JP2001011497A - Liquid detergent product filled in thin-wall plastic bottle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide liquid detergent products which are suitably used in cleaning ordinary household kitchen stains such as oil spots, dirt with the hands, resinous stains, and incrustations which are adhered to hard surfaces and housing stains. SOLUTION: A liquid detergent composition containing an acid or an alkali as component (A) and a hydrophilic solvent or a chelating agent as component (B) with a compounding amount of component (B) of at least not less than 1/50 of component (A) by weight ratio is filled in a thin-wall plastic bottle having a wall thickness of 150-300 μm to give a liquid detergent product filled in a thin plastic bottle which prevents the weight loss due to permeation and volatilization of the detergent component, breakage and discoloration of the container, and deterioration of odor and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid detergent product filled in a plastic bottle, and more particularly, to a liquid detergent product filled in a plastic bottle.
The present invention relates to a liquid detergent product filled in a plastic bottle suitably used for cleaning general household kitchen stains and house stains attached to hard surfaces such as oil stains, hand stains, tar stains, and water stains.

[0002]

2. Description of the Related Art Conventionally, plastic bottles made of polyethylene terephthalate, polyethylene or polypropylene (hereinafter sometimes simply referred to as "bottles") have been used as containers for filling liquids such as liquid detergents and drinking water. It has been actively used. The liquid products filled in these bottles are consumed in large quantities in every scene of daily life, but it is desired to provide them to consumers at lower cost. Further, since an increase in consumption causes an increase in garbage and adversely affects the environment, a product that reduces the amount of garbage is required today.

Conventionally, bottles having a thickness of about 350 to 700 μm have been generally used as containers for liquid detergent products, but in view of the above-mentioned economical and environmental problems, etc. In order to minimize the amount of resin used in the bottle molding, a device has been considered. As the amount of resin used for molding one bottle is reduced and the thickness of the bottle becomes thinner, gas permeability increases, and there is a disadvantage that long-term storage cannot be performed, such as deterioration of the content liquid. . In general, these products require a period of storage in a warehouse or display at a store, and if the components in the aqueous liquid permeate out of the bottle during this period, they may be considerably longer than the body of the bottle. In the vicinity of the spout of the liquid molded into a thin shape, the liquid level is significantly reduced due to the decrease in the amount of the filling, and deformation (twist) such as twisting of the whole bottle is caused, and A state where a concave portion is formed in a part is seen. For this reason, conventionally, it is considered that a bottle having a thickness of about 350 to 700 μm is appropriate, and such a bottle has been used.

[0004] On the other hand, as a liquid detergent filled in a thin bottle, for example, Japanese Patent Application Laid-Open No. 9-31 by the present applicant is disclosed.
JP-A-6499 and JP-A-10-30100 disclose detergents containing linear or cyclic polyhydric alcohols, polyoxyethylene glycols, and low-molecular-weight organic acid salts. At present, there is no disclosure of an agent which uses an acid or alkali suitable for kitchen stains and residential stains. In addition, a cleaning agent containing an acid or an alkali, if the thickness of the container is not sufficient, causes deformation or breakage of the container, and furthermore, there is a problem such as permeation and volatilization, discoloration, and deterioration of odor in the contents. ,
Filling thin bottles is not suitable.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has been made to solve the problem. The thickness of a conventional bottle is reduced from one half to one third. Regarding liquid detergent products filled into bottles, even after filling liquid detergents containing acids and alkalis into thin-walled bottles, weight loss due to permeation and volatilization of components over time, breakage of containers, discoloration, deterioration of odor, etc. It is an object of the present invention to provide a liquid detergent product filled in a thin-walled plastic bottle which prevents the occurrence of the liquid detergent.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems of the prior art, and as a result, a liquid cleaning agent containing an acid or an alkali was added to a specific hydrophilic solvent or The present inventors have found that by combining a chelating agent, a liquid detergent product of the above-mentioned purpose which can be filled in a thin plastic bottle having a thickness of 150 to 300 μm at the same time is obtained, and the present invention has been completed. That is, the liquid detergent product filled in the thin plastic bottle of the present invention contains an acid or alkali as the component (A) and a hydrophilic solvent or chelating agent as the component (B). A liquid detergent composition in which the amount of the component is at least 1/50 or more of the component (A) by weight,
It is characterized by being filled in a thin plastic bottle having a thickness of 150 to 300 μm.

[0007]

Embodiments of the present invention will be described below in detail. The liquid detergent product filled in the thin plastic bottle of the present invention contains an acid or alkali as the component (A) and a hydrophilic solvent or chelating agent as the component (B). The liquid detergent composition having a compounding amount of at least 1/50 or more of the component (A) by weight is filled in a thin plastic bottle having a thickness of 150 to 300 μm.

The material of the thin plastic bottle in the present invention includes, for example, polyethylene terephthalate resin, polyethylene resin, polypropylene resin, polycarbonate resin, vinyl chloride resin and the like. Any of these resins can be used as long as the liquid detergent composition containing an acid or an alkali can be filled and stored in a container, and is not limited to the above-mentioned resins. The thickness of the plastic bottle of the present invention is 150
３００300 μm, preferably 180-250 μm. If the thickness is less than 150 μm, bottle molding is difficult, productivity is deteriorated, and the thickness is 300 μm.
If it exceeds m, the economic effect cannot be sufficiently achieved, and it is not practical and is not preferable. The “thickness of the bottle” as used herein refers to the body, and is not limited to the mouth and the bottom.

In manufacturing the plastic bottle container having the above-mentioned thickness range used in the present invention, a usual molding method such as injection molding and blow molding can be used, and the present invention is limited to a specific molding method. Not something. In addition, resins include stabilizers, plasticizers, coloring agents, fillers, antioxidants,
Compounding agents such as ultraviolet absorbers are appropriately compounded during resin production,
It can be contained in a molded resin. Among these, various known UV absorbers can be used. Examples thereof include salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based agents. Specific examples of the salicylic acid-based ultraviolet absorber include, for example, phenyl salicylate and p-tert-butylphenyl salicylate. Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybinzophenone and 2-hydroxy-4-methoxybenzophenone, and examples of the benzotriazole ultraviolet absorber include 2 (2′-hydroxy-5′-). Methylphenyl) benzotriazole, 2- (2-hydroxy-3′-tert-butyl-5′-methylphenyl)-
5-chlorobenzotriazole, and examples of cyanoacrylate-based ultraviolet absorbers include, for example, 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, ethyl-2-cyano-3,3′-diphenylacrylate and the like. No. Further, for details of ultraviolet absorbers used in plastic additives, for example,
Substances described in “Chemical Products of 13398”, pages 1047 to 1054, published by Chemical Daily on January 28, 1998, can also be used as appropriate.

(A) Used in the liquid detergent composition of the present invention
The acid component of the component is not particularly limited, but a region where the expression of the component (B) is particularly remarkable is pH 4 or less. Specific examples of the acid component in the pH range of 4 or less include, in addition to inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid,
Organic acids such as citric acid, malic acid, succinic acid, phthalic acid, maleic acid, benzoic acid, acetic acid, and glycolic acid are included. These acid components can be used alone or in combination of two or more. The amount of the acid component is not particularly limited, but is preferably 10% by weight or less based on the total amount of the liquid detergent composition, and more preferably,
It is desirably 0.1 to 5% by weight. Even if the amount of the acid component exceeds 10% by weight, no particular improvement in cleaning performance is observed, which is not economically preferable.

(A) Used in the liquid detergent composition of the present invention
The alkali component of the component is not particularly limited, but a region where the expression of the component (B) is particularly remarkable has a pH of 9 or more. Examples of the alkali component in the pH range of 9 or more include, in addition to inorganic alkalis such as caustic soda and potassium hydroxide, particularly preferably, organic amines such as alkanolamine and morpholine represented by the following general formula (I). .

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Specific examples of organic amines include monoethanolamine, diethanolamine, N-methylethanolamine, N-ethylethananolamine, N-butylethanolamine, and N-butylethanolamine. Among these, preferred alkanolamines include monoethanolamine, diethanolamine and N-butylethanolamine from the viewpoint of detergency. These alkali components can be used alone or in combination of two or more. The amount of the alkali component is not particularly limited, but is preferably 10% by weight or less, more preferably 0.1 to 5% by weight, based on the total amount of the liquid detergent composition. Even if the amount of the alkali component exceeds 10% by weight, no remarkable improvement in the performance of the detergent is observed, which is not economically preferable.

(B) used in the liquid detergent composition of the present invention
As the hydrophilic solvent of the components, it is necessary to keep each component of the liquid detergent composition in a uniformly dissolved state, and a glycol solvent or a lower alcohol represented by the following general formula (II) is particularly preferable. These solvents may be used alone or in combination of two or more.

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Specific examples of the glycol solvent represented by the general formula (II) include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether,
Examples thereof include propylene glycol diethylene glycol monobutyl ether, dipropylene glycol ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, and triethylene glycol monophenyl ether.

Further, specific examples of the lower alcohol include:
Methanol, ethanol, propanol, isopropanol, butanol, isobutanol and the like can be mentioned. Among them, ethanol is preferable. As the ethanol, fermentation or synthesis ethanol is used, and a general denatured alcohol is also used.
As general denatured alcohols, methanol-denatured, benzol-denatured, triol-denatured, methyl ethyl ketone-denatured, denatonium benzoate-denatured, perfume-denatured general denatured alcohols, ethylene glycol monoethyl ether,
Chloroform, diethyl carbonate, ethyl acetate, ethyl propionate, ethyl butyrate, hexane, industrial ethyl ether, geraniol, 8-acetylated sucrose, phenylethyl ether, diethyl phthalate, brucine, linalool acetate, flavor H-No. 4. Flavor H
-No. 6, flavor H-No. 9. Flavor H-
No. 11, flavor H-No. 1. Flavor H-
No. 3, flavor H-No. 10. Flavor H-
No. 12, flavor H-No. 13. Flavor T
-No. 100, flavor T-No. 101, flavor T-No. 102, flavor T-No. 103,
Flavor T-No. 107, flavor S-No. 2
01, Hexane, linalool, alkylbenzene sulfonate aqueous solution, vinyl acetate monomer, heptane, isopropyl alcohol, selective denatured alcohol such as butanol denatured, ethyl acrylate, benzyl acetate, methanol / 10% denatonium benzoate alcohol solution, flavor H-No. 14. Seed vinegar and water (acid amount 10% or more,
Alcohol 15% or less), high acidity brewed vinegar (acid content 10%)
Above), flavor T-No. 3. Flavor T-N
o. 4, flavor H-No. 2, Flavor TN
o. 104, flavor T-No. 105, flavor T-No. 106, methanol / formalin / rhodamine B, methyl ethyl ketone / 8 acetylated sucrose / isopropyl alcohol, butyl parahydroxybenzoate, white lac or specially modified alcohol such as purified shellac or shellac.

(B) used in the liquid detergent composition of the present invention
The chelating agent of the component is not particularly limited, but particularly preferred are organic phosphonic acids, aminocarboxylic acids and salts thereof represented by the following general formula (III).

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Specific examples of the organic phosphonic acids include 1-
Examples thereof include acids such as hydroxyethane-1,1-diphosphonic acid and 1-hydroxypropane-1,1-diphosphonic acid and salts thereof. Specific examples of aminocarboxylic acids include ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, and cyclohexane-1,2.
-Acids such as diaminetetraacetic acid and salts thereof. These chelating agents can be used alone or in combination of two or more.

In the present invention, the amount of the hydrophilic solvent or chelating agent of the component (B) blended in the liquid detergent composition is not particularly limited as long as the performance of the detergent is maintained. , Prevents deformation and breakage of containers during storage in thin-walled plastic bottles, and prevents transmission and volatilization of contents,
In order to demonstrate discoloration prevention and odor deterioration prevention,
It is necessary that at least (B) / (A) be at least 1/50 or more by weight with respect to the acid or alkali component ((A) component), and preferably 1/2 to 10/1. . When the mixing ratio of the hydrophilic solvent or the chelating agent of the component (B) is 1
If the ratio is less than / 50, the effect of preventing deformation and breakage of the container, the suppression of volatilization of the contents, the prevention of discoloration, odor deterioration, and the like cannot be sufficiently exhibited, which is not preferable.

Further, the liquid detergent composition of the present invention may optionally contain a surfactant in an appropriate amount. As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used, and these are not limited to specific ones. Representative examples of the surfactant that can be used include the following (1) to (4). (1) anionic surfactant alkyl sulfate, alkyl polyoxyethylene sulfate,
Alkyl benzene sulfonate, α-olefin sulfonate, fatty acid salt, ether carboxylate, monoalkyl phosphate and the like. Counter ions (cations) of these anionic surfactants include alkali metal ions, alkaline earth metal ions, alkanolamine ions, ammonium ions and the like. (2) Cationic surfactant Alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl ammonium salt, alkyl benzyl dimethyl ammonium salt and the like can be mentioned. The counter ion (anion) of these cationic surfactants is a halogen ion or the like. (3) Amphoteric surfactants Alkyl carboxy betaines, alkyl sulfo betaines and the like. (4) Nonionic surfactant Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid diethanolamide, amine oxide, amidoamine oxide and the like can be mentioned.

Further, the liquid detergent composition of the present invention may optionally contain an appropriate amount of a fragrance component, an antiseptic, an antifungal agent and the like. The fragrance component is not particularly limited, but specific examples thereof include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons, and aromatic hydrocarbons, and alcohols such as aliphatic alcohols, terpene alcohols, and aromatic alcohols. , Aliphatic ethers, ethers such as aromatic ethers, aliphatic oxides, oxides such as terpene oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes,
Aldehydes such as thioaldehyde and aromatic aldehyde,
Aliphatic ketones, terpene ketones, hydrogenated aromatic ketones,
Ketones such as aliphatic cyclic ketones, non-benzene aromatic ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids Acids such as acids, acid amides, aliphatic lactones, macrocyclic lactones, terpene lactones, hydrogenated aromatic lactones,
Lactones such as aromatic lactones, aliphatic esters, furan carboxylic esters, aliphatic cyclic carboxylic esters, cyclohexyl carboxylic esters, terpene carboxylic esters, esters such as aromatic carboxylic esters, nitromusks, Synthetic fragrances such as nitriles, amines, pyridines, quinolines, pyrroles, nitrogen-containing compounds such as indole, and natural fragrances from plants can be used, and these can be used alone or in combination of two or more kinds of components. it can. These fragrances can be blended in consideration of improving the odor such as amine odor in the case of blending an alkanolamine or the like and giving a pleasant odor, and the blending amount is based on the total amount of the liquid detergent composition. On the other hand, 0 to 0.5% by weight is optimal.

The preservatives that can be used in the present invention are not particularly limited, but include, for example, sodium benzoate, isonebutyl butyl paraoxybenzoate, isopropyl paraoxybenzoate, ethyl paraoxybenzoate, methyl paraoxybenzoate, paraoxybenzoate. Benzoic acid preservatives such as butyl benzoate and propyl paraoxybenzoate, sorbic acid preservatives such as sorbic acid and potassium sorbate, dehydroacetic acids, propionic acids, diphenyls such as diphenyl, orthophenylphenol and sodium , Thiabenzol, imazalil and the like. The amount of the preservative is from 0% by weight to 0.5% by weight based on the total amount of the liquid detergent composition.

Further, the liquid detergent composition of the present invention may contain an appropriate amount of a hydrotrope, an ultraviolet absorber, a coloring agent, a thickener and the like as optional components. The compounds used for these optional components are not particularly limited as long as they are usually used in detergents.

In the liquid detergent composition of the present invention, the balance is adjusted with water (purified water, ion-exchanged water, etc.), and the pH and viscosity indicating its properties are both important factors that affect the properties and performance of the product. Is a factor. These liquid detergent compositions usually have a pH of 4 in order to exhibit their performance.
It is assumed that it is used below or 9 or more. Also,
Since it is used after being transferred to a trigger and a dispenser bottle, the viscosity is usually 300 CP
S or less, preferably from the viewpoint of the performance of the cleaning agent,
It is desirable that it be 100 CPS or less.

In the liquid detergent product filled in the plastic bottle thus constituted, a liquid detergent containing an acid or alkali component as the component (A) is combined with a hydrophilic solvent or a chelating agent as the component (B). As a result, even when a thin plastic bottle having a thickness of 150 to 300 μm is filled for the first time, a liquid detergent product that prevents weight loss due to permeation and volatilization of components, damage to containers, discoloration, deterioration of odor, and the like over time. (This point and the like will be further described in Examples and the like which will be described later).

[0025]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the compounding quantity in a table | surface is "weight%", and the whole quantity is 100 weight%.

The following compositions were used for the fragrances in the table. (Flavoring composition: weight%) β-pinene 5.0 peppermint oil 2.0 lemon oil 2.0 citral 10.0 citronellol 8.0 geraniol 10.0 linalool 12.0 linalyl acetate 5.0 liranol 2.0 limonene 30.0 Eugenol 5.0 1-Menthol 3.0 Camphor 3.0 γ-Decalactone 3.0

Examples 1 to 4 and Comparative Examples 1 to 3 An acidic detergent composition was prepared according to the composition shown in Table 1 below. The obtained acidic cleaning composition was filled into the following test bottles, and the following test methods were used to evaluate the permeation volatilization suppressing effect (residual weight), the bottle deformability (bottle state), change in color tone, and change in odor. did. The results are shown in Table 1 below. [Examples 5 to 8 and Comparative Examples 4 and 5] Alkaline detergent compositions were prepared according to the composition shown in Table 2 below. The obtained alkaline cleaning composition was filled into the following test bottles, and the following test methods were used to evaluate the permeation volatilization suppressing effect (residual weight), the bottle deformability (bottle state), the change in color tone, and the change in odor. did. The results are shown in Table 2 below.

[Properties of Test Bottle] As the test bottle, the following conventional high-density polyethylene cylindrical bottle was used.

(1) Test Method for Permeation Volatilization Inhibition Effect The above test bottle was filled with 400 ml of the liquid detergent composition, and the bottle was sealed and stored at 50 ° C. for one month. The volatilization weight was determined from the difference from the above, and the result was used as the effect of suppressing passage volatilization.

(2) Test method for bottle deformability The above test bottle was filled with 400 ml of the liquid detergent composition, and the bottle was sealed and stored at 50 ° C. for one month. And evaluated as the deformability of the bottle. Evaluation criteria: ：: Deformation (twist) and occurrence of concave portions are hardly recognized. Δ: It can be seen that deformation (twist) and occurrence of concave portions are well observed. ×: Deformation (twist) or occurrence of concave portions can be immediately recognized. .

(3) Test Method for Preventing Discoloration The above test bottle was filled with 400 ml of the liquid detergent composition, sealed, and stored at 50 ° C. for 1 month. The color tone was also stored at room temperature for 1 month. It was visually evaluated according to the following evaluation criteria in comparison with those. Evaluation criteria: ：: There is almost no difference in color tone between the product stored at 50 ° C. and the product stored at room temperature. Δ: The color tone of the product stored at 50 ° C. and the product stored at room temperature are slightly different. X: The color tone of the product stored at 50 ° C. and the product stored at room temperature are clearly different.

(4) Test Method for Prevention of Odor Deterioration The above test bottle was filled with 500 ml of the liquid detergent composition, and the bottle was sealed and stored at 50 ° C. for one month. The odor was also stored at room temperature for one month. Five panelists evaluated according to the following evaluation criteria. Evaluation criteria: ：: All five persons cannot recognize the difference in odor between the product stored at 50 ° C. and the product stored at room temperature. Δ: One or two out of five persons recognized the difference in odor between the product stored at 50 ° C. and the product stored at room temperature. ×: Three or more of the five persons recognized the difference in odor between the product stored at 50 ° C. and the product stored at room temperature.

[0033]

[Table 1]

[0034]

[Table 2]

As is evident from the results of Tables 1 and 2, Examples 1 to 8 which are within the scope of the present invention are superior to Comparative Examples 1 to 5 which are outside the scope of the present invention in the effect of suppressing permeation and volatilization. ,
It was found that there was no change in bottle deformability (bottle state), color tone and odor.

[0036]

According to the present invention, there is provided a liquid detergent product filled in a thin plastic bottle which prevents weight loss due to permeation and volatilization of the detergent component, damage to the container, discoloration and deterioration of odor.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 7/36 C11D 7/36 17/04 17/04 17/08 17/08 (72) Inventor Toshiaki Nabeya (3) Inventor Nobuyuki Takada 1-3-7 Honjo, Sumida-ku, Tokyo Lyon Co., Ltd. F-term (reference) 4H003 AB15 BA12 BA21 DA05 DA17 DB01 DB02 EA03 EB08 EB16 EB24 ED02 ED28 ED29 FA07 FA08 FA16 FA25 FA26 FA28 FA30

Claims (1)

[Claims] 1. An acid or alkali as component (A),
A liquid detergent composition containing a hydrophilic solvent or a chelating agent as the component (B), and the compounding amount of the component (B) is at least 1/50 or more of the component (A) by weight,
A liquid detergent product filled in a thin plastic bottle, which is filled in a thin plastic bottle having a thickness of 150 to 300 μm.