JP3169584B2 - Bleach detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bleaching detergent composition having excellent aroma stability.

[0002]

BACKGROUND OF THE INVENTION Problems to be Solved by the Invention
Bleach activator as disclosed in JP 9-78093
Bleach detergent compositions containing percarbonates, surfactants, alkalis and perfumes are known. However, when a highly lipophilic ester-based fragrance and a lipophilic acyloxybenzene-type bleach activator are blended, there is a problem that an unpleasant odor remains in the clothing after washing and dehydration. Although the cause is not clear, the odor changes during storage or washing because the lipophilic ester-based fragrance is denatured and decomposed by contact with an organic peracid or alkaline agent generated from a lipophilic bleach activator. I think that the.

[0003] It is therefore an object of the present invention to provide a bleaching detergent composition which ameliorates these disadvantages.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides: (a) a percarbonate; (b) a bleach activator having a solubility of 5 g or less in 100 g of water (pH 6) at 20 ° C. (c) an ester-based fragrance (d) Bleaching detergent composition containing particles containing an anionic surfactant, a water-soluble polymer having an anionic group and a carbonate, wherein the carbonate is unevenly distributed inside (hereinafter simply referred to as a composition)
I will provide a.

[0005]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, (a) a percarbonate is blended. The counter ion of the component (a) is an alkali metal such as sodium. As the component (a), a percarbonate coated with an inorganic compound or the like can be used. For example, it can be produced by a known method such as a method of coating sodium percarbonate with borate described in Example 1 of JP-A-59-196399.
Component (a) is preferably contained in the composition in an amount of 0.1 to 5% by weight, particularly 0.5 to 3% by weight, from the viewpoints of the bleaching effect and storage stability.

In the present invention, (b) a bleach activator is blended. As the component (b), in terms of lipophilic stain cleaning power,
Those having high lipophilicity are preferred. The bleach activator of the present invention
The solubility in 100 g of water (pH 6) at 20 ° C. is 5 g or less, preferably 3 g or less. Here, the solubility in water is pH
After adding 10 g of the bleaching activator to 100 g of water of No. 6 and stirring for 40 minutes, the mixture was filtered off with a membrane filter (0.2 μm).
It can be determined by analyzing the filtrate by high performance liquid chromatography. In addition, it is used for the measurement of solubility.
The pH 6 water is prepared by appropriately adding a 1 / 10N-sodium hydroxide aqueous solution and / or a 1 / 10N-sulfuric acid aqueous solution to ion-exchanged water.

As the bleaching activator (b), a bleaching activator of the following general formula (I) or (II) is particularly preferred.

[0008]

Embedded image

Wherein R is an alkyl group having 10 to 13 carbon atoms,
R ′ is an alkyl group having 7 to 11 carbon atoms, and M represents a hydrogen atom or an alkali metal, alkaline earth metal, ammonium or alkanolamine. ].

The component (b) is preferably contained in the composition in an amount of 0.1 to 2% by weight, particularly 0.1 to 1.5% by weight, from the viewpoints of bleaching effect and aroma stability.

(B) The bleach activator is preferably incorporated into the composition as granules. The amount of bleach activator in the granulate is 1-90% by weight, preferably 10-70% by weight, more preferably 30-70% by weight. In order to improve the solubility of the bleaching activator in the washing bath, an anionic surfactant, particularly an alkyl sulfate or a polyoxyethylene alkyl ether sulfate or a mixture thereof is added to the granulated product. It is preferable to add 0 to 50% by weight, preferably 5 to 45% by weight, more preferably 10 to 40% by weight in the granules. The alkyl sulfate has 10 to 18 carbon atoms and is preferably an alkali metal salt such as a sodium salt, and particularly preferably sodium lauryl sulfate or sodium myristyl sulfate. As the alkyl ether sulfate, a polyoxyethylene alkyl ether sulfate having 10 to 18 carbon atoms is preferable, and an alkali metal salt such as a sodium salt is preferable. The average number of moles of ethylene oxide added (hereinafter referred to as EOP) is 1 to 10, especially 1 to 5
Is good. Particularly, sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate having EOP of 2 to 5 are preferable.

The granulated bleach activator can be formulated using a binder selected from polyethylene glycol or fatty acid. The average molecular weight of the polyethylene glycol is preferably 2,000 to 20,000, preferably 4000 to 10,000, and more preferably 4000 to 8000. In addition, the fatty acid has 8 to 20 carbon atoms, preferably 10 to 18, more preferably 12 to
18, which may be in the form of sodium or potassium soaps. Such a binder substance is incorporated in the granulated product in an amount of 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight.

If desired, an acidic substance may be added to the granulated product for the purpose of improving the stability of the bleaching activator. Carboxylic acids are preferred as the acidic substance, especially succinic acid,
Maleic acid, fumaric acid, citric acid, glycolic acid, p
At least one selected from -hydroxybenzoic acid is preferred. The compounding amount of the acidic substance is 0 to 20% by weight in the granulated material,
Preferably 1 to 15% by weight, more preferably 1 to 10% by weight
Is preferred.

The granulated product of the bleaching activator can be obtained by mixing and granulating the above-mentioned components by an arbitrary method. In particular, a part or all of the bleaching activator and the anionic surfactant are firstly used. And then adding a binder substance. Further, it is preferable to add the binder substance after melting it in advance. The binder material is added by melting at 40 to 100 ° C, preferably 50 to 100 ° C, more preferably 50 to 90 ° C. These are stirred and mixed until they become uniform, and then formulated by a usual granulator. Extrusion granulation can be mentioned as a preferable granulation method, and the average particle size is 500 to 50.
Granules of 00 μm, preferably 500-3000 μm are preferred. Further, as another granulation method, a granulation method using a briquette machine and the like can be mentioned.

In the present invention, (c) an ester flavor is blended. The boiling point of ester flavor is 220 from the point of residual fragrance.
C. or higher, particularly preferably 250 to 300.degree. Examples of such ester-based fragrances include those described in “Chemistry of fragrances” (edited by The Chemical Society of Japan, Industrial Chemistry Series, Ryoichi Akahoshi, Dai Nippon Tosho Co., Ltd.), and specifically, benzyl salicylate ( Pt-butylcyclohexyl acetate (boiling point 232 ° C), terpinyl acetate (boiling point 300 ° C)
220 ° C), phenylethyl acetate (boiling point 245 ° C),
Phenylethyl formate (boiling point 226 ° C), n-bornyl acetate (boiling point 223 ° C), geranyl acetate (boiling point
245 ° C), citoneryl propionate (boiling point 242 ° C),
Geranyl propionate (boiling point 253 ° C), terpinyl propionate (boiling point 240 ° C), benzyl salicylate
(Boiling point: 300 ° C.), particularly preferably pt-butylcyclohexyl acetate, phenylethyl acetate, and geranyl propionate. (C) ester-based fragrances
0.01 to 5% by weight, preferably 0.1 to 3% by weight in the composition
Be blended.

[0016] The composition of the present invention comprises an anionic surfactant,
Particles containing a water-soluble polymer having an anionic group and a carbonate, wherein the carbonate contains particles (d) unevenly distributed therein. Here, the uneven distribution means that in the structure of the particle, more carbonate is present inside the particle than near the surface. The uneven distribution of carbonate can be confirmed as follows.
First, the particle surface (depth about 20μm) by FT-IR / PAS
Measure the IR intensity of CO ₃ . Next, the particles are ground in a mortar, and the IR intensity of CO ₃ is measured by the same FT-IR. When the former strength is smaller than the latter strength, the carbonate is unevenly distributed inside. At this time, (IR intensity of particle surface) /
(IR strength after grinding) is preferably less than 0.8, particularly preferably less than 0.5.

As the carbonate, an alkali metal salt such as sodium carbonate and potassium carbonate is preferable from the viewpoint of solubility.

The particles (d) of the present invention contain an anionic surfactant. Examples of the anionic surfactant include an alkylbenzene sulfonate, an alkyl sulfate, and an alkyl ether sulfate. The anionic surfactant is preferably used in the composition in an amount of 15 to 40% by weight, particularly 20 to 40% by weight in view of detergency and foaming during washing.

Among the anionic surfactants, the alkylbenzene sulfonate preferably has 10 to 20 carbon atoms,
Alkali metal salts such as sodium or potassium salts are preferred. The alkyl sulfate or alkyl ether sulfate is the same as that used for the granulated bleach activator.

In the present invention, if desired, a nonionic surfactant may be added to the particles (d). Examples of the nonionic surfactant include polyoxyethylene or polyoxypropylene or a copolymer thereof, polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, Alkyl glycosides and the like can be mentioned, and in particular, a polyoxyethylene alkyl ether having an alkyl group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, and having an EOp of 4 to 20, preferably 5 to 15 is preferable.

The particles (d) may contain a cationic surfactant or an amphoteric surfactant. Quaternary ammonium salts and the like are used as the cationic surfactant, and amine oxide, sulfobetaine,
Carbobetaine and the like.

The particles (d) of the present invention contain a water-soluble polymer having an anionic group. Such polymers include polyacrylates, polymethacrylates, polymaleates, polystyrenesulfonates and the like, which are homopolymers or copolymers of two or more. Of these, polyacrylates having a molecular weight of 4000 to 20,000 and acrylic acid-maleic acid copolymers having a molecular weight of 20,000 to 100,000 are particularly preferable.

The particles (d) of the present invention may contain a crystalline or amorphous silicate or a sequestering agent. The silicates are added to the composition at 1 to 30% by weight, preferably 5 to 20% by weight, and the sequestering agent is added to the composition at 1 to 50% by weight, preferably 2 to 30% by weight. Zeolite, citric acid, succinic acid, nitrilotriacetate,
Organic carboxylate such as ethylenediaminetetraacetate is preferred.

The average particle size of the particles (d) of the present invention is 200
800800 μm is preferred.

Usually, the bleaching detergent composition is obtained by pulverizing a water slurry of a builder component or a surfactant by a method such as spray drying, and then granulating or sizing the granules with a granulator or a granulator.
Further, it is manufactured by a method of mixing components such as a builder component, a fragrance, and an enzyme. In the present invention, it is preferable to add a carbonate to a water slurry before spray drying. The concentration of carbonate in the water slurry is 1 to 50% by weight, preferably 5 to 30% by weight. In addition, anionic surfactant is 10 to 50% by weight,
Preferably it is 15 to 40% by weight. The water-soluble polymer having an anionic group is 0.5 to 20% by weight, preferably 1 to 20% by weight.
10% by weight. Further, the sequestering agent is 5 to 30% by weight, preferably 7 to 25% by weight. Further, the amount of water is such that the solid content of the above components is 40 to 80% by weight, preferably 50 to 70% by weight. In the present invention, a preferable result is obtained by setting the weight ratio of the carbonate to the total of the anionic surfactant and the polymer having an anionic group in the water slurry to 1/10 to 1/5. The temperature at which the water slurry is spray-dried is 150 ° C to 220 ° C, preferably 170 ° C to 2 ° C.
20 ° C. By setting such very narrow spray drying conditions, the carbonate can be unevenly distributed inside the particles.

The alkaline agent may be added to the composition within a range that does not impair the effects of the present invention. However, most of the alkaline agent must be incorporated unevenly in the particles (d) of the present invention. Is preferred. Further, other fragrances other than the ester-based fragrance may be blended as long as the effects of the present invention are not impaired.

[0027]

According to the present invention, it is possible to provide a bleaching detergent composition comprising an ester-based fragrance and an acyloxybenzene-type bleaching activator, which is excellent in the stability of aroma and the odor of clothes after washing and dehydration. it can.

[0028]

EXAMPLES (1) Preparation of Granulated Bleaching Activator Granules shown in Table 1 were prepared by the following method using the following compounds. A-1: Sodium lauryl sulfate [Emal 10 powder, manufactured by Kao Corporation] A-2: Sodium polyoxyethylene lauryl ether sulfate [Emal A 70C, manufactured by Kao Corporation] B-1: Polyethylene glycol [molecular weight: 8,000, manufactured by Aldrich Corporation B-2: Myristic acid [Lunac MY-98, manufactured by Kao Corporation] C-1: Sodium lauroyloxybenzenesulfonate [Solubility in water 0.1 g / 100 g or less (20 ° C., pH 6)] C-2: Deca Noyloxybenzoic acid (solubility in water 0.1
g / 100 g or less (20 ° C., pH 6)] C′-1: Sodium nonanoyloxybenzenesulfonate [solubility in water 8.4 g / 100 g (20 ° C., pH 6)] D-1: Succinic acid • Granulation Method Fukae Kogyo Co., Ltd. so that the components shown in Table 1 would be 5 kg in total.
Was mixed and heated at a jacket temperature of 80 ° C, a spindle rotation speed of 200 rpm, and a crushing blade rotation speed of 1500 rpm, and the powder temperature reached 70 ° C. By the way, I pulled it out. Then, the obtained mixture is extruded with a granulator (Fuji Paudal Co., Ltd., Pelletter Double EXD-
(Type 100) through a screen having a pore size of 800 μm. Vibration cooler (Vibration / Flow dryer VDF / 6000 type, manufactured by Fuji Paudal Co., Ltd.)
Then, the mixture was pulverized with a granulator (a knife cutter FL-200 type, manufactured by Fuji Paudal Co., Ltd.). The obtained crushed product was classified to obtain a granulated product having an average particle size of 900 μm.

[0029]

[Table 1]

(2) Preparation of sodium percarbonate Sodium percarbonate PC-1 coated with 5% of sodium metaborate tetrahydrate was prepared according to Example 1 of JP-A-59-196399.

(3) Fragrance A fragrance composition shown in Table 2 below was used.

[0032]

[Table 2]

(4) Preparation of Particle (d) Particle A 2 kg of linear alkyl (C10-13) sodium benzenesulfonate (Alken L manufactured by Nippon Oil Detergent Co., Ltd.), sodium alkyl sulfate (Kao Corp.) 0.5 kg of polyoxyethylene alkyl ether (Emulgen 510L manufactured by Nippon Shokubai Co., Ltd.), 0.3 kg of acrylic acid-maleic acid copolymer (Sokaran cp-5 manufactured by BASF), 0.3 kg of sodium tallow fatty acid, 0.3 kg of sodium carbonate 0.6kg, 1
No. silicate 1.5kg, 4A type zeolite 1.5kg, sodium sulfate, polyethylene glycol (molecular weight 800
0) A water slurry having a solid content of 60% from 0.1 kg is prepared and spray-dried (at a drying temperature of 190 ° C.), and the resulting particles are subjected to a high speed mixer (FS-GC-10) manufactured by Fukae Kogyo Co., Ltd. And granulation was carried out to obtain particles A. Average particle size 400 μm, bulk density 750 g / L. Carbonate / (anionic surfactant + water-soluble polymer) = 0.194.

Particle B: 1.5 kg of straight chain alkyl (C10-13) sodium benzenesulfonate (Alken L manufactured by Nippon Oil Detergent Co., Ltd.), 0.5 kg of sodium alkyl sulfate (Emal 10 powder manufactured by Kao Corporation), 0.3 kg of polyoxyethylene alkyl ether (Nippon Shokubai Co., Ltd. Emulgen 510 L), sodium carbonate 2.
0 kg, No. 1 silicate 0.6 kg, Acrylic acid-maleic acid copolymer (Socaran cp-5 manufactured by BASF) 0.3 kg, Sodium tallow fatty acid 0.3 kg, Glauber's salt used for balance, polyethylene glycol (molecular weight 8000) 0.1 kg to 30% solids Water slurry is prepared and spray-dried (250 ° C.), and the resulting particles are subjected to a high speed mixer (FS) manufactured by Fukae Kogyo Co., Ltd.
-GC-10 type) and granulated. Then blend,
Particle B was obtained. Average particle size 400μm, bulk density 730g / L.
Carbonate / (anionic surfactant + water-soluble polymer) = 0.
77.

<Measurement of Na ₂ CO ₃ distribution> Photoacoustic spectrometer (MT
Using an FT-IR device (PAS-300 manufactured by EC Co., Ltd.) (FTS-60A manufactured by Bio-Rad Co., Ltd.), the depth of the particles was 20 μm.
The FT-IR of m was measured. Next, each particle was ground in a mortar and measured by FT-IR. Mashed in a mortar
Assuming that the intensity of CO ₃ absorption is 1, the intensity of CO _{3 on} the particle surface is 0.43 for particle A, 0.95 for particle B, and Na ₂ CO ₃
Were unevenly distributed inside, and it was confirmed that the particles B had Na ₂ CO ₃ almost uniformly present in the particles.

(5) Preparation of bleaching detergent composition and performance evaluation The above-mentioned granulated bleaching activator, PC-1, perfume and (d)
The bleaching detergent compositions of Table 3 were prepared using the particles. Their bleaching performance and aroma stability were evaluated by the following methods. Table 3 shows the results.

<Evaluation of Aroma Stability> 20 g of the composition was added to a 50 ml ternary container and stored for one month at 40 ° C./80% humidity. Thereafter, the odor was evaluated by ten skilled panelists, and the evaluation was performed according to the following criteria, and the average score was determined for each.
An average score of 3.5 to 4.0 is represented by ◎, a score of 3.0 to less than 3.5 is represented by ○,
2.0 to less than 3.0 were rated as “△”, and less than 2.0 were rated as “×”. Table 3 shows the results. 4: Same as before storage 3: Slightly changed before storage but not noticeable 2: Changed before storage 1 ... Changed significantly before storage and not endurable <Bleaching performance and after dehydration Aroma evaluation> 1 mL of commercially available lard oil was dropped from a dropper onto a 10 × 10 cm cotton / gold cloth # 2003, and dried at a stage where the liquid had sufficiently spread in a well-ventilated shade for 1 day to prepare a lint-contaminated cloth. Composition shown in Table 3 0.833
g was dissolved in 1 L of tap water, and five rag oil-contaminated cloths were washed with a tergotometer (20 ° C., 10 minutes, 100 rpm). afterwards,
Rinsing / dehydration was performed, and the odor after dehydration was evaluated by 10 panelists according to the following criteria, and the average score of each was determined. An average score of 3.5 to 4.0 is indicated by ◎, a score of 3.0 to less than 3.5 is indicated by ○, 2.
0 to less than 3.0 was rated as “△”, and less than 2.0 was rated as “×”. Table 3 shows the results. 4 ... Refreshing scent remains 3 ... Slight odor in the scent but not noticeable 2 ... Slight odor in the scent 1 ... Feel a strong odor Then press the stained cloth after dehydration, The bleaching ratio was calculated by the following equation.

[0038]

(Equation 1)

The reflectivity was measured by NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd.
Measured using a 460 nm filter.

[0040]

[Table 3]

The products of the present invention all showed good results in both bleaching performance and odor stability. However, the particles B used in Comparative Product 1 had poor aroma stability (residual odor after washing) because the alkaline agent was present on the particle surface. In addition, comparative product 2
Since a bleach activator having a solubility in water of 5 g / 100 g or more was used, it was inferior in bleaching detergency against lipophilic stains.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazutoshi Ide 1334 Minato, Wakayama-shi, Wakayama Kao Corporation Laboratory (56) References JP-A-9-78093 (JP, A) JP-A-8-1557878 (JP) , A) JP-A-10-251685 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 3/10-3/50

Claims (5)

(57) [Claims] 1. A percarbonate (b) A bleach activator having a solubility of 5 g or less in 100 g of water (pH 6) at 20 ° C. (c) An ester-based fragrance (d) An anionic surfactant, an anionic group a particle containing a water-soluble polymer and a carbonate having the ratio (particle surface of the IR intensity of the CO ₃ after the carbonate was triturated with IR intensity and particles of CO ₃ ubiquitous within [particle surface IR intensity) /
(IR strength after grinding) is less than 0.8]. 2. (a) 0.1 to 5% by weight of percarbonate (b) 0.1 to 2% by weight of a bleach activator having a solubility of 5 g or less in 100 g of water (pH 6) at 20 ° C. (c) Ester fragrance 0.01 to 5% by weight (d) Particles containing an anionic surfactant, a water-soluble polymer having an anionic group and a carbonate, wherein the carbonate is unevenly distributed inside [the IR intensity of CO _{3 on} the surface of the particle and the particle Ratio of IR intensity of CO ₃ after grinding (IR intensity of particle surface) /
(Meaning that the IR intensity after grinding) is less than 0.8], and the proportion of an anionic surfactant in the composition is 15 to 40% by weight. 3. The bleach activator according to the general formula (I) or (II)
The bleaching detergent composition according to claim 1 or 2, which is a compound represented by the formula: Embedded image Wherein R is an alkyl group having 10 to 13 carbon atoms, and R ′ is an alkyl group having 7 carbon atoms.
And M is a hydrogen atom or an alkali metal, alkaline earth metal, ammonium or alkanolamine. ] 4. A water-soluble polymer having an anionic group,
Polyacrylate having a molecular weight of 4000 to 20000 and a molecular weight of 2000
Selected from ~ 100,000 acrylic acid-maleic acid copolymers
A bleaching detergent composition according to any one of claims 1 to 3.
object. 5. An anionic surfactant, wherein (d) is an anionic surfactant.
0.5 to 20% by weight of a water-soluble polymer having a hydroxyl group and a carbonate
1 to 50% by weight, and an anionic surfactant and an anionic surfactant.
Carbonate based on the total of water-soluble polymers having ionic groups
Spray drying of water slurry with weight ratio of 1/10 to 1/5
5. The particles according to claim 1, wherein the particles are obtained by the following method.
Bleaching detergent composition.