JP3448358B2 - Contaminated liquid for preparing artificially stained cloth for cleaning evaluation and method for producing artificially stained cloth - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an artificially contaminated cloth using artificial dirt, which is useful for measuring the detergency of detergents.

[0002]

2. Description of the Related Art It is desirable to use natural dirt to evaluate the detergency of detergents.
Since the stains are non-uniform, a pair of comparative evaluations are required, and the determination takes time and labor. Also, because it is difficult to always obtain a uniform contaminated cloth due to seasons, individual differences, etc.,
Generally, artificially contaminated cloth is widely used.

Since the artificially contaminated cloth can produce a large amount of uniform and constant-quality contaminated cloth, it is indispensable for improving the efficiency of detergency evaluation and obtaining reproducible data. Therefore, contaminated cloth has been marketed or developed by each manufacturer.

[0004] As the artificially contaminated cloth, many contaminated cloths having various stains as models have been developed. However, the manufacturing method thereof varies depending on the kind of dirt and easiness of preparation. For example, a conventional manufacturing method is to use it in a solvent. Wet method or pad method of dissolving or emulsifying dirt and dipping cloth in the dirt solution, spray method of spraying dirt solution, and dirt in which dirt solution is attached and dispersed on a carrier such as sea sand There is a dry method of applying sand to the cloth in a dry manner, but both require solvents or carriers (sea sand etc.), so it is not possible to apply only dirt directly to the cloth and it adheres to the natural dirt cloth The mechanism is different. As a result, it has a great influence on the cleaning property of the detergent. In other words, when the detergent cleaning power is tested using a contaminated cloth made by the method of dispersing dirt with a large amount of conventional solvent, when the result shows that the cleaning results of actual collar dirt and sleeve dirt are different. Are often seen. That is, there is a problem that the performance of the detergent cannot be evaluated correctly. In particular, when a chelating agent for divalent metal ions (calcium ion or magnesium ion) is blended as a builder for detergent, it shows a tendency different from the actual cleaning result of collar stains and sleeve stains.
There was a drawback that an accurate detergency evaluation could not be performed.

Further, in the conventional method, the use of a solvent may limit the soil components, such as the fact that oil-soluble stains and water-soluble stains cannot be adhered at the same time. It was difficult to apply.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors divided dirt into oil-soluble dirt and water-soluble dirt, and formed a liquid crystal phase in water. By adding an emulsifier having the property of forming a W / O emulsion, an artificially contaminated cloth can be produced without using a solvent,
In addition, it makes it possible to apply all types of dirt (oil-soluble dirt and water-soluble dirt) evenly in the state closest to nature (applying dirt directly to cloth). By producing in this way, the cleaning behavior is very similar to that of natural soiled cloth, and the cleaning behavior of the detergent composition containing a chelating agent for divalent metal ions, which has been a problem in the past, has the same cleaning behavior. An artificial stain cloth for cleaning evaluation is provided.

The present invention comprises a W / O emulsion using an emulsifier having a property of forming a liquid crystal phase in water, and a solvent-free contaminated liquid for preparing artificially contaminated cloth, and a cloth surface. The present invention also provides a method for producing an artificially contaminated cloth, which comprises depositing the contaminated liquid for preparing the artificially contaminated cloth on.

The contaminated liquid for preparing artificially contaminated cloth of the present invention is W / O.
Although it is composed of a system emulsion, the oil phase (O
Phase) consists of organic substances suitable as oil-soluble soil. Examples of such organic substances include organic acids having 6 to 24 carbon atoms, paraffin, squalene, polyol compounds and 6 to 24 carbon atoms.
An ester compound of 24 organic carboxylic acids, an ester compound of glycerin and an organic carboxylic acid having 6 to 24 carbon atoms,
30 to 95 of one or more organic substances selected from ester compounds of alcohols having 6 to 24 carbon atoms and organic carboxylic acids having 6 to 24 carbon atoms and ester compounds of cholesterol and organic carboxylic acids having 6 to 24 carbon atoms It is preferable to contain it by weight%. In particular, waxes, squalene, triglycerides, fatty acids and the like, which are components derived from human sebum, are preferable, and it is better to use a plurality of them than to use them individually. Fatty acids and glycerides, which are especially high in sebum components, are necessary to bring the cleaning performance close to that of natural products. Therefore, as a composition for making the cleaning performance closer to natural, wax 1 to 10% by weight, squalene 1 to 20% by weight,
A range of 10 to 40% by weight of triglyceride and 20 to 70% by weight of fatty acid is preferable. In addition, wax has an alkyl chain length of 10
Wax containing an ester compound composed of a fatty acid of 20 to 20 and a monohydric alcohol having an alkyl chain of 6 to 20 as a main component is preferable, a triglyceride of oleic acid is preferable as the triglyceride, and a saturated chain having an alkyl chain of 12 to 18 is used as the fatty acid. And / or unsaturated fatty acids are preferred.

The water component used is preferably distilled water or tap water, and particularly when an organic acid is used as the organic component, the pH of the water is preferably weakly alkaline. To make it slightly alkaline, a trace amount of water-soluble alkaline component, for example,
An alkaline agent such as sodium hydroxide may be added.

As water-soluble dirt, chemical components of sweat (sodium, potassium, calcium, magnesium,
Inorganic components such as phosphorus, sulfur, iodine, copper, manganese, iron, urea, lactic acid, amino acids, ammonia, creatine,
Uric acid, glucose, pyruvic acid, organic components such as vitamins), and carbohydrates (sugars, starches, etc.) that are stains of foods and the like.

A surfactant is preferred as the emulsifier having the property of forming a liquid crystal phase in water. As the surfactant, anionic, amphoteric, nonionic or cationic surfactant is used. In particular, any W / O type surfactant having excellent emulsion stability may be used. In order to prepare a fine and stable W / O emulsion, it is preferable to use a combination of the surface chemical method and the mechanical force method. Of course, both methods may be used alone or in combination. J. Soc. Cosmet. Chem. 28 , 285-314 (1977) shows an emulsification method utilizing amino acids. While stirring the amino acid aqueous solution, a surfactant is added thereto to form a gel in which water is dispersed in the lamellar liquid crystal. This is a method in which this gel is dispersed in an oil phase and then emulsified while adding an aqueous phase. Here, the surfactant is used in the W / D (water / surfactant) phase, that is, the continuous phase. Examples in which addition of sugars in addition to amino acids is effective are JP-A-53-86045 and JP-B-57-27.
735 and JP-A-56-147622. As described above, water is an essential component for forming the liquid crystal phase, and it is preferable to further add an amino acid and a saccharide. The lamellar liquid crystalline phase of lecithin is Journal of Lipid Research 8 , 551-557
(1967), a W / O emulsion can be prepared by emulsifying a liquid crystal using such a liquid crystal phase. There is no problem with the stability of the W / O emulsion as long as it is stable while the artificial dirt is applied to the cloth.

The composition of the organic component of 30 to 95% by weight is W /
It is necessary to maintain the emulsion stability of O type. further,
It is necessary to use an emulsifier that forms a liquid crystal phase in 30 to 95% by weight of the organic component.
It is 0.05 to 5% by weight, and if the organic component is less than 30% by weight or the emulsifier component is less than 0.05%, there is a problem in emulsion stability. On the other hand, if the organic component exceeds 95% by weight or the emulsifier component exceeds 5% by weight, the cleaning behavior may change as compared with the natural soiled cloth.

In addition, an inorganic component and carbon black can be added in order to measure the cleaning behavior of the contaminated cloth by the surface reflectance. As the inorganic component, soil, clay, dust, iron oxide or the like is used, and particularly, soil containing 50% by weight or more of particles having a particle diameter of 100 μm or less is most preferable. If the content of the inorganic component is 40% by weight or more, there is a problem that the cleaning behavior is changed as compared with natural dirt. When the content of the inorganic component is 1% by weight or less, the surface reflectance becomes high, and the cleaning behavior cannot be understood only by the surface reflectance. Most preferably, carbon black specified by the Japan Oil Chemistry Society. When carbon black is contained in an amount of 2% or more, there are problems that the change of the cleaning rate becomes difficult to understand and that the cleaning behavior is changed as compared with natural soiled cloth due to recontamination of carbon black. On the other hand, if it is 0.01% by weight or less, the surface reflectance becomes high, and there is a problem that the cleaning behavior cannot be understood only by the surface reflectance.

Furthermore, amino acids can be included. As amino acids, aspartic acid, glutamic acid, lysine, arginine, histidine and the like are particularly preferable. These amino acids may stabilize the liquid crystal formation of the emulsifier. It can also include proteins. Examples of proteins include gelatin, casein, albumin, keratin and the like. By including these proteins, the effect of the enzyme (protease, etc.) becomes easier to understand.

A liquid in which a carbon black component is mixed and dispersed in a solution in which an emulsifier component is dissolved in the above organic component,
A contaminated liquid for preparing an artificially contaminated cloth for cleaning evaluation of the present invention, which is a W / O emulsion by mixing a liquid in which a mud component is dissolved or dispersed in a water component using a mechanical force such as a homogenizer Can be produced. By using a contaminated cloth produced by applying, dipping, etc. this contaminated liquid onto a cloth, unlike conventional artificially contaminated cloth, an artificial cloth that matches the cleaning behavior of a natural collar or sleeve dirt cloth will be used. A dirty cloth can be made.

In the present invention, "to form a liquid crystal phase" does not need to be a complete liquid crystal phase.
Any material containing a liquid crystal phase may be used. That is, a part of the D phase of the W / D (water / surfactant) phase formed by the emulsifier can be used as long as it becomes a liquid crystal. By forming a liquid crystal phase using an emulsifier having such properties, it becomes possible to retain a large amount of water, and stabilization of the emulsion can be achieved as compared with the case of using an ordinary emulsifier other than these. .

The artificially contaminated cloth of the present invention may be squeezed with a roller or the like in order to apply a fixed amount on the cloth. Here, the most useful coating device is Japanese Patent Application No. 6-63273.
It is the gravure coater described in the issue. Since a certain amount can be applied in a manner similar to natural dirt, the surface reflectance can be maintained at 30 to 50%. The coating amount is 0.1-
10 mg / cm ² is the most reproducible and the washing behavior matches that of natural soiled cloth. In particular, a chelating agent for divalent metal ions (calcium ion or magnesium ion) (for example, sodium tripolyphosphate, zeolite, sodium nitrilotriacetate, sodium citrate, sodium polyacrylate, sodium ethylenediaminetetraacetate) was added as a builder for detergents. In this case, unlike the conventional artificially contaminated cloth, it shows the same tendency as the actual cleaning result of collar stains and sleeve stains, and there is an advantage that more accurate cleaning power evaluation can be performed.

[0018]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition,
In the examples, "%" is based on weight unless otherwise specified.

Example 1 Various artificial dirt solutions were prepared using the dirt components shown in Table 1.

[0020]

[Table 1]

(1) The liquid crystal forming emulsifier component (component c) is prepared as follows.

11.37 g of arginine hydrochloride in 80 ml of distilled water,
Dissolve 4.20 g of histidine and 2.44 g of serine, and add pH with concentrated hydrochloric acid.
Adjust to 5.0. By thoroughly mixing this solution with lecithin (soybean lecithin or egg white lecithin) or monoolein with a mixer, a lecithin or monoolein liquid crystal substance was obtained. It was confirmed by a polarizing microscope that these liquid crystals exhibited polarized light.

(2) As for the inorganic component, Kanuma Akatama soil was dried at 105 ° C. for 5 hours, crushed with an attritor, and 150 mesh passed product was used as mud.

(3) Organic component (a component), water component (b component), inorganic component (d component), carbon black component (e)
Ingredients) were weighed according to the blending amounts in Table 1. All organic components were mixed and heated at 80 ° C. until a uniform solution was obtained. Next, the organic component and the emulsifier component (component c)
The mixture was stirred and dissolved while heating at 70 ° C., then the carbon black component was added, and the mixture was stirred and uniformly dispersed. Furthermore, 70 ℃
The heated water component and the inorganic component were added, and the mixture was thoroughly mixed at 70 ° C. using a homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd., model M2-2.5] and used as an artificial dirt liquid when uniform. .

(4) The artificial soiling liquid was attached to a cloth to prepare an artificially soiled cloth. The artificial dirt liquid was attached to the cloth by using a gravure-type contaminating machine disclosed in Japanese Patent Application No. 6-63273. Fabrication conditions are gravure roll cell capacity 58 cm ³
/ Cm ² , coating speed 1.0 m / min, drying temperature 100 ° C., drying time 1 minute. The cloth used was a cotton kin 2003 cloth (purchased from Yatomi Shoten). Table 2 shows the characteristics of the manufactured artificially contaminated cloth.

[0026]

[Table 2]

Example 2 Using the artificially contaminated cloth of Example 1, cleaning evaluation was carried out. Detergents having the five compositions shown in Table 3 were prepared, and the effects of improving the cleaning rate by adding a builder (chelating agent) were evaluated. In the table, "LAS" is sodium dodecylbenzene sulfonate, "Nonion" is alkyl chain length 12, average E
Polyoxyethylene alkyl ether with 7 moles of O added, "STPP" is sodium tripolyphosphate, "NTA"
Is trisodium nitrilotriacetic acid.

[0028]

[Table 3]

Washing Conditions and Evaluation Method 5 sheets of 6 × 6 cm cotton artificially contaminated cloth were placed in 1 liter of an aqueous detergent solution for evaluation and washed under the following conditions at 100 rpm with a tergotometer. <Washing conditions> Washing time 10 minutes Detergent concentration 0.0833% Water hardness 4 ° DH Water temperature 20 ° C Rinse with tap water for 5 minutes Detergency is 550 nm of original cloth before and after cleaning
Reflectivity in a self-recording colorimeter [Z-3 manufactured by Nippon Denshoku Co., Ltd.
00A], and the cleaning rate (%) was determined by the following formula (the table shows the average cleaning rate for 5 contaminated cloths).

[0030]

[Equation 1]

Also, using a collar cloth with natural dirt attached,
A paired comparative evaluation according to JIS K-3371 was performed. The standard detergent was detergent (1), and evaluation was performed by comparing detergents (2) to (5) with detergent (1). (Evaluation Criteria) +2: Clearly superior +1: Slightly superior 0: Almost no difference -1: Slightly inferior -2: Apparently inferior The three judges made a score in comparison with the detergent (1), and the jacket 1 The average score per sheet was used as the evaluation score. The results of these evaluations are also shown in Table 4. As is clear from the results shown in Table 4, the artificial stain cloths of the present invention are preferable for evaluation because they all have a high correlation with the detergency of the collar cloth, that is, they show similar cleaning behavior to the natural dirt cloth. I understand.

[0032]

[Table 4]

Example 3 Using the artificially soiled cloth having the artificial soil composition 4 of Example 1, cleaning evaluation was performed. Also, as a comparative artificially contaminated cloth, a wet artificial contaminated cloth (cotton) manufactured by the Society of Washing Science, WFK10C manufactured by Krefeld
(Cotton), EMPA101 (cotton), St made by Test fabrics
Andard (cotton) was used.

The detergents of the five compositions shown in Table 5 were prepared,
As a builder (chelating agent), zeolite, citric acid,
Each of HEIDA, STPP, NTA, EDTA, and PAS was used to evaluate how the effect of improving the cleaning rate by adding these builders appears. In the table, “LAS” is sodium dodecylbenzenesulfonate, “Nonion” is a polyoxyethylene alkyl ether having an alkyl chain length of 12 and an average EO addition mole number of 7, and “HEIDA” is disodium hydroxyethyliminodiacetic acid, and “STPP”. Is sodium tripolyphosphate, “NTA” is trisodium nitrilotriacetate, “EDTA” is tetrasodium ethylenediaminetetraacetate, and “PAS” is sodium polyacrylate (average molecular weight 8,000).

[0035]

[Table 5]

Washing Conditions and Evaluation Method 5 sheets of 6 × 6 cm (5 × 5 cm only wet artificial stain cloth manufactured by the Society of Laundry Science) artificial cotton stain cloth were put into 1 liter of the detergent aqueous solution for evaluation , and 100 rpm was applied with a tergo meter. It was washed under the following conditions. <Washing conditions> Washing time 10 minutes Detergent concentration 0.0833% Water hardness 4 ° DH Water temperature 20 ° C Rinse with tap water for 5 minutes Detergency is 550 nm of original cloth before and after cleaning
Reflectivity in a self-recording colorimeter (Z-3 manufactured by Nippon Denshoku Co., Ltd.)
00A) and the cleaning rate (%) was determined by the following formula. (The table shows the average cleaning rate of 5 sheets of contaminated cloth.)

[0037]

[Equation 2]

Also, using a collar cloth with natural dirt attached,
A paired comparative evaluation according to JIS K-3371 was performed. Detergent (6) was used as the standard detergent, and evaluation was performed by comparison with a detergent (10) composition containing various builders. (Evaluation Criteria) +2: Clearly superior +1: Slightly superior 0: Almost no difference -1: Slightly inferior -2: Apparently inferior The three judges made a score in comparison with the detergent (6), and the jacket 1 The average score per sheet was used as the evaluation score. The evaluation results are shown in Tables 6, 7 and 8. As the results show,
By using the artificially contaminated cloth of the present invention, the detergency effect of the builder, which could not be evaluated by the conventional artificially contaminated cloth, is more clearly understood, and according to the present invention, the behavior of the natural collar dirt cloth is approached. An artificial stain cloth for cleaning evaluation is provided.

[0039]

[Table 6]

[0040]

[Table 7]

[0041]

[Table 8]

Continuation of the front page (72) Inventor, Kiyoshi Matsumoto 1-1, Minato No. 605, Rene Minato 1-1, Wakayama City, Wakayama Prefecture (56) References JP 55-26473 (JP, A) JP 55-26474 (JP, JP, 26-4744) A) JP-A-63-41597 (JP, A) JP-A-6-10,000 (JP, A) JP-A-6-116589 (JP, A) JP-A-6-128590 (JP, A) JP-A-7 -96162 (JP, A) JP-A-7-270395 (JP, A) JP-B-62-28838 (JP, B1) Takao Karime, "Design of Cleaning and Cleaning Agents", Surface Control & Cleaning Design, Japan, Modern editor, 1988, No. 38, pp. 62-69 (58) Fields investigated (Int.Cl. ⁷ , DB name) G01N 1/00-1/44 C09K 3/00 G01N 33/00 D06L 1/00

Claims (5)

(57) [Claims] 1. A W / O emulsion using an emulsifier having a property of forming a liquid crystal phase in water,
An artificial stained cloth prepared for contamination liquid without using a solvent, the
The W / O emulsion contains 1 to 40% by weight of an inorganic component, and
The W / O emulsion is an organic acid containing 6 to 24 carbon atoms,
Ins, squalene, polyol compounds and 6 to 24 carbon atoms
Ester compounds with organic carboxylic acids, glycerin and charcoal
Ester compounds with charcoal of 6 to 24, charcoal
Alcohol with 6 to 24 primes and organic cal with 6 to 24 carbons
Ester compound with boric acid and cholesterol and carbon number
Selected from 6 to 24 ester compounds with organic carboxylic acids
Dissolve an emulsifier that forms a liquid crystal phase in one or more organic substances
A solution in which carbon black is mixed and dispersed in the dissolved solution and water
A person who mixes with a liquid in which inorganic components are dissolved or dispersed in
Contaminated liquid for preparing industrial contaminated cloth. 2. The contaminated liquid for preparing artificially contaminated cloth according to claim 1, wherein the W / O emulsion contains the organic substance in an amount of 30 to 95% by weight in total. 3. The contaminated liquid for preparing an artificially contaminated cloth according to claim 1, which contains 0.01 to 2% by weight of carbon black. 4. An emulsifier having a property of forming a liquid crystal phase,
Artificially stained cloth prepared for contamination solution of any one of claims 1 to 3 is a lecithin or monooleate. 5. A process for producing an artificial stained cloth, characterized in that to attach the artificially stained cloth prepared for contamination solution of any one of claims 1-4 to the fabric surface.