JPH07109490A - Bleaching detergent composition - Google Patents

Abstract

PURPOSE:To obtain a bleaching detergent showing excellent solubility in a wide range of temperatures, having excellent bleaching performance and being effective for deterging especially vegetable protein dirt such as grass juice. CONSTITUTION:This detergent composition comprises 0.1-50wt.% mixture of a bleaching activator of formula I with a bleaching activator of formula II in a (I)/(II) ratio of 100/1 to 5/1 by weight and 0.5-90wt.% hydrogen-peroxide- releasing substance. In the formulas, R is an 11-13C linear alkyl; and L is an eliminable group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bleaching detergent composition having good solubility and excellent bleaching performance. More specifically, the present invention relates to a bleaching detergent and a bleaching agent that have excellent solubility in a wide range of temperatures, have excellent bleaching performance, and are particularly effective against plant protein stains such as grass juice.

[0002]

BACKGROUND OF THE INVENTION Peroxide compounds such as perborates, percarbonates, perphosphates and persilicates are found in both dyed and white textile products. It is effective for chemical bleaching of stains found in. However, these peroxide compounds are not suitable for use at high washing temperatures, for example, at boiling washing temperatures or in the vicinity thereof.
Most effective, but less effective at lower temperatures.

Therefore, an organic peracid having a higher bleaching effect has been proposed, and it is known in the art to use an organic peracid precursor (hereinafter abbreviated as a bleach activator) which generates an organic peracid. Is. This bleach activator reacts with hydrogen peroxide in aqueous solution to generate the corresponding organic peracid. Most such bleach activators contain hydrolyzable N-acyl or O-acyl residues.

Many investigators have investigated bleach activators, for example the inventions described in British Patent Nos. 836,988 and 854,798 represent an early invention in the art. These specifications disclose several bleach activators, including the esters of sodium acetoxybenzene sulfonate and sodium phenol sulfonate. Further, for example, British Patent No. 855,735 discloses an acylorganamide to which N, N, N ', N'-tetraacetylethylenediamine (TAED) belongs.

In recent patent specifications, European Patent No. 017413
2 and 0185522 and U.S. Pat.No. 4412934 and
Bleach activators are disclosed in specifications such as 4248928. The use of these bleach activators is effective in bleaching and washing at low temperatures, but it is not yet at a satisfactory level.

[0006]

Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that when a specific bleach activator is mixed in a specific ratio and used, excellent bleaching performance is obtained. It has been found that it has a very high bleaching performance especially against plant protein stains such as grass juice, and has completed the present invention. That is, the present invention provides (A) a bleach activator represented by the general formula (I) and a bleach activator represented by the general formula (II): (I) :( II) = 100
Mixture in the range of 1: 1 to 5: 1 (weight ratio) 0.1 to 50% by weight

[0007]

[Chemical 3]

(In the formula, R represents a linear alkyl group having 11 to 13 carbon atoms, and L represents a leaving group.) (B) A hydrogen peroxide releasing substance is contained in an amount of 0.5 to 90% by weight. A bleaching detergent composition is provided.

The bleach activator, which is an essential component of the present invention, is a mixture of the bleach activator represented by the general formula (I) and the bleach activator represented by the general formula (II). The mixing ratio is (I) :( II) = 100: 1 to 5: 1, preferably 100: 1 to 10: 1, and more preferably 99: 1 to 49: 1.
(Weight ratio) range. When the mixing ratio of the bleaching activator represented by the general formula (I) exceeds the above range, the solubility of the bleaching activator is lowered and the bleaching rate is lowered. When the mixing ratio of the bleaching activator represented by the general formula (I) is less than the above range, the bleaching performance is deteriorated.

In the above general formulas (I) and (II), R
Is a straight-chain alkyl group having 11 to 13 carbon atoms. R 1 having 10 or less carbon atoms is unstable and easily decomposed, and those having 14 or more cannot obtain a preferable bleaching power. In addition, L is a leaving group, but as the leaving group L, the formula --COOM or --SO ₃ M (M
Represents H 2, an alkali metal, an alkaline earth metal or an ammonium ion). Counter ion
Examples of M 1 include Na, K 2, ammonium ion and the like, with preference given to Na and K 2. Particularly preferred as the bleach activator of the component (A) is a mixture of the bleach activator represented by the general formula (III) and the bleach activator represented by the general formula (IV).

[0011]

[Chemical 4]

The content of the bleach activator in the bleaching detergent composition of the present invention is 0.1 to 50% by weight, preferably 1 to 30%.
%, Particularly preferably 2 to 25% by weight. If it is less than 0.1% by weight, a sufficient bleaching effect is not observed, and if it exceeds 50% by weight, the concentration of the organic peracid becomes high, and the generated organic peracid reacts with the unreacted bleach activator, so that the bleaching effect is increased. Because it will get worse.

This bleaching activator is preferably granulated when blended with the bleaching detergent composition of the present invention. For example, it can be mixed with a granulation binder such as polyethylene glycol (PEG) and molded with a Fuji Paudal-type pelleter-double type extrusion granulator or the like, or agitated rolling granulation with a high speed mixer or the like.

The hydrogen peroxide releasing substance which is an essential component of the present invention is not particularly limited, and examples thereof include percarbonate, perborate, perphosphate and persilicate. Percarbonate is particularly effective. The content of the hydrogen peroxide releasing agent in the composition of the present invention is 0.5 to 90% by weight, preferably 2 to 80% by weight. If the blending amount is less than 0.5% by weight, the concentration of hydrogen peroxide in the system is too low to make it difficult to react with the bleaching activator. Is also limited, which is not preferable.

In addition to the above essential components, the bleaching detergent composition of the present invention contains general detergent components such as anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants. It can be blended. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate,
Examples thereof include α-sulfo fatty acid salt or ester salt, alkyl or alkenyl ether carboxylate salt, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl or alkenyl phosphate ester or salt thereof. Among them, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate is preferable. As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyethylene glycol fatty acid ester,
Examples thereof include polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glycoside, and alkylamine oxide.
Among these nonionic surfactants, polyoxyethylene alkyl ethers, particularly ethylene oxide adducts of linear or branched primary or secondary alcohols having 10 to 14 carbon atoms, having an average addition mole number of 5 to The addition of 15 ethylene oxides is preferred. Examples of amphoteric surfactants include sulfobetaine-type surfactants, carbobetaine-type surfactants, hydroxysulfobetaine-type surfactants and the like, and cationic surfactants include ammonium salt-type surfactants and the like. . The above surfactant can be added to the composition of the present invention in an amount of 0.5 to 60% by weight.

It is also preferable to add a chelating agent for softening hard water. As the chelating agent, for example, a crystalline aluminosilicate represented by the following formula (V), a non-crystalline aminosilicate represented by the following formula (VI), a following formula (VII)
And a crystalline silicate represented by or a hydrate thereof.

Na ₂ O / Al ₂ O ₃ / v (SiO ₂ ) / w (H ₂ O) (V) (In the formula, v is 1.8 to 3.0 and w is a number of 1 to 6.) x ( M ₂ O) / Al ₂ O ₃ / y (SiO ₂ ) / z (H ₂ O) (VI) (In the formula, M represents a sodium atom and / or a potassium atom, and x, y, and z represent each part. Indicates the number of moles, x is 0.7
-2.0, preferably 0.7-1.2, y is 1-6, preferably 1-5, and z is an arbitrary integer. ) A (M ' ₂ O) / b (SiO ₂ ) / c (Me _m O _n ) (VII) (In the formula, M'is a hydrogen atom or a group Ia element of the periodic table, and Me is a group IIa or IIb of the periodic table. , IIIa, IVa or VIII group element, b / a = 0.5 to 4.0, c / a = 0 to 1.0, n / m = 0.5 to 2.0
Indicates. Among these, the crystalline silicate represented by the formula (VII) or a hydrate thereof is particularly preferable. In the above formula (VII),
M ′ is selected from a hydrogen atom or an element of group Ia in the periodic table, and examples of the element of group Ia include Na and K. These may be used alone or as a mixture of, for example, Na ₂ O and K ₂ O to give M ′.
_It may also constitute a ₂ O component. Me is IIa, IIb in the periodic table
, IIIa, IVa, or VIII group elements, and specific examples include Mg, Ca, Zn, Y, Ti, Zr, Fe, and the like.
These are not particularly limited, but Mg, Ca and Fe are particularly preferable. These may be used alone or in admixture of two or more, and for example, MgO, CaO, etc. may be mixed to form a Me _m O _n component.

The crystalline silicate represented by the above formula (VII) may be used in the form of a hydrate. In this case, the hydration amount is H ₂ O.
It is usually 0 to 15 in terms of molar amount. In the formula (VII), b / a is 0.5 to 4.0, preferably 1.0 to 1.
8 If b / a is less than 0.5, the water resistance is insufficient,
If it exceeds 4.0, the ion exchange capacity will be low, and it will be insufficient as an ion exchanger. c / a is 0 to 1.0, preferably
When it is 0.01 to 0.8, and c / a exceeds 1.0, the ion exchange capacity becomes low and it is insufficient as an ion exchanger. a, b,
c is not particularly limited as long as it is the relationship shown in b / a and c / a in the previous term. As described above, if aM ′ ₂₀ is a′Na ₂ 0 / a ″ K ₂ 0, then a is a ′ + a ″. This relationship is the same for c. Also, n / m is 0.5 to 2.
At 0, the number of oxygen ions coordinated to the element is shown, and it is substantially selected from the values of 0.5, 1.0, 1.5 and 2.0.

The method for preparing the crystalline silicate represented by the above formula (VII) is not particularly limited, but for example, the desired values of a, b and c of the crystalline silicate can be obtained. The raw material components are mixed in a predetermined amount ratio, usually 300 to 1500 ° C,
Preferably 500-1000 ° C, more preferably 600-900 ° C
A method of calcination by firing in the range of is exemplified. In this case, if the heating temperature is lower than 300 ° C, crystallization is insufficient and the water resistance is poor, and if it exceeds 1500 ° C, coarse particles are formed and the ion exchange ability is lowered. The heating time is usually 0.1 to 24 hours.
Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace. Further, after firing, it is crushed as needed to adjust to a predetermined particle size. The particle size is not particularly limited, but is preferably 0.01 to 100 μm, particularly preferably
It is in the range of 0.1 to 50μ.

The bleaching detergent composition of the present invention comprises the above (A)
In addition to the essential components and the cleaning components of (B), components that can be generally blended with a detergent or a bleaching agent may be blended. Examples of such components include organic chelating agents, alkaline agents,
Dispersants and the like are included, for example, amorphous silicates, carbonates,
Examples thereof include alkali agents such as sesquicarbonate, extenders such as Glauber's salt, divalent metal ion scavengers such as nitrilotriacetic acid salt, ethylenediaminetetraacetic acid salt, citrate salt, and isocitrate salt. Further, usually, for example, antifouling agents such as polyvinyl alcohol, carboxymethyl cellulose, polyacrylic acid salts, decolorization inhibitors such as polyvinylpyrrolidone, enzymes and enzyme stabilizers such as protease, esterase, lipase, cellulase, anti-caking Agent,
You may mix | blend well-known small addition components, such as a stabilizer of a peroxide, an antioxidant, a fluorescent dye, a bluing agent, and a fragrance | flavor.

The method for producing the composition of the present invention is not particularly limited. For example, a cleaning component prepared by separately granulating a bleaching component (a hydrogen peroxide releasing substance such as sodium percarbonate and a bleaching activator) is used. A method of dry blending with particles is preferable,
The method for granulating the cleaning component is described in, for example, JP-A-5-209200, JP-A-61-69897, JP-A-61-69899, and JP-A-61-69.
The method described in each publication of No. 900 can be used.

[0022]

EXAMPLES Synthesis examples of the bleach activator and examples of the present invention are shown below, but the present invention is not limited to these examples. In the examples,% is based on weight unless otherwise specified.

Synthesis Example of Bleach Activator (1) Method for Synthesizing Bleach Activator (i) 100 g (0.46 mol) of sodium p-phenolsulfonate, which had been dehydrated in advance, was added to dimethylformamide (DMF).
The mixture was dispersed in 300 g, and an equimolar amount of sodium lauric chloride and p-phenolsulfonate was added dropwise at 50 ° C. over 30 minutes while stirring with a mechanical stirrer, and the reaction was carried out for 3 hours after completion of the addition. Then, the DMF was depressurized (0.5
˜1 mmHg), distilled off at 100 ° C., washed with acetone, and then recrystallized in a water / acetone (= 1/1 mol) solvent to obtain a bleaching activator represented by the following formula (i). . Yield 85% (2) Method for synthesizing bleach activator (ii) In the same manner as in the method for synthesizing bleach activator (i), except that myristic acid chloride was used as the alkyl source instead of lauric acid chloride. A bleaching activator represented by the following formula (ii) was obtained. Yield 75% (3) Method for synthesizing bleach activator (iii) In the method for synthesizing bleach activator (i), a dehydrated product of sodium p-phenolcarboxylate is used instead of sodium p-phenolsulfonate. A bleaching activator represented by the following formula (iii) was obtained in the same manner except that it was used. Yield 65% (4) Method for synthesizing bleach activator (iv) In the above method for synthesizing bleach activator (i), sodium o-phenolsulfonate was used instead of sodium p-phenolsulfonate. Similarly, a bleaching activator represented by the following formula (iv) was obtained. Yield 50% (5) Method for synthesizing bleach activator (v) In the method for synthesizing bleach activator (ii) above, sodium o-phenolsulfonate was used instead of sodium p-phenolsulfonate. Similarly, a bleaching activator represented by the following formula (v) was obtained. Yield 68% (6) Method for synthesizing nonanoyloxybenzenesulfonic acid sodium In the same manner as in the method for synthesizing the bleach activator (i), except that nonyl acid chloride was used as the alkyl source instead of lauric acid chloride. Thus, sodium nonanoyloxybenzenesulfonate represented by the following formula (vi) was obtained. Yield 87
% (7) Method for synthesizing sodium heptanoyloxybenzenesulfonate In the method for synthesizing the bleach activator (i), the following formula (A) is used in the same manner except that heptanoic acid chloride is used as the alkyl source instead of lauric acid chloride. The sodium heptanoyloxybenzene sulfonate represented by vii) was obtained.
Yield 86%

[0024]

[Chemical 5]

Example 1 Of the bleaching detergent composition having the composition shown in Table 1, the bleaching components (bleach activator, sodium percarbonate and SKS-6) were removed, and the detergent components were made into a slurry having a water content of 60%. , Spray dried. The particles were put in a stirring granulator and granulated, and then the bleaching component was mixed to prepare a detergent powder. The washing rate when various compositions of the bleach activator were changed was determined by the following method. The results are shown in Table 2.

<Method of measuring the washing rate> 500 g of spinach was sufficiently crushed in a mortar, 100 cc of water was added and wrapped in a cloth, and then squeezed to remove the fiber portion, and spinach juice was applied to a cotton cloth (4 × 4 cm, 1.2 ml of gold cloth 2003) was evenly applied, and the cotton cloth was dried in a constant temperature bath at 60 ° C. for 1 hour and used as a contaminated cloth. Four sets of these contaminated cloths are used as one set, washed with a tergotometer under the following conditions, dehydrated, and then 300cc
Rinse with tap water for 1 minute before and after washing.
The reflectance in nm was measured, and the cleaning rate was calculated by the following formula. Cleaning rate (%) = (L ₂ −L ₁ ) / (L ₀ −L ₁ ) × 100 L ₀ : Reflectivity of original cloth L ₁ : Reflectivity of contaminated cloth before cleaning L ₂ : Reflection of contaminated cloth after cleaning Rate cleaning conditions hardness 4 ° DH, temperature 20 ° C, rotation speed 100 rpm, time 15 minutes, detergent concentration 0.11 g / 1 liter

[0027]

[Table 1]

Note) * 1: Alkyl group having a carbon number of 12 to 14 straight chain alkylbenzene sulfonate * 2: Alkyl group having a carbon number of 12 to 16 sodium alkyl ether sulfate * 3: Hoechst layered silicate

[0029]

[Table 2]

Note) * 1: N, N, N ', N'-tetraacetylethylenediamine Example 2 With respect to the bleaching detergent composition having the composition shown in Table 3, cleaning was performed when the composition of the bleach activator was variously changed. The rate was calculated by the following method. The cleaning agent was prepared by a method of dry blending with a kneader. The results are shown in Table 4. <Washing rate measurement method> 500 g of spinach was sufficiently crushed in a mortar, 100 cc of water was added, wrapped in a cloth, and then squeezed to remove the fiber portion, and spinach juice was applied to a cotton cloth (4 x 4
cm, gold cloth (2003 cloth) so that 1.2 ml of the solution was evenly applied, and the cotton cloth was dried in a constant temperature bath at 60 ° C. for 1 hour and used as a contaminated cloth. One set of 4 pieces of this contaminated cloth is immersed and washed in the beaker under the following conditions, dehydrated, and then washed with 300cc of tap water.
After rinsing for minutes, the reflectance at 420 nm before and after washing was measured, and the washing rate was calculated by the same formula as in Example 1. Cleaning conditions Hardness 4 ° DH, Temperature 30 ° C, Immersion time 60 minutes, Concentration 1.1g / 1
liter

[0031]

[Table 3]

Note) * 1: Polyoxyethylene alkyl ether (alkyl group has 12 carbon atoms, ethylene oxide average addition mole number is 8) * 2: Alkyl group having 12 to 14 carbon atoms, linear alkylbenzene sulfonic acid sodium

[0033]

[Table 4]

Note) * 1: N, N, N ', N'-tetraacetylethylenediamine Example 3 A bleaching detergent composition was prepared according to the formulation shown in Table 5, and the cleaning bleaching effect was measured by the following method. did. The results are shown in Table 5. The bleach activators (1) to (4) in Table 5 have the compositions shown in Table 6.

<Method for measuring cleaning bleaching effect> Squalene and linoleic acid (weight ratio 100), which are considered to be the components of the yellowing component.
/ 1) is dissolved in chloroform (10% concentration), 0.4 ml of a cotton cloth (gold cloth 2003 cloth, 4 x 4 cm) is evenly applied, and the cloth is kept in a constant temperature bath at 50 ° C. After being left for one week, a cloth having a b value of 7 or more was used as a yellowed model-contaminated cloth. Four sets of this contaminated cloth were washed with a tergotometer under the following conditions, the b values before and after washing were compared, and the washing rate was calculated by the following formula. Note that b
The value is generally known as an index for measuring yellowness. Cleaning rate (%) = (b ₂ −b ₁ ) / (b ₀ −b ₁ ) × 100 b ₀ : b value of original fabric b ₁ : b value of contaminated fabric before cleaning b ₂ : b of contaminated fabric after cleaning Value Washing condition Hardness 4 ° DH, Temperature 20 ° C, Rotation speed 80rpm, Time 15 minutes, Cleaning agent concentration 0.1g / 1L, Rinse 3 minutes (300cc tap water)

[0036]

[Table 5]

Note) * 1: Alkyl group containing 12 to 14 carbon atoms of linear alkylbenzene sulfonic acid soda * 1: Polyoxyethylene alkyl ether (alkyl group containing 12 carbon atoms, ethylene oxide average addition mole number 8) * 3: Hoechst layered silicate

[0038]

[Table 6]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C11D 3:34 3:39)

Claims (4)

[Claims] 1. A bleaching activator represented by the general formula (I) (A) and a bleaching activator represented by the general formula (II) (I):
(II) = 100: 1 to 5: 1 (weight ratio) mixture
0.1 to 50% by weight [Chemical formula 1] (In the formula, R represents a linear alkyl group having 11 to 13 carbon atoms, and L represents a leaving group.) (B) Bleaching washing characterized by containing 0.5 to 90% by weight of hydrogen peroxide releasing substance Agent composition. 2. A bleach activator leaving group, L, is of the formula --CO.
OM or -SO ₃ M (M is H, alkali metal, an alkaline earth metal or ammonium ion) bleaching detergent composition according to claim 1, wherein a group represented by. 3. The bleaching detergent composition according to claim 1, wherein the hydrogen peroxide releasing agent as the component (B) is a percarbonate. 4. The bleaching activator of the component (A) has the general formula (II
The bleaching detergent composition according to claim 1, which is a mixture of the bleaching activator represented by I) and the bleaching activator represented by the general formula (IV). [Chemical 2]