number distribution of ethylene oxide or propylene oxide is not particularly limited. For example, when ethylene oxide or propylene oxide is added to a higher alcohol or the like using an alkali catalyst, the addition mole number distribution of ethylene oxide or propylene oxide becomes relatively wide. Further, when an ethylene oxide or propylene oxide is added to a higher alcohol or the like using an alkoxylation catalyst such as magnesium oxide to which a metal ion described in Japanese Patent Publication No. 6-15038 is added, distribution of added moles of ethylene oxide or propylene oxide Becomes relatively narrow. One or both of these can be used as the component (B).

A compound in which X is O (alkyl (alkenyl) ether type nonionic surfactant), or a compound in which X is COO and R ³ is an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms (alkyl (Alkenyl) ester type nonionic surfactants) are preferred.
When X is O, the carbon number of R ² is preferably 10 to 18 and more preferably 12 to 16 because the detergency is more excellent. R ³ is preferably a hydrogen atom. s is a number of 2 to 20, and is preferably a number of 2 to 9, more preferably a number of 3 to 7, from the viewpoint of superior cleaning power and liquid stability.

When X is COO, the carbon number of R ² is preferably 9 to 18, and more preferably 11 to 18 because the detergency is more excellent. R ³ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. s is preferably a number from 15 to 20.
The compound in which X is COO is preferably a compound in which R ³ is an alkyl group having 1 to 6 carbon atoms and t is 0, that is, a polyoxyethylene fatty acid alkyl ester, and a polyoxyethylene in which R ³ is a methyl group. Fatty acid methyl esters (hereinafter sometimes referred to as “MEE”) are more preferred.

  Examples of the compound in which X is O or COO include, for example, trade name Diadol (C13, C represents the number of carbon atoms and the same shall apply hereinafter) manufactured by Mitsubishi Chemical Corporation, trade name Neodol (C12 / C13) manufactured by Shell, Nonionic surfactant obtained by adding 12 mol equivalent or 15 mol equivalent ethylene oxide to alcohol such as Sasol 23 (C12 / C13) manufactured by Sasol; Product names CO-1214 and CO-1270 manufactured by P & G Nonionic surfactant added with 12 mol equivalent or 15 mol equivalent ethylene oxide with respect to natural alcohol of C7; 7 mol with respect to C13 alcohol obtained by subjecting C12 alkene obtained by trimerization of butene to oxo method Nonionic surfactant with a corresponding addition of ethylene oxide (BASF, trade name Lutens) l TO7); Nonionic surfactant (trade name Lutensol XA60, manufactured by BASF Corporation) obtained by adding ethylene oxide corresponding to 6 mol, 7 mol or 9 mol to C10 alcohol obtained by subjecting pentanol to garvet reaction. Lutensol XL70, Lutensol XP90); nonionic surfactants (trade name Softanol 90, Softanol 150, manufactured by Nippon Shokubai Co., Ltd.) added with 9 mol equivalent or 15 mol equivalent ethylene oxide to secondary alcohol having 12 to 14 carbon atoms ); Nonionic surfactant obtained by adding 15 moles of ethylene oxide to coconut fatty acid methyl (lauric acid / myristic acid = 8/2) using an alkoxylation catalyst (15 moles of polyoxyethylene coconut fatty acid methyl ester EO) Etc. It is.

The content of the component (B) is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more with respect to the total mass of the liquid detergent. It is excellent in the detergency with respect to solid fat as it is more than the lower limit of the said range. Although the upper limit of content of (B) component is not specifically limited, From a usability viewpoint, 50 mass% or less is preferable and 30 mass% or less is more preferable.
In the liquid detergent, the mass ratio of the contents of both components represented by (A) component / (B) component is preferably 3 or less, and more preferably 2 or less. When it is 3 or less, the liquid stability is excellent.
The lower limit value of component (A) / component (B) is not particularly limited and is more than 0, preferably 0.001 or more, and more preferably 0.01 or more.

<Water>
The liquid detergent preferably contains water as a solvent from the viewpoints of ease of handling during production, solubility in water when used for washing, and the like.
The content of water is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 80% by mass or more with respect to the total mass of the liquid detergent. When the water content is at least the lower limit of the above range, the solubility of the liquid detergent in water (washing liquid) is excellent in washing using water.
The upper limit value of the water content is not particularly limited. For example, 99.9 mass% or less is preferable, 98.9 mass% or less is more preferable, and 98 mass% or less is further more preferable.

<Optional component>
In the liquid cleaning agent of the present invention, optional components other than the components described above may be blended as necessary within a range not impairing the effects of the present invention.
The optional component is not particularly limited, and components blended in the liquid detergent can be used as appropriate.
For example, other surfactants that do not fall under either component (A) or component (B), solvents other than water, hydrotropes, pH adjusters, bleaching components, metal scavenging components, radical trapping agents, fragrances, etc. It is done.
The sum total of (A) component, (B) component, water, and an arbitrary component is 100 mass% (total mass of a liquid cleaning agent).
The total content of the surfactant containing the component (A) and the component (B) is preferably 1.5 to 50% by mass, more preferably 2 to 40% by mass with respect to the liquid detergent. 30 mass% is more preferable.
The total amount of the component (A) and the component (B) is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, and 50 to 100% by mass with respect to the total surfactant content. Further preferred.

[solvent]
Examples of the solvent other than water include a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms, or a glycol ether solvent.
Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
As an example of the glycol ether solvent, general formula (c): R ⁴ — (OR ⁵ ) _r OH (wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ Is an alkylene group having 2 to 4 carbon atoms, r represents an average number of OR ⁵ repeats, and is 1 to 5.).
Examples of the compound represented by the general formula (c) include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether. Etc.
A solvent may be used individually by 1 type and may be used in combination of 2 or more type.
When the liquid detergent contains a solvent, the content of the solvent is preferably 0.5% by mass or more, and more preferably 1% by mass or more with respect to the total mass of the liquid detergent. When the content of the solvent is not less than the lower limit of the above range, the liquid stability and appearance are more excellent. The upper limit of the content of the solvent is not particularly limited, but is preferably 30% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less with respect to the total mass of the liquid detergent in terms of odor.

[PH adjuster]
Examples of the pH adjuster include hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, ammonia and the like.
5-8 are preferable and, as for pH (25 degreeC) of a liquid detergent, 6-7.5 are more preferable. A pH adjuster is added as necessary.
The pH of the liquid detergent (controlled at 25 ° C.) is a value measured by a pH meter (“HM-30G” manufactured by Toa DKK Corporation).

[Fragrance]
The fragrance includes a fragrance raw material alone, or a fragrance composition comprising a fragrance raw material, a fragrance solvent, a fragrance stabilizer, and the like, and is a liquid detergent for clothes, a liquid bleach detergent, a liquid bleach. The fragrance | flavor normally used for etc. can be mix | blended. In the liquid detergent, the content of the fragrance is preferably 0.01 to 1.0 mass% with respect to the total mass of the liquid detergent.

[Others]
The liquid detergent of this invention may contain the arbitrary component normally used for the liquid detergent composition for clothes other than the said component.
Examples of optional components include chelating agents, radical trapping agents, buffers, enzymes such as protease, antioxidants such as dibutylhydroxytoluene, preservatives such as sodium benzoate, enzyme stabilizers such as calcium chloride and sodium lactate, Examples thereof include coloring agents such as pigments.

<Method for producing liquid detergent>
The manufacturing method in particular of a liquid detergent is not restrict | limited, It manufactures by a conventionally well-known manufacturing method.
For example, the (A) component, the (B) component, and optional components blended as necessary are mixed and dissolved in a solvent (for example, water such as ion-exchanged water), and if necessary, a predetermined pH It can be adjusted to be manufactured.

<How to use liquid detergent>
The method of using the liquid detergent is, for example, a method in which the liquid detergent is poured into water together with the object to be washed at the time of washing, the object to be washed in a liquid detergent aqueous solution prepared by dissolving the liquid detergent in water in advance. Examples include a dipping method. Alternatively, the liquid cleaning agent may be applied directly to the object to be washed and left for a certain period of time, and then washing with water (washing liquid) may be performed (application cleaning).
The liquid detergent of the present invention is used for washing textile products. Examples of items to be washed include clothes, cloths, towels, sheets, and the like.
The content of the liquid detergent in water (washing liquid) used for washing is not particularly limited. The amount of liquid detergent added to water (laundry liquid) is, for example, 0.1 to 20 mL of liquid detergent per 10 L of water.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In this example, “%” indicates “% by mass” unless otherwise specified.
The raw materials used in this example are as follows.
<(A) component>
A-1: Sorbitan laurate (a compound in which R ¹ is an alkyl group having 11 carbon atoms in formula (a)).
A-2: Sorbitan caprylate (a compound in which R ¹ is an alkyl group having 7 carbon atoms in formula (a)).
<(B) component>
B-1: A mixture of an alcohol having 12 carbon atoms (C12OH) and an alcohol having 14 carbon atoms (C14OH) (mass ratio C12OH / C14OH = 75/25) with an average of 6 mol of ethylene oxide (formula ( b) a compound in which R ² is an alkyl group having 12 carbon atoms or an alkyl group having 14 carbon atoms, X is O, s is 6, t is 0, and R ³ is a hydrogen atom) Product name “Leox CL-60”, manufactured by Lion Corporation. )
B-2: A compound obtained by adding an average of 5 moles of ethylene oxide to a mixture of a secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms (in the formula (b), R ² is a ^second carbon atom having 12 carbon atoms. A compound having a secondary alkyl group or a secondary alkyl group having 14 carbon atoms, wherein X is O, s is 5, t is 0, and R ³ is a hydrogen atom), manufactured by Nippon Shokubai Co., Ltd., trade name “Softanol 50”.
B-3: A mixture of an alcohol having 12 carbon atoms (C12OH) and an alcohol having 14 carbon atoms (C14OH) (mass ratio C12OH / C14OH = 75/25) with an average of 15 moles of ethylene oxide (formula ( b) a compound in which R ² is an alkyl group having 12 carbon atoms or an alkyl group having 14 carbon atoms, X is O, s is 15, t is 0, and R ³ is a hydrogen atom) (Product name “LMAO-90” manufactured by Lion Chemical Co., Ltd.).
<Optional component>
Solvent: Diethylene glycol monophenyl ether (manufactured by Nippon Emulsifier Co., Ltd., trade name “PhDG (90)”)
Hydrotrope agent: p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Inc.).
Water: Purified water.

[Manufacture of liquid detergents]
Table 1 shows the composition (formulation component, content (unit: mass%)) of the liquid detergent of each example. “Balance” means that water is blended so that the total blending amount (% by mass) of all the blending components contained in the liquid detergent of each example is 100% by mass.
In the table, when there is a blank blending component, the blending component is not blended.
In the table, the content of the compounding component indicates a pure equivalent amount.

(Examples 1-12)
Examples 1 to 10 are examples, and examples 11 and 12 are comparative examples.
According to the composition shown in Table 1, component (A), component (B), and optional component were added to water and mixed to produce a liquid detergent for each example. The pH adjusting agent was added in such an amount that the pH (25 ° C.) of the liquid cleaning agent was 7 (described as an appropriate amount in the table). The addition amount of the pH adjuster in Examples 1 to 12 was in the range of 0 to 5.0% by mass.
About the liquid cleaning agent of each case, solid fat cleaning power was evaluated with the following method. The evaluation results are shown in Table 1.

[Evaluation of solid fat cleaning power]
(1) Manufacture of oil-stained soil cloth Polyester tropical cloth obtained by diluting beef tallow 5 times with chloroform and adding 0.030 mL of a solution containing 0.01% oil red to 3 cm x 3 cm (Tanigami Shoten) The oil-stained dirt cloth was then dripped onto the product and air-dried at room temperature for 2 to 3 hours.
(2) Cleaning test 0.12 mL of the same liquid cleaning agent was applied to each of the five oil-stained soil cloths so as to cover the entire area where the oily soil was adhered, and left for 5 minutes.
Next, in Terg-O-Tometer (manufactured by UNITED STATES TESTING) filled with 900 mL of tap water at 15 ° C., 5 g of oil-stained dirt cloth and 0.3 g of commercially available detergent (“TOP NANOX” manufactured by Lion Corporation) Then, a clean knitted fabric was added so that the bath ratio would be 20 times, and washed at 120 rpm for 10 minutes.
Next, 5 oil-stained soil cloths after washing are taken out, and the oil-stained soil cloths are rinsed with running water for 3 minutes with a 2-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation), Next, after dehydration for 1 minute, it was air-dried.
(3) Evaluation of solid fat detergency Using a calorimetric color difference meter (Nippon Denshoku Co., Ltd., trade name SE2000), the raw cloth before the soil adhesion (polyester tropical cloth), and the oil dirt soil cloth before and after the washing test The Z value was measured, and the washing rate was calculated from the following formula. A larger value of the cleaning rate means higher cleaning power.
Washing rate (%) = (Z value of the oily soiled cloth after washing−Z value of the oily soiled cloth before washing) / (Z value of the raw soiled dirt cloth−Z value of the oily soiled dirt cloth before washing) ) × 100
Then, the solid fat cleaning power was evaluated according to the following evaluation criteria using the average value of the cleaning rate calculated for the five oil-stained and dirty cloths as an index. When the average value of the cleaning rate is 15% or more, it is determined to be acceptable.
(Evaluation criteria)
○: The average value of the cleaning rate is more than 30%.
Δ: The average value of the cleaning rate is 15% or more and less than 30%.
X: The average value of the cleaning rate is less than 15%.

As shown in Table 1, the liquid detergents of Examples 1 to 10 to which the present invention was applied showed high detergency against solid fat.
(A) Example 11 which does not contain a component was inferior in solid fat cleaning power. In Example 12, in which the component (A) / component (B) exceeded 3, the solid fat detergency was inferior.

Claims (2)

(A) component: a sorbitan fatty acid ester represented by the following general formula (a), and (B) component: a compound represented by the following general formula (b),
A liquid detergent composition for textiles, wherein the mass ratio represented by the component (A) / the component (B) is 3 or less and contains 30% by mass or more of water.

[Wherein, R ¹ represents a monovalent aliphatic hydrocarbon group having 6 to 20 carbon atoms. ]

[Wherein R ² is a monovalent hydrocarbon group having 8 to 18 carbon atoms, X is O, COO or CONH, R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 2 carbon atoms. -6 is an alkenyl group, EO is an oxyethylene group, s is an average number of repetitions of EO and is a number of 2 to 20, PO is an oxypropylene group, and t is an average number of repetitions of PO It is a number from 0 to 6. ]   The liquid detergent composition for textiles according to claim 1, comprising 0.05 to 10% by mass of the component (A).