Bottled liquid cleaning agent

Abstract

To provide a novel bottled liquid detergent excellent in recyclability in spite of including a hydrophobic component of a SP value of at most 9.5 in a liquid detergent composition.SOLUTION: The bottled liquid detergent is comprised of a liquid detergent composition filled in a laminated film container. The liquid detergent composition includes the following components A to C, with the content of the component C in the liquid detergent composition being 43 mass% or less, the laminated film container being formed of a film laminate including a base material film and a water-soluble film, the water-soluble film being formed so as to constitute the innermost layer of the laminated film container. The component A: a nonionic surfactant and / or an anionic surfactant. The component B: a compound of a SP value of 9.5 or less. The component C: water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a bottled liquid detergent, a laminated film container used for the bottled liquid detergent, and a method for recycling the used container. [Background technology]

[0002] Multilayer films have traditionally been used as materials for packaging containers for liquid ingredients such as shampoo and beverages, and solid ingredients such as food (Patent Document 1). Many of the materials used for such films contain polyolefins, and there has been an increasing need for recycling them in recent years. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-123642 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when containers used for liquid detergents containing hydrophobic components such as volatile or low-volatility compounds are recycled, it has been found that these hydrophobic components may permeate the recycled resin. In such cases, it is difficult to remove the hydrophobic components that have permeated the recycled resin by washing with water, which reduces the recyclability of the containers.

[0005] The present invention relates to providing a novel bottled liquid detergent composition that contains a hydrophobic component with an SP value of 9.5 or less, yet has excellent recyclability. [Means for solving the problem]

[0006] The present invention relates to the following [1] to [3]. [1] A container-packed liquid detergent in which a liquid detergent composition is filled in a laminated film container, the liquid detergent composition comprising the following components A to C, the content of component C in the liquid detergent composition being 43 mass% or less, the laminated film container being formed from a laminate of films including a base film and a water-soluble film, and the water-soluble film being formed as the innermost layer of the laminated film container. Component A: Nonionic surfactant and / or anionic surfactant Component B: Compounds with an SP value of 9.5 or less Component C: Water [2] A laminated film container used for the bottled liquid detergent described in [1] above. [3] A method for recycling used containers of the bottled liquid detergent described in [1], comprising separating the base film and the water-soluble film, and using the resulting base film as a raw material for recycling. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a novel bottled liquid detergent composition that contains a hydrophobic component with an SP value of 9.5 or less, yet has excellent recyclability. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a photograph showing one embodiment of the bottled liquid detergent of the present invention. [Figure 2] FIG. 1 shows the results of a penetration test using the liquid detergent composition formulated in Example 1. [Figure 3] FIG. 1 shows the results of a penetration test using the liquid detergent composition formulated in Example 2. [Figure 4] FIG. 1 shows the results of a penetration test using the liquid detergent composition formulated in Example 3. [Figure 5] FIG. 1 is a graph showing the results of a penetration test using a liquid detergent composition formulated as Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0009] After extensive research into the above-mentioned problems, the inventors have newly discovered that the penetration of hydrophobic components into the base film can be effectively suppressed by filling a specific liquid detergent composition into a laminated film container formed from a laminate of films including a base film and a water-soluble film, with the water-soluble film being the innermost layer of the laminated film container.

[0010] Furthermore, we have newly discovered that by separating the base film and the water-soluble film during recycling and using the resulting base film as the raw material for recycling, the number of times the recycled resin needs to be washed and the amount of washing water used can be significantly reduced.

[0011] <Containerized liquid detergent> The bottled liquid detergent of the present invention is a liquid detergent composition filled in a laminated film container.

[0012] <Liquid detergent composition> The liquid detergent composition according to the present invention contains the following components A to C. Component A: Nonionic surfactant and / or anionic surfactant Component B: Compounds with an SP value of 9.5 or less Component C: Water

[0013] The nonionic surfactant of Component A may contain a nonionic surfactant known to be used in liquid detergent compositions, such as polyalkylene glycol-type nonionic surfactants such as polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbite fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, and polyoxyalkylene (hydrogenated) castor oil; polyhydric alcohol ester-type nonionic surfactants such as sucrose fatty acid esters, polyglycerin alkyl ethers, and polyglycerin fatty acid esters; alkyl glycoside-type nonionic surfactants; amine oxide-type nonionic surfactants; and fatty acid alkanolamide-type nonionic surfactants. One or more types of nonionic surfactants may be contained.

[0014] The anionic surfactant of Component A may contain an anionic surfactant known to be used in liquid detergent compositions, such as sulfate salts, sulfonate salts, carboxylate salts, phosphate salts, and amino acid salts. Specific examples of sulfate salts include alkyl sulfate salts, polyoxyalkylene alkyl ether sulfate salts, polyoxyalkylene alkenyl ether sulfate salts, and polyoxyalkylene alkylphenyl ether sulfate salts. Examples of sulfonate salts include linear alkylbenzene sulfonate salts, alkyl sulfosuccinate salts, alkyl polyoxyalkylene sulfosuccinate salts, alkane sulfonate salts, acyl isethionate, and acyl methyl taurate. Examples of carboxylate salts include higher fatty acid salts and polyoxyalkylene alkyl ether acetate salts. Examples of phosphate salts include alkyl phosphate salts and polyoxyalkylene alkyl ether phosphate salts. Examples of amino acid salts include acyl glutamate salts, alanine derivatives, glycine derivatives such as potassium N-coconut oil fatty acid acylglycine, and arginine derivatives. From the viewpoint of availability, these salts are preferably alkali metal salts, more preferably sodium salts. One or more anionic surfactants may be contained.

[0015] From the viewpoint of suppressing penetration of the hydrophobic component into the substrate film, the content of Component A in the liquid detergent composition according to the present invention is preferably from 26 to 80% by mass, more preferably from 29 to 75% by mass, and even more preferably from 32 to 70% by mass. When two or more types of Component A are contained, the content refers to the total amount of Component A.

[0016] Component B is a hydrophobic component, and is a compound having an SP value of 9.5 or less, preferably 9.5 or less, more preferably 9.4 or less, and even more preferably 9.3 or less. The lower limit can be, for example, 7 or more, 7.1 or more, or 7.2 or more, and the range can be any combination of these upper and lower limit values. Examples of component B include fats and oils, fragrances, etc. In the present specification, the SP value refers to the solubility parameter (unit: (cal / cm)) calculated by the Fedors method. 3 ) 1 / 2 ) and are described in, for example, references such as "SP Value Basics, Applications and Calculation Methods" (Johokikansha, 2005) and Polymer Handbook Third Edition (A Wiley-Interscience publication, 1989).

[0017] Examples of the oils and fats of component B include oleic acid (SP value: 9.1), isotridecyl isononanoate (SP value: 8.5), glyceryl tri-2-ethylhexanoate (SP value: 9.1), neopentyl glycol dicaprate (SP value: 8.9), hexyl laurate (SP value: 8.6), isopropyl laurate (SP value: 8.5), isopropyl myristate (SP value: 8.5), isopropyl palmitate (SP value: 8.5), isopropyl oleate (SP value: 8.6), squalane (SP value: 8.0), isododecane (SP value: 7.2), olive oil, jojoba oil, palm kernel oil, coconut oil, and castor oil. Examples of the fragrance of component B include one or more fragrance compounds selected from compounds described in "Synthetic Fragrances: Chemistry and Product Knowledge, Revised and Enlarged Edition" by Genichi Indo (published by The Chemical Daily, 2005) and "Fundamentals of Fragrances and Perfume Blending" by Mototaka Nakajima (published by Sangyo Tosho, 2005).

[0018] The content of Component B in the liquid detergent composition according to the present invention is preferably 0.01% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 12% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less. When two or more types of Component B are contained, the content refers to the total amount of Component B.

[0019] Component C is water. From the viewpoint of suppressing penetration of hydrophobic components into the substrate film, the content of component C in the liquid detergent composition according to the present invention is 43% by mass or less, preferably 0.01% by mass or more and 43% by mass or less, more preferably 0.1% by mass or more and 42% by mass or less, and even more preferably 1% by mass or more and 41% by mass or less.

[0020] The liquid detergent composition according to the present invention may further contain the following component D. Component D: Compounds with an SP value of more than 9.5

[0021] Component D includes organic compounds that are more hydrophilic than component B, such as diethylene glycol monobutyl ether, acetyl triethyl citrate, tributyl citrate, triethyl citrate, PEG-400, glycerin, propanediol, sorbitol, propylene glycol, phenoxyethanol, phenoxyisopropanol, ethylene glycol monobutyl ether, propylene diglycol, phenoxypropanediol, and monoethanolamine.

[0022] From the viewpoint of suppressing penetration of the hydrophobic component into the substrate film, the content of component D in the liquid detergent composition according to the present invention is preferably from 0.1 to 25% by mass, more preferably from 1 to 23% by mass, and even more preferably from 3 to 20% by mass. When two or more types of component D are contained, the content refers to the total amount of component D.

[0023] In addition to the above, the liquid detergent composition of the present invention may optionally contain other components that are commonly used in liquid detergent compositions, such as a pH adjuster, a solubilizer (also known as a viscosity reducer), a texture improver, an antioxidant, a colorant, and a zwitterionic surfactant.

[0024] Examples of pH adjusters include citric acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid, cumenesulfonic acid, etc. These acids may be used alone or in combination of two or more.

[0025] Examples of solubilizing agents (also called viscosity reducing agents) include paratoluenesulfonic acid or its salts, cumenesulfonic acid or its salts, benzoic acid or its salts, and urea.

[0026] Examples of the texture improver include silicone oils having a modifying group, such as polyether-modified silicone, aminopolyether-modified silicone, amidepolyether-modified silicone, and alkylpolyether-modified silicone. One type of texture improver may be used alone, or two or more types may be used in combination. The inclusion of a texture improver can improve the texture of clothing after drying.

[0027] Examples of the antioxidant include butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogen sulfite, etc. The antioxidant may be used alone or in combination of two or more kinds.

[0028] Examples of colorants include general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Blue No. 403, Green No. 3, Green No. 202, Red No. 106, Yellow No. 203, Turquoise P-GR (all trade names), and BLUE HP (manufactured by Milliken, trade name "LIQUITINT Blue HP"). One type of colorant may be used alone, or two or more types may be used in combination.

[0029] Examples of amphoteric surfactants include alkyl betaine, alkyl amide betaine, imidazoline, alkyl amino sulfonic acid, alkyl amino carboxylic acid, alkyl amide carboxylic acid, amide amino acid, and phosphoric acid surfactants. One type of amphoteric surfactant may be used alone, or two or more types may be used in combination.

[0030] The liquid detergent composition according to the present invention can be prepared by mixing the above-mentioned components using a known stirrer or the like.

[0031] <Laminated film container> The laminated film container according to the present invention is formed from a laminate of films including a base film and a water-soluble film. The laminated film container according to the present invention is formed so that the water-soluble film is the innermost layer, and may take any known form that can be produced using a laminated film. For example, a bag may be formed by stacking two laminated films so that the water-soluble film is the innermost layer, or by folding one laminated film in the center and stacking them, and then heat-sealing the edges of the film. However, the present invention is not limited to these forms. When using a laminated film container of these forms to produce a bottled liquid detergent, the container is heat-sealed except for the opening for filling, and then filled with a liquid detergent composition. The opening is then heat-sealed, whereby a bottled liquid detergent as shown in FIG. 1 can be produced.

[0032] The substrate film preferably contains a polyolefin or the like, and may be optionally surface-modified. Examples of polyolefins include polyethylene, polypropylene, and ethylene-vinyl alcohol copolymers. From the viewpoint of recyclability, polyethylene is preferred. Examples of polyethylene include commercially available polyethylenes such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). Examples of surface-modifying treatments include corona treatment and ozone treatment.

[0033] The thickness of the substrate film is not particularly limited, but is preferably 50 μm or more and 190 μm or less, more preferably 60 μm or more and 180 μm or less, and even more preferably 70 μm or more and 170 μm or less. In the present specification, the thickness is measured by the method described in the examples below.

[0034] The water-soluble film preferably contains a polymer containing a hydroxyl group, and more preferably contains a polyvinyl alcohol-based resin. Examples of polyvinyl alcohol-based resins include unmodified polyvinyl alcohol and anion-modified polyvinyl alcohol. Other examples of polymers containing a hydroxyl group include poly(meth)acrylate, (meth)acrylate copolymers, cellulose derivatives, and natural polymers, such as pullulan, carboxymethylcellulose, hydroxypropylmethylcellulose, guar gum, xanthan gum, carrageenan, starch, hydroxypropylated starch, and copolymers thereof.

[0035] From the viewpoint of suppressing penetration of hydrophobic components into the substrate film, the viscosity of the polyvinyl alcohol resin used in the water-soluble film is preferably from 1 mPa·s to 100 mPa·s, more preferably from 2 mPa·s to 70 mPa·s, and even more preferably from 3 mPa·s to 50 mPa·s. The viscosity is measured at 20°C using a Brookfield viscometer on a 4% aqueous solution of the polyvinyl alcohol resin. The degree of saponification is preferably from 75 mol% to 97.4 mol%, more preferably from 78 mol% to 97.0 mol%, and even more preferably from 80 mol% to 96.5 mol%.

[0036] The thickness of the water-soluble film is preferably 10 μm or more and 120 μm or less, more preferably 20 μm or more and 110 μm or less, and even more preferably 30 μm or more and 100 μm or less.

[0037] In the water-soluble film, a plasticizer can be used in combination, preferably in a range of 0% by mass to 28% by mass, more preferably 0% by mass to 25% by mass. Examples of the plasticizer include glycerin, propanediol, sorbitol, propylene glycol, phenoxyethanol, propylene diglycol, and phenoxypropanediol.

[0038] The laminated film can be prepared by a known manufacturing method. For example, a method of thermocompression bonding a base film and a water-soluble film, or a method of coating a base film with an aqueous polymer solution of the water-soluble film layer by a cast or gravure method and drying the coated film, etc. From the viewpoint of recyclability, a preferred embodiment is one in which the base film and the water-soluble film are weakly bonded directly or via another layer.

[0039] The laminated film container according to the present invention can include, in addition to the base film and water-soluble film, other layers such as PET, Ny, paper, etc. The film may be optionally surface-modified. Furthermore, a gas layer such as air can be provided between the films to make the container self-supporting.

[0040] <Recycling method> The recycling method of the present invention is a method for recycling used containers of the containerized liquid detergent of the present invention. Since the containerized liquid detergent of the present invention suppresses penetration of hydrophobic components into the base film, the base film and the water-soluble film in the used container can be separated, and the resulting base film can be suitably used as a raw material for recycling. Separation methods include physically peeling the films apart and dissolving the water-soluble film in water to separate them. Known recycling methods can be used, and recycled resins such as resin pellets can be produced by optionally washing and shredding the material, followed by melt-kneading. [Example]

[0041] EXAMPLES The present invention will be specifically explained below by showing examples and comparative examples, but the present invention is not limited to the following examples.

[0042] Preparation of Liquid Detergent Compositions Examples 1 to 3, Comparative Example 1 A liquid detergent composition was used in which 5% by mass of six components shown in Table 2 were added to 95% by mass of the composition shown in Table 1.

[0043] Details of the components used in Tables 1 and 2 are shown below. Neopelex GS: Kao Corporation, alkylbenzene sulfonic acid (alkyl carbon number 10-14) Emeral 20C: manufactured by Kao Corporation, polyoxyethylene (3) lauryl ether sodium sulfate Emulgen 120: Kao Corporation, polyoxyethylene (12) lauryl ether Lunac L-55: Palm kernel oil, manufactured by Kao Corporation Salacos 913: Isotridecyl isononanoate, manufactured by Nisshin Oillio Group Co., Ltd. Exepar TGO: Manufactured by Kao Corporation, glyceryl tri-2-ethylhexanoate

[0044] [Table 1]

[0045] [Table 2]

[0046] Penetration Test A penetration test for each component listed in Table 2 was conducted using containers with only a low-density polyethylene (LLDPE) film on the bottom ("LLDPE (with water washing)" and "LLDPE (without water washing)" in Figures 2 to 5) and containers with a low-density polyethylene (LLDPE) film on the bottom and a polyvinyl alcohol (PVA) film with different degrees of saponification laminated thereon ("LLDPE (97 mol% saponified PVA peeled)," "LLDPE (86 mol% saponified PVA peeled)," and "LLDPE (80 mol% saponified PVA peeled)" in Figures 2 to 5). The liquid detergent compositions of Examples 1 to 3 and Comparative Example 1 were poured into each of the containers. After 3 days of contact, the PVA film was peeled off from the latter container, and the LLDPE film was dried at 60°C for 2 hours under reduced pressure. The dried LLDPE film was immersed in ethyl acetate and extracted at 60°C for 2 hours. The extract was analyzed by GC to determine the amount of adsorption of hydrophobic components. The results are shown in Figures 2 to 5. The bar graphs for each formulation in Figures 2 to 5 show the results of penetration tests conducted on the six liquid detergent compositions prepared above under the following conditions (from left to right): "LLDPE (with water washing)," "LLDPE (without water washing)," "LLDPE (97 mol% saponified PVA stripped)," "LLDPE (86 mol% saponified PVA stripped)," and "LLDPE (80 mol% saponified PVA stripped)." In the test for "LLDPE (with water washing)," water washing was performed before the drying treatment under reduced pressure. In the other cases, drying was performed without water washing.

[0047] Details of the ingredients used in each of the above containers are shown below. The film thickness was measured using a Digimatic Micrometer (MDC-25MX). The PVA film was prepared by dissolving the PVA (30 g) shown below in water (270 g), applying it to an LLDPE film using a film applicator (gap of 500 μm), and then drying. The thickness of the PVA film after drying was 60 μm in all cases. LLDPE: Futamura Chemical Co., Ltd. "LL-XMTN", film thickness 150 μm 97 mol% saponified PVA: Kuraray Co., Ltd. "Kuraray Poval 27-96", 95.5 to 96.5% saponified 86 mol% saponified PVA: "VP-18PE" manufactured by Nippon Vinyl Acetate & Poval Co., Ltd., 86-90 mol% saponified 80 mol% saponified PVA: Kuraray Co., Ltd. "Kuraray Poval 5-82", 80-83 mol% saponified

[0048] The conditions for GC analysis are as follows: Instrument: Agilent Technologies 6850 Column: DB-1 (30 m × 250 um × 0.25 um) Injection volume: 1 uL Inlet temperature: 200℃ Split ratio: 50 / 1 Column temperature: 50 °C - 10 °C / min → 300 °C (5 min) Detector temperature: 320℃ Detector: FID Analyzed compound: Exepar TGO Instrument: Agilent Technologies 7820A Column: DB-17 (30 m × 250 um × 0.25 um) Injection volume: 1 uL Inlet temperature: 200℃ Split ratio: 50 / 1 Column temperature: 50 °C - 10 °C / min → 280 °C (5 min) Detector temperature: 280℃ Detector: FID Analyzed compounds: hexyl cinnamaldehyde, acetyl triethyl citrate, tributyl citrate, triethyl citrate, Salacos 913

[0049] As shown in Figures 2 to 5, the formulations of Examples 1 to 3 were superior in inhibiting the permeation of hydrophobic components compared to the formulations of Comparative Example 1, which contained a high water content, and the formulations of Examples 1 to 3 were superior in inhibiting the permeation of hydrophobic components compared to the formulation of Comparative Example 1, which contained a high water content. [Industrial Applicability]

[0050] According to the present invention, a new recycling technology can be provided.

Claims

1. A container-packed liquid detergent in which a liquid detergent composition is filled in a laminated film container, the liquid detergent composition comprising the following components A to C, the content of component C in the liquid detergent composition being 43 mass% or less, the laminated film container being formed from a laminate of films including a base film and a water-soluble film, and the water-soluble film being formed so as to be the innermost layer of the laminated film container. Component A: Nonionic surfactant and / or anionic surfactant Component B: a compound with an SP value of 9.5 or less Component C: water

2. 2. The bottled liquid detergent of claim 1, wherein the substrate film comprises a polyolefin.

3. The bottled liquid detergent according to claim 1 or 2, wherein the water-soluble film comprises a polymer containing hydroxyl groups.

4. The bottled liquid detergent according to any one of claims 1 to 3, wherein the water-soluble film contains a polyvinyl alcohol-based resin.

5. A laminated film container used for the bottled liquid detergent according to any one of claims 1 to 4.

6. A method for recycling used containers of the bottled liquid detergent described in any one of claims 1 to 4, comprising separating the base film and the water-soluble film, and using the resulting base film as a raw material for recycling.

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