JPH09316499A - Water-based liquid detergent filled in thin-walled plastic bottle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject product resistant to the loss of the volume of a liquid detergent caused by the permeation and dissipation of the components even by the lapse of some time after the filling of the liquid detergent by filling a water-based liquid detergent composition compounded with a low-molecular organic acid (or its salt) in a thin-walled plastic bottle. SOLUTION: A water-based liquid detergent composition containing 0.1-10wt.%, preferably 3-8wt.% (in terms of a low-molecular organic acid) of the low-molecular organic acid (e.g. caproic acid or glycolic acid) or its salt is filled in a thin-walled plastic bottle having a wall thickness of 150-220μm. The material for the plastic bottle is e.g. a polyethylene terephthalate resin or a polyethylene resin. The surfactant component of the above water-based liquid detergent is e.g. an anionic surfactant or an amphoteric surfactant. The composition may be incorporated with arbitrary components such as colorant, antibacterial agent and a hydrotropic agent. The amount of the arbitrary component is usually 3 wt.% based on the liquid detergent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent product used for various kinds of washing of vegetables, fruits, dishes, cooking utensils filled in plastic bottles.

[0002]

2. Description of the Related Art Bottles made of plastic such as polyethylene terephthalate, polyethylene or polypropylene (hereinafter also simply referred to as "bottle") are widely used as containers for filling liquids such as liquid detergent and drinking water. Has been used. Since the liquid products filled in these bottles are consumed in large amounts in every scene of daily life, it is desired to provide them to consumers at a lower cost. Conventionally, liquid cleaning product containers have a thickness of 35
Bottles of the order of 0-450 μm have been commonly used. When pursuing economy, that is, cost reduction, from the viewpoint of the container, a device that minimizes the amount of resin used for molding one bottle can be considered first. When a bottle is molded based on this idea, it is natural that the bottle becomes thinner. However, it is generally known that as the thickness of the bottle becomes thinner, the gas permeability increases, which causes a problem as a container for long-term storage. Specifically, when a product in which a thin bottle is filled with an aqueous liquid detergent and hermetically sealed is stored for a while in a warehouse or displayed at a store, the components in the aqueous liquid permeate and volatilize from inside the bottle to the outside. I do. When such a phenomenon that the detergent component permeates and evaporates through the bottle occurs, the liquid level is reduced due to the reduction of the filling material near the spout of the liquid which is formed into a considerably thinner shape than the body of the bottle. Is noticeable, and because the inside of the bottle is depressurized, the entire bottle is deformed (twisted) as if it were kinked, and a recess is formed in a part of the container. Can be For these reasons, it is conventionally considered that the thickness of the bottle is appropriate to the above-described thickness, and the above-described thickness has been used.

[0003]

SUMMARY OF THE INVENTION An object of the present invention relates to a liquid detergent product filled in a conventional plastic bottle having a wall thickness of ½ to ⅓, and the time after the liquid detergent is filled for a while. An object of the present invention is to provide an aqueous liquid detergent product contained in a plastic bottle, which prevents a reduction in weight due to permeation and volatilization of components even after the passage.

[0004]

According to the present invention, a low molecular weight organic acid or a salt thereof is converted to a low molecular weight organic acid in an amount of 0.1 to 0.1.
An aqueous liquid detergent composition containing 10% by weight has a wall thickness of 150 to
An aqueous liquid detergent product filled in a thin plastic bottle is provided, which is filled in a thin plastic bottle of 220 μm.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The material of the plastic bottle used in the present invention includes polyethylene terephthalate resin, polyethylene resin, polypropylene resin, polycarbonate resin and vinyl chloride resin. As such a resin, any resin can be used as long as the liquid detergent can be filled and stored in the container, and is not limited to the above-mentioned resin. The bottle of the present invention has a wall thickness of 150 to 220 μm. Naturally, a thicker layer than 220 μm can be used, but it is not practical to use such a thick layer because the economical effect cannot be sufficiently achieved. When manufacturing the thick container used in the present invention, a usual molding method such as injection molding can be used, and the method is not limited to a specific molding method. Processing such as stretching and crosslinking can be performed.
Further, a compounding agent such as a stabilizer, a plasticizer, a colorant, a filler, an antioxidant and an ultraviolet absorber may be compounded with the resin at the time of resin molding and contained in the molded resin. As the ultraviolet absorber among these, various known ones can be used. Examples thereof include salicylic acid-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, and the like. Specifically, salicylic acid-based UV absorbers include phenyl salicylate, p-tert-butylphenyl salicylate, and benzophenone-based UV absorbers. 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, benzotriazole as an ultraviolet absorber 2 (2'-hydroxy-5 ')
-Methylphenyl) benzotriazole, 2- (2-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-ethylhexyl-2- as a cyanoacrylate-based UV absorber
Cyano-3,3'-diphenyl acrylate, ethyl-
2-Cyano-3,3'-diphenyl acrylate may be mentioned. Further, for details of the ultraviolet absorber used as a plastic additive, for example, "12996 Chemical Products" Publisher: Kagaku Kogyo Nipposha, January 2, 1996
Issued on the 4th, pp. 995-1001, and the substances described therein can be appropriately used.

The cleaning surfactant component of the aqueous liquid detergent used in the present invention includes anionic surfactants, amphoteric surfactants, nonionic surfactants, and cationic surfactants.

[0007] Anionic surfactants include -CO
Examples thereof include compounds having groups such as O ⁻ , —OSO ₃ ⁻ , and —SO ₃ ^— , and specific examples include the following. (1) Carboxylic acid type anionic surfactant-C _{10 to} C ₁₈ fatty acid-Succinic acid monoalkyl ester salt having 3 to 15 carbon atoms in the ester portion-General formula R0 (EO) nCH ₂ COOM (in the formula, R Is an alkyl group or an alkenyl group having 10 to 18 carbon atoms, n is 1 to 6, M is an alkali metal or an alkaline earth metal)
(2) Sulfuric acid ester-based anionic surfactants ・ C ₁₀ -C ₁₈ alkyl sulfates ・ Alkyl or alkenyl alkyl (or alkenyl) polyethoxy sulfates having 10 to 18 carbon atoms ( the average addition mole number P = 2 to 7 ethylene oxide) (3) the number of carbon atoms of the olefin sulfonates, alkyl alkanesulfonates, C ₁₀ -C ₁₈ sulfonic acid anionic surfactants, C ₁₀ -C ₁₈ Is a C ₁₀ -C ₁₈ alkylbenzene sulfonate (4) an acyl amino acid salt having 8 to 18 carbon atoms, specifically a C ₁₂ N methyl β-alaninate sodium salt. Salts, alkaline earth metal salts, ammonium salts, alkanolamine salts and the like are exemplified.

Examples of the amphoteric surfactant include lauryl dimethylamine oxide, coconut fatty acid amide propyl betaine, alkyl dimethylamino hydroxysulfobetaine, lauryl dimethylamino acetic acid betaine and the like.

Examples of the nonionic surfactant include ethylene oxide adducts of higher alcohols (saturated or unsaturated alcohols, which may be linear or branched, and alcohols having an average carbon chain length of 7 to 15). The number of moles of ethylene oxide added is not particularly limited, but is usually about 5 to 25 mol). Mono- or diethanolamides of fatty acids are also exemplified. Dialkanolamides derived from saturated or unsaturated fatty acids having 8 to 14 carbon atoms are preferred. Other,
C ₆ -C ₁₆ of N- methyl glucamide, alkyl glucosides C ₈ -C _14, polyoxyethylene sorbitan esters of C ₅ -C _14, sucrose fatty acid esters of C ₈ -C _18, glucose derivatives, alkyl saccharide compound , Sugar amide compounds, C ₆ -C ₁₂ methyl or ethyl glucoside esters, and the like.

[0010] These surfactants are mixed and used as a liquid detergent composition. Table 1 shows specific examples of the mixed composition. The numerical value representing the composition is% by weight.
In the present invention, the ratio of the liquid detergent composition can be appropriately changed as needed, and is not limited to this specific example.

[0011]

[Table 1]

The following can be mentioned as optional components added to the liquid detergent. Fragrances, pigments,
Antibacterial agents, preservatives, antioxidants, hydrotropes such as ethanol, ultraviolet absorbers, solid dispersion emulsion latex. These optional components are added as appropriate, and the amount added is not limited, but is usually about 3% by weight of the liquid detergent.

As the ultraviolet absorber among these optional components, various ones known in the field of detergents can be used. Examples thereof include salicylic acid, para-aminobenzoic acid, and derivatives thereof. Specific examples include ethyl para-aminobenzoate, ethyl hexyl para-dimethylamino benzoate, sinoxate, ethyl hexyl para-methoxycinnamate, and 2- (2-hydroxy- 5-
Methylphenyl) benzotriazole, oxybenzone, urocanic acid and the like. For details of the ultraviolet absorber used in the cleaning composition, see, for example, “1.
2996 Chemical Products "(Issue: Chemical Daily 19
Published on January 24, 1996, pages 955-1001) and "Latest Cosmetic Science" (published by Yakuji Nippo Co., Ltd. Showa 5)
The substances described in these publications can be appropriately selected and used.

The pigments in these optional components are used to color the detergent composition, and “express a specific image as a specific form”, “make a product have a strong impact”, “ Coloring is a useful means for increasing the value of a product, for example, in order to provide a role such as "distinguishing a product from another product." Conventionally known dyes can be used for the dye, but a dye is generally used for a liquid detergent. When using pigments in kitchen cleaners,
The pigments are regulated by the Food Sanitation Law, and the following 15 types (food additives: 11 types, others: 4 types)
Is actually usable. These can be used alone,
Also, they can be used in combination. Colors of food additives include red 2, 3, 102, 104, 105, 1
No. 06, Yellow No. 4, No. 5, Green No. 3, Blue No. 1 and No. 2. Other pigments include Industrene Blue RS, Wool Green BS, and Quinoline Yellow Patent Blue V ("Food Sanitation Small Six Law" Published by Shin Nihon Hoki Shuppan Co., Ltd. (published on January 5, 1988) 767))).

As the fragrance, any fragrance that can be used for a detergent can be used. These are not only alone,
Several types can be used in combination. Table 2 shows an example of the fragrance composition used.

[0016]

[Table 2- (1)]

[0017]

[Table 2- (2)]

[0018]

[Table 2- (3)]

[0019]

[Table 2- (4)]

The viscosity and p indicating the properties of the liquid detergent composition
H is an important factor that affects the properties of the product. In a household kitchen cleaning composition, the viscosity is usually 8
The range is from 0 CPS to 400 CPS, and the pH is from 6.2 to 7.2.

In the present invention, a low molecular weight organic acid or a salt thereof is added to the above liquid detergent comprising water, a detergent for washing and optional components. It may be used as a low-molecular weight organic acid upon blending, or may be used in a state of equivalent neutralization or partial neutralization after the low-molecular weight organic acid is added and the pH of the composition is adjusted with an alkaline agent. The low-molecular organic acid referred to in the present invention is an organic acid having 1 to 9 carbon atoms, and examples thereof include a monovalent aliphatic carboxylic acid, an oxycarboxylic acid, an aromatic carboxylic acid, and an aromatic sulfonic acid. Can be done. As a specific example, for example, monovalent carboxylic acids include oxalic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, and divalent carboxylic acids include succinic acid, glutaric acid, and adipic acid. Examples of the trivalent carboxylic acid include tricarballylic acid, and examples of the oxycarboxylic acid include glycolic acid, lactic acid, malic acid, tartaric acid, glycolic acid and citric acid. Benzoic acid as the aromatic carboxylic acid, benzene sulfonic acid, xylene sulfonic acid, toluene sulfonic acid as the aromatic sulfonic acid,
Examples include cumene sulfonic acid. Examples of salts of these low molecular weight organic acids include their alkali metal salts, that is, sodium salts and potassium salts, monoethanolamine salts, triethanolamine salts and the like. The blending amount of these is 0.
It is necessary that 1 to 10% by weight be present. If this amount is less than 0.1%, the effect of suppressing volatilization is insufficient, and even if it is used in excess of 10% by weight, the effect of suppressing volatilization does not improve any more, and on the contrary, deterioration of properties such as low temperature stability occurs. It causes undesirable effects such as causing undesired. It is more preferably 3 to 8% by weight.

[0022]

Embodiments are described below. The measurement of the effect of suppressing permeation volatilization and the deformability of the bottle in the examples were performed by the following methods. As the bottle, the following conventional cylindrical bottle made of polypropylene was used. Stabilizer: 2- (2-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole 0.1% (1) Permeation and volatilization suppression effect In the above bottle, the liquid detergent composition Fill 500 ml,
The capped material was stored for 1 month under the condition of 50 ° C., and the residual weight was measured, and the volatilization weight was determined from the difference between the weight at the start of storage and the residual weight, and this was taken as the passing volatilization suppression effect. (2) Deformability of Bottle Similarly, the above bottle was filled with 500 ml of the liquid detergent composition, and the bottle was sealed and stored at 50 ° C. for one month, and the degree of deformation of the bottle was evaluated according to the following criteria. And the deformability of the bottle. Evaluation State of bottle ○: Deformation (twist) and occurrence of depression are hardly noticed △: Deformation (twist) and occurrence of depression are clearly seen ×: Deformation (twist) and occurrence of depression are clearly seen

Examples 1 to 7 and Comparative Examples 1 to 3 Concrete cleaning compositions of the present invention were prepared (blending amount was wt%), and their volatilization suppressing effects (residual weight) and bottle deformability ( Bottle condition) was evaluated and the results are shown in Table 3.
Are shown together.

[0024]

[Table 3] * 1 The following surfactants were used. _{· C 12 AES-Na: C} 12 POE (P = 3) Sodium lauryl sulfate · C14AOS: C14α-olefin sulfonate sodium salt · C ₁₂ amine oxide: C ₁₂ dimethylamine oxide · C14APCBE: dodecanoic acid amidopropyl carboxy betaine · POE alkyl Ether: POE (P = 12) lauryl ether ・ Alkyl glucoside: RGz (R is an alkyl group C _{10 to} C
A mixture of ₁₂ , G is a residue derived from a reducing sugar, specifically glucose, and Z is 1.4. ) ・ Alkanolamide: Lauric acid / Palm fatty acid (= 1)
/ 1) Diethanolamide * 2 As the alcohol, a mixture having a weight ratio of ethanol: propylene glycol: glycerin of 5: 3: 2 was used. * 3 A 10% caustic soda aqueous solution was used as the neutralizing alkaline agent. * 4 The flavors shown in Table 2 above were used. * 5 A mixture of blue No. 1 and quinoline yellow having a weight ratio of 4: 6 was used. * 6 Antioxidants are dehydroacetic acid: erythorbic acid:
A mixture having a weight ratio of isopropyl phenate of 2: 4: 4 was used.

According to the results shown in Table 3, when the low-molecular weight organic acid in the range of 0.1 to 10% by weight is used in the aqueous liquid detergent (Examples 1 to 7), the amount of the low-molecular organic acid is less than the above range. It can be seen that the volatilization weight is large and the deformation of the bottle is small as compared with the case where the molecular organic acid is used (Comparative Examples 1 and 3) and the case where the low molecular organic acid is not used (Comparative Example 2).

[0026]

According to the present invention, it is possible to prevent the components of the liquid cleaning composition during storage from permeating through the plastic bottle and volatilizing.

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Claims (1)

[Claims] 1. A thin plastic bottle having a wall thickness of 150 to 220 μm is filled with an aqueous liquid detergent composition containing a low molecular weight organic acid salt or a salt thereof in an amount of 0.1 to 10% by weight in terms of a low molecular weight organic acid. An aqueous liquid detergent product filled in a thin-walled plastic bottle, characterized in that