JP5567255B2 - Liquid bleach composition for clothing - Google Patents

Description

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

  Among oxygen bleaches, sodium percarbonate and sodium perborate are used as powder bleaches, and hydrogen peroxide is used as a liquid oxygen bleach, which is directly applied to clothing. It is especially preferred because it is easy to apply.

By the way, when the liquid oxygen bleach is applied directly to clothing, the viscosity of the liquid affects the ease of use. Patent Document 1 discloses a viscosity control method using two types of nonionic surfactants. Further, in Patent Document 2, at least two kinds of specific nonionic surfactants are blended in a specific combination and a specific ratio, whereby a change in viscosity is small with respect to a change in temperature, and during storage. A liquid oxygen bleach having excellent hydrogen peroxide stability is disclosed.
WO94 / 11474 pamphlet JP-A-9-188895

  However, the bleaching composition disclosed in Patent Document 1 has a problem that the viscosity is remarkably changed by a change in temperature, and it is difficult to use in a scene where it is actually used. Further, in Patent Document 2, the change in viscosity with respect to the change in temperature is small, but the composition in which the blending ratio of the low HLB nonionic surfactant that expresses high performance by application is high is stable at a high temperature. It is desirable to improve the properties and stability of hydrogen peroxide.

  Therefore, the object of the present invention is to exhibit high stability in a system containing a low HLB nonionic surfactant that expresses high performance by coating use, and furthermore, can exhibit higher bleachability and detergency. It is to provide a liquid bleach composition for clothing.

In the present invention, the following (a) component 0.1 to 30% by mass, (b) component 0.5 to 15% by mass, (c) component 0.1 to 7.5% by mass, and (d) component 0. It is related with the liquid bleach composition for garments which contains 1-5 mass% and whose mass ratio of (b) component and (c) component is (b) / (c) = 100/1-2/1.
(A) Component: Hydrogen peroxide (b) Component: Nonionic surfactant represented by the following general formula (1) R ¹ —O (C ₂ H ₄ O) _p —H (1)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 16 carbon atoms. p is a number of C ₂ H ₄ O and the average molar number of addition of 3-7. ]
Component (c): Nonionic surfactant represented by the following general formula (2) R ¹ —O (C ₂ H ₄ O) _q —H (2)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 16 carbon atoms. q is the average added mole number of C ₂ H ₄ O and represents a number of 9 to 13. ]
(D) Component: Compound represented by the following general formula (3) R ² —O (C ₂ H ₄ O) _r —H (3)
Wherein, R ² represents an alkyl or alkenyl group having 16 to 18 carbon atoms. r is a number of is 50 to 200 average addition number of moles of C ₂ H ₄ O. ]

  ADVANTAGE OF THE INVENTION According to this invention, the liquid bleach composition for garments which shows high stability and can express higher bleaching property and washability is further provided. Since the liquid bleach composition for clothing of the present invention exhibits very high permeability to oil stains, it can exhibit high bleaching and detergency. In addition, since it contains a low HLB nonionic surfactant that exhibits high performance in coating use, it is suitable as a bleaching agent for coating.

[(A) component]
The liquid bleach composition for clothing of the present invention contains hydrogen peroxide as the component (a). (A) Content as hydrogen peroxide of a component is 0.1-30 mass% in the liquid bleach composition for garments, Preferably it is 0.5-20 mass%, More preferably, it is 1-15 mass%, Especially preferably, it is 1-10 mass%. In such a range, an excellent bleaching effect can be obtained.

[Component (b)]
The liquid bleach composition for clothing of the present invention contains a nonionic surfactant represented by the following general formula (1) as the component (b).
R ¹ —O (C ₂ H ₄ O) _p —H (1)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 16 carbon atoms. p is a number of C ₂ H ₄ O and the average molar number of addition of 3-7. Preferably p is a number from 4 to 6.5, more preferably from 5 to 6.5. ]

  The HLB obtained by the method of Mr. Davis (b) is preferably 2.2 to 6.5, more preferably 2.9 to 6.1, from the viewpoint of improving the permeability to dirt and the bleaching property. More preferably, it is 3.8 to 5.8. The HLB by Davis' method is “Surfactant Properties, Applications, Chemical Ecology” 7th edition, page 24, Fumio Kitahara, Yasukatsu Tamai, Shigeo Hayano, Ichiro Hara, Kodansha Scientific (1990) Year issue).

  In addition, a suitable example of the nonionic surfactant represented by the general formula (1) includes a polyoxyethylene alkyl ether type nonionic surfactant.

Specific examples of the polyoxyethylene alkyl ether type nonionic surfactant include, but are not limited to, compounds represented by the following general formula.
_{C 12 H 25 -O (C 2} H 4 O) p -H (p = 3~7)
_{C 14 H 29 -O (C 2} H 4 O) p -H (p = 3~7)

  More specifically, polyoxyethylene lauryl ether (oxyethylene average addition mole number 6, HLB13.1) is mentioned.

  The content of the component (b) is 0.5 to 15% by mass in the composition, preferably 1.0 to 12% by mass, from the viewpoint of improving the liquid stability at high temperatures and improving the bleaching performance. 10 mass% is more preferable.

[Component (c)]
The liquid bleach composition for clothing of the present invention contains a nonionic surfactant represented by the following general formula (2) as the component (c).
R ¹ —O (C ₂ H ₄ O) _q —H (2)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 16 carbon atoms. q is the average added mole number of C ₂ H ₄ O and represents a number of 9 to 13. Preferably q is a number from 9.5 to 12.5, more preferably from 10 to 12. ]

  In addition, a suitable example of the nonionic surfactant represented by the general formula (2) includes a polyoxyethylene alkyl ether type nonionic surfactant.

Specific examples of the polyoxyethylene alkyl ether type nonionic surfactant include, but are not limited to, compounds represented by the following general formula.
_{C 12 H 25 -O (C 2} H 4 O) q -H (q = 9~13)
_{C 14 H 29 -O (C 2} H 4 O) q -H (q = 9~13)

  More specifically, polyoxyethylene lauryl ether (oxyethylene average addition mole number 10) is mentioned.

  The content of the component (c) is 0.1 to 7.5% by mass, preferably 0.5 to 5% by mass, in the composition, from the viewpoint of improving liquid stability at high temperatures and improving bleaching performance. 0.8-3 mass% is more preferable.

  In the liquid bleach composition for clothing of the present invention, the mass ratio of the component (b) to the component (c) is (b) / (c) = 100/1 to 2/1. From the viewpoint of further improving the permeability of the liquid bleach composition for clothing, preferably (b) / (c) = 20/1 to 2.5 / 1, more preferably 10/1 to 2. 5/1, and more preferably 7/1 to 3/1.

[Component (d)]
The liquid bleach composition of the present invention contains a compound represented by the following general formula (3) as the component (d).
R ² —O (C ₂ H ₄ O) _r —H (3)
Wherein, R ² represents an alkyl or alkenyl group having 16 to 18 carbon atoms. r is a number of is 50 to 200 average addition number of moles of C ₂ H ₄ O. ]

R ² in the general formula (3) is preferably an alkyl group. R is preferably 60 to 180, more preferably 90 to 160.

  The content of the component (d) is from 0.1 to 5% by mass, preferably from 0.5 to 4% by mass in the composition from the viewpoint of improving the liquid stability at high temperatures and improving the bleaching performance. 7-3 mass% is more preferable.

  In the liquid bleach composition for clothing of the present invention, from the viewpoint of improving the liquid stability at high temperatures and improving the bleaching performance, the mass ratio of the component (b), the sum of the components (c) and the component (d) is (b ) + (C) / (d) = 100/1 to 2/1, preferably (b) / (c) = 20/1 to 3/1, more preferably 10/1 to 4 / 1.

  In the present invention, two specific types of nonionic surfactants, (b) component and (c) component are contained in a specific ratio, and (d) component is further contained, so that very high stability is achieved. Furthermore, since it shows very high permeability to oil stains, high bleaching and detergency can be expressed. The component (b) is a low HLB nonionic surfactant, and a liquid bleaching composition having a high blending ratio of a low HLB nonion such as the component (b) is excellent in detergency, but is stable at high temperatures. When anionic surfactants, solvents, hydrotropes, etc. that are commonly used to improve high-temperature stability are added, the high-temperature stability is improved, but the permeability to oil stains is reduced, bleaching, The cleaning performance is reduced. As a result of intensive studies, the present inventors, as a component (b), have a nonionic surfactant having a suitable addition number of ethylene oxide (hereinafter referred to as EO) limited from the viewpoint of detergency, and (c) ) The nonionic surfactant which is an EO adduct having an EO average addition mole number which is limited as a component and is several moles more than the component (b) as a main component as a cleaning agent is mixed at a predetermined mass ratio. Thus, it has been found that both the improvement in the stability of the viscosity with respect to the temperature of the product and the permeability to oil stains can be achieved. This effect is obtained by mixing the (b) component and the (c) component while the EO addition mole number distribution close to the normal distribution is obtained when the nonionic surfactant is synthesized by a normal synthesis method. The distribution of the EO addition mole number of the nonionic surfactant after mixing is considered to be manifested by making the distribution of the EO addition mole number different from the synthetic product in which only the average addition mole number is combined. Such chain length distribution of the EO chain affects the association state of the nonionic surfactant in the bath, changes the emulsified state and the state of adsorption to the soil, and the average added mole number of EO is relatively high. In spite of the components (b) and (c) which are close to each other, it is considered that the viscosity stability and the permeability to oil stains are significantly improved by mixing. Therefore, in order to achieve an optimal EO average addition mole number distribution, a compound having an alkyl group or an alkenyl group corresponding to the component (b) or the component (c) and having an EO average addition mole number of more than 7 and less than 9 is Even if it is not blended or blended, the blending amount of the component (b) or the component (c) is preferably equal to or less. Furthermore, it has been found that by using the component (d) selected in the present invention, not only the high-temperature stability and the stability of hydrogen peroxide are improved, but also higher bleaching and washing performance is exhibited. This is because the presence of a compound having a structure such as the component (d) having higher hydrophilicity improves the stability of the composition at a high temperature. Furthermore, the component (b) and ( This is because the solubility of the component c) is improved and the effects of the component (b) and the component (c) are increased.

The liquid bleach composition of the present invention can further contain the following components.
[(E) component]
The liquid bleach composition of the present invention may contain a bleach activator as the component (e) from the viewpoint of improving bleachability. Examples of the bleach activator include those described in paragraph [0010] of JP-A No. 10-251689.

  The content of the component (e) is preferably 0.2 to 15% by mass, more preferably 0.3 to 10% by mass in the composition from the viewpoint of improving liquid stability and bleaching performance, and 0.4 to 3 mass% is still more preferable.

[Metal sequestering agent]
The liquid bleach composition of the present invention may contain a metal sequestering agent from the viewpoint of improving the stability of the component (a). As the metal sequestering agent, a phosphonic acid type is preferably used. Specific examples thereof include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid salt, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid. And organic phosphonic acid derivatives such as ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid, and ethylenediaminetetrakismethylenephosphonic acid. These can be used alone or in combination of two or more. Of these, 1-hydroxyethane-1,1-diphosphonic acid, ethylenediaminetetrakismethylenephosphonic acid and the like are preferable. The content of the metal sequestering agent is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, in the liquid bleach composition of the present invention.

[Radical trapping agent]
The liquid bleach composition for clothing of the present invention may contain a radical trapping agent from the viewpoint of improving the stability of hydrogen peroxide and the bleach activator. As the radical trapping agent, phenol-based compounds, that is, derivatives having phenolic OH groups, derivatives thereof such as ester derivatives and ether derivatives thereof are preferable. Preferable examples include dimethoxyphenol, catechol, hydroquinone, methoxyphenol, dibutylhydroxytoluene (BHT) and the like.

  In addition, the liquid bleach composition for clothing of the present invention may contain optional components such as hydrotropes, silicones, bactericides, enzymes, fragrances, and fluorescent dyes. The liquid bleach composition of the present invention contains water, and usually the balance of the composition is water.

  As a fragrance | flavor, the fragrance | flavor as described in paragraph [0007]-[0022] of Unexamined-Japanese-Patent No. 2003-213295 can be used, for example.

  As the fluorescent dye, for example, a fluorescent dye described in JP-A No. 2004-308070 can be used.

[PH]
The liquid bleach composition for clothing of the present invention preferably has a pH at 20 ° C. of 1.5 to 6.0, more preferably 2.0 to 5.5, still more preferably 2.3 to 5.0. . At a pH in this range, the stability of hydrogen peroxide can be improved, and excellent bleach washing performance can be exhibited.

  PH adjusting agents for adjusting to such pHs include inorganic acids such as hydrochloric acid and sulfuric acid, or acid agents such as organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, etc. Or alkali agents such as sodium hydroxide, potassium hydroxide, ammonia and derivatives thereof, amine salts (monoethanolamine, diethanolamine, triethanolamine, etc.), sodium carbonate, potassium carbonate and the like can be used alone or in combination. . Among these, it is particularly preferable to use an inorganic acid selected from hydrochloric acid and sulfuric acid, or an inorganic base selected from sodium hydroxide and potassium hydroxide.

  The viscosity of the liquid bleach composition for clothing of the present invention is preferably 3 to 50 mPa · s, more preferably 4 to 40 mPa · s, and still more preferably 5 to 35 mPa · s at 20 ° C. This viscosity was measured using a B-type viscometer (model BM) manufactured by Tokyo Keiki Co., Ltd.

  The liquid bleach composition of the present invention can also be applied to textile products other than clothing.

[Method for producing liquid bleach composition]
The liquid bleach composition of the present invention is a composition comprising the above components (a) to (d), and further optional components such as the component (e). In this invention, 0.1-30 mass% of (a) component, 0.5-15 mass% of (b) component, and 0.1-7.5 mass of (c) component on the basis of the total amount of a mixing | blending raw material. % By mass, 0.1 to 5% by mass of component (d), and further containing (e) component, 0.2 to 15% by mass of component (e), and components (b) and (c) By using these components at a ratio such that the mass ratio is (b) / (c) = 100/1 to 2/1, a liquid bleach composition for clothing can be produced. Therefore, the content of the components (a) to (e) described above may be the blending amount at the time of preparation.

Especially, the liquid bleaching agent composition containing (e) component can be manufactured from the method of including the following process (I)-(II) from a viewpoint of stability of a (e) component, and manufacture ease. preferable.
Step (I): Step (II) for preparing a solution containing 5 to 20% by mass of component (e) and 5 to 20% by mass of component (b): The solution obtained in the above step (I) ( c) Step of mixing with component-containing solution (a) Component, component (b), component (d) are blended in solution containing component (c) or obtained in step (I) And it can mix | blend with the solution (the same or different solution) different from the solution containing (c) component, and can mix | blend in process (II).

The liquid bleach composition for clothing of the present invention is in a liquid state and exhibits an excellent bleaching effect when applied to clothing. Therefore, it is preferable to use for the bleaching method apply | coated to clothing and processing. Specifically, application to clothing includes application, spraying, dipping, and the like, and application is preferable. As an example, the application amount (especially the application amount) to clothing is preferably 0.1 to 1 ml, more preferably 0.3 to 1 ml per 1 cm ² of the cloth area. The liquid bleach composition of the present invention can also be applied to textile products other than clothing.

Examples 1-5, Comparative Examples 1-5
A liquid bleach composition for clothing having the composition shown in Table 1 was prepared using the following components. The pH was adjusted with NaOH. About this liquid bleach composition for clothing, the stability and bleaching performance of the composition were evaluated by the following methods. The results are shown in Table 1.

<Blending ingredients>
(A) Component a-1; hydrogen peroxide

Component (b) _{· b-1; C 12 H} 25 O- (C 2 H 4 O) 6.0 H
B-2; C ₁₄ H ₂₉ O— (C ₂ H ₄ O) _6.5 H
_{· B-3; C 12 H} 25 O- (C 2 H 4 O) 4.0 H
B′-4; C ₁₂ H ₂₅ O— (C ₂ H ₄ O) _2.5 H

Component (c) _{· c-1; C 12 H} 25 O- (C 2 H 4 O) 10.5 H
_{· C-2; C 12 H} 25 O- (C 2 H 4 O) 13.0 H
_{· C'-3; C 12 H} 25 O- (C 2 H 4 O) 15.0 H

Component (d) _{· d-1; C 18 H} 37 O- (C 2 H 4 O) 130 H
_{· D-2; C 18 H} 37 O- (C 2 H 4 O) 60 H
_{· D'-3; C 18 H} 37 O- (C 2 H 4 O) 30 H

Component (e) · e-1; lauryl oxybenzene sodium sulfonate _{(n-C 11 H 23 COOC} 6 H 4 SO 3 Na)

(F) Component f-1; ethane-1-hydroxy-1,1-diphosphonic acid (Daiquest 2010, manufactured by Solusia)

<Liquid feel stability>
A sealed glass container (with an internal volume of 100 mL) was filled with the liquid bleach composition, and left in a thermostatic chamber at 60 ° C. for 1 month. When the liquid bleaching composition after storage was a transparent uniform solution, the evaluation was evaluated as “◯”, the white turbidity as “Δ”, and the separation as “x”.

<Hydrogen peroxide stability>
The glass container 1 shown in FIG. 1 (with an internal volume of 1000 mL) is filled with a liquid bleach composition and left in a thermostatic chamber at 50 ° C. for 1 month, and the amount of gas generated (mL) can be measured up to a scale of 2 (100 mL) ). The generated gas is oxygen obtained by decomposing hydrogen peroxide, and the fact that the amount of gas generated is small indicates that the decomposition of hydrogen peroxide is small and the composition is highly stable.

<Bleaching performance>
1 ml of the liquid bleach composition was applied to each meat sauce-contaminated cloth (4 sheets) prepared by the following method using Pipetteman (Gilson, P-1000), left at 20 ° C. for 5 minutes, and then 0.0667 mass It was washed with a targotometer using an aqueous solution of% detergent (Attack (Kao Lot No. W153137). The reflectance of the fabric surface before and after the treatment was measured, and the bleaching rate was determined by the following formula.

・ Preparation of Meat Sauce Contaminated Cloth Solid content of Meat Sauce (Ripe Tomato Meat Sauce (Expiration Date: June 20, 2009, Lot No .: D7620JG) / Canned 295 g of Canned Foods) manufactured by Kagome Co., Ltd. (mesh opening; 500 μm) ), And the resulting liquid was heated until boiling. Cotton gold cloth # 2003 was immersed in this solution and boiled for 40 minutes. After removing from the fire as it was for about 2 hours and leaving it to 30 ° C., the cloth was taken out and the excess liquid was removed with a spatula and allowed to dry naturally. Then, it was pressed and subjected to an experiment as a 10 cm × 10 cm test cloth.

Bleaching rate (%) = (reflectance after bleaching−reflectance before bleaching) / (reflectance of white cloth−reflectance before bleaching) × 100

  Comparative Example 1 showed (b) / (c) mass ratio with b′-4 as the component (b).

In Examples and Comparative Examples, the apparatus is used for measuring the amount of gas generated.

Claims (3)

Following component (a) 0.1 to 30 wt%, (b) component 0.5 to 15 wt%, (c) component 0.1 to 3 wt%, and 0.1 to 5 wt% (d) component A liquid bleaching composition for coating for clothing, wherein the mass ratio of the component (b) to the component (c) is (b) / (c) = 10/1 to 2.5 / 1.
(A) Component: Hydrogen peroxide (b) Component: Nonionic surfactant represented by the following general formula (1) R ¹ —O (C ₂ H ₄ O) _p —H (1)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 16 carbon atoms. p is a number of C ₂ H ₄ O and the average molar number of addition of 3-7. ]
Component (c): Nonionic surfactant represented by the following general formula (2) R ¹ —O (C ₂ H ₄ O) _q —H (2)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 16 carbon atoms. q is the average added mole number of C ₂ H ₄ O and represents a number of 9 to 13. ]
(D) Component: Compound represented by the following general formula (3) R ² —O (C ₂ H ₄ O) _r —H (3)
[Wherein R ² represents an alkyl group having 16 to 18 carbon atoms. r is a number of is 50 to 200 average addition number of moles of C ₂ H ₄ O. ] Furthermore, the liquid bleach composition for application | coating of the clothing of Claim 1 containing the following (e) component 0.1-3 mass%.
(E) Component: Bleach activator The liquid bleach composition for application | coating of clothing of Claim 1 or 2 whose viscosity in 20 degreeC is 4-40 mPa * s.

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