JPH05194995A - Bleach and bleach/detergent composition - Google Patents

Abstract

PURPOSE:To obtain a bleach or the subject composition improved in bleaching power (detergency) by mixing a specified oligomer with hydrogen peroxide and a bleach activator which reacts with hydrogen peroxide to form an organic peroxy acid. CONSTITUTION:The objective bleach or composition comprises 0.01-10wt.% oligomer of the formula (wherein Y1 is H or CO-T1; Q1 and T1 are each 1-4C alkyl, and n1 is 1-16) or its alkali metal salt, 1-95wt.% hydrogen peroxide or another peroxide which forms hydrogen peroxide in an aqueous solution and 0.1-50wt.% bleach activator which reacts with hydrogen peroxide to form an organic peroxy acid. As the peroxide, a sodium carbonate/hydrogen peroxide adduct is desirable. As the bleach activator, an organic peroxy acid containing a quat. ammonium group is particularly desirable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has an excellent bleaching (cleaning) power,
In particular, the present invention relates to a bleaching agent and a bleaching detergent composition which exhibit excellent bleaching (cleaning) power against stains and stains containing metals.

[0002]

2. Description of the Related Art Chlorine bleaching agents are limited in the fibers that can be used, cannot be used in colors and patterns, and have a unique odor. Oxygen-based bleaching agents, which do not have the above-mentioned drawbacks, have recently become extremely popular. As the oxygen-based bleaching agent, sodium percarbonate and sodium perborate are particularly used in view of bleaching performance and stability. However, the oxygen-based bleaching agent has a weaker bleaching power than the chlorine-based bleaching agent, and various bleaching activators are used together. This bleach activator includes nitriles represented by acetonitrile and the like, O-acetylated products represented by glucose pentaacetate (GPAC), N represented by tetraacetylethylenediamine (TAED) and the like.
-Acid anhydrides, acid anhydrides represented by maleic anhydride and the like can be mentioned.

Further, as a result of the research conducted by the present inventors, Japanese Patent Laid-Open No. 63-63
-233969, JP-A-63-315666, JP-A-64-
Compounds that react with hydrogen peroxide to form an organic peracid having a quaternary ammonium group, as exemplified in 68347 and JP-A-1-190654, are extremely excellent as bleach activators. Have been found.

On the other hand, unlike the case where sodium percarbonate or sodium perborate and a bleach activator are used as described above, it is also considered to directly use an organic peracid. Typical examples thereof include organic peracids described in JP-A-2-196771 such as peroxydecanoic acid, 1,12-diperoxidedecanedioic acid, and 4-phthalimidoperbutyric acid. However, the organic peracid present in the bleaching agent solution is rapidly decomposed in the presence of heavy metals, and therefore various chelating agents are added to stabilize the organic peracid. For example, JP-A-53-31871, JP-A-54-74287, JP-A-55-142100, JP-B-56-21799 and JP-B-
58-51998 and JP-B-59-23596 disclose aminopolycarboxylic acid salts, triazole compounds, imidazole compounds, amino acid salts, di (tri) peptides, (hydroxyethyl) iminodiacetic acid salts, hydroxyethyl compounds. Chelating agents such as ethylene diamino triacetate have been disclosed. Further, JP-A-52-103386 discloses a bleaching stabilizer composed of sodium poly-α-hydroxyacrylate (PHAS) having very excellent performance.

However, the bleaching power or bleaching detergency of the bleaching agent provided by these methods is not sufficient yet, and further improvement is desired.

[0006]

As a result of earnest research, the present inventors have heretofore proposed a phosphonic acid oligomer proposed as a stabilizer for hydrogen peroxide in an alkaline bleaching solution (Japanese Patent Publication No. 3-35428). However, it was found that a bleaching agent and a bleaching detergent composition having improved bleaching (detergency) power can be obtained by using this oligomer in combination. The present invention has been completed.

That is, the present invention provides (a) 0.01 to 10% by weight of an oligomer represented by the following general formula (I) or an alkali metal salt thereof.

[0008]

[Chemical 3]

(In the formula, Y ₁ is hydrogen or —CO-T ₁ , and R ₁ ,
Q ₁ and T ₁ are each an alkyl group having 1 to 4 carbon atoms, and n ₁ is a number of 1 to 16) (b) Hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution 1 ˜95% by weight (c) A bleaching and bleaching detergent composition comprising 0.1 to 50% by weight of a bleaching activator which reacts with hydrogen peroxide to produce an organic peracid, and the above general formula (I The present invention provides a bleaching agent and a bleaching detergent composition containing 0.01 to 10% by weight of an oligomer represented by the formula (1) or an alkali metal salt thereof and (d) 1 to 90% by weight of an organic peracid.

The component (a) of the present invention is a phosphonic acid oligomer represented by the above general formula (I).
It is possible to use the oligomers described in No. Representative examples of such oligomers are shown below.

[0011]

[Chemical 4]

The oligomer of the component (a) is added to the composition in an amount of 0.01 to
10% by weight, preferably 0.1-5% by weight.

As the peroxide which generates hydrogen peroxide in the aqueous solution which is the component (b) of the present invention, sodium carbonate / hydrogen peroxide adduct, sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyrophosphate / Hydrogen peroxide adduct,
Urea / hydrogen peroxide adduct, 4Na ₂ SO ₄ 2H ₂ O ₂ .NaCl, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium peroxide, calcium peroxide and the like can be mentioned. Of these, sodium carbonate / hydrogen peroxide adduct is particularly preferable. The component (b) is contained in the composition in an amount of 1 to 95% by weight, and in the bleaching system, it is 50 to 95% by weight, particularly 50 to 80% by weight, and in the bleaching detergent system, 3 to 30% by weight, particularly 10 to 20% by weight is preferable.

The bleach activator (c) which reacts with hydrogen peroxide to produce an organic peracid used in the present invention includes glucose pentaacetate (GPAC), tetraacetylethylenediamine (TAED) and nonanoyloxybenzene. Typical examples are sodium sulfonate (NOBS) and the like. As the bleach activator, those that generate an organic peracid having a quaternary ammonium group are particularly preferable, and examples thereof include those having the following structures.

[0015]

[Chemical 5]

A, b is a = 0, b = 0, or a =
1 and b = 1. R ₂ and R ₃ are alkyl groups having 1 to 2 carbon atoms.

The linking group is not particularly limited,
Examples thereof include linear or branched alkylene groups, cycloalkylene groups, phenylene groups or alkylenephenylene groups, oxyalkylene groups (—CH ₂ CH ₂ O—) and the like.

The leaving group is not particularly limited, but for example,

[0019]

[Chemical 6]

[0020]

[Chemical 7]

In the above general formula (II), the linking group is -C _p.
H _2p- (p is 1 to 12, particularly preferably 1 to 5) and the leaving group is (a), (b), (c), (d), (f), (to), (wa) , (Mosquito),
(Yo), (ta), (re) represented by the structural formula, R ₅ is a C _{1 to} C ₂ alkyl group, R ₆ and R ₇ are H or a C _{1 to} C ₂ alkyl group, R ₈ is C ₁
To C ₂ alkyl group and R ₉ is a C _{1 to} C ₃ alkylene group are desirable, and compounds represented by the structural formulas (yo) and (ta) are particularly desirable.

Further, a nitrile compound represented by the following general formula (III) is also useful.

[0023]

[Chemical 8]

Among these bleach activators, those particularly desirable are those represented by the following formulas.

[0025]

[Chemical 9]

[Wherein R ₁ and m are the same as above, and p is 1 to
The integer of 10 and the leaving group are groups represented by the above (yo) and (ta). In the present invention, the peroxide (b) and the bleach activator (c) are in the range of (b) / (c) in a weight ratio of 100/1 to 1/20, preferably 50/1 to 1/1. Used in.

Organic peracid used as component (d) of the present invention
(d) is 1,12-diperoxidedecanedioic acid,
4-phthalimidoperbutyric acid and the like can be mentioned, and particularly preferable are organic peracids having a quaternary ammonium group, for example, those having the following structures.

[0028]

[Chemical 10]

A, b is a = 0, b = 0, or a =
1 and b = 1. R ₂ and R ₃ are alkyl groups having 1 to 2 carbon atoms. Z ⁻ represents an organic or inorganic counter ion.
The linking group is not particularly limited, for example, a linear or branched alkylene group, cycloalkylene group, phenylene group or alkylenephenylene group, oxyalkylene group
(-CH ₂ CH ₂ O-) and the like. Among these, particularly desirable ones are represented by the following equations.

[0030]

[Chemical 11]

In the formula, R ₁ and m are the same as above, and p is 1 to 10
, An integer of Z ⁻ represents an organic or inorganic counterion. The component (d) is incorporated in the composition in an amount of 1 to 90% by weight.

The bleaching agent and bleaching detergent composition of the present invention are
In addition to the above essential components, known components usually added to bleaching agents or bleaching detergent compositions can be added. For example, as a builder, sulfate, carbonate, bicarbonate, silicate, water-soluble inorganic builder such as phosphate, other water-insoluble inorganic builder such as zeolite, ethylenediaminetetraacetate, nitrilotriacetic acid salt, tartrate salt, Organic builders such as citrate can be used. Also known as stabilizers of peroxides or hydrogen peroxide adducts are magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide and magnesium hydroxide, and silicic acid such as sodium silicate. Salts can be used. Further, if necessary, anti-contamination agents such as carboxymethyl cellulose, polyvinylpyrrolidone, and polyethylene glycol, alkyl sulfates, alkane sulfonates, alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, higher fatty acids. Anionic surfactant such as soap, polyoxyethylene alkylphenol ether,
Polyoxyethylene alkyl ether, higher fatty acid mono- or diethanolamide, nonionic surfactants such as amine oxide, amphoteric surfactants such as betaine,
Enzymes such as protease, lipase, amylase and cellulase, optical brighteners, dyes, pigments and fragrances can be added.

[0033]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 A phosphonic acid oligomer represented by the following formula (Japanese Patent Publication No.
Various bleaching compositions shown in Table 1 were prepared using the bleaching activator) and the bleaching activator, and the bleaching effect of each was examined.

[0035]

[Chemical 12]

Measurement of bleaching effect Sodium percarbonate is dissolved in 300 ml of water at 20 ° C. so that the available oxygen becomes 0.05%, and the bleaching activator is adjusted to 1/16 equivalent of hydrogen peroxide in this solution. In the proportions shown in Table 1, and 2% by weight of (a-1) and (a-2),
Perform immersion bleaching for 30 minutes using tea-stained cloth ^* 5 sheets were prepared in the following way, wash, after drying, was determined bleaching rate by the following equation.

[0037]

[Equation 1]

The reflectance is NDR-1001D manufactured by Nippon Denshoku Industries Co., Ltd.
Measured at P using a 460 nm filter.

* Black tea-contaminated cloth: 80 g of Nitto black tea (yellow package) was boiled in 3 liters of ion-exchanged water for about 15 minutes, and then rubbed with de-salted cotton.
003 Soak the cloth and boil for about 15 minutes. It was removed from the heat as it was, left to stand for about 2 hours, naturally dried, washed with water until the washing liquid became colorless, dehydrated, pressed, and made into a test piece of 8 cm × 8 cm, which was used for the experiment. The results of the bleaching test are shown in Table 1.

[0040]

[Table 1]

Example 2 Various bleaching compositions shown in Table 2 were prepared by using the phosphonic acid oligomer shown in Example 1 and the organic peracid represented by the following formula, and the bleaching effect of each was examined.

[0042]

[Chemical 13]

Measurement of bleaching effect: The composition shown in Table 2 was dissolved in 300 ml of water at 20 ° C. so that the available oxygen was 0.05%, and the bleaching experiment was conducted in the same manner as in Example 1. The results are shown in Table 2.

[0044]

[Table 2]

Example 3 A bleaching agent composition of the present invention containing the following non-phosphorus, low phosphorus, phosphorus-containing detergent was obtained. The obtained bleaching compositions all showed good bleaching power and detergency.

[Phosphorus-free compounding] -Linear sodium dodecylbenzene sulfonate 14% by weight-Polyoxyethylene alkyl ether 6 (C _{12 to} C ₁₃ , the number of moles of ethylene oxide added is 10 mol) -Hardened tallow sodium fatty acid 2-2 No. 2 silicic acid Sodium 5 ・ Sodium carbonate 10 ・ 4A type zeolite 25 ・ Sodium sulfate balance ・ Sodium percarbonate 10 ・ (c-1) 3 ・ (a-1) 2 ・ Polyethylene glycol (Mw = 6000) 2 ・ Protease 2 ・ Water 4 [ Low phosphorus content] ・ Linear sodium dodecylbenzene sulfonate 10% by weight ・ Sodium dodecyl sulfate 2 ・ Polyoxyethylene alkyl ether 8 (C _{12 to} C _13, ethylene oxide addition mol number 7.7 mol) ・ Hardened tallow fatty acid sodium 2 ・ No. 1 Sodium silicate 5 Sodium carbonate 10 4A type zeolite 2・ Sodium birosulfate 15 ・ Sodium sulfate balance ・ Sodium percarbonate 10 ・ (c-2) 3 ・ (a-2) 3 ・ Polyethylene glycol (Mw = 11000) 1 ・ Sodium sulfite 1 ・ Protease 2 ・ Water 4 [with phosphorus Blending) -Polyoxyethylene alkyl ether 20% by weight (R: tallow alcohol, ethylene oxide addition mole number 8.6 mol) -hardened tallow fatty acid sodium 2-sodium tripolyphosphate 30- (d-2) 5- (a-1) 5- No. 2 sodium silicate 5 ・ Sodium carbonate 10 ・ Sodium sulfite 1 ・ Polyethylene glycol (Mw = 6000) 2 ・ Protease 2 ・ Water 6 ・ Sodium sulfate balance

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C11D 3:37 3:39 1:90)

Claims (4)

[Claims] 1. (a) 0.01 to 10% by weight of an oligomer represented by the following general formula (I) or an alkali metal salt thereof: (In the formula, Y ₁ is hydrogen or -CO-T ₁ , R ₁ , Q ₁ and T ₁ are each an alkyl group having 1 to 4 carbon atoms, and n ₁ is a number of 1 to 16) (b) 1 to 95% by weight of peroxide that generates hydrogen peroxide in hydrogen peroxide or an aqueous solution (c) 0.1 to 50% by weight of a bleach activator that reacts with hydrogen peroxide to produce an organic peracid. A bleaching agent and a bleaching detergent composition containing the same. 2. The bleaching agent and bleaching detergent composition according to claim 1, wherein the bleaching activator (c) is a bleaching activator which produces an organic peracid having a quaternary ammonium group. 3. (a) 0.01 to 10% by weight of an oligomer represented by the following general formula (I) or an alkali metal salt thereof: (In the formula, Y ₁ is hydrogen or -CO-T ₁ , R ₁ , Q ₁ and T ₁ are each an alkyl group having 1 to 4 carbon atoms, and n ₁ is a number of 1 to 16) (d) A bleaching agent and a bleaching detergent composition containing 1 to 90% by weight of an organic peracid. 4. The bleaching agent and bleaching detergent composition according to claim 3, wherein the organic peracid (d) is an organic peracid having a quaternary ammonium group.