JPH1060490A - Bleaching detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the composition having a low toxicity, not having a smell of chlorine and a running down property, showing a marked volume expansion suppressing effect and an excellent bleaching effect, and useful for a bath room use, etc., by containing a peroxide, a water-based thickening agent and a specific compound. SOLUTION: This bleaching detergent composition consists of (A) one or more kinds of peroxides selected from hydrogen peroxide, a peroxocarbonate and a peroxoborate as an oxygen-based bleaching agent, (B) a water-based thickening agent, (C) at least one or more kinds selected from a polyphosphoric acid salt expressed by the formula: Mn+2 .Pn .O3n+1 [M is an alkali metal of Li, Na, K or H; (n) is 100>=(n)>=2] and a polyhydroxyacrylic acid salt expressed by another formula. Further, e.g. as the component (B), a polyvinyl alcohol, etc., are preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleaching detergent composition for removing stains such as mold on a hard material surface such as a cement joint in a bathroom.

[0002]

2. Description of the Related Art Black-brown stains in bathrooms in houses are often caused by mold. To remove the stains, wet the stains with water, apply a solution containing a chlorine-based bleach using a spray or the like, and leave it for a few minutes to bleach the mold pigment, then use a sponge, brush, etc. A method of rubbing with water and rinsing with water is used ("Dirt and Detergent of Building (Residential Building)", Kao Institute of Life Science, Building Maintenance Magazine, August 1984, separate volume p33).

[0003] In household disinfectant and bleaching detergents, those containing sodium hypochlorite as the chlorine bleaching agent are widely used. However, since chlorine bleach has a peculiar odor, the technique of blending fragrances has been developed.
No. 25514. Japanese Patent Publication No. 5-65558 discloses a technique for increasing the viscosity of a solution so that the solution does not scatter and enter the eyes.

[0004] A large number of spray-type mold removers containing the above-mentioned chlorine bleach as a main component are commercially available, but there is a problem in that it is difficult to handle discomfort due to chlorine odor, musk rash and the like. Also,
Chlorine bleach is highly toxic, so splashes may get in your eyes,
Care must be taken not to inhale the generated gas.

The above problems can be avoided by using an oxygen bleach. For example, Japanese Patent Publication No. 6-45798 discloses hydrogen peroxide, sodium carbonate hydrogen peroxide adduct (sodium peroxocarbonate) as an oxygen bleaching agent,
A composition in which sodium perborate (sodium peroxoborate) and peroxysulfate and a fibrous double-chain structure type inorganic clay mineral are dispersed in an aqueous solvent is described.

Oxygen-based bleaching agents have the advantage of being less toxic than chlorine-based bleaching agents, but because of their slow onset of bleaching effect, they do not sag when used as a bleaching detergent and come into contact with stains. It is necessary to adopt a configuration that can hold the state for a certain period of time. Further, the holding needs to be performed in a wet state.

Generally, oxygen bleaching agents are inferior to bleaching agents such as mold in comparison with chlorine bleaching agents such as sodium hypochlorite. Therefore, it is known that bleaching power is improved by blending glucose pentaacetate, N, N, N ', N'-tetraacetylethylenediamine (TAED), tetraacetylglycoluril, or the like as a bleaching activation aid.

For example, when N, N, N ', N'-tetraacetylethylenediamine and sodium peroxocarbonate are added to an aqueous thickener such as a clay mineral, the bleaching effect against mold stains and the like is improved. However, there is a problem that the gas simultaneously violently generated from sodium peroxocarbonate stays in the gelled composition by the aqueous thickener and overflows from the container when used, which makes commercialization difficult. Further, after mixing with water or an aqueous solvent composed of water and a water-soluble organic solvent, the amount of available oxygen in the composition rapidly decreases, so that it is desired to use it within 30 minutes to 1 hour after mixing, There is a disadvantage that the pot life is short.

Even when a bleaching activator is not used, hydrogen peroxide, sodium peroxocarbonate, sodium peroxoborate, etc., which are usually used as oxygen-based bleaching agents, are mixed with the above-mentioned aqueous solvent in the presence of a thickener. At that time, oxygen gas is gradually generated from the oxygen-based bleach, and the available oxygen amount decreases. The reaction is further accelerated by the presence of heavy metal ions such as iron, manganese and copper in the composition. The generated gas stays in the composition gelled by the inorganic clay mineral, causing an apparent volume expansion of the composition, and the same problem occurs when the composition is used.

[0010]

SUMMARY OF THE INVENTION In view of the above problems, the present invention provides a thickened oxygen-based bleaching composition without using a chlorine-based bleaching agent which requires careful use. It is an object of the present invention to provide a bleaching detergent composition having a small apparent volume expansion after mixing with an object and having a long-lasting cleaning effect.

[0011]

The bleaching detergent composition of the present invention comprises, as an oxygen bleaching agent, one or more peroxides (A) selected from hydrogen peroxide, peroxocarbonate, and peroxoborate. , Water-based thickener (B), _{Mn + 2} · _Pn · O
_{3n + 1} (M is an alkali metal salt or H being any one of Li, Na and K, H, 100 ≧ _n ≧ 2) a polyphosphate represented by the general formula and polyhydroxyacrylic acid represented by the formula (1) And at least one compound (C) selected from salts.

[0012]

Embedded image

As the oxygen bleach (A), hydrogen peroxide,
A peroxide selected from peroxoborate and peroxocarbonate is used alone or as a mixture of two or more.
When the amount of the oxygen-based bleaching agent in the bleaching detergent composition is small, the bleaching action is weakened, and when the amount is large, it becomes difficult to apply and adhere to a vertical soiled surface.
% By weight.

These react with water to exhibit bleaching performance. Therefore, water must be present at the time of bleach washing, but if oxygen bleach is in contact with water during storage, the reaction may end by the time of use. .

Therefore, when using peroxoborate or peroxocarbonate, the composition containing the aqueous solvent and the composition containing the oxygen-based bleach may be separately stored and mixed when used. preferable. Hydrogen peroxide is usually stored as an aqueous solution. As an example of a compound stored together with an aqueous solvent, when an aqueous emulsion is used as an aqueous thickener, the solid content of the emulsion is generally made to coexist with water.

In order for the peroxocarbonate or peroxoborate to exhibit a sufficient bleaching effect, the amount of water is preferably at least 10% by weight in the bleaching detergent composition.

The above-mentioned water can also serve to adjust the effect of the thickener. The appropriate amount of water varies depending on the thickener used, but if the amount of water is too large, the coating operation becomes difficult. In addition, depending on the thickener, the dispersion state is stable in the presence of alcohol, but in such a case, if the viscosity of the entire aqueous solvent containing a water-soluble organic solvent such as an aliphatic lower alcohol is adjusted to thicken the effect Good. The content of the water-soluble organic solvent in the aqueous solvent is preferably 0.1 to 70% by weight.

When water is added in advance as described above, it is necessary to adjust the amount of the aqueous solvent to be added at the time of use in consideration of the water. If hydrogen peroxide is used as the oxygen-based bleach, the composition containing a compound that may decompose hydrogen peroxide (such as TAED) and the solvent composition containing hydrogen peroxide are separated. It is desirable to mix and use at the time of use.

In the present invention, since an oxygen bleaching agent is used as a bleaching active species, the oxidizing power is weaker than that of a chlorine bleaching detergent, and the detergency for stains is inferior. Therefore, when applying to a vertical surface such as a wall, it is necessary to adhere the cleaning agent to the dirty surface for a long time, and it is necessary to prevent the cleaning agent from dripping.

As a means for preventing dripping, an aqueous thickener (B) is used. Examples of the aqueous thickener include a water-soluble organic polymer, an aqueous emulsion, and a clay mineral. As the water-soluble organic polymer, for example, polyvinyl alcohol or a derivative thereof, polyethylene glycol or a derivative thereof, polyvinylpyrrolidone, polyacrylic acid or a derivative thereof, alginic acid or a derivative thereof, cellulose or a derivative thereof, starch or a derivative thereof, pullulan or a derivative thereof Is mentioned.

Examples of the polyvinyl alcohol derivative include acetalized polyvinyl alcohol, butyralized polyvinyl alcohol, formalized polyvinyl alcohol,
Examples include cation-modified polyvinyl alcohol and anion-modified polyvinyl alcohol. Further, a product obtained by reacting polyvinyl alcohol with dialdehyde, side chain aldehyde, polyacrolein, ester, diisocyanate or the like may be used.

As the polyethylene glycol derivative,
Carboxylated polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can be mentioned.

Examples of the polyacrylic acid derivative include aldehyde polyacrylic acid and polyacrylic acid ester.

As the starch derivatives, acetate esters,
Starch esters such as succinate, nitrate, phosphate, xanthate, allyl ether, methyl ether, carboxymethyl ether, carboxyethyl ether hydroxyethyl ether, hydroxypropyl ether, starch ethers such as positive starch, formaldehyde Cross-linked starch, epichlorohydrin cross-linked starch, phosphate cross-linked starch,
Acrolein cross-linked starch and the like.

Pullulan derivatives include pullulan acetate, and cellulose derivatives include carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, and ethylhydroxyethylcellulose.

When the above water-soluble organic polymer is used, the amount of the water-soluble organic polymer in the bleaching detergent composition is as follows:
When the amount is reduced, the effect of preventing the bleaching detergent composition from dripping when applied to a vertical wall surface is small, and when the amount is increased, the flowability of the bleaching detergent composition is deteriorated and application becomes difficult.
% By weight is preferred.

As the aqueous emulsion, for example,
Examples include a vinyl acetate emulsion, a modified vinyl acetate emulsion composed of a copolymer of vinyl acetate and vinyl chloride, ethylene, an acrylate ester, etc., a polyethylene emulsion, a polypropylene emulsion, a rubber latex, and the like.

When an aqueous emulsion is used, the solids content of the aqueous emulsion in the bleaching detergent composition decreases and the sagging prevention effect when the bleaching detergent composition is applied to a vertical wall decreases, while the solids content increases. Since the fluidity of the bleaching detergent composition deteriorates and application becomes difficult, the content is preferably 5 to 70% by weight.

Examples of the clay mineral include an amorphous structure type clay mineral such as aferon, dickalite, nacryte, kaolinite, anoxite, halloysite, and the like.
1: 1 structural clay minerals such as metahalosite, chrysotile, lizardite, serpentine, antigorite, montmorillonite, sauconite, stevensite, nontronite, saponite, beidellite, hectorite, vermiculite, illite, sericite, sea green 2: 1 Structural clay minerals such as stones, chlorite, mica-montmorillonite, chlorite-montmorillonite, laurite-montmorillonite, chlorite-vermiculite, etc., ordered mixed layer lattice, attapulgite, sepiolite, palygorsite, etc. Chain structure type clay minerals are exemplified.

Of the above, swelling clay minerals such as montmorillonite, sauconite, stevensite, beidellite, nontronite, saponite, hectorite, vermiculite and the like are particularly preferred.

When the above clay mineral is used, when the amount of the clay mineral in the bleaching detergent composition is small, the effect of preventing the sag when the bleaching detergent composition is applied to a vertical wall surface is small, and when the amount is large, the amount is small. Since the fluidity of the bleaching detergent composition deteriorates and application becomes difficult, 0.1 to 30% by weight is preferable.

In addition, in order to further increase the viscosity,
A natural polymer such as gum arabic, guar gum and xanthan gum or an inorganic thickener such as silica gel may be added.

The polyphosphate used in the present invention is M
_{n + 2} · _Pn · O3n _{+ 1} (M is an alkali metal salt or H, which is one of Li, Na, and K, 100 ≧ _n ≧ 2)
Is selected from compounds having a structure in which two or more PO ₄ tetrahedra represented by the following chemical formula have a vertex oxygen atom and are linearly connected.

The degree of polymerization of the PO ₄ tetrahedron is 100 ≧ _n ≧ 2, and if _n = 1, no good effect of suppressing volume expansion is exhibited. In M, the alkali metal salt of Li, Na, or K may be hydrogen. Specific examples of polyphosphates include Na
₄ P ₂ O ₇ (sodium diphosphate), Na ₅ P _30
10 (sodium triphosphate), Na ₆ P ₄ O ₁₃ , Na ₇
P ₅ O _{16 and the} like.

When the amount of the above polyphosphate in the bleaching detergent composition is reduced, the effect of suppressing the volume expansion is reduced, and when the amount is increased, the flowability of the bleaching detergent composition is deteriorated, and the bleaching detergent composition is difficult to apply. % By weight.

The polyhydroxyacrylate used in the present invention is a polymer compound in which two or more compounds having the structure represented by the formula (1) are linked, and are bonded to an alkali metal salt of Li, Na, or K or a proton. It is desirable to use it as an acid. Any polyhydroxyacrylate can be used as long as the degree of polymerization is 2 or more, but n = 10
It is desirable to use those having a size of ~ 1000.

When the amount of the polyhydroxyacrylate in the bleaching detergent composition is reduced, the effect of suppressing the volume expansion is reduced. When the amount is increased, the viscosity of the bleaching detergent composition is reduced, and the bleaching detergent composition sags when applied to a vertical surface. It is preferable that the content is 0.1 to 30% by weight because it causes dropping.

In the bleaching detergent composition of the present invention, a compound which reacts with an oxygen-based bleach in an aqueous solution to form an organic peracid or the like can be added as an activator of the oxygen-based bleach. . Such a bleach activator is not particularly limited, and examples thereof include nitrile compounds such as acetonitrile and phthalonitrile; o-acetyl compounds such as glucose pentaacetate and pentaerythritol tetraacetate; N, N, N ′, N N-acyl compounds such as '-tetraacetylethylenediamine (TAED), N, N, N ", N"'-tetraacetylglycoluril (TAGU) and diacetylmethyleneformaldehyde; acids such as phthalic anhydride and succinic anhydride Anhydrous: cyanamide, halogenated triazine and the like. These may be used alone or as a mixture of two or more.

[0039] TAED is a commercially available product obtained by coating a raw powder with a nonionic surfactant, and can be easily obtained. In the present invention, the raw powder coated with a surfactant is also used in the present invention. However, it can be used without any trouble.

A surfactant may be added to the bleaching detergent composition of the present invention in order to improve the wettability on the surface to be washed. As surfactants, cationic, anionic,
Any of non-ionic, zwitterionic and the like can be used. The amount of the surfactant added is 1 to 15 of the bleaching detergent composition.
% By weight is preferred. If necessary, a sequestering agent, p
Additives such as H adjusters, inorganic salts, antibacterial agents, preservatives, fragrances, plasticizers, humectants (eg, glycerin) can also be added.

[0041]

Embodiments of the present invention will be described below. (Example 1) Polyvinyl alcohol (trade name "PVA-117", manufactured by Kuraray Co., Ltd.) as a water-based thickener was dissolved in a mixed solution of purified water and isopropyl alcohol (Nacalai Tesque, Inc.), and sodium polyhydroxyacrylate was further dissolved. (Molecular weight 2000-4000, manufactured by Nippon Peroxide Co., Ltd., trade name “Pale Plaque 250”). Sodium peroxocarbonate (trade name "PC-M", manufactured by Nippon Peroxide Co., Ltd.) was mixed with the above solution as an oxygen bleaching agent to obtain a bleaching detergent composition of the present invention. The composition of the mixture is as shown in Table 1.

Example 2 Without using isopropyl alcohol, polyvinylpyrrolidone (trade name "K-30", manufactured by Gokyo Sangyo Co., Ltd.) was dissolved in purified water as an aqueous thickener, and sodium polyhydroxyacrylate was further dissolved. (Molecular weight 10
A bleaching detergent composition was obtained in the same manner as in Example 1 except that 000 to 14000, manufactured by Nippon Peroxide Co., Ltd., trade name "Pale Plaque 1200") was dissolved. The composition of the mixture is shown in Table 1.

Example 3 As a water-based thickener, a saponite-based inorganic clay mineral (manufactured by Kunimine Industries Co., Ltd., trade name "Smecton-SA") was dispersed in purified water, and sodium polyhydroxyacrylate (molecular weight 30,000-7000) was further dispersed.
0, manufactured by Nippon Peroxide Co., Ltd.
000 ") sodium diphosphate (Wako Pure Chemical Industries, Ltd.)
And TAED (4016, Hoechst) were dissolved or dispersed. Otherwise in the same manner as in Example 1, a bleaching detergent composition was obtained. The composition of the mixture is as shown in Table 1.

Example 4 Sodium carboxymethylcellulose (manufactured by Daicel Chemical Industries, Ltd.) was dissolved in purified water in place of the saponite-based inorganic clay mineral, and sodium peroxoborate (manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of sodium peroxocarbonate. Product name "Perbons")
A bleaching detergent composition was obtained in the same manner as in Example 3 except that sodium polyhydroxyacrylate was not used. The composition of the mixture is as shown in Table 1.

Example 5 The saponite-based inorganic clay mineral used in Example 3 was used instead of sodium carboxymethylcellulose, and sodium triphosphate was used instead of sodium diphosphate (manufactured by Wako Pure Chemical Industries, Ltd.). A bleaching detergent composition was obtained in the same manner as in Example 4 except for using. The composition of the mixture is as shown in Table 1.

Example 6 In place of polyvinylpyrrolidone, a hectorite-based inorganic clay mineral (manufactured by Kunimine Industries, Ltd.)
Bleaching and washing in the same manner as in Example 2 except that the product name “Smecton-HE”) was dispersed in purified water and 30% hydrogen peroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of sodium peroxocarbonate. Agent composition was obtained. The composition of the mixture is as shown in Table 1.

Example 7 A montmorillonite-based inorganic clay mineral (Kunimine Industry Co., Ltd., trade name “Kunipia F”) was dispersed in purified water as an aqueous thickener, and sodium peroxocarbonate was used as a bleaching agent. A gel bleaching detergent composition was obtained in the same manner as in Example 1 except that sodium triphosphate used, glycerin (manufactured by Nacalai Tesque) as a humectant, and TAED used in Example 3 were dissolved or dispersed. . The composition of the mixture is as shown in Table 1.

Comparative Example 1 A bleaching detergent composition was obtained in the same manner as in Example 3 except that sodium polyhydroxyacrylate and sodium diphosphate were not used. The composition of the mixture is as shown in Table 1.

Comparative Example 2 A bleaching detergent composition was obtained in the same manner as in Comparative Example 1 except that trisodium phosphate was dissolved in the gel composition in advance. The composition of the mixture is as shown in Table 1.

<Evaluation of bleaching performance> The bleaching detergent solutions of Examples 1 to 7 and Comparative Examples 1 and 2 were applied to the joints on the wall surface of the bathroom where mold was generated using a brush. After being left for 1 hour in this state, the detergent was removed and the degree of mold removal was visually determined according to the following criteria. Table 1 shows the determination results. ◎ It became completely white. ○ Although it was white, some remaining dirt was observed. B: Bleaching action was observed, but most stains remained. C: No bleaching action was observed.

<Judgment of Apparent Volume Expansion of Bleach Detergent> 30 g each of bleach detergents of Examples 1 to 7 and Comparative Examples 1 and 2.
Is a 50 ml polyethylene wide-mouth bottle (3 cm diameter,
(Height: 7 cm) and allowed to stand for 3 hours, and the apparent volume expansion of the contents was visually determined based on the following criteria. The results are shown in Table 1. A: Almost no volume expansion was observed. : Volume expansion of about 7 to 14 cm ³ was observed. Δ: Volume expansion of more than 14 and less than 28 cm ³ was observed. ×: Volume expansion of 28 cm ³ or more was observed, and the composition overflowed from the container.

[0052]

[Table 1]

As can be seen from Table 1, the compositions of Examples 1 to 7 in which a polyphosphate and / or a polyhydroxyacrylate are blended with an oxygen bleach show a good bleaching effect due to a good mold-removing action. The effect of suppressing volume expansion was observed. On the other hand, in Comparative Examples 1 and 2 in which the polyphosphate or the polyhydroxyacrylate was not blended, the mold removing action was good, but volume expansion occurred and the composition overflowed from the container.

[0054]

As described above, the bleaching detergent composition of the present invention has a low toxicity because it uses an oxygen-based bleaching agent, and does not cause discomfort due to chlorine odor. Further, since the water-based thickener, the polyphosphate and at least one of the polyhydroxyacrylates are used, they do not sag even when applied to a vertical surface or the like, and exhibit an excellent bleaching effect. In addition, the effect of suppressing volume expansion is remarkable, handling is easy, and coating operation is easy.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C11D 7:18 7:22)

Claims (1)

[Claims] 1. An oxygen bleaching agent, one or more peroxides (A) selected from hydrogen peroxide, peroxocarbonate, and peroxoborate, an aqueous thickener (B), _{Mn + 2} ·
_Pn · O3n _{+ 1} (M is an alkali metal salt or H, which is one of Li, Na, and K, H, 100 ≧ _n ≧ 2), and a polyphosphate represented by the general formula (1) A bleaching detergent composition comprising a compound (C) comprising at least one selected from polyhydroxyacrylates. Embedded image