JP2001187898A - Powder detergent product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a powder detergent product which has excellent flowability and solubility at a low temperature even when stored at a high temperature or at a high humidity by preparing a detergent based on a specific indan derivative or an alkylbenzenesulfonate containing a specific amount of an alkyltetralinsulfonate with a specific amount or less of water and by packing the detergent in a package with a specific water vapor transmission. SOLUTION: The powder detergent product contains 5-30 wt.% of an indan derivative or an alkylbenzenesulfonate containing 0.01-5 mass % of an alkyltetralinsulfonate and has a bulk density of 0.5-1.2 g/mL and a water content of 5-10% and is packed in a package with a water vapor transmission of 5-30 g/m2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to powder detergent products for clothing.

[0002]

2. Description of the Related Art In recent years, downsizing of powder detergent has been widely accepted by consumers and distribution from the viewpoint of convenience and transportability.
Spread rapidly. On the other hand, technically, since the detergency must be improved with a small amount of use, in particular, in recent years, polyacrylic acid-based polymers have been used as sequestering agents. JP-A-11-035989 discloses that the weight average molecular weight produced with a specific polymerization initiator is 15,000 to
As disclosed in the detergent composition having excellent detergency by using an acrylic acid copolymer of 80,000, an acrylic acid-based polymer having a high sequestering ability has a molecular weight of about 15,000 to 80,000. It is known. These form a network in the detergent, which hinders the solubility of the detergent particles, especially at low water temperatures such as in winter, so that there is a problem that the detergent remains undissolved in the clothes even after washing, rinsing and dehydrating. It is known that the solubility is improved by increasing the water content of the powder detergent. However, when water is added to the detergent component in an amount of 10% or more, the enzyme to be added together is inactivated or the fluidity of the detergent is reduced. There has been a problem of significant deterioration.

[0003]

As a result of a detailed study of the relationship between low-temperature solubility in a concentrated detergent composition, the present inventors have found that a specific indane derivative or an alkylbenzene sulfone containing a specific amount of an alkyltetralin sulfonate is contained. After adjusting the detergent below a certain amount of water to the acid salt based system, by filling in a container having a specific moisture permeability,
The present inventors have found that a powder detergent product excellent in fluidity and low-temperature solubility can be obtained even when stored under high temperature or high humidity, and completed the present invention.

[0004]

The powder detergent product of the present invention comprises: 1) an indane derivative or an alkylbenzene sulfonate having an alkyltetralin sulfonate content of 0.01 to 5% by mass: 5 to 30% by weight. %, Bulk specific gravity 0.5 ~
A powder detergent composition having a water content of 5 to 10% having 1.2 g / mL is filled in a container having a moisture permeability of 5 to 30 g / m ² .

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The alkylbenzene sulfonate described in the present invention is an indane derivative or a linear alkylbenzene sulfonate having an alkyltetraline sulfonate content of 0.05 to 5% by mass. As a method for obtaining the same, a commercially available linear alkylbenzene having a low content of an indane derivative or an alkyltetraline sulfonate, for example, Nippon Oil Co., Ltd. “Alken L: about 1% by mass of an indane derivative or an alkyltetraline derivative” is sulfonated. And, if necessary, a method of neutralizing, or purifying the linear alkylbenzene to reduce the content of the indane derivative or the alkyltetralin derivative to 5%.
A method using less than 5% by mass, or a method using a high-purity linear alkylbenzene sulfonate having a content of an indane derivative or an alkyltetralin derivative of less than 5% by mass is exemplified. In the present invention, the straight-chain alkylbenzene used for the production of the straight-chain alkylbenzene sulfonate is usually a straight-chain paraffin obtained by fractionating light kerosene as a starting material, and this is used in a chlorinated paraffin method or an olefin method. Can be synthesized by introducing halogen and then adding benzene. This linear alkylbenzene is obtained in a mixture,
The alkyl group preferably has 8 to 22 carbon atoms,
To 14 are more preferred. The benzene substitution positions are distributed from the 2nd to 7th positions of the linear paraffin.

It is believed that during the synthesis of this linear alkylbenzene, disubstituted halogens of linear paraffin are by-produced, and indane and tetralin derivatives are produced as by-products when benzene is added thereto. . As these by-products, indane derivatives include indane or derivatives thereof, and tetralin derivatives include tetralin or derivatives. The linear alkyl benzene sulfonic acid salt of the present invention is obtained by blowing, for example, SO ₃ gas into the above-mentioned linear alkyl benzene, and then neutralizing the linear alkyl benzene. Has a distribution both in the number of carbon atoms in the alkyl group and the benzene substitution position, and contains impurities of by-products such as indane and tetralin derivatives (including sulfonated products). Indane derivative or alkyltetralin sulfonate content of 0.0
It is important that the linear alkylbenzene sulfonate is 1 to 5% by mass. If these contents are less than 0.01 mass, the solubility of the detergent at low temperatures will be poor. On the other hand, if it exceeds 5% by mass, the powder properties such as fluidity are greatly deteriorated, which is not preferable.

[0007] Detergent water is 5 to 5 from the viewpoint of fluidity.
It is important that it is in the range of 10%. Preferably 5
Less than 9%, particularly preferably less than 6 to 8%, and if the water content of the detergent is 10% or more, the fluidity immediately after production or after storage is unfavorably deteriorated. If it is less than 5%, the low-temperature solubility decreases.

It is further important that the detergent thus obtained is filled in a container having a moisture permeability of 5 to 30 g / m ² . If the water vapor transmission rate is less than 5 g / m ² , the detergent moisture is not released to the outside of the container at a high temperature and adheres to the wall surface, so that the detergent is solidified on the bonding surface with the detergent. Further, when the moisture permeability exceeds 30 g / m ² , the detergent adsorbs water under high humidity, and the fluidity of the detergent deteriorates.
It is not preferable because the enzyme is easily deactivated.

The following containers can be used as specific containers that can be used in the present invention. 1. Container The container outer surface in Neosando structure consisting of sheet thickness 1mm coated with polypropylene resin film (50 [mu] m) (moisture ^{permeability; 25g / m 2 / 24hr)} 2. A container (moisture permeability: 7.5 g / m) in which the inner and outer surfaces of the container are coated with a polypropylene resin film (50 μm).
² / 24hr) 3. The above 1. The container of which uses a part of polyethylene for the container frame.

[0010] In addition to the above essential components, the following various components can be added to the powder detergent product of the present invention as required. The powder detergent product of the invention may be blended with a polyacrylic acid polymer to further enhance the cleaning power. As the polyacrylic acid-based polymer, a copolymer of acrylic acid and maleic acid is preferable, and the molar ratio of acrylic acid to maleic acid is 70:30 to 40:60, preferably 65:35 to 50:50. When the acrylic acid content is higher than this ratio, the calcium-capturing ability is reduced and the detergency is insufficient, and when the acrylic acid content is lower than this ratio, the polymerizability is reduced and the production of the copolymer is difficult. Will be. The weight average molecular weight of the copolymer is 20,
000-100,000, preferably 30,000-7
It is 0000. If it is smaller than this molecular weight,
If it does not exhibit sufficient detergency and is larger than this molecular weight, the viscosity will increase and it will be difficult to incorporate it into the detergent. The copolymer of acrylic acid and maleic acid is contained in the detergent product of the present invention in an amount of 0.5 to 10% by mass, preferably 1.0 to 10% by mass.
It can be blended at 7.0% by mass, more preferably 2 to 5% by mass.

The copolymer of acrylic acid and maleic acid of the present invention can be used even if it is unneutralized acid form or neutralized with ammonia, alkali metal ions or amines. It is preferably used as an alkali metal salt, particularly preferably as a sodium salt, from the viewpoint of economy and handling. The copolymer of acrylic acid and maleic acid used in the present invention can be obtained by polymerizing acrylic acid and maleic acid with a polymerization initiator. As the polymerization initiator, persulfate or hydrogen peroxide is used, and the polymerization proceeds by radicals generated by thermally decomposing the polymerization initiator, so that a copolymer can be obtained.

[0012] The powder detergent product of the present invention also contains a protease, a carbohydrate-degrading enzyme, a percarbonate, a perborate, an organic peracid precursor, and a metal supplement which are usually added to detergents and bleaching agents. , A re-staining agent, a fluorescent agent, a fragrance, and the like. As the enzyme, Novonor Disk's cannase 24T,
Cannase 12T, Savinase 12T, Evalase 8
T, Cellulase, Lipolase Ultra, Termamyl 60
T, 120T, etc., and are usually blended in an amount of about 0.1 to 2%.
As other components, sodium silicate, sodium sulfite, sodium sulfate, and magnesium sulfate can be used as inorganic salts, and usually 1 to 30% in a detergent.
Although it is used, 5% to 25% is preferable. The percarbonate includes sodium percarbonate, and the perborate includes sodium perborate monohydrate and tetrahydrate. From the viewpoint of stability, the percarbonate used is a coated one described in JP-A-4-31498. Is preferred. The organic peracid precursor is disclosed in
There are alkanoyloxybenzene derivatives described in JP-A-8-157876 and JP-A-8-218096, TAED which is widely used in Europe, and the like. Granulation is performed using a binder such as PEG # 6000 from the viewpoint of securing stability in a detergent. It is preferable to use them. Examples of the metal scavenger include inorganic phosphorus typified by A-type zeolite, P-type zeolite tripolyphosphate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, nitrilotriacetate, and 1-hydroxyethane-1,1-diphosphonate. There are compounds, organic phosphonates represented by polyphosphonic acids and phytic acid. Examples of the anti-staining agent include polyvinyl alcohol and carboxymethyl cellulose, and examples of the fluorescent whitening agent include a binaphthyl type (Tinopearl CBS-X, Ciba Specialty Chemicals) and a stilbene type (Tinopearl A).
MS-GX). JP-A-4-116 as a fragrance
Perfume described in No. 99 can be used. In addition, impurities derived from raw materials may be contained as long as they do not adversely affect the performance. Sodium methyl sulfate, sodium methanesulfonate, and α-sulfofatty acid disalts contained in α-sulfofatty acid methyl ester salts. A monomer of acrylic acid or maleic acid, or a salt thereof, contained in a copolymer (salt) of acrylic acid and maleic acid. Higher alcohol, polyethylene glycol (molecular weight: 20) contained in nonionic surfactant
0 to 5000).

[0013]

According to the present invention, as a result of closely examining the relationship of low-temperature solubility in a concentrated detergent composition, it has been found that a benzocycloalkane derivative or an alkylbenzene sulfonate containing a specific amount of an alkyltetralin sulfonate is used. A powder detergent with excellent fluidity and low-temperature solubility even when stored under high temperature or high humidity by filling a system with a certain amount of water or less detergent and filling it in a container with specific moisture permeability. Products can be provided.

[0014]

EXAMPLES Prior to the examples, the evaluation method will be described below. <Manufacture of powder detergent> After the components other than the nonionic activator, sodium percarbonate, organic peracid precursor, enzyme, and fragrance shown in Table 1 are mixed with a slurry and spray-dried, the nonionic activator is added to the dry powder.
After adding an appropriate amount of water, kneading and granulating, and pulverizing with zeolite, the remaining components were added to obtain a high-density granular detergent having a bulk specific gravity of 0.8 g / mL. This production method is an example, and the methods described in and may be used as other production methods.

<Moisture content of powder detergent> JIS K3362
The loss on heating (% by mass) was taken as the water content according to the method described. <Moisture Permeability of Powder Detergent Container> Based on the method described in JIS Z-0208, the moisture permeability is calculated by the following equation 1, and is calculated according to JIS.
Rounded to two significant digits by Z-8401.

[0016]

(Equation 1)

<Fluidity of Detergent> 1 kg of the powder component is placed in each of containers A to D, and covered with a lid at 25 ° C. (65% relative humidity 8 hours).
1 in a recycling tank at 45 ° C (85% relative humidity 16 hours)
After storage for months, the angle of repose was measured according to JIS after the storage. <Evaluation of Solubility> 3DH hard water at 5 ° C. is immersed in a 1L beaker, and a constant speed stirring spring of 250 rpm and 2 × 4 cm are attached. After performing the same storage test as above on the granular detergent compositions shown in Tables 1 and 2, the granulated detergent compositions were sized to 710 to 1000 μm,
5 g of this are poured under stirring. Using a conductivity meter, the value at which the conductivity became constant after about 20 minutes of stirring was defined as 100, and 90
The time showing% conductivity is read. The time was taken as a measure of solubility. <Measurement of Enzyme Residual Rate> 1 kg of the detergent composition was placed in each of containers A to D, and the temperature was 25 ° C. (65% relative humidity 8 hours) 45 ° C.
% Relative humidity of 16 hours), the enzyme was picked up, the dimethylcasein decomposing activity was measured, and determined as the residual ratio of proteolytic enzyme. <Solidification of detergent> The detergent composition stored under the same conditions as the residual enzyme ratio was gently discharged onto a 4-mesh mesh sieve and the detergent mass remaining on the sieve without passing through the mesh. % Was taken as the solidification rate.

[0018]

[Table 1]

[0019]

[Table 2]

LAS1: potassium linear alkylbenzene sulfonate having an alkyl chain of C10 to C13 (raw material alkylbenzene: trade name ROB-1 manufactured by Mitsubishi Chemical Corporation)
0) (benzocycloalkane derivative, alkyltetralin sulfonate content: 1.0% by mass) LAS2: potassium linear alkylbenzene sulfonate having an alkyl chain of C10 to C13 (raw material alkylbenzene: Nippon Oil Co., Ltd.) LAS3: sodium straight-chain alkylbenzene sulfonate having an alkyl chain of C10-13 (raw material: alkylbenzene: kyowa oil) LAS4: Sodium linear alkylbenzene sulfonate of LAS3 (raw material: alkylbenzene: Kyowa Oil) Nakken N- Purified distillation product derived from 00) (indan derivative, alkyltetralin sulfonate content: 0% by mass) AS: sodium alkyl sulfate of C12 to C14 α-SF: sodium α-sulfofatty acid methyl ester of C14 / 16 = 2/8 Soap : C8-C18 fatty acid sodium Nonionic activator: Diadol 13 (Mitsubishi Chemical) with 12 mol of ethylene oxide adduct A type zeolite: Mizusawa Chemical Co., Ltd., average particle size 2 μm Fluorescent agent A: Tinopearl CBS-X (Ciba) Specialty Chemicals) Fluorescent agent B: Tinopearl AMS-GX (Ciba Specialty Chemicals) Sodium percarbonate: Mitsubishi Gas Chemical Co., Ltd. (SPC-D): Average particle size 600 μm Protease: Kannase 12T Novo Nordisk Bio Industrial lipolytic enzyme: Lipolase Ultra Novonol Organic peracid precursor manufactured by Disk Bioindustry: 4-decanoyloxybenzoic acid / PE
G6000 / C14AOS = 70/25/5 rod-shaped granulated material (diameter 0.8 mm x length 4 mm) White carbon: Tokusil N (Tokuyama Corporation) Sodium carbonate: Pure chemical reagent Class 1 (average particle size 400μ)
m)

[0021]

[0022]

[0023] <type of container> A: paper thickness 1mm consisting Neosando structure container outer surface of the polypropylene resin film (50 [mu] m) in coating containers :( ^breathable: 25g / m 2 / 24hr) I: the A container Container with inner and outer surfaces coated with a polypropylene resin film (50 μm): moisture permeability: (7.5 g /
m ² / 24hr) c: coat of polyethylene 40μm ball (500g /
m2) and a 0.7 mm three-layered container sandwiched between kraft (70 g / m ² ): (50 g / m ² /
D: 1 mm thick polypropylene container: (moisture permeability: 0 g)
/ M ² / 24hr) All lids are low density polyethylene 2m
those of m (the moisture permeability ^0g / m 2 / 24hr) was used. (A) For the container, polyethylene was partially used for the container frame and support.

Claims (2)

[Claims] An indane derivative or a linear alkylbenzene sulfonate having an alkyltetralin sulfonate content of 0.01 to 5% by mass, and 5 to 30% by mass,
Water content 5-1 having a bulk specific gravity of 0.5 to 1.2 g / mL
A powder detergent product, characterized in that 0% of the powder detergent composition is filled in a container having a moisture permeability of 5 to 30 g / m ² . 2. Further, 2) a molecular weight of 2,000 to 100,000
The powdery detergent product according to claim 1, wherein the product contains 0.5 to 10% of a polyacrylic acid-based polymer.