JP6663803B2 - How to remove stains - Google Patents

Description

  The present invention relates to a stain remover.

There is a high need to easily remove stains, such as food, cosmetics, and sweat, attached to clothes at home, and many stain removers are commercially available. However, even when stains can be removed, ring stains may remain around the stains.
In Patent Document 1, a container in which the content is quantitatively supplied to the application pressing surface at the tip is filled with a stain remover, an absorbent sheet is placed under the object to be washed, and a stain portion is formed on the application pressing surface of the container. A method has been proposed in which a stain remover is permeated into an object to be washed by tapping, and a stain component is moved to the stain remover and absorbed by an absorbent sheet, thereby removing stain stains while suppressing ring stains. ing.

JP 2004-231759 A

However, the method disclosed in Patent Document 1 cannot always say that the effect of suppressing ring spots, which can be produced when removing persistent dirt, is not always sufficient for cotton cloth, and further improvement is required.
An object of the present invention is to provide a stain removing agent having an excellent ring spot suppressing effect.

The present invention has the following aspects.
[1] Stain removal containing the following components (A), (B) and (C), and wherein (A) / (B), which represents the mass ratio of component (A) to component (B), is 1 or more Agent.
(A): at least one selected from the group consisting of polyoxyethylene hydrogenated castor oil, fatty acid esters of polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, and fatty acid esters of polyoxyethylene castor oil.
(B): at least one selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides.
(C): Nonionic surfactant that does not correspond to any of (A) and (B).
[2] The stain remover according to [1], containing 80% by mass or more of water.

[3] A stain removing agent in a container, wherein the container from which the contents are discharged from the tip end is filled with the stain removing agent of [1].
[4] A stain removal kit comprising the container-based stain remover of [3] and an absorbent sheet.

  The stain remover of the present invention is excellent in the effect of suppressing ring spots.

  The stain remover of the present invention contains the components (A), (B) and (C). The components (A) and (B) are specific nonionic surfactants, respectively, and the component (C) is a nonionic surfactant that does not correspond to any of the components (A) and (B).

<(A) component>
The component (A) is at least one selected from the group consisting of polyoxyethylene hardened castor oil, fatty acid esters of polyoxyethylene hardened castor oil, polyoxyethylene castor oil, and fatty acid esters of polyoxyethylene castor oil.
The component (A) is preferably at least one compound represented by the following formula (1).

In the formula (1), R ₁ is (CH ₂ ) ₁₀ or (CH ₂ ) ₇ —CH ＝ CHCH ₂ , a, b and c are each independently a number of 0 or more, l, m and n Is independently a number of 0 or more, a + b + c + l + m + n is a number of 5 to 100,
X, Y and Z are each independently H or COR ₂ (where R ₂ is an alkyl or alkenyl group having 11 to 21 carbon atoms), and X is preferably H.
R ₂ may be linear or branched. The carbon number of R ₂ is preferably 11 to 17.

  The content of the component (A) is preferably from 0.1 to 10% by mass, more preferably from 0.2 to 7% by mass, even more preferably from 0.5 to 5% by mass, based on the total mass of the stain remover. When the content of the component (A) is within the above range, the ring-spot suppression effect is excellent and the low-temperature stability is also excellent.

<(B) component>
The component (B) is at least one selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides.
The alkyl group or alkenyl group which is a fatty acid residue (monovalent hydrocarbon group obtained by removing a carboxy group from a fatty acid) of the fatty acid alkanolamide may be linear or branched, and is preferably linear. The fatty acid residue preferably has 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms, and particularly preferably 12 to 14 carbon atoms. The fatty acid alkanolamide may have a monoalkanolamide structure or may have a dialkanolamide structure. Those having a dialkanolamide structure are preferred from the viewpoint that the ring stain suppression effect and the low-temperature stability are further enhanced.
The polyoxyethylene fatty acid alkanolamide is obtained by adding ethylene oxide to the above fatty acid alkanolamide, and the number of moles of the added ethylene oxide is 1 to 5, preferably 1 to 3, and particularly preferably 2.

Specific examples of the component (B) include coconut oil fatty acid monoethanolamide, lauric acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, isostearic acid monoethanolamide, and lauric acid monoethanolamide. Fatty acid monoalkanolamides such as isopropanolamide;
Polyoxyethylene coconut oil fatty acid monoethanolamide, polyoxyethylene lauric acid monoethanolamide, polyoxyethylene myristic acid monoethanolamide, polyoxyethylene palmitic acid monoethanolamide, polyoxyethylene stearic acid monoethanolamide, polyoxyethylene isostearin Polyoxyethylene fatty acid monoalkanolamides such as acid monoethanolamide and polyoxyethylene lauric acid monoisopropanolamide;
Fatty acid dialkanolamides such as coconut oil fatty acid diethanolamide, lauric acid diethanolamide, myristic acid diethanolamide, palmitic acid diethanolamide, stearic acid diethanolamide, isostearic acid diethanolamide, lauric acid diisopropanolamide;
Polyoxyethylene coconut oil fatty acid diethanolamide, polyoxyethylene lauric acid diethanolamide, polyoxyethylene myristic acid diethanolamide, polyoxyethylene palmitic acid diethanolamide, polyoxyethylene stearic acid diethanolamide, polyoxyethylene isostearic acid diethanolamide, poly Polyoxyethylene fatty acid dialkanolamides such as oxyethylene lauric acid diisopropanolamide;
In particular, a fatty acid dialkanolamide is preferred because of its excellent effect of suppressing ring spots. As the fatty acid dialkanolamide, it is more preferable to use one or more selected from the group consisting of coconut oil fatty acid diethanolamide, lauric acid diethanolamide and lauric acid diisopropanolamide, and it is particularly preferable to use at least lauric acid diethanolamide.

The content of the component (B) is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and further preferably 0.5 to 1.5% by mass, based on the total mass of the stain remover. preferable. When the content of the component (B) is not less than the lower limit of the above range, the effect of suppressing ring spots is excellent, and if it is not more than the upper limit, the low temperature stability is excellent.
(A) / (B) representing the mass ratio of the component (A) to the component (B) is 1 or more, preferably more than 1, and more preferably 2 or more. When (A) / (B) is 1 or more, the effect of suppressing ring spots is excellent. Also has excellent low temperature stability. The upper limit of (A) / (B) is preferably 20 or less, more preferably 5 or less.

<(C) component>
The component (C) is a nonionic surfactant that does not correspond to any of the components (A) and (B). A known nonionic surfactant can be used as a detergent component.
For example, a polyoxyalkylene-type nonionic surfactant in which an alkylene oxide is added to a higher alcohol, an alkylphenol, a higher fatty acid or a higher amine, a polyoxyethylene polyoxypropylene block copolymer, a polyhydric alcohol fatty acid ester or an alkylene oxide adduct thereof, an alkyl (Or alkenyl) amine oxides, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like. Any of these may be used alone or in combination of two or more.

As the component (C), a polyoxyalkylene nonionic surfactant is preferable. For example, a compound represented by the following formula (2) is preferable.
_{R 3 -Q - [(EO)} d / (PO) e] -R 4 ... (2)
In the formula (2), R ₃ is a hydrocarbon group, R ₄ is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, —Q— is —O— or —COO—, and R ₃ and Q has a total of 8 to 22 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, d is a number of 1 to 30 indicating an average addition mole number of EO, and e is PO Is a number from 0 to 5 indicating the average number of moles added.

d is preferably 2 to 20, more preferably 4 to 15, and still more preferably 5 to 10.
e is preferably from 0 to 3, and more preferably from 0 to 2.
R ₃ is preferably a hydrocarbon group having 8 to 22 carbon atoms. Examples of the hydrocarbon group include an alkyl group and an alkenyl group, and may be linear or branched. As for carbon number, 8-18 are more preferred, and 8-16 are especially preferred.
Examples of the hydrocarbon group for R ₄ include an alkyl group, and specific examples include a methyl group, an ethyl group, and a propyl group.
If -Q- is -O-, the number of carbon atoms of _{R 3} is preferably 8 to 22 is, _{R 4} is preferably a hydrogen atom.
When -Q- is -COO-, R ₃ preferably has 7 to 21 carbon atoms, and R ₄ is preferably an alkyl group having 1 to 3 carbon atoms.
Note that EO and PO may be arranged in a mixture, and (EO) _d / (PO) _e may be such that EO and PO may be added at random or may be added in a block shape. Is also good.

The content of the component (C) is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 5% by mass, even more preferably from 1 to 3% by mass, based on the total mass of the stain remover. When the content of the component (C) is within the above range, stain stain removal is excellent, and high-temperature stability is also good.
The compound represented by the above formula (2) is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and still more preferably 45 to 100% by mass, based on the total mass of the component (C). .
(C) / (A + B + C) representing the mass ratio of the component (C) to the total mass of the component (A), the component (B) and the component (C) contained in the stain remover is 0.2 to 0.8. Preferably, 0.3 to 0.6 is more preferable, and 0.4 to 0.55 is further preferable. When the mass ratio of (C) / (A + B + C) is equal to or more than the lower limit of the above range, the stability is excellent.

<(D) component: solvent>
The stain remover of the present invention preferably contains a solvent (D). The solvent (D) is preferably water or a mixture of water and a water-miscible organic solvent.
“Water-miscible organic solvent” refers to an organic solvent that dissolves in an amount of 20 g or more in 1 L of ion-exchanged water at 25 ° C. The water-miscible organic solvent may be any as long as it becomes a uniform solution when mixed with water. For example, a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms, the following formula ( The glycol ether solvent represented by 3) is mentioned. The water-miscible organic solvent may be used alone or in combination of two or more.
R _5- (OR ₆ ) _f O-R ₇ (3)
[Wherein, R ₅ is an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a carbonyl group, R ₆ is an alkylene group having 2 to 4 carbon atoms, and R ₇ is a hydrogen atom or 1 to 3 carbon atoms. Is an alkyl group. f represents the average number of repetitions and is 1 to 5. ]

Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol and 1-butanol.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, and glycerin. Propylene glycol is preferably 1,2-propanediol, 1,3-propanediol, or a mixture thereof.
Examples of the glycol ether-based solvent include ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like.

When the solvent (D) contains water, the content of water is preferably at least 80% by mass, more preferably at least 85% by mass, based on the total mass of the stain remover. When the water content is within the above range, the stains are excellently removed and the high-temperature stability is good.
When the solvent (D) contains a water-miscible organic solvent, the content of the water-miscible organic solvent is preferably from 2 to 20% by mass, more preferably from 4 to 12% by mass, based on the total mass of the stain remover. When the content of the water-miscible organic solvent is not less than the lower limit of the above range, the stability is excellent, and when it is not more than the upper limit, the stain removal property is excellent.

<Other ingredients>
As other additives, preservatives, defoamers, pH adjusters, chelating agents, bleaching agents, fragrances, and the like can be optionally contained. These can use a well-known component.
As the preservative, those known in the art can be used and are not particularly limited.
Specific examples include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, alcohol-based compounds, and iodine-based compounds.
Examples of the isothiazolone-based organic sulfur compound include 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, Examples include phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one (MIT), and mixtures thereof. Can be Specific examples of CMIT include Kathon CG-ICP (manufactured by Dow Chemical), and specific examples of MIT include Neolone 950 (manufactured by Dow Chemical).
Examples of benzisothiazoline-based organic sulfur compounds include 1,2-benzisothiazolin-3-one (BIT) and the like, and dithio-2,2-bis (benzmethylamide) and the like can be used as related compounds. Specific examples of the BIT include Proxel BDN (manufactured by Lonza Japan Co., Ltd.) and Nipide BIT 20 (manufactured by Clariant Japan Co., Ltd.).
When a plurality of kinds of benzisothiazoline-based organic sulfur compounds are used, they can be used at an arbitrary mixing ratio.
Specific examples containing MIT and BIT include Acticide MBS (manufactured by Saw Japan) and AN-1000 (manufactured by Lonza Japan Co., Ltd.).
Examples of alcohol compounds include 2-bromo-2-nitropropane-1,3-diol.
Examples of the iodine-based compound include 3-iodo-2-propynyl N-butyl carbamate.
Examples of the benzoic acids include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, and benzyl paraoxybenzoate. Can be.
The content of the preservative is set within a range that functions as a preservative. For example, it is preferably 0.0001 to 1% by mass based on the total mass of the stain remover.
Examples of antifoaming agents include self-emulsifying silicone compounds and silicone-based antifoaming agents such as silicone emulsions.
The fragrance can be used in a range that does not affect the ring spot.

The pH of the stain remover at 25C is preferably 4 to 8, more preferably 5 to 7.5, and even more preferably 6 to 7.5. When the pH of the stain remover is within the above range, the effect of preventing deterioration of the fiber product to which the stain remover is applied is excellent.
Examples of the acidic compound as the pH adjuster include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and carboxylic compounds such as citric acid and malic acid. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, ammonia, monoethanolamine, diethanolamine, and triethanolamine.

  The viscosity of the stain remover at 25 ° C. (B-type viscometer, first rotor: 1 minute) is preferably 1 to 15 mPa · s. When it is 15 mPa · s or less, it has excellent penetrating power to textiles, easily moves to a patch or an absorbent, and hardly remains in textiles, and thus has an excellent effect of suppressing ring spots. When it is 1 mPa · s or more, it is easy to control the amount of application to textiles.

<How to use>
The stain remover of the present invention is preferably used by a method in which an absorbent sheet is placed under an object to be washed, and the stain remover is applied to a stain (stain) portion of the object to be washed and hit. By hitting, the stain remover penetrates into the stain portion of the article to be washed, the stain component is moved to the stain remover, and the stain component and the stain remover can be absorbed by the absorbent sheet.
As the product form of the stain remover of the present invention, a stain remover in a container filled in a container for discharging the contents from the tip is preferable.
Further, a product form of the container-containing stain remover and a stain removal kit having an absorbent sheet is also preferable.
It is preferable that a pressing surface for hitting an object to be washed is provided at a tip portion of the container, and a liquid supply path for quantitatively supplying the stain removing agent in the container is opened on the pressing surface. As such a container, for example, a known container such as a container described in JP-A-2004-231759 can be used.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Raw materials>
The raw materials shown in Table 1 are as follows.
[(A) component]
(A-1): Polyoxyethylene hydrogenated castor oil (in the formula (1), R ₁ is (CH ₂ ) ₁₀ , a = b = c = 0, 1 + m + n = 20, X, Y, and Z are H) Compound), (product name: Brownon CW-20-90, manufactured by Aoki Yushi Kogyo Co., Ltd.).
[Component (B)]
(B-1): Diethanolamide laurate (product name: Amizol LDE-G, manufactured by Kawaken Fine Chemical Co., Ltd.).

[(C) component]
(C-1): polyoxyethylene alkyl ether (product name: Rheox CL60, manufactured by Lion Specialty Chemicals Co., Ltd., having 12 to 14 carbon atoms in the alkyl group, and having an average number of moles of ethylene oxide of 6 added).
(C-2): Polyoxyethylene alkyl ether (product name: NLME90, manufactured by Lion Specialty Chemicals Co., Ltd., having 12 to 14 carbon atoms in the alkyl group and 5 average moles of ethylene oxide added).
[(D) component: solvent]
(D-1): 1,2-propanediol.
(D-2): diethylene glycol monobutyl ether (product name: butyl diglycol (BDG), manufactured by Nippon Emulsifier Co., Ltd.).
(D-3): diethylene glycol monoethyl ether (product name: Seafozol DG, manufactured by Nippon Shokubai Co., Ltd.).
(D-4): monoethylene dipropylene glycol monobutyl ether _{(C 4 H 9 O (C} 2 H 4 O) 1 (C 3 H 6 O) 2 H, product name: Reosorubu 703B, Lion Specialty Chemicals Inc. Made)
Water: purified water.
[Other ingredients]
pH adjuster: citric acid.
Preservative.

<Examples 1 to 4, Comparative Examples 1 to 4>
Example 4 is a reference example.
According to the composition shown in Table 1, the components (A) to (C), other components, and water were all mixed, and a pH adjuster was added so that the pH at 25 ° C became 7, to prepare a stain remover. .
The composition of Comparative Example 4 corresponds to the stain removing composition (a) described in Table 3 of JP-A-2004-231759.
The water content “balance” is an amount necessary to make the stain removing agent a total of 100% by mass. “(A) / (B)” in the table indicates the mass ratio of the component (A) to the component (B) in the stain remover. The blending amounts in the table are converted to pure components.
The viscosity of the stain remover at 25 ° C. was 5 mPa · s in each case.
With respect to the stain remover of each example, the ring stain suppression effect and the low-temperature stability were evaluated by the following methods.
Table 1 shows the evaluation results.

<Method for preparing stains for evaluation>
6 mg of lipstick (manufactured by Kao Corporation, product name: Aube Couture Excellent Stay Rouge OR803) was evenly applied to a cotton cloth (Yuka Kayoufu) in a circular shape. What was left as it was at room temperature for one week to form a stain on the cloth was used as an evaluation cloth.

<Stain removal operation and wheel stain evaluation>
The stain removing agent was used by filling a container having a coating pressing surface at the tip (a container described in the example of JP-A-2004-231759, the tip of which is shown in Table 1A).
After the absorbent sheet C described in the example of JP-A-2004-231759 was laid on the back side of the stain adhering portion of the evaluation cloth, the stain was removed by tapping the coating and pressing surface of the container filled with the stain removing agent. Was. The entire stain-attached portion was hit uniformly, and when the tap was hit 500 times, the spread of the stain remover was confirmed, and it was determined whether the stain removal agent was 3 cm or less. The size of the spread of the stain remover is the same as the size of the ring stain. Thereafter, the stained portion was hit about 30 times with a towel wetted with water and squeezed tightly, and then air-dried at room temperature. After air-drying, the appearance of the ring jimi was visually evaluated. The ring spot suppression effect was determined according to the following criteria.
(Judgment criteria)
5 points: Ring spots are hardly visible, and the size is 3 cm or less.
4 points: Ring jigs are hardly visible, and the size is larger than 3 cm.
3 points: Ring spots are slightly visible, and the size is 3 cm or less.
2 points: The ring spot is slightly visible, and its size is larger than 3 cm.
1 point: Ring stains are clearly visible.

<Low-temperature stability evaluation method>
A glass bottle (PS6 bottle) was filled with 50 mL of the stain remover, the cap was tightly closed, and the container was allowed to stand in a constant temperature room at −5 ° C. and 0 ° C. for 24 hours, and then the appearance was visually evaluated. It was determined according to the following criteria.
(Evaluation criteria)
A: Uniform and transparent at -5 ° C.
：: Uniform transparency is not maintained due to precipitation or dust at -5 ° C, but uniform transparency at 0 ° C.
X: Precipitation or smudge occurs at 0 ° C, and uniform transparency is not maintained.

  As shown in the results of Table 1, in Examples 1 to 4 in which the component (A), the component (B) and the component (C) were used in combination and the ratio (A) / (B) was 1 or more, the ring-stain suppression effect was obtained. And low-temperature stability was also good.

Claims (3)

It contains the following components (A), (B) and (C), contains water in an amount of 80% by mass or more, and (A) / (B) represents the mass ratio of the (A) component to the (B) component. One or more stain removers are applied to the stained portion of the textile, and an absorbent sheet is placed under the textile and hit to absorb the stain component and the stain remover into the absorbent sheet. Method.
(A): at least one selected from the group consisting of polyoxyethylene hydrogenated castor oil, fatty acid esters of polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, and fatty acid esters of polyoxyethylene castor oil.
(B): at least one selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides.
(C): Nonionic surfactant that does not correspond to any of (A) and (B). The stain remover contains 0.1 to 10% by mass of the component (A), 0.1 to 5% by mass of the component (B), and 0.1 to 10% by mass of the component (C). The method for removing stains according to claim 1 . The stain removal method according to claim 1 or 2, wherein the stain removal agent contains 2 to 12% by mass of a water-miscible organic solvent .