JPH09235600A - High bulk density bleaching detergent composition packed in transparent bottle container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high bulk density bleaching detergent composition causing no blocking with the passage of time by packing a high bulk density bleaching detergent containing specific amounts of sodium percarbonate, a specific bleaching activator and an anionic surfactant in a transparent synthetic resin bottle container which permits extremely low transmittance of the light at a specific wavelength. SOLUTION: This bleaching composition contains (A) 1-25wt.% of an oxidative bleaching base agent generating hydrogen peroxide in water (preferably sodium percarbonate), (B) 1-15wt.% of a bleaching activator of formula I or formula II (R<1> is a 9-13C alkyl, alkenyl; R<2> is a 7-13C alkyl, alkenyl; M is H, a cation which makes the bleaching activator soluble in water) and (C) 5-50wt.% of a surfactant and is in the form of granules with a bulk density of 0.6-1.2g/cc. The granular detergent is packed in a container made of a transparent synthetic resin having transmittance of <=2% to the light of 350nm wavelength. The component B is desirably added in the form of granules and an organic binder is preferably used for granulation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a high bulk density bleaching detergent composition used for washing clothes and the like, and more particularly to a high bulk density bleaching detergent composition contained in a transparent container.

2. Description of the Related Art Conventional granular detergents are generally made of processed paper as a container from the viewpoints of low cost and ease of manufacture and molding. Therefore, there are drawbacks that the contents cannot be confirmed after the detergent is filled and that the detergent is easily solidified because moisture can easily pass therethrough. On the other hand, as in the case of the kitchen / household detergent or the hair shampoo / rinse, even in granular detergents, it is generally practiced to add a small amount of pigments or dyes to give a beautiful appearance and enhance the image of the product. Further, a high bulk density detergent composition has been put on the market to improve the flowability and usability, and a high bulk density bleaching detergent composition has also been proposed. Therefore, in order to improve the usability and appearance of the high bulk density granular bleaching detergent, it is considered preferable to use a transparent synthetic resin container. However, it was found that when a high-bulk density bleaching detergent containing sodium percarbonate, a bleaching activator and an anionic surfactant is stored in a transparent resin container, the high-bulk density bleaching detergent solidifies with time. .

[0002]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high bulk density bleaching detergent with improved solidification over time.

According to the present invention, a high bulk density bleaching detergent containing sodium percarbonate, a specific bleaching activator and an anionic surfactant in a specified amount has an extremely low transmittance for light of a specified wavelength. This was done based on the finding that the above problem can be solved by storing the transparent synthetic resin in a container. That is, the present invention comprises (a) 1 to 25% by weight of an oxygen-based bleaching base compound that generates hydrogen peroxide in water,
(B) 1 to 15% by weight of the bleach activator represented by the general formula (I) or (II) and 5 to 50% by weight of the surfactant (c).
A granular detergent having a bulk density of 0.6 to 1.2 g / cc containing
Provided is a high bulk density bleaching detergent composition in a transparent container, which is housed in a transparent synthetic resin container having a transmittance of light having a wavelength of 350 nm of 2% or less.

[0003]

Embedded image

(R ¹ is an alkyl group or alkenyl group having 9 to 13 carbon atoms, R ² is an alkyl group or alkenyl group having 7 to 13 carbon atoms, and M is hydrogen or bleaching activator. It is a cation.)

BEST MODE FOR CARRYING OUT THE INVENTION As the oxygen-based bleaching base compound which generates hydrogen peroxide in water as the component (a) used in the present invention, percarbonates such as sodium percarbonate and potassium percarbonate and sodium perborate are used. Among these, one or a mixture of two or more such as perborate and the like can be mentioned, and sodium percarbonate is preferable. The amount of the component (a) in the bleaching detergent composition is preferably 1 to 25% by weight (hereinafter abbreviated as%), more preferably 2 to 10%. The bleach activator used in the present invention is represented by the general formula (I) or (II) above.
It is represented by. In the formula, examples of M include hydrogen and alkali metals such as sodium and potassium, amines such as ammonium and alkanolamine.
Of these, alkali metals are preferred. In the formula, the SO ₃ M group and COOM group can be in the ortho, meta or para position, but the para position is preferred.

In the present invention, these bleaching activators can be used alone or as a mixture of two or more kinds. These bleach activators can be used in an amount of about
Since it is obtained as a plate-like crystal having a size of m to 100 μm, it may be pulverized by an ordinary method so that the average particle size is smaller than 300 μm, preferably about 200 to 100 μm. However, if the average particle diameter is obtained as less than 300 μm, preferably about 200 to 100 μm by the method for producing a bleach activator, it can be used as it is. In the present invention,
A raw material bleach activator having an average particle size of more than 300 μm may be used.

In the present invention, the bleaching activator can be added as it is to the bleaching detergent composition, but it is preferable to add it as a granulated product, and especially the one which is granulated with an organic binder is added. Preferably. The organic binder used here is preferably a water-soluble one that is solid at room temperature and melts by applying heat, more preferably having a melting point of 25 to 100 ° C., further preferably 25 to 80 ° C.
The organic binder is at 40 ° C, most preferably 40 to 80 ° C. Among these, especially the average molecular weight is 400 to 30,000.
It is preferable to use polyethylene glycol, more preferably 1000 to 20000, and most preferably 4
000 to 20,000 polyethylene glycol.
It is also preferable to use a polyethylene glycol addition type nonionic surfactant, specifically, a carbon number of 8 to 20.
Ethylene glycol is 3 to 80 mol, preferably 1 to 1 mol (preferably 10 to 18) of aliphatic alcohol.
Those added with 0 to 50 moles are preferable. Particularly, when polyethylene glycol and / or polyethylene glycol-added nonionic surfactant is used among various organic binders, the solubility of the resulting bleach activator granules can be improved. Further, if necessary, an anionic surfactant such as a linear alkylbenzene sulfonate, an alkyl sulfate, an α-sulfo fatty acid ester salt, an α-olefin sulfonate may be used.

The use ratio of the bleach activator and the organic binder can be arbitrary, but the content of the bleach activator is 5
0% or more, preferably 50 to 90%, more preferably 6
It is preferable that 5% to 80% and the balance be an organic binder. The nonionic surfactant as the organic binder used here is also the component (c) used in the present invention. The amount of component (b) in the bleaching composition is preferably 1 to 15%, more preferably 1 to 10%. The bleach activator granulated product can be produced, for example, by the following method. First, a bleaching activator and an organic binder (binder) were introduced into a kneading extruder, preferably a closed compaction treatment device, more preferably a horizontal continuous kneader, and both were mixed in the kneader. After that or while mixing, the binder is melted and a shearing force is applied to it to 25 to 100.
The consolidation treatment is performed at ℃, preferably 45 to 80 ℃. or,
In addition to the kneader, a single-screw or twin-screw extruder can be used. As the kneading extruder used here, specifically, KRC manufactured by Kurimoto Iron Works Co., Ltd.
Kneader and so on. By such kneading and extrusion, it is preferable to obtain a consolidated product having a bulk density of 0.3 to 0.9 g / ml.

A kneaded extrudate having an arbitrary shape can be obtained by the above kneading extrusion, but a cylindrical shape, a prism or a triangular prism having a diameter of 0.5 to 30 mm, preferably 0.7 to 20 mm, more preferably about 1 to 20 mm. It is preferable to extrude such as a strand, a spherical, plate-shaped, or noodle-shaped granulated product. As an extruding method, a mesh plate with a hole may be attached to the outlet of the consolidating device, and a granulated product may be obtained through the plate. In this case, a specific example of the processing apparatus used is Extruded Omics manufactured by Hosokawa Micron Corporation. Further, an extruder may be used for such a granulated product. Examples of the extruder include a pelletizer double (Fuji Paudal Co., Ltd.) and a twin dome gran (Fuji Paudal Co., Ltd.).

As the surfactant as the component (c) used in the present invention, a linear or branched alkyl (average carbon chain length 8 to 1
8) Benzenesulfonate, long-chain alkyl (average carbon chain length 10 to 20) sulfonate, long-chain olefin (average carbon chain length 10 to 20) sulfonate, long-chain monoalkyl (average carbon chain length 10 to 10) 20) Sulfate ester salt, polyoxyethylene (average degree of polymerization 1-10) long-chain alkyl (average carbon chain length 10-20) Ether sulfate ester, polyoxyethylene (average degree of polymerization 3-30) alkyl (average carbon chain) Length 6-12) Phenyl ether sulfate ester salt, α
-Sulfo fatty acid ester salt (average carbon chain length 10 to 2
0), long-chain monoalkyl, dialkyl or sesquialkyl phosphates, polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates and the like are used. These anionic surfactants may be added in the form of acid,
It may be used as an alkali metal salt such as sodium or potassium, an amine salt or an ammonium salt.

Various nonionic surfactants can be used, for example, primary or secondary nonionic surfactants having 8 to 18 carbon atoms.
EO-added nonionic surfactant obtained by adding 4 to 50 mol of ethylene oxide on average to a primary alcohol, carbon number 8
To 18 primary and secondary alcohols with an average of 4 to 50 mol of ethylene oxide and an average of 3 with propylene oxide.
To 15 mol of EO-PO-added nonionic surfactant, sugar-fatty acid ester type nonionic surfactant obtained from fatty acid having 6 to 16 carbon atoms and sugars such as glucose, and alcohol having 6 to 16 carbon atoms It is preferable to use one kind or a mixture of two or more kinds of sugar-alcohol ether type nonionic surfactants obtained from sugars such as glucose. Also, amphoteric surfactants such as alkyl betaines can be used.

The above surfactants can be used alone or as a mixture of two or more. Of the above-mentioned surfactants, linear alkylbenzene sulfonates, olefin sulfonates, α-sulfo fatty acid ester salts, and alkyl sulfates are preferable. The amount of component (c) in the bleach composition is
It is preferably 5 to 50%, more preferably 10 to
40%. The bleaching detergent composition of the present invention can contain various optional components in addition to the above components. For example, alkali builder such as tripolyphosphate, pyrophosphate, sodium carbonate, potassium carbonate, organic chelate builder such as EDTA, neutral builder such as sodium sulfate, silicon dioxide, zeolite, bentonite, talc, clay, titanium oxide, calcium carbonate. , Fragrances, dyes, optical brighteners, etc. can be contained. Of these, the fluorescent whitening agent is preferably contained in the bleaching detergent composition in an amount of 0.05 to 2.0%, more preferably 0.1 to 1.0%.

The high bulk density bleaching detergent of the present invention is, for example,
First, a detergent kneaded product of 0.7 to 1.5 containing the component (c) and the above optional components is prepared. Such a detergent kneaded product,
The spray-dried product such as the above-mentioned surfactant and other components are kneaded together with a kneader such as a kneader, or the high-concentration slurry or powder of the above-mentioned surfactant is kneaded with the other components together such as a kneader. It can be easily prepared by kneading with a machine. It is also possible to use the same kneader as that used to produce the kneaded product of the bleach activator and organic binder described below. The production conditions of the kneaded product are, for example,
It is described in JP-A-6-39599, and the contents of this publication are included in the present specification. In the present invention, the detergent kneaded product produced in this manner may be of any size, but the diameter is 5 to 2
It is preferable to use one having a size of 0 mm and a length of 10 to 30 mm.

Next, the high-density detergent kneaded product is pulverized in the presence or absence of the bleach activator granule. Grinding is preferably performed using a crushing granulator, and a mixture of a high-density detergent kneaded product and a bleach activator granule may be crushed and granulated, or bleaching may be performed during crush-granulation of the high-density detergent kneaded product. The activator granules may be added to crush and granulate. The bleach activator granules are used in an amount defined in the present invention per 100 parts by weight of the high-density detergent kneaded product. The bleaching agent can be mixed in advance with a high-bulk density bleaching detergent or a bleaching activator granule, but a high-density detergent kneaded product is crushed and granulated in the presence of the bleaching activator granulation. After that, the bleaching agent is preferably added and mixed. Thus, a high bulk density bleaching detergent composition having a bulk density of 0.6 to 1.2 g / cc, preferably 0.7 to 0.9 g / cc can be easily prepared.

In the present invention, such a high bulk density bleaching detergent composition is stored in a transparent synthetic resin container having a transmittance of 2% or less for light having a wavelength of 350 nm. For such a container, synthetic resin such as nylon, polyethylene, polypropylene, vinyl chloride, polystyrene, polyethylene terephthalate, etc. is used, and in addition to the one having a transmittance of 2% or less by itself, an ultraviolet absorber is kneaded in the resin. It can also be easily prepared by incorporating or coating. Here, examples of the ultraviolet absorber that can be used include Tinuvin 316 (manufactured by Ciba Geigy). Further, an antistatic agent or an antioxidant such as Armostat 310 (manufactured by Lion Chemical Co., Ltd.) is kneaded into the resin, or
It can also be applied.

According to the present invention, the solidification property of a high bulk density bleaching detergent composition during long-term storage can be improved. Next, the present invention will be described with reference to examples.

[0015]

【Example】

Example 1 A bleach activator granule was produced by the following methods (1) and (2). (1) Circulating hot water in the jacket of S-2KRC Kneader manufactured by Kurimoto Iron Works Co., Ltd.
Warmed to a temperature of ° C. Next, 1.5 kg of bleach activator and 0.5 kg of organic binder were added to the kneader and kneaded. The resulting kneaded product was extruded using a pelleter double made by Fuji Paudal Co., Ltd. equipped with a die having a hole diameter of 1 mmφ to obtain a bleach activator granule in the form of a noodle having a length of 2 to 3 mm (granulation. Item 1) (2) Bleach activator (1.5 kg) and organic binder (0.5 kg) were added to Hosokawa Micron Ltd. Extruded Ohmics heated to 60 to 80 ° C by circulating hot water, and an intermediate orifice 6 mm, And granules having a length of 5 to 20 mm through a discharge orifice 1 mm were obtained (granulates 2 and 3). The bleach activators used are shown in Table 1 and the types of organic binders are shown. -2.

[0016]

[Table 1] Table 1 Bleaching activator Bleach Activator No. R X AC ₉ H ₁₉ COOH BC ₉ H ₁₉ SO ₃ Na CC ₇ H ₁₅ COOH The bleach activator in the table is represented by the following formula (III).

[0017]

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[0018]

[Table 2] Table-2

The binders in the table are as follows. Organic binder No. 1: PEG6000 Organic binder No. 2: Polyoxyethylene lauryl ether (ethylene oxide average addition mole number 50) Method for producing bleaching detergent (detergents a, b, c) Of which, nonionic surfactants,
A detergent slurry having a solid content of 60% by weight was prepared using an enzyme (Durazyme), sodium percarbonate, a part of zeolite, sodium carbonate, and a bleach activator granulated product shown in Table 2. This slurry was dried at a hot air temperature of 200 to 280 ° C. to a water content of 5% by weight using a countercurrent spray dryer to obtain a spray dried product. Next, a non-ionic surfactant and, if necessary, water were added to the spray-dried product, and the mixture was kneaded with an S-2KRC kneader manufactured by Kurimoto Iron Works Co., Ltd. Using a tardable, a 10 mmφ × 20 mm pellet (water content 8% by weight) in the form of a high density detergent kneaded product was obtained. The temperature of the pellet product was the same as that of the kneaded product, and the product was discharged at 50 to 55 ° C. The pellets were quantitatively fed to a crusher (Okada Seiko S-Bead Mill ND-30). At this time, cold air at 15 ° C. was introduced together with this crushed material at a ratio of 15 liter / kg of crushed material. After crushing, rotate a crushing blade with a diameter of 15 cm at 3000 rpm with 4 stages of cross,
The screen used was a punching metal with a diameter of 2 mm and an aperture ratio of 20%.

Next, 97 parts by weight of the crushed product obtained and 3 parts by weight of A-type zeolite having an average primary particle size of 3 μm were added to a rolling drum (D).
= 30 cmφ, L = 60 cm) Quantitative feed, 30 ppm,
Coating with a distillation time of 5 minutes, powder blending with sodium percarbonate, enzyme, and bleach activator granules, and high bulk density of 0.8 to 0.9 (g / cc) with the composition shown in Table-3. A granular detergent composition having a) was obtained. Method for producing bleaching detergent (d) A solid content of 60 using each component of Table 3 excluding nonionic activator and enzyme, sodium percarbonate, and bleach activator granules.
% Of the detergent slurry was dried using a countercurrent spray dryer at a hot air temperature of 200 to 280 ° C. to a water content of 5% to obtain a spray dried product. Then, a spray-dried product, a nonionic surfactant, and water as needed are added, and a high-speed granulator (FS-GS
Model 55: manufactured by Fukae Kogyo Co., Ltd., was stirred and granulated, and then powdered with an enzyme (protease and lipase), sodium percarbonate, and a bleach activator granulated product to prepare a bleaching detergent.
The particles obtained in this have an average particle size of 500 microns and a bulk density.
0.75 to 0.90 g / cm ³ (Note that after adding the bleaching activator granules and sodium percarbonate, enzyme, nonionic activator, the bleaching detergent should be 100% in the slurry. Adjusted sodium carbonate and dried).

[0021]

[Table 3] Table-3 High-bulk density bleaching detergent composition ──────────────────────────────── Composition (wt%) Detergent a Detergent b Detergent c Detergent d LAS-Na 15 10 20 0 AS-Na 0 0 10 0 α-SF-Na 0 15 0 0 AOS-K 15 5 0 0 Soap 5 5 5 5 Nonionic surfactant 5 5 5 20 Potassium carbonate 5500 Polyethylene glycol 2 2 2 2 Fluorescent agent CBS 0.2 0.2 0.2 0.2 Zeolite (4A type) 20 20 20 20 Sodium silicate 5 0 5 5 MA / AA-Na 5 5 3 3 Sodium percarbonate 10 10 10 10 Bleach activator 3 3 3 3 Durazyme 1 1 1 1 Moisture 5 5 5 5 Sodium carbonate Remainder Remainder Remainder Remainder

LAS-Na: C _{10 to} C ₁₄ sodium linear alkylbenzene sulfonate AS-Na: C _{12 to} C ₁₄ sodium alkylsulfate α-SF-Na: C _{12 to} C ₁₈ α-sulfo fatty acid methyl ester Sodium AOS-K: C _{14 to} C ₁₈ potassium α-olefinsulfonate Soap: C _{8 to} C ₁₈ fatty acid sodium Nonionic surfactant: C _{12 to} C ₁₆ alcohol ethylene oxide average 9 mole adduct Polyethylene glycol: weight Average molecular weight 6000 MA / AA-Na: sodium maleate / sodium acrylate copolymer (copolymerization ratio 7/3, weight average molecular weight 50,000 to 70,000) Fluorescent agent CBS: "Tinopearl CBS-X" (Ciba Geigy Durazyme: Durazyme 6.OT (Novo Industry Co., Ltd.)

Measurement of solidification property The following transparent container was filled with 750 g of the detergent composition, and the sealed container was closed at 45 ° C./85% RH × 16 hours and 25 ° C./65°
% RH × 8 hours, alternately stored in a room for 2 weeks, the container was taken out after the storage was completed, the detergent composition was slowly discharged onto a 4 mesh sieve, and the weight remaining on the sieve was Was measured, and the solidification property was evaluated according to the following criteria. Solidification rate (%) = 100 × (weight of detergent remaining on the sieve)
/ (Weight of the stored detergent) <Judgment criteria> A: Solidification rate 0 to less than 20% B: Solidification rate 20 to less than 40% C: Solidification rate 40 to less than 60% D: Solidification rate 60 to less than 80% E: Solidification rate 80-100%

The containers shown in Table 4 were prepared by kneading the following synthetic resin with an ultraviolet absorber (Tinuvin 316 (manufactured by Ciba Geigy) in the amount shown in Table 4) and then narrowing the width 100 mm and the height 200 mm. It is molded into a container (outlet diameter 30 mm) (wall thickness of each part is 1 mm or more).
The transmittance with respect to light having a wavelength of m was measured on a 1 mm flat plate made of the same material as the transparent container. The abbreviations indicating the synthetic resin materials have the following meanings. PET: polyethylene terephthalate, PVC: polyvinyl chloride, PE: polyethylene PP: polypropylene The results are shown in Table-4.

[0025]

[Table 4] Table-4 (Evaluation result) ─────────────────────────────────── 1 2 3 4 5 6 7 8 * 9 * 10 * 11 12 Detergent used a a a a b b b b a a a a b Bleach activator structure A A A B B B B C A A A A A B Container material PP PE PET PP PE PET PE PP PET PET PE PE UV absorber amount (%) * 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0 0 0 0 0 0 UV transmittance (%) * 2 1 1 1 1 1 1 1 1 1 20 40 40 2 2 Solidification A A A A A A A A C D D A A * 1: Amount of UV absorber kneaded into the resin (% by weight) * 2: 1% in the table indicates a transmittance of 1% or less (hereinafter the same). 8 * to 10 * in the table are comparative examples.

[0026]

[Table 5] Table-4 (continued) ─────────────────────────────────── 14 15 16 17 18 19 20 21 * 22 * 23 * 24 25 Detergent used c cc d d d d d c c d c c d Bleach activator structure A A A A B B B B B A A B A A B Container material PP PE PET PP PE PET PVC PP PET PET PE PE UV absorber amount (%) * 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0 0 0 0 0 0 UV transmittance (%) * 2 1 1 1 1 1 1 1 1 1 20 40 40 2 2 Solidification A 21 * to 23 * in the A A A A A A A C A D D A A table are comparative examples.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C11D 3/395 C11D 3/395 7/18 7/18 7/26 7/26 7/34 7 / 34 7/54 7/54

Claims (1)

[Claims] 1. (a) 1 to 25% by weight of an oxygen-based bleaching base compound that generates hydrogen peroxide in water, (b) a bleaching activator represented by the general formula (I) or (II) 1 to A granular detergent having a bulk density of 0.6 to 1.2 g / cc, which contains 15% by weight and (c) a surfactant of 5 to 50% by weight, is used at 350 nm.
A high-bulk-density bleaching detergent composition in a transparent container, which is housed in a transparent synthetic resin container having a transmittance of 2% or less with respect to the light of the wavelength. Embedded image (R ¹ is an alkyl group or alkenyl group having 9 to 13 carbon atoms, R ² is an alkyl group or alkenyl group having 7 to 13 carbon atoms, M is hydrogen or a cation that imparts water solubility to the bleaching activator. is there.)