JP2001003092A - Powdery detergent in container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a powdery detergent improved in powder adhesion to a film surface in a container by filling a container having a containing section formed from surface-treated paper with a group of detergent particles which contains a specified amount of a nonionic surfactant and of which the particle size and the quotient obtained from the division of standard deviation of particle size distribution by particle size are specified. SOLUTION: The container is filled with a group of detergent particles which contains 5-30 wt.% nonionic surfactant and of which the average particle size is 150-500 μm and the quotient obtained by the division of standard deviation of particle size distribution by average particle size is 0.55 or lower. The containing section of the container for containing a detergent is formed so that a covered surface is in contact with the group of detergent particles. The surface covering is preferably done by laminating an olefinic polymer film or by applying a varnish. The film thickness is preferably 5-100 μm. A varnish containing a polymer derived from an acrylic, epoxy, urethane, or olefinic monomer is preferable, and the amount of the varnish applied is preferably 5-50 g/m2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a powder detergent filled in a paper container.

[0002]

2. Description of the Related Art It is known that detergent particles containing a large amount of a nonionic surfactant have a high detergency against sebum stains. In addition, nonionic surfactants having high detergency against sebum stains often have a melting point of 40 ° C. or less,
When a large amount of the nonionic surfactant is incorporated, the nonionic surfactant exudes particularly under high temperature conditions such as in summer. When such a detergent particle group is filled in a paper container such as a commercially available one, dark spots are generated because the exuded nonionic surface activity permeates the paper container and produces a wet color. Significantly impairs product value. In addition, during long-term storage, there is a problem in that the nonionic surfactant attacks the printed surface of the container surface and significantly deteriorates the appearance of the product. In such a problem, a detergent in which the inner surface of a paper container is coated with a film is commercially available, but when a detergent particle group or a detergent particle group having a high moisture content that does not sufficiently suppress bleeding is filled, the detergent particle adheres to the film surface and looks like. There was a problem that worsened. The tendency is remarkable because detergent particles having a small average particle size and a broad particle size distribution, as seen in conventional detergents, have a high filling efficiency and increase the contact surface with the inner surface of the container.

[0003]

An object of the present invention is to provide a product in which detergent particles containing a nonionic surfactant having excellent sebum detergency are filled in a paper container coated with a polymer film or the like. The present invention is to provide a detergent having improved powdering property of the detergent on the film surface in the above.

[0004]

According to the present invention, there is provided a detergent particle group containing 5 to 30% by weight of a nonionic surfactant in a container having an accommodating portion made of paper coated with a surface, and comprising Is 150 to 500 μm, and a powdered detergent in a container filled with detergent particles having a value obtained by dividing the standard deviation of the particle size distribution by the average particle size is 0.55 or less.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The container according to the present invention has an accommodating portion formed by applying a surface coating to a paperboard generally used as a container paper substrate. The accommodating portion of the cleaning agent of the container is formed such that the surface coated surface is in contact with the detergent particles. The surface coating is preferably performed by laminating an olefin polymer film or applying a varnish.
Lamination with an olefin-based polymer film is obtained by coating and fixing a resin made of a polymer obtained by polymerizing an olefin-based monomer by a method such as extrusion lamination or dry lamination. As the olefin-based polymer, polyethylene and polypropylene are preferred because they are excellent in stretchability, rupture resistance and moisture permeability, and can prevent an increase in the water content of the detergent particles. The thickness of the olefin polymer film is preferably 5 to 100 μm. The varnish is preferably one obtained by polymerizing one or more of acrylic, amide, fluorine, epoxy, urethane, and olefin monomers and / or oligomers, and one containing a mixture of these polymers. . Among them, those containing a polymer derived from an acrylic, epoxy, urethane or olefin monomer are preferred. Varnish, the above polymer ethyl acetate,
It is obtained by dissolving in a solvent such as alcohol or water. A gravure coater, a wire coater, or the like is used for coating the varnish. Amount of coating is, 5 to 50 g / m ² is preferred. Also, on the surface of the paper coated with varnish, put absorbent cotton soaked with a nonionic surfactant containing detergent particles,
It is further preferable to select a varnish that does not show any deepening of the paper after being left at 40 ° C. for 12 hours. In addition, for the purpose of improving bleeding control, pretreatment such as impregnation of the paperboard of the container with a fluorine-based sizing agent and anchor coating treatment, and varnish 2
It is preferable to perform heavy coating.

In the present invention, the detergent particles are detergent particles containing a surfactant, a builder, and the like, and the detergent particle group means an aggregate thereof. Detergent components (eg, builder granules, enzymes, defoamers,
A composition containing (bleach, bleach activator) is called a powder detergent.

Next, the detergent particles according to the present invention will be described. The nonionic surfactant preferably has a melting point of 40 ° C. or lower. For example, from the viewpoint of detergency, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, and polyoxyethylene polyoxypropylene block polymer are preferable. Especially 10 to 18 carbon atoms
Polyoxyethylene alkyl ether obtained by adding an average of 4 to 20 moles of ethylene oxide (hereinafter referred to as EO) to the alcohol, or 4 to 20 moles of the EO to the alcohol and 0.3 to 4 moles of the propylene oxide (hereinafter referred to as PO). Those added in blocks, such as mol and EO / PO / EO, are preferred. The HLB based on the Griffin method is preferably 6.5 to 14.0. The compounding amount of the nonionic surfactant is from 5% by weight to 30% by weight in the detergent particle group from the viewpoint of detergency against sebum dirt and powder properties.
% By weight, preferably 8 to 25% by weight, more preferably 8% by weight.
１８18% by weight.

Further, the detergent particles may contain an anionic surfactant, a cationic surfactant and an amphoteric surfactant. Examples of the anionic surfactant include an alkyl benzene sulfonate, an alkyl or alkenyl ether sulfate, an alkyl or alkenyl sulfate, an α-olefin sulfonate, an α-sulfofatty acid salt or an ester thereof, an alkyl or alkenyl ether carboxylate, Fatty acid salts and the like. The content of the anionic surfactant is preferably 1 to 30% by weight, more preferably 5 to 30% by weight of the detergent particles in terms of detergency. Alkali metal ions are suitable as counter ions from the viewpoint of improving detergency. In particular, from the viewpoint of improving the dissolution rate, potassium ions are preferable, and potassium ions in all the counter ions are preferably 5% by weight or more, more preferably 20% by weight or more, and particularly preferably 40% by weight or more. Examples of the cationic surfactant include an alkyltrimethylammonium salt and the like, and examples of the amphoteric surfactant include a carbobetaine type and a sulfobetaine type surfactant.

The detergent particles may contain an alkali agent such as a silicate, a carbonate, a sesquicarbonate, and a crystalline silicate.
In particular, crystalline silicates have an alkaline buffering capacity in a high pH range,
Further, it also has a sequestering ability for metal ions, so that it is preferable to enhance the detergency. The crystalline silicate is SKS-6 (manufactured by Clariant Japan KK), European Patent No. 0630855 No. 18
Those described in Example 23 of the page and JP-A-7-89712 can be used. Alkaline agent is contained in detergent particles
４０40% by weight.

Further, an amorphous aluminosilicate can be incorporated in the detergent particles for the purpose of suppressing the exudation of the nonionic surfactant. The amorphous aluminosilicate has an oil absorption capacity of 100 ml / 100 g or more, preferably 120
Those having a ml / 100 g or more are suitable. SiO ₂ / Al ₂ O ₃ (molar ratio) is preferably 5.0 from the viewpoint of maintaining high solubility (not deteriorating) even after long-term storage.
Or less, more preferably 4.0 or less, still more preferably 3.
Those having 3 or less are preferred. Examples of the amorphous aluminosilicate include those described in JP-A-6-179899, column 12, line 12 to column 13, line 1, and column 17, line 34 to column 19, line 17. Above all, a pore size measured with a mercury porosimeter (“SHIMADZU Pore Sizer 9320” manufactured by Shimadzu Corporation) is 0.015 to 0.
5 μm volume 0-0.7 mL / g, pore size 0.5-2 μm
It is preferable that the volume of m is 0.30 mL / g or more.
Amorphous aluminosilicate is 0 to 10% by weight in detergent particles
Be blended.

It is preferable that polyethylene glycol is incorporated in the detergent particles. This not only suppresses the exudation of nonionic surfactants, but also incorporates them into the mixed liquid when a manufacturing method is used in which a mixed liquid of anionic surfactant and nonionic surfactant is contained in the spray-dried dough. Then, it can be used also as a viscosity reducing agent of the activator mixture. Polyethylene glycol having an average molecular weight of 4,000 to 15,000 is preferable from the viewpoint of performance, handleability, and the like.

It is preferable that a soap is incorporated in the detergent particles. Incorporation of the soap keeps the nonionic surfactant in the soap gel, so that the nonionic surfactant can be prevented from bleeding. As the soap, those having 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms are preferable. The soap is incorporated in the detergent particles in an amount of 0.5 to 5% by weight.

The detergent particles include, for example, extenders such as sodium sulfate, crystalline aluminosilicate, orthophosphate, pyrophosphate, tripolyphosphate, nitrilotriacetate, ethylenediaminetetraacetate, citrate, and the like. Scavenger such as divalent metal ion such as isocitrate, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, polyacrylate, anti-recontamination agent such as acrylic acid-maleic acid copolymer or a salt thereof, anti-caking agent, peroxidation It may contain a product stabilizer, an antioxidant, a fluorescent dye, a bluing agent, a light-activated bleach, a fragrance, and the like.

The detergent particles used in the present invention preferably have a water content of 1.5 to 9.0% by weight. This water content is defined by the weight that is reduced by drying at 105 ° C. for 2 hours. The water content is 1.5 to 9.0% by weight, preferably 2.0 to 8.0% by weight, and more preferably 2.5 to 7.0% from the viewpoint of preventing powder adhesion on the inner surface of the container and productivity.
% By weight. The adjustment of the water content may be performed by previously controlling the water content of the detergent raw material, or the detergent particles may be dried later. As a drying method, it is preferable to use a rotary kiln or a fluidized bed.

The detergent particles used in the present invention are JIS
Z 8801 standard sieve (2000-125μ aperture)
m) for 5 minutes, the average particle diameter (median diameter) obtained from the weight fraction according to the sieve size is 150 to
It is 500 μm, preferably 220 to 450 μm. Furthermore, the value obtained by dividing the standard deviation of the particle size distribution by the average particle size (CV value)
Is 0.55 or less, preferably 0.45 or less, and more preferably 0.40 or less. With the average particle diameter in this range, a good dissolution rate and a good detergency can be obtained. Also, the CV in this range
With this value, good powder adhesion prevention properties can be obtained. The average particle size is determined using a sieve specified in JIS Z8801. For example, the aperture is 2000 μm, 1400 μm, 1000
μm, 710 μm, 500 μm, 355 μm, 250 μ
m, 180 μm, and 125 μm using a 9-stage sieve and a saucer, and a low tapping machine (HEIKO SEISAK).
USHO, tapping: 156 times / min, rolling:
290 times / min), 100 g of sample was shaken for 10 minutes and sieved.
80 μm, 250 μm, 355 μm, 500 μm, 71
When the weight frequency is integrated on the tray and each sieve in the order of 0 μm, 1000 μm, 1400 μm, and 2000 μm, the opening of the first sieve having the integrated weight frequency of 50% or more is set to a μm, and one step larger than a μm. When the opening of the large sieve is b μm, the integration of the weight frequency from the tray to the aμm sieve is c%, and the weight frequency on the aμm sieve is d%.
Where, the average particle size = 10 (50- (cd / (log b-log a) x log b)) / (d / (lo
g b-log a)). The sieve used is appropriately adjusted so that the particle size distribution of the measured powder can be accurately estimated.

The CV value is obtained by dividing the standard deviation of the particle size distribution when sieved with the above sieve, by the average value of the particle size distribution. Specifically, the particle size distribution is obtained from the weight frequency obtained by the above method, the standard deviation and average value of the particle size distribution are calculated from the logarithmic average of the residual particles between the sieves and the weight frequency (%), and the standard deviation is averaged. It is determined by dividing by a value.

The particle size composition can be adjusted by attaching and granulating an activator or inorganic powder with particles having a sharp particle size distribution, such as salt particles, as a nucleus, or by adjusting a detergent particle group using a mixing sieve. good.

The method of producing the detergent particles is as follows. The detergent particles are obtained by drying a slurry containing water-insoluble inorganic salts, a water-soluble polymer, and a water-soluble salt. It is desirable to carry a mixture of surfactants. The dry particles obtained according to the present method have a sharp particle size distribution, and are generally used when producing a high bulk density detergent because the dry particles have an oil absorbing ability to carry a surfactant. It is difficult for the particles to grow in the granulation step to be performed, and a group of detergent particles suitable for obtaining the effects of the present invention can be obtained.

[0019]

According to the present invention, it is possible to obtain a powder detergent in a container which does not cause the powder of the detergent on the inner surface of the container or exudation of the nonionic surfactant.

[0020]

[Example] <Container manufacturing method> Basis weight 20 as container paperboard
A paperboard formed by laminating a back liner paper having a basis weight of 60 to 300 g / m ² through a coated resin ball of 0 to 600 g / m ² via an extruded polyethylene resin layer was used, and the surface was coated with an olefin polymer film or varnish. As the olefin polymer film, polyethylene and polypropylene were used, and as the varnish, acrylic, urethane, epoxy varnish and varnish obtained by mixing acrylic and urethane resin were used. The olefin polymer film was extruded by lamination so as to have a thickness of 20 μm, and the varnish was applied by a gravure coater so that the coating thickness was 20 μm. The paperboard was treated with a fluorine-based sizing agent (Asahigard AG-530: Asahi Glass Co., Ltd.), and an acrylic varnish was applied under the above conditions. The surface-coated paper was assembled in a box shape of L × W × H = 150 mm × 90 mm × 130 mm, and bonded with a vinyl acetate resin emulsion type adhesive to obtain a container.

<Preparation Method 1 of Detergent Particle Group> Of the components shown in Table 1, 7% by weight of zeolite and 3% of nonionic surfactant
An aqueous slurry having a water content of 50% was prepared by weight% of components other than the amorphous aluminosilicate, the enzyme, the fragrance and the crystalline silicate, and spray-dried. The obtained spray-dried particles, 3% by weight of nonionic surfactant and 4% by weight of zeolite were charged into a high-speed mixer (stirring-rolling granulator, Fukae Kogyo Co., Ltd.) to perform granulation. . Further, 3% by weight of zeolite, amorphous aluminosilicate, and crystalline silicate were added to perform surface modification to obtain a detergent particle group. The obtained detergent particles were put in a rotary kiln, the enzyme was blended, and simultaneously a fragrance was sprayed to obtain a powder detergent. The water content was controlled by spray drying conditions and fluidized bed drying of the granulated particles. The particle size was controlled by cutting fine particles and coarse particles using a sieve.

<Method 2 for producing detergent particles> Among the components shown in Table 1, zeolite, soda ash, sodium sulfate, sodium sulfite,
A homogeneous aqueous slurry containing 50% by weight of water containing sodium polyacrylate, sodium chloride and a fluorescent dye was spray-dried to obtain spray-dried particles. The spray-dried particles (50 parts by weight) are heated to 80 ° C. and introduced into a Redige mixer (Matsuzaka Giken Co., Ltd.) equipped with an 80 ° C. jacket. Spindle speed 1
While stirring at 50 RPM, a mixture of an anionic surfactant, a nonionic surfactant, and polyethylene glycol heated to 80 ° C. is sprayed into a Loedige mixer.
Stir and mix for 10 minutes after the end of spraying, then crystalline silicate,
An amorphous aluminosilicate is introduced. Spindle speed 200R
PM and stirring and mixing were performed for 2 minutes at a chopper rotation speed of 2000 RPM to obtain a detergent particle group. The obtained detergent particles were put in a rotary kiln, the enzyme was blended, and simultaneously a fragrance was sprayed to obtain a powder detergent. The water content was adjusted by controlling spray drying conditions and controlling the water content in the activator mixture.

<Powder Adhesion Test> 1.2 kg of a powder detergent containing detergent particles in the combinations shown in Tables 1 and 2 was filled in a detergent filling container, and the opening was closed with a paper seal and a plastic lid. After that, 3 ° C. under the condition of 30 ° C. and 60% relative humidity.
Stored for 0 days. After storage, the opening of the container was opened, and the filled powder detergent was taken out by rolling the container upside down, and the powdering property to the inner surface of the container was evaluated by the following method. The evaluation method was evaluated in five steps based on the powder adhesion weight per unit area. 1: 0.43 mg to less than 0.55 mg / cm ² 2: 0.55 mg to less than 1.25 mg / cm ² 3: 1.25 mg to less than 2.60 mg / cm ² 4: 2.60 mg to less than 5.10 mg / cm ² cm ² 5: 5.10 mg or more and less than 10.90 mg / cm ²

[0024]

[Table 1]

[0025]

[Table 2]

The components in Tables 1 and 2 will be described below in detail. LAS: straight chain alkyl (C12-13) sodium benzenesulfonate AS: alkyl (C12-18) sodium sulfate α-SFE: sodium α-olefin sulfonate (C18-18) Soap : Sodium tallow fatty acid • AE: Polyoxyethylene alkyl (C12 to C1)
6) Average number of moles of ether and ethylene oxide added 9.
5 • PEG: average molecular weight 8500 • amorphous aluminosilicate: an amorphous aluminosilicate of Synthesis Example B-1 described in JP-A-6-179899. Oil absorption capacity: 285 ml / 100 g ・ Zeolite: 4A type zeolite, average particle size 3 μm (manufactured by Tosoh Corporation) ・ Amorphous silicate: No. 1 sodium silicate (Tosoh Corporation)
・ Crystalline silicate: Powder SKS-6 (manufactured by Clariant Japan KK) pulverized to an average particle diameter of 20 μm ・ Sodium polyacrylate: Weight average molecular weight is 800
0 ・ Fluorescent dye: Tinopearl CBS-X (manufactured by Ciba Specialty Chemicals) ・ Enzyme: Sabinase 18.0T Type Whit
e, 0.1 equivalent of cellzyme, 60T of Termamyl (all manufactured by Novo Nordisk)

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hiroshi Ogurisu 1334 Minato 1334 Minato, Wakayama City, Wakayama Pref. Person Hiroyuki Saijo 1334 Minato, Wakayama-shi, Wakayama Pref.

Claims (4)

[Claims] 1. A detergent particle group containing 5 to 30% by weight of a nonionic surfactant in a container having an accommodating portion made of paper coated with a surface, the average particle size of which is 150 to 500.
μm, the value obtained by dividing the standard deviation of the particle size distribution by the average particle size is 0.
A powder detergent in a container, which is filled with a detergent particle group of 55 or less. 2. The powder detergent in a container according to claim 1, wherein the surface coating is a laminate of an olefin polymer film. 3. The method according to claim 1, wherein the surface coating is a varnish coating.
The powder detergent in a container according to the above. 4. The method according to claim 1, wherein the detergent particles are obtained by drying a slurry containing a water-insoluble inorganic salt, a water-soluble polymer and a water-soluble salt. The powder detergent in a container according to any one of claims 1 to 3, which carries a mixed solution of an ionic surfactant.