JP3425346B2 - Liquid bleach composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid bleaching composition suitable for cleaning stains on cloth products, especially stains on clothes.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents can be classified into chlorine type and oxygen type, but chlorine type bleaching agents are limited in the fibers that can be used and cannot be used for colored patterns. Oxygen-based bleaches, which do not have these drawbacks, have recently become remarkably popular because of their unique pungent odor.

As the oxygen-based bleaching agent, sodium percarbonate and sodium perborate are used as a powder bleaching agent, and hydrogen peroxide is used as a liquid bleaching agent.
Among them, the liquid oxygen bleaching agent is widely used as a cleaning agent for such applications because it is suitable for cleaning by directly applying it to partial stains and stains on clothing collars, cuffs and the like. However, when applying the liquid oxygen bleach to stains and stains, the liquid spreads to a wide area other than stains and stains during application,
Dripping from the applied part causes problems such as not being applied in an amount sufficient for removing stains, or using an excessive amount.

As a method of solving such a problem, there is a method of suppressing the osmotic force or increasing the viscosity. However, if the osmotic force is suppressed or the viscosity is increased, the above-mentioned problem can be solved, but on the other hand, the bleaching agent is difficult to soak into the soiled portion and the cleaning effect is deteriorated.

Therefore, the present invention provides a liquid bleaching composition capable of enhancing the cleaning and bleaching effect by easily permeating and holding an appropriate amount of the bleaching solution in the stain-stained portion of the object to be washed such as clothes.

[0006]

When applying a liquid agent to cleaning and bleaching partial stains and stains, the present inventors have two factors: the penetrating power of the liquid agent and the holding power (adhesive force) of the liquid agent on the object to be cleaned. As a result of repeated studies paying attention to the fact that is particularly important, the present invention has been completed by finding a combination of the composition of the liquid agent and the characteristics of the liquid agent for satisfying the above two factors.

That is, the present invention uses 0.5 to 6 weight parts of hydrogen peroxide.
%, Nonionic surfactant 0.5 to 20% by weight, sequestration
0.1 to 3% by weight of the agent, thickener and water , the viscosity at 20 ° C is 10 to 200 mPa · s, and nonionic surface active
The agent has the following general formula (I): R- (AO) _n (BO) _m- X (I) [wherein, R represents an alkyl group having 8 to 20 carbon atoms, and A represents
-C ₂ H ₄ - are shown, B is branched which may _-C have 3 H
_6- , and AO and BO are arranged in blocks or randomly.
May be in line, n and m may be the same or different
Also, each represents a number of 0 to 20, and n + m is 5 to 2.
Represents the number of 0 and X represents a hydrogen atom or a methyl group]
The thickener is a porosity with a saponification degree of 80% or more.
Rivinyl alcohol, thickener and nonionic surfactant
The liquid bleaching composition is characterized in that the content ratio with the agent is 1/5 to 1/1 by weight .

[0008]

DETAILED DESCRIPTION OF THE INVENTION Hydrogen peroxide used in the present invention is a component which becomes a bleaching active species. The content of hydrogen peroxide in the liquid bleaching composition is 0.5 to 6% by weight in order to prevent the container from bulging during storage and to obtain a sufficient bleaching effect.

As the nonionic surfactant used in the present invention, for example, the following general formula (I): R- (AO) _n (BO) _m -X (I) [wherein, R is 8 to 8 carbon atoms] an alkyl group of 20, a is _-C 2 _{H 4} - are shown, B is branched which may _-C have 3 H
_6- , AO and BO may be arranged in blocks or randomly, n and m may be the same or different, each represents a number of 0 to 30, and n + m is 4 to 5
Which represents the number of 0 and X represents a hydrogen atom or a methyl group]. In the general formula (I), n and m are preferably 0-20, more preferably 3-20, and n + m is preferably 5-20.

As an example of the nonionic surfactant represented by the general formula (I), C ₁₀ H ₂₁ (OC ₂ H ₄ ) _n (OC ₃ H ₆ ) _m -OH C ₁₂ H ₂₅ ( _{OC 2 H 4) n (OC} 3 H 6) m -OH C 14 H 29 (OC 2 H 4) n (OC 3 H 6) m -OH C 16 H 33 (OC 2 H 4) n (OC 3 H ₆ ) _m- OH etc. can be mentioned, and these can be used 1 type or in combination of 2 or more types.

The content of the nonionic surfactant in the liquid bleaching composition is 0.5 in order to provide sufficient detergency.
Is about 20% by weight.

As the sequestering agent used in the present invention, acetic acid, propionic acid, butanoic acid, hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, glycolic acid, lactic acid, succinic acid, Organic carboxylic acids such as citric acid, fumaric acid, benzoic acid, salicylic acid, phthalic acid, terephthalic acid and trimetic acid; percarboxylic acids such as dodecane diperacid and monoperphthalanol acid; non-carboxylic acids such as acrylic acid, methacrylic acid and maleic acid Polycarboxylic acids such as homopolymers or copolymers obtained from saturated carboxylic acids; alkyl sulfates, alkyl ether sulfates, α-sulfo fatty acids, α-sulfo fatty acid esters, alkylbenzene sulfonic acids, p-toluene sulfonic acid, p-hydroxy Organic sulfonic acid such as sulfonic acid Organic sulfates; 1-
Hydroxy-1,1-diphosphonic acid, ethanehydroxy-
Phosphonic acids such as 1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid; inorganics such as sulfuric acid, phosphoric acid, hydrochloric acid, polyphosphoric acid, nitric acid and silicic acid Mention may be made of acids. These are 1
One kind or a combination of two or more kinds can be used.

The content of the sequestering agent in the liquid bleaching agent composition is 0.1 to 3% by weight in view of economic efficiency and suppression of decomposition of hydrogen peroxide.

The thickener used in the present invention is polyvinyl alcohol.
The weight average of polyvinyl alcohol is
The molecular weight is preferably 2,000 to 500,000.
Particularly preferably from 5,000 to 100,000
Can be mentioned. Also, polyvinyl alcohol
Has a saponification degree of 80% or more, and is particularly preferable.
Is 85% or more.

The content of the thickener in the liquid bleaching composition is appropriately adjusted within a range that allows the viscosity of the composition to be set within a predetermined range.

The content ratio of the thickener to the nonionic surfactant is 1/5 to 1/1 by weight in order to impart appropriate penetrating power and adhesive force to the liquid bleaching composition.

The liquid bleaching composition of the present invention may further contain a bleaching activator represented by the following general formula (II) or (III).

[0018]

[Chemical 2]

[M represents hydrogen, an alkali metal, an alkaline earth metal or an ammonium ion, and R ¹ is substituted with an alkyl group or an alkenyl group having 7 to 18 carbon atoms or an alkyl group having 1 to 12 carbon atoms. Represents an optional aryl group].

Among the bleaching activators represented by the general formula (II) or (III), sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzoic acid, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, 3 Preferred is 5,5,5-trimethylhexanoyloxybenzoic acid.

The blending amount of the bleach activator is preferably 0.01 to 20% by weight in order to prevent precipitation and increase in viscosity and to impart sufficient bleaching detergency.
It is particularly preferably 0.1 to 10% by weight, and further preferably 0.5 to 10% by weight.

The mixing ratio of the thickener and the bleach activator is preferably 1/2 to 50/1 in terms of weight ratio in order to impart appropriate penetrating power and adhesive force to the liquid bleach composition. Particularly preferably, it is 1/1 to 10/1.

The liquid bleaching composition of the present invention may further contain a surfactant other than the nonionic surfactant. Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates. , Α-sulfofatty acid salts, α-sulfofatty acid esters, and the like. Among these, C
Preferred are _{10- C18} alkylbenzene sulphonates, polyoxyethylene alkyl ether sulphates or aliphatic alcohol sulphates. Examples of the cationic surfactant include quaternary ammonium salts and the like, and examples of the amphoteric surfactant include amine oxide, sulfobetaine, carbobetaine and the like. The blending amount of these surfactants is appropriately adjusted within the same amount range as the above-mentioned nonionic surfactant.

The liquid bleaching composition of the present invention may further contain the following enzymes, fragrances and defoaming agents. (1) Enzymes Enzymes (which are enzymes that inherently perform an enzymatic action during the washing step) include hydrolases, oxidoreductases, lyases, transferases, and isomerases when classified according to the reactivity of the enzyme. However, any of the present invention can be applied. Particularly preferred are proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases. Specific examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain,
Promelin, carboxypeptidases A and B, aminopeptidases, aspergillopeptidases A and B, which are commercially available products such as sabinase, alcalase (Novo Industry Co., Ltd.), API21 (Showa Denko KK), Maxacar (Gistprocay). (Death), JP-A-5-2549
Protease K-14 or K-16 described in JP-A-2 can be mentioned. Specific examples of esterases include:
Examples thereof include gastric lipase, buncreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotase. Specific examples of lipases include commercially available lipases such as lipolase (Novo Industry Co., Ltd.) and liposam (Showa Denko KK). Also, as cellulase, commercially available cellzyme (Novo Industry Co., Ltd.), JP-A-6
Examples thereof include cellulase according to claim 4 of JP-A-3-26469, and examples of amylase include commercially available Termamyl (Novo Industry Co., Ltd.). The enzyme is separately granulated as stable particles and used in a dry blended state with detergent dough (particles). (2) Fragrance As a fragrance, a fragrance that has been conventionally blended in detergents, for example, a fragrance described in JP-A-63-101496, dimethylbenzylcarbinyl acetate, tricyclo [5.2.1.0]
2,6] -Dec-3-en-8-yl acetate, tricyclo
[5.2.1.02,6] -Dec-3-ene-8-isopropionate, 3-amyl-4-acetoxytetrahydropyran, 4-ter
t-butylcyclohexyl acetate, 2-tert-butylcyclohexyl acetate, p-tert-butyl-α-methylhydrocinnamic aldehyde, 4- (4-hydroxy-4-
Methylpentyl) -3-cyclohexene-1-carboxaldehyde, α-hexylcinnamic aldehyde, α-amylcinnamic aldehyde, α, α′-dimethyl-p-
Examples thereof include ethylhydrocinnamic aldehyde. Of course, in order to prevent deterioration due to other detergent components, the type of each fragrance component to be blended and, depending on the case, the blending ratio and blending amount are considered. (3) Defoaming Agent As the defoaming agent, there can be mentioned conventionally known silicone / silica type defoaming agents. The defoaming agent is described in JP-A-3-186307, page 4, An antifoaming agent granulated product produced by the method described in the lower left column may be used. First, 20 g of Dow Corning silicone (compound type, PS antifoam) as an antifoaming component is added to and mixed with 100 g of maltodextrin (enzyme-modified dextrin) manufactured by Nippon Starch Chemical Co., Ltd. to obtain a homogeneous mixture. Next, after mixing 50% of the obtained homogeneous mixture, 25% of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25% of neutral anhydrous Glauber's salt at 70-80 ° C., an extrusion granulator manufactured by Fuji Paudal Co., Ltd. Granulate with (Model EXKS-1) to obtain a granulated product.

The liquid bleaching composition of the present invention has a viscosity at 20 ° C. of 10 to 200 mPa · s, preferably 10 in order to obtain appropriate penetrating power and adhesiveness on the object to be washed.
To 150 mPa · s, particularly preferably 10 to 100 mPa
・ S.

[0026] Liquid bleaching compositions of the present invention, by having the above composition, those having the following characteristics (a) and (b).

Characteristic (a) is that 2 ml of the liquid bleach composition is
The following formula when naturally falling in a glass tube made of hard glass with an inner diameter of 1 mm and a length of 80 mm supported in the vertical direction: f = (16 · μ) / (d · u · ρ) [where u is Velocity (m / sec), d the pipe diameter (m), ρ the density of the composition (kg / m ³ ), μ the viscosity of the composition (kg / m · sec)] Friction coefficient (f)
Is in the range of 1 to 100, preferably 10 to 100, and particularly preferably 10 to 50. In this formula, the velocity (u) is a value obtained from 2.5478 (m) / fall time (sec). The density and viscosity are both 2
It is a value at 0 ° C. The glass tube is not particularly limited in shape and the like of other portions as long as it satisfies the above requirements.

Characteristic (b) is that a petri dish with a diameter of 15 cm
A cotton gold cloth 2003 # is stretched so as not to be wrinkled, and when 5 ml of the liquid bleaching composition is applied at one time, the spreading speed is 3 to 6 cm ² / sec. This spreading rate is preferably 3-5 cm ² / sec.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[0030]Examples and comparative examples Hydrogen peroxide (manufactured by Nippon Peroxide), a-1 to a-
3'sNonionic surfactant, b-1 sequestering agent, C-1
To c-6 thickeners andBleach activators d-1 to d-3To
A liquid bleach composition having the composition shown in Table 1 (numerical display is
Wt%) was obtained. In addition, in Table 1, c / a is non-polysaccharide and non-polysaccharide.
Indicates the content ratio with ionic surfactant, c / d is the polysaccharide
And the content ratio of the bleach activator is shown. For these compositions
And measure the friction coefficient and spreading speed by the following methods.
Then, the bleaching performance was tested. The results are shown in Table 1. a-1: C₁₂H₂₅(OC_TwoH_Four)_Three(OC_ThreeH₆)
_Three-OH a-2: C₁₂H₂₅(OC_TwoH_Four)₆(OC_ThreeH₆)
_Three-OH a-3: C₁₂H₂₅(OC_TwoH_Four)₈-OH b-1: Phosphonic acid-based sequestering agent (manufactured by Monsanto Co., Ltd.
Quest 2010). c-1: Carrageenan (FMC, Gelcarin) c-2: carboxymethyl cellulose (manufactured by Henkel, De
hydazol) c-3: Kuraray Poval PVA-124 (saponification degree 99%) c-4: Kuraray Poval PVA-220 (saponification degree 88%) c-5: Kuraray Poval L-8 (saponification degree 71%) c-6: Carbopol ETD2691 (manufactured by BFGoodrich)

[0031]

[Chemical 3]

Test Example 1 (Measurement of Friction Coefficient) A glass instrument (made of hard glass manufactured by Iwaki Glass Co., Ltd.) having a shape and dimensions shown in FIG. 1 was vertically supported and fixed by a supporting tool, and an opening at the lower end was made of rubber. I plugged it up. Next, 2 ml of the liquid bleaching agent composition was put in from the upper end opening so that air did not enter, and then the rubber stopper was removed and the mixture was allowed to fall naturally. At this time, the time required when the liquid passed through a glass tube made of hard glass having an inner diameter of 1 mm and a length of 80 mm (80 mm from a position of 150 mm to a position of 230 mm from the upper end) was measured. This measurement is repeated 3 times and the speed (u) is calculated from the average time.
[u = 2.5478 (m) / falling average time (sec)] is calculated, and the following formula: f = (16 · μ) / (d · u · ρ) [wherein u represents velocity and d is The friction coefficient (f) was determined from the pipe diameter, ρ indicates the density of the composition, and μ indicates the viscosity of the composition. The test was conducted at room temperature.

Test Example 2 (Measurement of Spreading Speed) A cotton gold cloth 2003 # was stretched on a petri dish having a diameter of 15 cm so as not to wrinkle. Next, 5 ml of the liquid bleaching agent composition was applied at once to the vicinity of the central portion thereof with a pipette.
The area of the wet part of the cotton cloth was measured 10 seconds after the application, and the value obtained by dividing the area by 10 (sec) was defined as the spreading speed (cm ² / sec).

Test Example 3 (bleaching performance test) (1) Preparation of black tea-contaminated cloth 80 g of Nitto black tea (yellow package) was boiled in 3 liters of ion-exchanged water for about 15 minutes and then rubbed with de-squeezed cotton. A cotton gold cloth 2003 # was dipped in the solution and boiled for about 15 minutes. Remove from heat as it is, leave for about 2 hours,
Rinse with water until the washing liquid is no longer colored, dehydrate, press,
A 10 × 10 cm black tea stain cloth for testing was obtained. (2) Measurement of bleaching performance Five pieces of black tea-contaminated cloth were placed on different petri dishes each having a diameter of 7 cm, and 3 ml / piece of the liquid bleaching detergent composition was applied thereto by a pipette. 30 seconds later, put the tea-contaminated cloth in 2 liters of 0.067% detergent aqueous solution (commercial detergent),
Soaked for a minute. Then, the product was taken out from the detergent aqueous solution, thoroughly rinsed with tap water and heated and dried, and the reflectance was measured, and the bleaching ratio was calculated from the following formula. The reflectance is
The measurement was performed using NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

[0035]

[Equation 1]

[0036]

[Table 1]

[0037]

Since the liquid bleaching composition of the present invention has a well-balanced penetrating power and adhesive force, the liquid agent does not spread too much or drools down easily and reliably. Can be applied to. Therefore, it is possible to exert sufficient washing and bleaching power with a proper amount of the liquid bleaching agent composition without waste during use.

[Brief description of drawings]

FIG. 1 is a diagram for explaining a method of measuring a friction coefficient.

Front Page Continuation (72) Inventor Susumu Yamaguchi 1334 Kao Co., Ltd., Wakayama City, Wakayama Prefecture Kao Co., Ltd. (72) Inoue Shiro Aoyanagi 1334 Minato Minato, Wakayama City, Wakayama Prefecture (56) Reference JP 10 -72598 (JP, A) JP-A-8-295898 (JP, A) JP-A-7-3293 (JP, A) JP-A-8-295897 (JP, A) JP-A-5-214391 (JP, A) ) Japanese Patent Laid-Open No. 10-130693 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 3/395 C11D 17/08 D06L 3/02

Claims (3)

(57) [Claims] 1. 0.5 to 6% by weight of hydrogen peroxide, nonionic
Surfactant 0.5 to 20% by weight, sequestering agent 0.1 to 3
% By weight, a thickener and water , the viscosity at 20 ° C. is 10 to 200 mPa · s, and the nonionic surfactant has the following general formula (I): R— (AO) _n (BO) _m —X (I) [In the formula, R represents an alkyl group having 8 to 20 carbon atoms, and A is
-C ₂ H ₄ - are shown, B is branched which may _-C have 3 H
_6- , and AO and BO are arranged in blocks or randomly.
May be in line, n and m may be the same or different
Also, each represents a number of 0 to 20, and n + m is 5 to 2.
Represents the number of 0 and X represents a hydrogen atom or a methyl group]
The thickening agent is a polyvinyl alcohol having a saponification degree of 80% or more.
And the content ratio of thickener and nonionic surfactant is weight.
A liquid bleach composition characterized in that the ratio is 1/5 to 1/1 . 2. Further, the following general formula: [M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R1 is an aryl group which may be substituted with an alkyl group or an alkenyl group having 7 to 18 carbon atoms or an alkyl group having 1 to 12 carbon atoms. Indicates a group. Liquid bleaching compositions according to claim 1, further comprising a bleaching activator represented by. 3. A content ratio of the thickening agent and the bleach activator according to claim 1 or 2, the liquid bleach composition as claimed is 1/2 to 50/1 by weight.