KR20130093014A - Liquid bleaching composition for garment - Google Patents

Abstract

The present invention provides a bleaching composition having excellent antibacterial effect while suppressing adhesion of microorganisms to medical treatment as a laundry material even when washing with water containing a large amount of microorganisms such as the remaining water after bathing. Invention myeoeun hydrogen peroxide (A) and at least 0.1% by weight and the surfactant (B), the logarithmic value of the chelate stability constants for Ca ^{2 +} 5.5 or more, the logarithmic value of a chelating stability constant of the Fe ^{3 +} 10 or more, in addition, the chelating agent is the logarithmic value of a chelating stability constant of 10 or greater for the ^{Cu 2 + (C) 0.1 ~} 5 wt.% and, the non-No deugye polymers and dimethyl diallyl ammonium polymers cationic polymer one or more kinds selected from (D) It is related with the bleaching composition formed by containing 0.001-2 mass%.

Description

Medical Liquid Bleaching Composition {LIQUID BLEACHING COMPOSITION FOR GARMENT}

The present invention relates to a liquid bleaching composition for medical use.

This application claims priority based on Japanese Patent Application No. 2010-126937 for which it applied to Japan on June 2, 2010, and uses the content here.

In recent years, the remaining water after bathing is increasingly used as washing water for washing due to environmental consciousness and an increase in economies. The remaining water after the bath contains various microorganisms such as human origin and soil origin. In some countries and regions where the maintenance status of the water supply is poor, foreign materials such as microorganisms (including microorganisms mixed substances) and organic substances may be mixed in tap water. When water containing a large number of these microorganisms is used for washing, there is a problem in that microorganisms are attached to the medical treatment to generate unique odors or microorganisms attached to the medical treatment during drying of the laundry generate odors.

Generally, in order to suppress the odor of medical treatment after washing, a bleaching composition (bleach composition, bleach detergent composition, etc.), an antibacterial detergent, etc. have been used for washing.

As a bleaching composition, the liquid bleach composition which consists of hydrogen peroxide, a metal chelating agent, an anionic surfactant, a nonionic surfactant, an organic peracid precursor, for example is known (for example, patent document 1). According to the invention of Patent Literature 1, it is excellent in storage performance and can efficiently generate organic peracid during washing and can express a high bleaching effect.

As a bactericidal or antimicrobial component, biguanide compounds are known, and Patent Documents 2 to 4 propose bactericides and antibacterial agents containing a biguanide compound and a surfactant.

According to the invention of patent documents 2-4, hard surfaces, such as a toilet bowl of a toilet, can be sterilized effectively, or an antimicrobial property can be given to hard surfaces.

Japanese Patent Laid-Open No. 9-100492 Japanese Patent Publication No. 2003-531247 Japanese Patent Publication No. 2006-143620 Japanese Patent Publication No. 2006-143261

However, although the liquid bleach composition of patent document 1 aims at the improvement of the bleaching effect, it was not able to fully suppress adhesion of microorganisms to medical care. In addition, the antimicrobial agent of patent documents 2-4 aims at disinfecting hard surfaces, and providing antimicrobial property to hard surfaces, and does not assume washing of medical care. For this reason, even if the antimicrobial agent of patent documents 2-4 is used for medical washing, adhesion of microorganisms to the medical care from washing water containing many microorganisms cannot fully be suppressed.

Therefore, an object of the present invention is to provide a bleaching composition capable of suppressing adhesion of microorganisms to medical treatments as well as excellent antibacterial effect even when washing with water containing a large amount of microorganisms such as the remaining water after bathing.

As a result of careful investigation, the present inventors have found that microorganisms in water containing a large amount of microorganisms, such as the remaining water, may be present in stains such as fatty acids. It was difficult to contact bleach, and microorganisms had insufficient sterilization, so that knowledge could not be suppressed. As a result of conducting examination based on this knowledge, it was found that in a bleaching composition containing hydrogen peroxide and a surfactant, by using a specific chelating agent and a specific cationic polymer together, microorganisms in the washing water can be prevented from adhering to the laundry. The present invention has been completed.

That is, the medical liquid table people composition of the present invention is hydrogen peroxide (A) 0.1 mass% or more and a surfactant (B) and the logarithm of the chelate stability constants for Ca ^{2 +} 5.5 or more, chelating stability on the Fe ^{3 +} the algebraic value of the integer 10 or more, and Cu ^{2 +} with a chelating agent (C) 0.1~5% by mass of the logarithm of a chelating stability constant of 10 or greater on, the non-No deugye polymers and dimethyl diallyl ammonium polymer is selected from 1, It contains 0.001-2 mass% of species or more cationic polymer (D).

It is preferable that the mass ratio represented by the said chelating agent (C) / said cationic polymer (D) is 1-1000, The said surfactant (B) is the content of 1-60 mass%, The nonionic surfactant (b -1) and anionic surfactant (b-2).

0.5 mass% or more of said nonionic surfactant (b-1) and less than 20 mass%, and 1-10 mass% of said anionic surfactants (b-2) are contained, The said nonionic surfactant (b-1) contains It is at least 1 type selected from following General formula (1) and (2), The said anionic surfactant (b-2) is a linear alkylbenzene sulfonic acid or its salt, alkyl sulfate, polyoxyethylene alkyl ether sulfate, alpha-olefin It is preferable to use at least 1 type selected from a sulfonate and an alkanesulfonate.

[In formula (1), R <^1> is a C7-18 linear or branched alkyl group or alkenyl group, k represents the average added mole number of ethylene oxide, and is 3-15.]

[In formula (2), x and y are one or more numbers which show the number of methylene groups, respectively, and x + y = 5-13. z is a number from 5 to 30 indicating the average added mole number of ethylene oxide]

Moreover, 20-59 mass% of said nonionic surfactants (b-1) and 1-10 mass% of said anionic surfactants (b-2) are contained, The said nonionic surfactant (b-1) contains (2 ), (3), (4) and (5), and the anionic surfactant (b-2) is a linear alkylbenzene sulfonic acid or a salt thereof, alkyl sulfate, polyoxyethylene alkyl ether sulfate, It is preferable to set it as 1 or more types chosen from (alpha)-olefin sulfonate and alkanesulfonate.

[X, y in Formula (2) is 1 or more number which shows the number of methylene groups, respectively, x + y = 5-13, z shows the average added mole number of ethylene oxide, and is 5-30.]

[In Formula (3), R <^2> is a C8-18 linear or branched alkyl group or alkenyl group. k1 and n1 are 1 or more numbers which show the average added mole number of ethylene oxide, respectively, and are k1 + n1 = 3-30. m1 is the number of 0.2-5 which shows the average added mole number of a propylene oxide]

[In Formula (4), R <^3> is a C8-18 linear or branched alkyl group or alkenyl group. k2 and n2 are 1 or more numbers which show the average added mole number of ethylene oxide, respectively, and are k2 + n2 = 3-30. m2 is the number of 0.2-5 which shows the average added mole number of a propylene oxide]

[In formula (5), R <^4> is a C9-C13 linear or branched alkyl group or alkenyl group, R <^5> is a C2-C4 alkylene group, R <^6> is a C1-C3 alkyl group, p Is a number from 5 to 30 indicating the average added mole number of alkylene oxide]

(Effects of the Invention)

According to the medical liquid bleaching composition of the present invention, the antimicrobial effect is excellent also in washing using water containing a large amount of microorganisms such as the remaining water after bathing, and the adhesion of microorganisms to medical treatment as the laundry can be suppressed.

1 is a front view of a container used in Examples.

(Medical Liquid Bleach Composition)

The medical liquid bleaching composition (hereinafter sometimes referred to simply as liquid bleaching composition) of the present invention is hydrogen peroxide (A) (hereinafter (A) component), surfactant (B) (hereinafter (B) component), and chelate. (C) (following (C) component) and cationic polymer (D) (following (D) component).

A bleachable composition includes a detergent composition and a bleach composition. A bleach composition is a composition mainly aimed at the bleaching of a to-be-washed object, and a bleaching power is important, and a detergent composition is a composition mainly aimed at washing a to-be-washed object, and the bleaching power is inferior to a bleach composition, but it focused on cleaning power.

<(A) component: Hydrogen peroxide>

(A) component in this invention is hydrogen peroxide. Component (A) usually has an oxidizing power and bears the bleaching effect of the liquid bleaching composition. In the present invention, by further using in combination with the components (B), (C) and (D), it is possible to prevent the microorganisms in the wash water from adhering to the garment, especially when washing water containing a large number of microorganisms such as the remaining water after bathing is used during washing. (Microbial migration inhibitory effect).

Content of (A) component in a liquid bleaching composition is 0.1 mass% or more, Preferably it is 0.1-5.0 mass%, More preferably, it is 1-5 mass%. If it is in the said range, a higher bleaching effect can be obtained, and it can be set as the liquid bleaching composition excellent also in a bacterium migration inhibitory effect and stability. If it is less than 0.1 mass%, a preferable bleaching effect and a bacterium migration inhibitory effect will not be acquired, but when it exceeds 5 mass%, a container may expand when a liquid bleaching composition is put into a container and preserve | saved.

<Component (B): Surfactant>

(B) component in this invention is surfactant. (B) A component can be selected according to the use of a liquid bleaching composition, and nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, amideamine salt type surfactant, etc. are mentioned. Especially, it is preferable to use a nonionic surfactant (b-1) and anionic surfactant (b-2) from a viewpoint of the bleaching power, washing power, and stability which are the basic functions of a bleaching composition. By combining such a component (B) with the component (A), the component (C) and the component (D), even when water (hot water) containing a large amount of microorganisms such as the remaining water after bathing is used for washing, it is sterilized by a disinfectant or the like. It is possible to exert a bacterium migration inhibitory effect on the remaining bacteria that can not be.

Content of (B) component in a liquid bleaching composition is not specifically limited, For example, it is preferable to determine in 1-60 mass% of range. If it is less than 1 mass%, the dispersibility of microorganisms or stains containing microorganisms will become inadequate, and if it is more than 60 mass%, the storage stability of a liquid bleaching composition will fall. In addition, when using a liquid bleaching composition as a bleach composition, 1-30 mass% is preferable, and, as for content of (B) component in a liquid bleaching composition, 1.5-20 mass% is more preferable. Moreover, when using a liquid bleaching composition as a detergent composition, content of (B) component in a liquid bleaching composition is more than 20 mass% is preferable, and it is preferable to set it as more than 20 mass% and 60 mass% or less.

<(b-1) Component: Nonionic Surfactant>

As the nonionic surfactant (b-1), for example, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyethylene fatty acid ester oxyethylene propylene block polymer, alkyl (poly) glycoside, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, an amine oxide, etc. are mentioned, Especially, the compound (1)-(5) shown below is preferable.

Compound (1): a compound represented by the following general formula (1)

Compound (1) in this invention is a compound represented by following General formula (1).

In formula (1), R <^1> represents an alkyl group or an alkenyl group, and may be linear or may have a branch. k represents the average added mole number of ethylene oxide.

Carbon number of the alkyl group or alkenyl group represented by R <^1> is 7-18 pieces, Preferably it is 10-16 pieces, More preferably, it is 12-14 pieces. As a specific alkyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, etc. are mentioned, for example. Moreover, an alkenyl group corresponding to the said alkyl group is mentioned as an alkenyl group, For example, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, etc. are mentioned. have.

Compound (1) may be comprised from the same R <^1> , and the mixture of R <^1> may be different.

The average added mole number k of ethylene oxide is 3-15, Preferably 3-6 are preferable. If the average added mole number of ethylene oxide is within this range, a good bleaching effect on oil stains is obtained as a bleaching agent. In addition, good storage stability can be obtained, and the dispersibility of microorganisms or stains containing microorganisms can be improved, and a good bacterium migration inhibitory effect can be obtained.

When the component (b-1) is a compound represented by formula (1), the narrow ratio of ethylene oxide is preferably 55% by mass or more, more preferably 70% by mass or more, and the fragrance of the product. 80 mass% or more is more preferable from a viewpoint of making it good.

The narrow rate in this specification shows the ratio of the distribution of the alkylene oxide adduct from which the addition mole number of alkylene oxide differs, and means that it is represented by following formula (S).

Kmax in Formula (S) represents the addition mole number of the alkylene oxide of the alkylene oxide adduct which exists the most in all the alkylene oxide adducts.

i represents the number-of-moles of alkylene oxide added.

Yi represents the ratio (mass%) of the alkylene oxide adduct whose addition mole number of the alkylene oxide which exists in the whole alkylene oxide adduct is i.

The method for producing compound (1) having a high narrow ratio, that is, having a sharp distribution of ethylene oxide is not particularly limited. For example, the reaction product synthesized according to the conventional method from higher alcohol and ethylene oxide may be used in the required molecular weight range by distillation or the like. The method of preparing a thing is mentioned. For example, it is easily obtained by addition-reacting ethylene oxide to aliphatic alcohol etc. using a specific alkoxylation catalyst. In this case, as an alkoxylation catalyst, the alkoxylation catalyst described in Unexamined-Japanese-Patent No. 6-15038 can be used, for example. Specifically, there can be used the ^{3 +} Al, Ga ^{+ 3,} In ^{+ 3,} Tl ^{+ 3,} Co ^3+, Sc ^{+ 3,} La ^{+ 3,} Mn ^{+ 2,} etc., etc. of the magnesium oxide was added to the metal ion. For example, the polyoxyethylene alkyl ether represented by Formula (1) may be prepared by adding ethylene oxide to two or more kinds of alcohols.

It is preferable that hydrophobic parameter logP value is 2.0-5.0, and, as for compound (1), it is more preferable that it is 2.5-4.5. When the logP value is 2.0 to 5.0, the affinity with microorganisms or stains containing microorganisms is high, the effect of inhibiting bacteria movement is excellent, and the cleaning power against stains is also good. When logP value is 2.5-4.5, even if surfactant is low concentration, liquid bleaching composition can be made into a suitable viscosity, for example, splashing of liquid, such as refilling, can be reduced. Examples of the compound of formula (1) include R ¹ = C ₁₂ H ₂₅ , k = 5 (logP = 3.29), R ¹ = C ₁₄ H ₂₉ , k = 5 (logP = 4.08), R ¹ = C ₁₂ H ₂₅ , k = 10 (logP = 4.12), R ¹ = C ₁₂ H ₂₅ , k = 15 (logP = 4.94), and the like.

Hydrophobicity parameters are generally used as parameters representing the properties of the target compound. P (distribution coefficient) in logP value is expressed as P = Co / Cw as a ratio of the activity of the substance in the equilibrium state between water and octanol (wherein Co is the concentration Cw in octanol in water Concentration). Hydrophobicity parameters are described, for example, in Scientific Enrichment No. 122 (1979), page 73.

As a measuring method of the partition coefficient, the Flask Shaking method, the thin layer chromatography method, and the HPLC method are known, but it can be calculated by calculation using parameters such as Ghose, Pritchett, and Crippen (J. Comp. Chem., 9, 80 (1998).

Compound (2): a compound represented by the following general formula (2)

Compound (2) in the present invention is a compound represented by the following General Formula (2).

In Formula (2), x and y are one or more numbers which respectively show the number of methylene groups.

It is x + y = 5-13, Preferably it is 9-11. If it is less than 5, the dispersibility of microorganisms or stains containing microorganisms becomes insufficient, and if it exceeds 13, compatibility with other components in a liquid bleaching composition will fall.

z is the number of 5-30 which shows the average added mole number of ethylene oxide, Preferably it is 5-15. If it is less than 5, the storage stability of a liquid bleaching composition will fall, and if it exceeds 30, the dispersibility of the microorganism or the stain | microorganism containing a microorganism will become inadequate, and a bacterium movement inhibitory effect will fall.

Compound (3): a compound represented by the following general formula (3)

Compound (3) in the present invention is a compound represented by the following General Formula (3).

Equation (3) of _{- [(C 2 H 4 O} ) k1 / (C 3 H 6 O) m1] - shows that the ethylene oxide and propylene oxide are added at random.

In formula (3), R <^2> is a linear or branched alkyl group or alkenyl group. R ² is 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms. If it is less than 8, the dispersibility of microorganisms or stains containing microorganisms becomes insufficient, and if it is more than 18, compatibility with other components in a liquid bleaching composition will fall.

k1 and n1 are 1 or more numbers which show the average added mole number of ethylene oxide, respectively.

k1 + n1 = 3-30, Preferably it is 5-15. If it is less than 3, the storage stability of a liquid bleaching composition will fall, and if it exceeds 30, the dispersibility of the microorganism or the stain | microorganism containing a microorganism will become inadequate, and a bacterium movement inhibitory effect will fall.

m1 is the number of 0.2-5 which show the average added mole number of a propylene oxide, Preferably it is 0.5-5.

Compound (4): a compound represented by the following general formula (4)

Compound (4) in this invention is a compound represented by following General formula (4).

Formula (4) in _{(C 2 H 4 O) k2} - (C 3 H 6 O) m2 - (C 2 H 4 O) n2 represents that in which the ethylene oxide, propylene oxide added to each block.

In formula (4), R <^3> is a linear or branched alkyl group or alkenyl group. R <^3> is 8-18 carbon atoms, Preferably it is 8-16. If it is less than 8, the dispersibility of microorganisms or stains containing microorganisms becomes insufficient, and if it is more than 18, compatibility with other components in a liquid bleaching composition will fall.

k2 and n2 are 1 or more numbers which respectively show the average added mole number of ethylene oxide.

k2 + n2 = 3-30, Preferably it is 5-15. If it is less than 3, the storage stability of a liquid bleaching composition will fall, and if it exceeds 30, the dispersibility of the microorganism or the stain | microorganism containing a microorganism will become inadequate, and a bacterium movement inhibitory effect will fall.

m2 is the number of 0.2-5 which show the average added mole number of a propylene oxide, Preferably it is 0.5-5.

Compound (5): a compound represented by the following general formula (5)

Compound (5) in this invention is a compound represented by following General formula (5).

In formula (5), R <^4> is a linear or branched alkyl group or alkenyl group, Preferably it is a linear or branched alkenyl group.

R <^4> has 9-13 carbon atoms, and 11-13 pieces are preferable from a viewpoint of the storage stability of a liquid bleaching composition, and a bacterium migration inhibitory effect. If it is less than 9, the dispersibility of microorganisms or stains containing microorganisms becomes insufficient, and if it exceeds 13, compatibility with other components in a liquid bleaching composition will fall.

Thus, it is preferable that R <^4> is a C11-C13 linear or branched alkyl group or alkenyl group.

R <^5> is a C2-C4 alkylene group, A C2-C3 alkylene group is preferable and an ethylene group is more preferable. R <^5> may be the same alkylene group as the whole, and 2 or more types of alkylene groups may be mixed.

R <^6> is a C1-C3 alkyl group, Preferably it is a methyl group.

p is the number of 5-30 which show the average added mole number of alkylene oxide, Preferably it is 12-18. If it is less than 5, the storage stability of a liquid bleaching composition will fall, and if it exceeds 30, the dispersibility of the microorganism or the stain | microorganism containing a microorganism will become inadequate, and a bacterium movement inhibitory effect will fall.

When the liquid bleach composition is used as the bleach composition, the bleach composition is often used together with other medical detergents, so that the content of the component (B) is relatively small, and there is little fear of gelation during storage and deterioration in solubility in the wash water. For this purpose, as the component (b-1) used in the bleach composition, for the purpose of enhancing the bleaching effect on the oil stain (hydrophobic stain) of the laundry, Compound (1) and Compound (2) are preferred, and Compound (1) ) Is more preferred.

When making a liquid bleaching composition into the detergent composition containing the bleach of a concentrated type, as a component (b-1), a compound (2)-(5) is preferable and a compound (5) is more preferable. By using such a component (b-1), the detergent composition can ensure good liquidity without causing significant increase in viscosity (gelling) even if the component (B) is contained at a high concentration.

When mix | blending compound (5) with a detergent composition, the narrow ratio of the alkylene oxide in compound (5) is preferable 20 mass% or more, As an upper limit, 80 mass% or less is preferable substantially, 20-60 mass % Is more preferable, and 30-45 mass% is further more preferable from a viewpoint of the improvement of the aging stability at low temperature. The higher the narrow ratio, the better cleaning power is obtained.

Moreover, when a narrow ratio is 20 mass% or more, especially 30 mass% or more, the detergent composition with little raw material odor of compound (5) will be easy to be obtained. This is considered to be because p = 1 or 2 alkylene oxide adduct of General formula (5) contained in compound (5) becomes small. The narrow ratio can be calculated by substituting p in k in the formula (S).

In addition, the said narrow rate can be controlled by the manufacturing method of compound (5), etc. Although it does not specifically limit as a manufacturing method, For example, it can be easily manufactured by the method of addition-polymerizing alkylene oxide to fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (see Unexamined-Japanese-Patent No. 2000-144179). Can be.

The above-mentioned component (b-1) can be used individually by 1 type or in combination of 2 or more types.

The content of the component (b-1) in the liquid bleaching composition can be determined according to the use of the liquid bleaching composition.

When making a liquid bleaching composition into a bleach composition, 0.5 mass% or more and less than 20 mass% are preferable, and, as for content of (b-1) component in a liquid bleach composition, 3 mass% or more and less than 20 mass% are more preferable. If it is 0.5 mass% or more, by using together with (A) component, (C) component, and (D) component, the stain | microorganism containing microorganisms may be disperse | distributed favorably in wash water, and the bacterium movement inhibitory effect on a to-be-washed material can be improved more. . If it is less than 20 mass%, the compounding balance with another component will be taken, and the improvement of the bleaching effect with respect to a hydrophobic stain will be aimed at.

Moreover, when making a liquid bleaching composition into a detergent composition, 20-59 mass% is preferable, and, as for content of (b-1) component in a liquid bleaching composition, 30-55 mass% is more preferable. If the content of the component (b-1) is 20% by mass or more, good cleaning power can be obtained. In addition, it can be set as the concentrated type detergent composition containing a high concentration (B) component, and the effectiveness (product value) as a concentrated type detergent composition becomes high. When the content of the component (b-1) is 59% by mass or less, gelation of the detergent composition on the liquid surface with time becomes difficult to occur, and the film is difficult to be formed on the liquid surface. That is, the liquid stability can be improved.

Moreover, by combining with component (A), component (C) and component (D), it has a function as a detergent composition containing a surfactant at high concentration, improves the dispersibility of the stain containing microorganisms into the wash water, It can increase the effect of inhibiting bacteria movement.

<(b-2) Component: Anionic Surfactant>

(b-2) A component is an anionic surfactant. (b-2) In addition to being able to suppress the leakage of the laundry due to the use of a softening agent or the like (b-2), when the component (B) is contained at a high concentration, it becomes difficult to gel the liquid surface of the liquid bleaching composition; In addition, it is possible to further improve the bacteriostatic effect on the laundry.

It does not specifically limit as a component (b-2), The thing mix | blended with a conventional detergent composition and bleach composition can be used. Especially, linear alkylbenzene sulfonic acid or its salt (LAS), alkyl sulfate (AS), polyoxyethylene alkyl ether sulfate (AES), (alpha)-olefin sulfonate (AOS), and alkanesulfonate are used preferably.

As LAS, the C8-C16 thing of an alkyl group is preferable, and the C10-C14 thing is more preferable.

As AS, the C10-C20 thing of alkyl is preferable.

As AES, the C10-C20 thing of an alkyl group is preferable, and a C10-C14 thing is more preferable. Moreover, 1-10 are preferable and, as for the average added mole number of ethylene oxide, 1-4 are more preferable.

Moreover, AES has a distribution ratio of the ethylene oxide adduct which comprises AES, Preferably it is 55 mass% or more, More preferably, it is 55-75 mass%. The distribution ratio of ethylene oxide adducts is (tmax-1), tmax and (tmax +) for the total ethylene oxide adducts when the number of moles of ethylene oxide of the ethylene oxide adduct most present on a mass basis is set to "tmax". It can obtain | require as a ratio of the sum total of the ethylene oxide adducts of 1).

As AOS, the C10-C20 thing of an alkyl group is preferable.

As alkanesulfonate, it is preferable that carbon number of an alkyl group is 10-20, and it is more preferable that carbon number is 10-14. Moreover, it is preferable that it is a secondary alkanesulfonate.

Especially, linear alkylbenzene sulfonate, AES, and an alkanesulfonate are preferable, and an alkanesulfonate is more preferable.

These (b-2) components can be used individually by 1 type or in combination of 2 or more types.

Examples of the salt constituting the component (b-2) include alkali metal salts such as sodium salts and potassium salts, alkanolamine salts such as monoethanolamine salts and diethanolamine salts. Especially, alkali metal salts, such as a sodium salt and potassium salt, are preferable.

Although content of (b-2) component in a bleaching composition is not specifically limited, For example, 1-10 mass% is preferable, 1-5 mass% is more preferable, It is further more preferable that it is 2-5 mass%. When it is 1 mass% or more, there exists a possibility that the further improvement of the bacteriostatic effect on medical care may not be aimed at. In addition, there is a possibility that the effect of inhibiting the leakage of the laundry due to the use of the softening agent product may be insufficient, and when the component (B) is contained at a high concentration, there is a possibility of causing gelation of the liquid bleaching composition itself.

Surfactants other than (b-1) component and (b-2) component can be suitably used for the liquid bleaching composition of this invention according to a use or a purpose.

<(C) component: chelating agent>

In the present invention component (C) is the logarithmic value of the chelate stability constants for Ca ^{2 +} 5.5 or more, the logarithmic value of a chelating stability constant of the Fe ^{3 +} 10 or more, and the chelate stability constants for Cu ^{2 +} It is a chelating agent whose logarithm value is ten or more.

Component (C) is the common logarithm value of the chelate stability constant K for the Ca ^{2 +} (logK = chelating constant) is 5.5 or higher. By using such a component (C), the bacterium migration inhibitory effect can be exhibited.

It is considered that the microorganisms in the wash water containing a large amount of microorganisms are contained in stains of sebum and the like (including fatty acids and the like). These stains adhere to the laundry with the microorganisms during washing, after which the microorganisms increase in the laundry. The stain in the wash water containing a lot of microorganisms is believed to contain calcium derived from stains such as tap water, sebum, and the like, and these are used as binders attached to the laundry. It is preferable to use the chelating agent with a high chelating effect with respect to this calcium ion for (C) component, and can use together with (D) component mentioned later, and can suppress the adhesion of the stain | microbial-containing stain to the wash object.

LogK values for the Ca ^{2 +} a (C) component is at least 5.5, more preferably at least 6.5. If logK values for the Ca ^{2 +} is less than 5.5 can not be sufficiently captured calcium ions becomes insufficient bacteria migration inhibitory effect. The upper limit of logK is not particularly limited but is 15 or less.

Component (C) will more than logK values for Fe ^{3 +} 10, more preferably not less than 12 logK. When trace amount of iron ion exists in the composition containing hydrogen peroxide, the stability of the coexisting (A) component will fall, a bleaching effect will fall, and a bacterium movement inhibitory effect will become inadequate. In addition, when the liquid bleaching composition is preserved, there is a fear of clouding or coloring.

If logK values for Fe ^{3 +} is less than 10 can not be sufficiently captured iron ions lowers the bleaching effects as well as the bacteria become insufficient migration inhibitory effect. The upper limit of the logK for Fe ^{3 +} is not particularly limited, 30 or less.

Component (C) will more than logK values for Cu ^{2 +} 10, more preferably not less than 12 logK. When trace amount of copper ion exists in the composition containing hydrogen peroxide, the stability of the coexisting (A) component will fall, a bleaching effect will fall, and a bacterium movement inhibitory effect will become inadequate. In addition, when the liquid bleaching composition is preserved, there is a fear of clouding or coloring.

Can not sufficiently capture the copper ion is logK value is less than 10 lowers the bleaching effect of the Cu ^{2 +} as well as the bacteria become insufficient migration inhibitory effect. The upper limit of the logK for Cu ^{2 +} is not particularly limited, 25 or less.

Chelate stability constant is calculated | required by following formula (I).

Parallel reaction between metal ions and chelating agent M + AZ⇔MZ _A M: metal ion, Z: chelating agent, MZ: complex salt, A: number of Z bound to 1 M, [MZ _A ]: MZ The concentration of _A (mol / L), [M]: concentration of M (mol / L), and [Z]: concentration of Z (mol / L) are shown.

As the component (C), 1-hydroxy ethane-1,1-diphosphonic acid (logK value Fig tight Catalog 13th Edition, 1964 (from DOJINDO LABORATORIES catalog and BRIQUEST, ^{1994, ALBRIGHT &WILSON]; Ca 2} + such as ^{/ Fe 3 + / Cu 2 +} = 6.5 / 16.2 / 125, below shows the same), nitrilotriacetic methylenephosphonic acid (7.9 / 14.6 / 17.7), ethylenediamine tetrakis methylenephosphonic acid (94 / 19.6 / 23.2) Organophosphonic acid derivative, nitrilo triacetic acid (6.41 / 15.87 / 12.96), ethylenediamine tetraacetic acid (10.96 / 25.1 / 18.80), hydroxyethylethylenediamine triacetic acid (8.5 / 19.8 / 17.6), diethylenetriamine pentaacetic acid (10.74 / 28.6 / 21.53), organic acids, such as amino polyacetic acids, such as triethylene tetraamine hexaacetic acid (10.06 / 26.8 / 19.2), and tetrasodium dicarboxymethyl glutamic acid (11.0 / 20.5 / 17.5), are mentioned, for example. Among them, organic phosphonic acid derivatives are preferred, and 1-hydroxyethane-1,1-diphosphonic acid having a lower molecular weight is more preferred. The main commercial products of 1-hydroxyethane-1,1-diphosphonic acid include BRIQUEST ADPA (manufactured by ALBRIGHT & WILSON), Kirest PH-210 (manufactured by CHELEST CORPORATION), DEQUEST2010 (manufactured by Monsanto), and the like. Similar effects are obtained even when used.

0.1-5 mass% is preferable, and, as for content of (C) component in a liquid bleaching composition, 0.3-3 mass% is more preferable. If it is less than 0.1 mass%, there exists a possibility that a bacterium movement inhibitory effect may become inadequate, and when it exceeds 5 mass%, there exists a possibility that the stability of a liquid bleaching composition may be impaired.

<Component (D): Cationic Polymer>

Component (D) in the present invention is at least one cationic polymer selected from a biguanide-based polymer (hereinafter, (d-1) component) and a dimethyldiallylammonium-based polymer (hereinafter, (d-2) component). . The liquid bleaching composition can exhibit a bactericidal and antibacterial effect by containing the component (D), and also contain the component (C) and the component (D).

<(d-1) Component: Biguanide-based Polymer>

(d-1) A component is a biguanide type polymer. As a preferable (d-1) component, polyalkylene biguanide compounds, such as the polyhexamethylene biguanide compound represented by following General formula (6), are mentioned, for example.

In said formula (6), q is 2-14, Preferably it is 11-13, More preferably, it is 12.

HY represents an organic acid or an inorganic acid, hydrochloric acid, gluconic acid and acetic acid are preferable, and hydrochloric acid is more preferable.

As a polyhexamethylene biguanide compound, a commercially available thing can be used, The poly (hexamethylene biguanide) hydrochloride whose q of the said General formula (6) is 12, and a brand name Proxel IB (trademark) are mentioned.

<< (d-2) component: Dimethyl diallyl ammonium polymer >>

The component (d-2) is a dimethyldiallyl ammonium polymer. As a preferable (d-2) component, the polymer obtained by superposing | polymerizing the dimethyl diallyl ammonium salt shown to following General formula (7) is mentioned.

As an especially preferable polymer, it is represented by following General formula (8).

X <^-> in Formula (7) and (8) represents arbitrary anions, such as a chloride ion and a bromide ion. c is an average polymerization degree, It is preferable that it is the range of 6-30000, More preferably, it is 20-6000, More preferably, it is the range of 30-3000.

Commercially available products of such a component (d-2) include MERQUAT100 (manufactured by Calgon), Adekaka Cio Ace PD-50 (manufactured by ADEKA CORPORATION), DIDOL EC-004, DIDOL HEC, and DIDOL EC (DAIDO CHEMICAL CORPORATION). Can be mentioned.

As the above-mentioned component (D), one kind of d-phase selected from the component (d-1) and the component (d-2) can be used. Preference is given to poly (hexamethylenebiguanide) hydrochlorides having a valence of 12. By using (D) component in which such a main chain is comprised from the monomer which has a cationic group, a liquid bleaching composition can exhibit a bacterium migration inhibitory effect and an antibacterial effect.

0.001-2 mass% is preferable, and, as for content of (D) component in a liquid bleaching composition, 0.01-2 mass% is more preferable. If it is 0.001 mass% or more, a bacteria movement inhibitory effect and an antibacterial effect are favorable, and when it exceeds 2 mass%, there exists a tendency for the storage stability of a liquid bleaching composition to fall.

It is especially preferable that the mass ratio represented by (C) component / (D) component in a liquid bleaching composition is 1-1000. By carrying out in the said range, a bacteria movement suppression effect can be improved synergistically. If the component (C) / (D) is less than 1, calcium in the wash water cannot be sufficiently captured, and adsorption to the stain containing microorganisms of the component (D) tends to decrease, resulting in a deterioration of the bacteria movement inhibitory effect. . On the other hand, when (C) component / (D) component is more than 1000, the anionic part of (C) component and (D) component become easy to form a complex. When the (D) component forms a complex, cationicity will fall, adsorption to the stain | microorganism containing microorganisms will fall, and there exists a tendency for a bacterium movement inhibitory effect to fall.

<Optional ingredients>

The liquid bleaching composition can contain the following optional components as needed in the range which does not impair the effect of this invention.

<< bleach activator >>

As the bleach activator, tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate , Octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, decanoyloxybenzene, undecanoyloxybenzene And organic peracid precursors such as dodecanoyloxybenzene, and one or more of them can be used. Among them, sodium nonanoyloxybenzene sulfonate, sodium dodecanoyloxybenzene sulfonate, and decanoyloxybenzoic acid are preferable. Can be used.

0.1-5 mass% is preferable from a viewpoint of the improvement of bleaching power, storage stability, economy, etc., and, as for content of the bleach activator in a liquid bleaching composition, 0.1-2 mass% is more preferable.

<< radical trap agent component >>

As the radical trapping agent, a phenolic radical trapping agent is preferably used. In particular, when the pH of the liquid bleaching composition is 5 or more, the decomposition of the component (A) may not be sufficiently suppressed only by the addition of the component (C) described above. Preference is given to using together with the components. In addition, when the liquid bleaching composition is applied to clothing and left to stand for a long time, abnormal decomposition of component (A) may occur due to components such as metal (A) that are highly reactive with component (A), resulting in damage to the laundry. .

In such a case, when the phenolic radical trapping agent is added to the liquid bleaching composition, damage to the object to be washed can be suppressed.

Phenolic radical trapping agents are phenols and phenol derivatives, and examples of the phenol derivatives include compounds having phenolic OH groups, ester derivatives of phenolic OH groups, ether derivatives, and the like. The substitution position may be any of an ortho position, a meta position, and a para position. Especially, the compound which has phenolic OH group is more preferable. Among them, GE Penketh, J. Appl. Chem ", 7, 512-521 pages (1957) The compound whose redox potential (0.P.) _o is 1.25V or less is preferable, and the compound which is 0.75V or less is more preferable. Among these, dimethoxyphenol, catechol, hydroquinone, 4-methoxyphenol, dibutylhydroxytoluene (BHT), and the like are more preferable, and 4-methoxyphenol is particularly preferable.

The content of the radical trapping agent in the liquid bleaching composition is preferably 0.01 to 6% by mass, more preferably 0.05 to 1% by mass, from the viewpoint of the decomposition suppression effect of the component (A), economical efficiency, and the like.

<< pH regulator >>

As a pH adjuster, Inorganic acids, such as hydrochloric acid, a sulfuric acid, phosphoric acid; organic acids such as p-toluenesulfonic acid, citric acid and phosphonic acid derivatives; Sodium borate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen chloride, monoethanolamine, diethanolamine, triethanolamine, ammonia and the like can be used. It is preferable to set pH of the liquid bleaching composition of this invention to 2-7, and various pH adjusters can be used so that it may become desired pH.

<< high trough product >>

As a trotrope agent, Alcohol, such as ethanol, 1-propanol, 2-propanol, 1-butanol; Glycols such as propylene glycol, butylene glycol and hexylene glycol; Polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of about 200, polyethylene glycol having a weight average molecular weight of about 400, and dipropylene glycol; Water-miscible organic solvents, such as alkyl ethers, such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether, can be used. It is preferable that content of the said organic solvent is 0.1-15 mass% in a liquid bleaching composition.

In addition, the liquid detergent composition can use a viscosity reducing agent or solubilizer, such as paratoluenesulfonic acid, a benzoate, and urea. It is preferable that content of the said viscosity reducing agent or a solubilizer is 0.01-10 mass% in a liquid detergent composition. When measuring the viscosity of a liquid bleaching composition using a cap etc., it is preferable to adjust to 10 mPa * s-300 mPa * s.

Inorganic salts

As inorganic salts, sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium carbonate and the like can be used.

<< boric acid compound >>

Examples of the boric acid compound include orthoboric acid (H ₃ BO ₃ ); It can be given or (BO ₄ ^5-) a salt of making a salt thereof, or an anion which they are condensed (the condensed borate), etc. ^- boric acid ion ₍₃ BO ^3).

As a salt, Alkali metal salts, such as a sodium salt and potassium salt; Alkanolamine salts such as monoethanolamine salt and diethanolamine salt; Ammonium salt etc. are mentioned. Especially, an alkali metal salt is preferable and a sodium salt and potassium salt are more preferable.

Among the above-mentioned boric acid compounds, orthoborate, sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium tetraborate, ammonium tetraborate, and the like are particularly preferable, and orthoborate and sodium tetraborate are more preferable. As said sodium tetraborate, hydrous salts, such as sodium tetraborate pentahydrate and sodium tetraborate pentahydrate (borax), are especially preferable.

A boric acid compound can be used 1 type or in mixture of 2 or more types.

Content of the boric acid compound in a liquid bleaching composition is not specifically limited, 0.2-10.0 mass% is preferable, and 1-5 mass% is more preferable. If the content of the boric acid compound as the use of the sodium borate whiskers 4 also shows the 4-sodium borate (Na ₂ B ₄ O _7), a density (i.e., Na ₂ B ₄ O ₇ amount) calculated in terms of. When content of a boric acid compound is 0.2 mass% or more, the removal efficiency with respect to the aqueous stain of a liquid bleaching composition especially improves. On the other hand, when content of a boric acid compound is 10.0 mass% or less, the storage stability in low temperature at the time of using a liquid bleaching composition as a detergent composition improves.

"Spices"

You may mix | blend a fragrance with the liquid bleaching composition for the purpose of the value added improvement of a product, etc.

A fragrance | flavor is a fragrance | flavor composition which is a mixture which consists of a fragrance raw material single substance, a fragrance raw material, a fragrance | solvent solvent, a fragrance stabilizer, etc.

Although content of the fragrance | flavor in a liquid bleaching composition is not specifically limited, Preferably it is 0.0001-15 mass%, More preferably, it is 0.001-10 mass%.

A list of fragrance raw materials used as fragrances can be found in various literatures such as Perfume and Flavor Chemicals, Vol. I and II, Steffen Arctander, Allured Pu b. C0. (1994) and Synthetic Perfume Chemistry and Product Knowledge, Motoichi, India, Chemical Daily (1996) and Perfume and Flavor Materials of Natural Origin, Steffen Arctander, Allured Pub. C0. (1994) and Encyclopedia of Fragrances, Japan Fragrance Association, Asakura Bookstore (1989) and Perfumery Material Performance V.3.3, Boelens Aroma Chemical Information Service (1996) and Flower oils and Floral Compounds In Perfumery , Danute Laja ujis Anonis, Allured Pub. C. (1993) and the like.

As a fragrance solvent, for example, ethanol, acetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), ethylene glycol dibutylate, hexylene glycol, dibutyl sebacate, deltyl extra (iso) Propyl myristate), methylcarbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzoic acid benzyl, propylene glycol, diethyl phthalate, tripropylene glycol, ac Borin (dimethylphthalate), delta prime (isopropyl palmitate), dipropylene glycol DPG-FC (dipropylene glycol), farnesine, dioctyl adipate, tributyline (glyceryl tributanoate), hydrolite- 5 (1,2-pentanediol), propylene glycol diacetate, cetyl acetate (hexadecyl acetate), ethyl abietate, avarine (methyl abietate), citroflex A-2 (acetyl tree Tyl Citrate), Citroplex A-4 (tributylacetyl citrate), Citroflex N0.2 (triethyl citrate), Citroflex N0.4 (tributyl citrate), Drapix (methyldi Hydroaviate), MITD (isotridecyl myristate), polylimonene (limonene polymer), propylene glycol, 1, 3- butylene glycol, etc. are mentioned.

The content of the fragrance solvent in the fragrance composition is preferably 0.1 to 99% by mass, more preferably 0.1 to 10% by mass.

Examples of the fragrance stabilizer include dibutylhydroxytoluene, butylhydroxyanisole, vitamin E and its derivatives, catechin compounds, flavonoid compounds, and polyphenol compounds. Among them, dibutylhydroxytoluene is preferable.

Content of the fragrance stabilizer in fragrance composition becomes like this. Preferably it is 0.0001-10 mass%, More preferably, you may be 0.001-5 mass%.

(Manufacturing method)

The manufacturing method of the liquid bleaching composition of this invention is not specifically limited, It can manufacture according to a conventional method.

For example, the components (A) to (D) and optional components are dissolved in water (ion-exchanged water) so as to have a desired compounding amount in terms of the net fraction of each component, if necessary, and dissolved in a pH adjuster (acidic substance, By using an alkaline substance) to adjust to a predetermined pH.

(Storage container)

It does not specifically limit as a container which accommodates a liquid bleaching composition, It can accommodate in the container generally used. For example, a nozzle type container with a metering cap, an intermediate plug type container, a squeeze container or a pump container with an automatic metering device or a simple metering device, a trigger container or a squeeze container for spraying or foaming a liquid, And an application container having a coating surface to which liquid is applied, and a refill container (pouch, thin bottle, replacement bottle, etc.).

Although the container which accommodates the liquid bleaching composition in this invention is not specifically defined, As a container which accommodates a hydrogen peroxide formulation, it is disclosed by Unexamined-Japanese-Patent No. 2003-338997, Unexamined-Japanese-Patent No. 11-100594, etc., for example. It is preferable.

(How to use)

Examples of the method for using the liquid bleaching composition of the present invention include a method of putting the liquid bleaching composition into water together with the laundry to be washed, a method of dissolving it in water beforehand and immersing the laundry into it.

Moreover, after apply | coating a liquid bleaching composition to a to-be-washed thing, it may be left to stand suitably and you may perform normal washing after that.

As mentioned above, the liquid bleaching composition of this invention exhibits the outstanding bacterium movement suppression effect and antibacterial effect by containing (A)-(D) component. In particular, even when water containing a large amount of microorganisms such as the remaining water after bathing is used for washing, the bacterium migration inhibitory effect and the antibacterial effect are remarkable.

The mechanism by which the liquid bleaching composition of the present invention exerts the bacterium migration inhibitory effect and the antibacterial effect is not certain, but is estimated as follows. First, component (A) decomposes some of the microorganisms in the wash water and reduces the number of live bacteria in the wash water. In addition, the component (C) traps the calcium present in the form of fatty acid calcium and the like in the stain containing microorganisms, and the component (D) having cationicity in anionic portions such as fatty acids in the stain is easily adsorbed. The stain containing microorganisms can be improved in dispersibility in the wash water by covering the surface with the component (D), and can also be dispersed in the wash water by the component (B) to inhibit the attachment of the microorganisms to the laundry. It is considered to be possible. In addition, the component (D) is adsorbed on the laundry to exhibit an antibacterial effect after washing, and inhibits the growth of microorganisms adhered to the laundry.

As a result, the liquid bleaching composition is considered to exert a bacteriostatic effect and an antimicrobial effect in addition to the cleaning function and the bleaching function.

Example

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

(Raw materials used)

<(A) component: Hydrogen peroxide>

A-1: Hydrogen peroxide (made by MITSUBISHI GAS CHEMICAL COMPANY, INC.).

<Component (B): Surfactant>

<b-1: nonionic surfactant>

b-1-1: The nonionic surfactant which added an average of 5 mol of ethylene oxide to natural alcohol (C12 / C14 = 7/3), and the narrow ratio of ethylene oxide are 84 mass% (LION CHEMICAL CO., LTD. The NLME3-90 (90 mass% product of pure components) and the compounding quantity in a table | surface show a value (mass%) as a pure component, and is equivalent to compound (1).

b-1-2: C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₁₅ OCH ₃ / C ₁₃ H ₂₇ CO (OC ₂ H ₄ ) ₁₅ OCH ₃ = 8/2 (mass ratio), Narrow ratio 33 mass %, Composite. Equivalent to compound (5).

b-1-3: A nonionic surfactant obtained by randomly adding 4 mol of ethylene oxide and 2 mol of propylene oxide to a natural alcohol (C12 / C14 = 7/3) and then adding 10 mol of ethylene oxide. Equivalent to compound (3).

b-1-4: Polyoxyethylene alkyl ether (made by NIPPON SHOKUBAI CO., LTD., "SOFTANOL 90", the polyoxyethylene alkyl ether of x + y = 9 and z = 9 in the said General formula (2); , a mixture of polyoxyethylene alkyl ether having x + y = 11 and z = 9). Equivalent to compound (2).

b-1-5: Nonionic surfactant which added on average 8 mol of ethylene oxide to the natural alcohol (C12 / C14 = 7/3). Reox CC-80H-90 (90% by mass product) made by LION CHEMICAL CO., LTD. Equivalent to compound (1).

B-2: anionic surfactant

b-2-1: Neutralization of LAS and linear alkyl (10-14 carbon atoms) benzenesulfonic acid [manufactured by LION CORPORATION, "Lipon LH-200 (LAS-H)", pure 96 parts by mass)] with sodium hydroxide . The compounding quantity in a table | surface shows the value (mass%) as linear alkyl (C10-C14) benzenesulfonate sodium salt.

b-2-2: Secondary sodium alkanesulfonic acid (manufactured by Clariant (Japan) K.K., trade name "SAS30" (30% of pure fraction)), and the compounding quantity in a table | surface show the value (mass%) as pure component.

<< b-3: cationic surfactant >>

b-3-1: dodecyltrimethylammonium chloride (made by Tokyo Chemical Industry Co., Ltd.)

<(C) component: chelating agent>

Or less Ca ^{2 +} chelating constant logK values for the Ca ^{2 +,} Fe ^{3 +} chelate constant logK value, Cu ^{+ 2} chelate constant for Fe ^{3 +} represents a logK values for Cu ^{+ 2.}

C-1: 1- hydroxy ethane-1,1-diphosphonic acid (Rhodia Japan Ltd., trade name: "Perry Oaks 115"), Ca ^{2 +} chelating constant = 6.5, Fe ^{3 +} chelate constant = 16.2, Cu ^{2 +} Chelate integer = 12.5.

C-2 (comparative product): citric acid 1 beard (.. FUSO CHEMICAL CO, LTD claim), Ca ^{2 +} chelating constant = 4.68, Fe ^{3 +} chelate constant = 12.5, Cu ^{2 +} chelating constant = 4.35.

<Component (D): Cationic Polymer>

D-1: Poly (hexamethylene biguanide) hydrochloride, (Arch Chemicals Japan, Inc. make, brand name "Proxel IB")

D-2: dimethyldiallyl ammonium chloride polymer (made by NALCO company, brand name "Merquat100")

D-3 (comparative product): cationized cellulose (product made from TOHO Chemical Industry Co., Ltd., a brand name "casinal HC-100")

(Optional component)

Boric acid compound: Sodium tetraborate pentahydrate (Borax company make, brand name "Neobor").

Radical trapping agent: 4-methoxy phenol (made by Kawaguchi Chemical Industry Co., Ltd., brand name "MQ-F").

Hytrotropes A: Ethanol (NEDO company make, brand name "95vol% synthetic ethanol").

Butyl carbitol (made by Kyowa Hakko Kogyo Co., Ltd.), brand name "butyl carbitol 95-P".

Monoethanolamine (made by Nippon Shokubai Co., Ltd., brand name "monoethanolamine dilution product (75%)".

Propylene glycol (made by BASF Corporation).

In addition, the detail of sulfuric acid and sodium hydroxide used as a pH adjuster is as follows.

Sulfuric acid (product of TOHO ZINC CO., LTD.)

Sodium hydroxide (manufactured by TSURUMI SODA CO., LTD.)

Fragrance composition: Fragrance compositions A-D of Tables 1-6 were used.

Production Example 1 Synthesis of b-1-2

The synthetic product manufactured according to Production Example 1 in Examples described in JP-A-2000-144179 was used.

Firing obtained by calcining a hydroxide oxide alumina magnesium (manufactured by KYOWA CHEMICAL INDUSTRY CO. LTD., Kyowa 300) having a chemical composition of 2.5 MgO Al ₂ O ₃ nH ₂ O at 600 ° C. for 1 hour under nitrogen atmosphere. 2.2 g of hydroxide hydroxide alumina magnesium (unmodified) catalyst, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester were injected into a 4 L autoclave, and The catalyst was reformed at. Subsequently, after replacing the inside of the autoclave with nitrogen, the temperature was raised, and 1052 g of ethylene oxide was introduced and reacted while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa.

Furthermore, the reaction liquid was cooled to 80 degreeC, 159 g of water and 5 g of activated clay and diatomaceous earth were respectively added as a filtering aid, and the catalyst was filtered off and b-1-2 was obtained.

The narrow ratio of b-1-2 was 33 mass% by adjusting the alkali addition amount with respect to a catalyst.

Production Example 2 Synthesis of b-1-3

224.4 g of "CO-1270" made by P & G Co., Ltd. and 2.0 g of 30 mass% NaOH aqueous solution were extract | collected in the pressure-resistant reaction container, and the inside of the container was nitrogen-substituted. Subsequently, after dehydrating for 30 minutes at the temperature of 100 degreeC and the pressure of 2.0 kPa or less, temperature was heated up to 160 degreeC. While stirring the alcohol, 176 g of ethylene oxide (gas phase) and 116 g of propylene oxide were gradually added into the liquid of the alcohol while adjusting the rate of addition so that the reaction temperature did not exceed 180 ° C by using a blowing tube. Subsequently, 440 g of ethylene oxide (gas phase) was introduced to further react.

After completion of the addition, the mixture was aged at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide and propylene oxide were distilled off at a temperature of 180 ° C. and a pressure of 6.0 Pa or less for 10 minutes. Subsequently, after cooling the temperature to 100 degrees C or less, 70 mass% p-toluene sulfonic acid was added and neutralized so that pH of the 1 mass% aqueous solution of a reactant might be about 7, and b-1-3 was obtained.

(Assessment Methods)

<Bacteria migration inhibitory effect A>

As wash water, the thing after the bathing of the remaining water (41 degreeC, 160 L) after 4 adult males bathing for 10 minutes was used. About Examples 1-15 and Comparative Examples 1-10 (bleach composition), 1.2 g of detergent (JAFET standard detergent, textile product new functional evaluation meeting designation detergent), and 0.6 g of the liquid bleaching composition of each case were adjusted to 25 degreeC, It added to 900 mL of water, and set it as the washing | cleaning liquid. About Examples 16-26 and Comparative Examples 11-18 (detergent composition), 0.6 g of the liquid bleaching composition of each case was adjusted to 25 degreeC, and it added to 900 mL of water, and set it as the washing | cleaning liquid. The laundry was washed in the following order using an alcohol sterilized Terg-O-Tometer (Ueshima Seisakusho Co., Ltd., detergency tester MS-8220), and the effect of inhibiting bacterial migration to a test cloth was evaluated.

3cm × 3cm of 3cm × 3cm of Canekin No. 3 (test cloth) and 3cm × 3cm cut off from the toe side of the daily wearing socks of adult men Two fold cloths and a sterilized Maryas cloth were put, and this was wash | cleaned under the conditions of 120 rpm and 25 degreeC by 20 times of bath ratio (mass ratio represented by wash water / to wash object). The mass of the object to be washed is the sum of the test cloth, silo gupo and meriyasu cloth.

Then, dehydration was carried out for 1 minute, and rinsing was performed for 2 minutes with 900 mL of 25 degreeC tap water, and dehydration was carried out for 1 minute.

After dehydration, a food stamp (manufactured by NISSUI PHARMACEUTICAL CO., LTD.) Was pressed on a test cloth and incubated at 37 ° C. for 24 hours to measure colony count. This colony number was classified and evaluated by the following evaluation criteria.

"Evaluation standard"

◎: 0 to 9 pieces (slightly stained)

○: 10 to 29 (stained with hardness)

(Triangle | delta): 30-99 pieces (medium stain)

×: 100 or more (medium stain)

<Bacteria migration inhibitory effect B>

I assume tap water from the general domestic faucet of the area where the water environment is poor as washing water, and, as Staphylococcus aureus (1x10 ⁶ CFU / mL) and an organic substance, a protein (gelatin: product made by NITTA GELATIN INC., A brand name "gelatin APH-100 &quot;) was used to add 10 µg / mL. About Examples 1-15 and Comparative Examples 1-10 (bleach composition), the washing | cleaning which adjusted 1.2 g of detergents (JAFET standard detergent, textile product new functional evaluation meeting designation detergent), and 0.6 g of liquid bleaching compositions of each case to 25 degreeC It added to 900 mL of water, and it was set as the washing | cleaning liquid. About Examples 16-26 and Comparative Examples 11-18 (detergent composition), 0.6 g of the liquid bleaching composition of each case was added to 900 mL of wash water adjusted to 25 degreeC, and it was set as the washing liquid. The laundry to be washed was washed in the following procedure using Terg-O-Tometer (manufactured by Ueshima Seisakusho Co., Ltd., washing power measuring device MS-8220) that had been alcohol sterilized in advance, and the effect of inhibiting bacterial migration to a test cloth was evaluated.

3cm × 3cm of 3cm × 3cm of Canekin No. 3 (test cloth) and 3cm × 3cm cut off about 10cm from tiptoe side of adult men's daily wearing socks Two pieces of cloth) and a sterile Maryas cloth were put, and this was wash | cleaned under the conditions of 120 rpm and 25 degreeC by 20 times of bath ratio (mass ratio represented by the wash water / wash product). The mass of the object to be washed is the sum of the test cloth, silo gupo and meriyasu cloth.

Then, dehydration was carried out for 1 minute, and rinsing was performed for 2 minutes with 900 mL of 25 degreeC tap water, and dehydration was carried out for 1 minute.

After dehydration, the food stamp (product made by NISSUI PHARMACEUTICAL CO., LTD.) Was pressed on a test cloth, and colony number was measured after incubation at 37 ° C for 24 hours. This colony number was classified and evaluated by the following evaluation criteria.

"Evaluation standard"

◎: 0 to 9 pieces (slightly stained)

○: 10 to 29 (stained with hardness)

(Triangle | delta): 30-99 pieces (medium stain)

×: 100 or more (medium stain)

Sterilization Effect on Cleaning Solution

The bactericidal effect was evaluated by measuring the number of bacteria in the remaining water after the bath used in the evaluation of "<bacteria movement inhibitory effect A>" and the washing | cleaning liquid after washing | cleaning.

The remaining water after bathing or 1 mL of washing solution after washing was mixed in a 50 ° C standard agar medium (manufactured by NIHON PHARMACEUTICAL CO., LTD.) And cultured at 37 ° C for 24 hours, and then the number of colonies was measured. Saved. The susceptibility value was calculated | required by the following (i) formula from the calculated number of live bacteria.

Reduction value = log ₁₀ (the number of live bacteria of the remaining water after a bath)-log ₁₀ (the number of living bacteria of the washing liquid after washing) ... (i)

The obtained sensitization value was classified by the following evaluation criteria to evaluate the bactericidal effect on the cleaning liquid.

"Evaluation standard"

A: Reduction value is 2.0 or more

B: Decrease value is greater than 1.0 and less than 2.0

C: Decrease value is greater than 0 and less than 1.0

D: Decrease value is 0 or less

Antibacterial Effect

About Examples 1-15 and Comparative Examples 1-10 (bleach composition), 1.2 g of detergent (JAFET standard detergent, textile product new functional evaluation meeting designation detergent), and 0.6 g of liquid bleaching composition of each case were added to 900 mL of tap water, and a washing | cleaning liquid I did. About Examples 16-26 and Comparative Examples 11-18 (detergent composition), 0.6 g of the liquid bleaching compositions of each case were added to 900 mL of tap water, and it was set as the washing | cleaning liquid. 0.4g of 3cm × 3cm Kanekin No. 3, which had been sterilized using Terg-O-Tometer of USTesting Co., Ltd. (USA), which had been previously sterilized with alcohol, was placed in a sterilized Maryas cloth. 20 times and it wash | cleaned on 120 rpm and 25 degreeC conditions. It washed with 10 minutes, then dehydrated for 1 minute, rinsed with 900 mL of tap water for 2 minutes, and dehydrated for 1 minute. Washed 3 cm x 3 cm of Kanekin No. 3 was dried in a clean bench at room temperature for 24 hours to obtain a test cloth.

About this test cloth, bacteriostatic activity value was calculated | required by following formula (ii) according to the quantitative test method (bacterial liquid absorption method) of JISL1902 (antimicrobial test method and antibacterial effect of a textile product).

Bacteriostatic activity value = (Mb-Ma)-(Mc-Md) (ii)

Ma: Average value of the common logarithmic values of the viable cell count of 3 specimens of a standard cloth immediately after inoculation of test bacteria

Mb: The average value of the common logarithm value of the number of viable cells of 3 specimens after incubation for 18 hours at 35 ° C. of a standard cloth after inoculation of test bacteria.

Mc: Average value of the common logarithmic values of the live bacterial count of 3 specimens of the test cloth immediately after inoculation

Md: The average value of the common logarithm of the number of living bacteria of 3 specimens after incubation for 18 hours at 35 ° C. of the test cloth after inoculation of the test bacteria

Standard fabric: 3cm × 3cm canekin 3 after microsterilization

Test bacterium: Staphylococcus aureus

The bacteriostatic activity obtained by the formula (ii) was classified according to the following evaluation criteria to evaluate the antimicrobial effect.

"Evaluation standard"

A: bacteriostatic value is greater than 2.5

B: bacterium activity value is 2.0-2.5

C: bacteriostatic activity value is 1.0 or more and less than 2.0

D: bacteriostatic value is greater than 0 and less than 1.0

E: bacteriostatic value is 0 or less

<Storage stability>

500 mL of the liquid bleaching composition of each case was filled in the container made of plastic, the cap was tightly closed, it was left to stand in a constant temperature room of 50 degreeC for 1 month, and expansion of the container was visually judged by the following evaluation criteria.

The container used for the test of storage stability is demonstrated using FIG. 1 is a front view of a container 1 used for a test of storage stability.

As shown in FIG. 1, the container 1 includes a container main body 3, a nozzle cap 5 screwed to an inlet of the container main body 3, and a metering screw detachably screwed to the nozzle cap 5. It consists of a cap 2 schematically. The container main body 3 is a user cylindrical shape which consists of a substantially circular bottom part 3b in planar view, and the trunk part 3a which is located in the circumferential edge of the bottom part 3b. The bottom part 3b has a shape in which the center part Q is recessed toward the inside of the container main body 3.

The metering cap 2 is a single-layered cap having a single structure composed of a cap body 2a and a threaded portion 2b formed at the lower end side thereof. The nozzle cap part 5 is provided with the nozzle part which is not shown in figure, and a cap main body, and is an external fitting type in which the screw part in which the screw part 2b is screwed on the upper end side of the said cap body is formed.

The container body 3 consists of 97 mass% of high density polyethylene (made by Mitsui Chemicals, Inc.), and 3 mass% of blue pigments (PE-MAZ MAl058 blue, DAINICHISEIKA COLOR & CHEMICALS MFG.CO., LTD.), The average thickness of the trunk | drum 3a was set to 1.0 mm and the recessed depth D of the bottom part 3b = 5.0 mm. The material of the nozzle cap 5 is 98.0 mass% of polypropylene (manufactured by Mitsui Chemicals, Inc.), 2.0 mass% of yellow pigment (PP-M AZMA 1732 yellow, manufactured by DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD.), The metering cap 2 is 100 mass% of polypropylene (made by Mitsui Chemicals, Inc.). This container 1 has become 575 mL in full amount.

"Evaluation standard"

◎: expansion is not confirmed

○: the body part is slightly inflated

(Triangle | delta): A trunk part expands clearly, and shakes when it touches

X: The bottom part comes out and the container is inclined

(Examples 1-26, Comparative Examples 1-18)

According to the composition of Table 7-9, each raw material other than water (if there is an unblended raw material, it will not mix | blend) is put into a beaker, and 93 mass% of total amount (make 100 mass% whole quantity) Water was added and stirred as much as possible. Thereafter, pH was adjusted, and the remaining water was added to balance the total amount to 100% by mass to prepare a liquid bleaching composition of each example.

pH measurement adjusted the liquid bleaching composition to 25 degreeC, and measured using the glass electrode type pH meter (product name: Horiba F-22, the product made by HORIBA, Ltd.). The measuring method was performed based on JISK3362-1998.

About the bleaching composition of each obtained example, a bacteriostatic inhibitory effect, the bactericidal effect with respect to a washing | cleaning liquid, an antibacterial effect, and storage stability are evaluated, and the result is shown to Tables 7-9.

In Examples 1 to 26 to which the present invention was applied, all of the sterilizing effects on the cleaning liquid were "C" or "D". On the other hand, all the Comparative Examples 1-18 which do not apply this invention were the sterilization effect with respect to the washing | cleaning liquid "B"-"D". That is, the sterilizing power with respect to the cleaning liquid was almost equal regardless of whether or not the present invention was applied.

In Examples 1 to 26 to which the present invention was applied, all of the bacterium migration inhibitory effect and the antibacterial effect were "o" or "o". On the other hand, the comparative examples 1, 2, 11, and 15-18 which made content of (A) component less than 0.1 mass% were inferior to the bacteria movement inhibitory effect. In addition, the comparative example 8 which made (B) component less than 1 mass% was inferior to the bacteria movement inhibitory effect. In addition, Comparative Examples 9, 14, and Comparative Examples 3, 5, 9, 12, and 18, in which the contents of the Comparative Examples 9, 14 and (C) were changed to the component (C) and were less than 0.1% by mass or more than 5% by mass, were moved. The inhibitory effect was inferior. Moreover, all the comparative examples 4, 6, 7, 10, 13, and 18 which made content of (D) component less than 0.001 mass% or more than 2 mass% had a low bacterium migration inhibitory effect.

From the above results, it can be seen that the liquid bleaching composition of the present invention can exhibit excellent antibacterial effect while suppressing adhesion of microorganisms to medical treatment as a laundry by providing the components (A) to (D).

According to the medical liquid bleaching composition of the present invention, it is excellent in antibacterial effect even when washing with water containing a large number of microorganisms such as the remaining water after bathing, and it is possible to suppress the adhesion of microorganisms to medical treatment as the laundry. Very useful.

Claims (5)

0.1 mass% or more of hydrogen peroxide (A),
Surfactant (B),
The algebraic value of the chelate stability constants for Ca ^{2 +} 5.5 or more, the logarithmic value of a chelating stability constant of the Fe ^{3 +} 10 or more, and chelating agents than the logarithmic value of the chelate stability constants for Cu ^{2 +} 10 (C) 0.1-5 mass%,
A medical liquid bleaching composition comprising 0.001 to 2% by mass of at least one cationic polymer (D) selected from a biguanide polymer and a dimethyldiallylammonium polymer. The method of claim 1,
The mass ratio represented by the said chelating agent (C) / said cationic polymer (D) is 1-1000, The medical liquid bleaching composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The said surfactant (B) is 1-60 mass% in content, and contains the nonionic surfactant (b-1) and anionic surfactant (b-2), The medical liquid bleaching composition characterized by the above-mentioned. The method of claim 3, wherein
0.5 mass% or more and less than 20 mass% of said nonionic surfactant (b-1), and 1-10 mass% of said anionic surfactants (b-2),
The said nonionic surfactant (b-1) is 1 or more types chosen from following General formula (1) and (2), The said anionic surfactant (b-2) is a linear alkylbenzene sulfonic acid or its salt, alkyl sulfate Medical bleaching composition, characterized in that at least one selected from polyoxyethylene alkyl ether sulfate, α-olefin sulfonate and alkanesulfonate.

[In formula (1), R <^1> is a C7-18 linear or branched alkyl group or alkenyl group, k represents the average added mole number of ethylene oxide, and is 3-15.]

[In formula (2), x and y are one or more numbers which show the number of methylene groups, respectively, and x + y = 5-13. z is a number from 5 to 30 indicating the average added mole number of ethylene oxide] The method of claim 3, wherein
20-59 mass% of said nonionic surfactants (b-1) and 1-10 mass% of said anionic surfactants (b-2),
The nonionic surfactant (b-1) is at least one selected from the following general formulas (2), (3), (4) and (5), and the anionic surfactant (b-2) is a linear alkyl. A medical liquid bleaching composition, characterized in that at least one selected from benzenesulfonic acid or its salts, alkyl sulfates, polyoxyethylene alkyl ether sulfates, α-olefin sulfonates and alkanesulfonates.

[X, y in Formula (2) is 1 or more number which shows the number of methylene groups, respectively, x + y = 5-13, z shows the average added mole number of ethylene oxide, and is 5-30.]

[In Formula (3), R <^2> is a C8-18 linear or branched alkyl group or alkenyl group. k1 and n1 are 1 or more numbers which show the average added mole number of ethylene oxide, respectively, and are k1 + n1 = 3-30. m1 is the number of 0.2-5 which shows the average added mole number of a propylene oxide]

[In Formula (4), R <^3> is a C8-18 linear or branched alkyl group or alkenyl group. k2 and n2 are 1 or more numbers which show the average added mole number of ethylene oxide, respectively, and are k2 + n2 = 3-30. m2 is the number of 0.2-5 which shows the average added mole number of a propylene oxide]

[In formula (5), R <^4> is a C9-C13 linear or branched alkyl group or alkenyl group, R <^5> is a C2-C4 alkylene group, R <^6> is a C1-C3 alkyl group, p Is a number from 5 to 30 indicating the average added mole number of alkylene oxide]

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