JP2016160279A - Liquid detergent article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent article which is prepared by packing a liquid detergent composition in a container, the trunk part of which container is deformed to discharge a fixed amount of a liquid, from which article another fixed amount of the liquid detergent composition can be discharged even if air temperature is changed between the summer and winter seasons and in which article problems such as liquid dripping are not caused.SOLUTION: The liquid detergent article is prepared by packing the liquid detergent composition for automatic dishwashers in the container. The liquid detergent composition for automatic dishwashers contains an anionic surfactant (a), a cationic surfactant (b), a polysaccharide-based polymer (c), a metallic sealant (d) and water (e) and has the viscosity of 100-4,000 mPa s at 20°C, a mass ratio [((a)+(b))/(c)] of 3-20, and another mass ratio [(a)/(b)] of 1-10.SELECTED DRAWING: None

Description

  The present invention relates to a liquid detergent article and a method for discharging a liquid detergent.

Normally, the recommended amount of liquid cleaning agent used in general households is set according to the object to be cleaned, and an operation for measuring an appropriate amount and providing it for cleaning is performed in each household.
The liquid detergent product form commonly found in liquid detergents for clothing is filled with liquid detergent in a bottle with a measuring cap, and the amount of liquid poured into the measuring cap is measured using the scale on the cap. A form is mentioned. In such a product form, an operation of opening the cap, an operation of tilting the bottle and weighing with the cap, an operation of adding liquid to the object to be cleaned, and an operation of closing the cap are performed.
In addition, as a product form often found in liquid detergents used for hand-washing tableware, there is a form in which liquid is discharged to a sponge from a hole formed in the upper part of the bottle and used for cleaning. While this method allows the content liquid to be easily attached to the object to be cleaned, it does not have meterability.
Therefore, development of a container that can measure and discharge the content liquid by a simple method has been performed. Patent Documents 1 and 2 describe a quantitative discharge squeeze container including a container main body made of plastic that can be squeezed and deforming the container main body to discharge a predetermined amount of liquid from the discharge port.
Patent Document 3 discloses a liquid detergent for tableware containing a surfactant, a thickener, and a chelating agent.

JP 2011-121604 A JP 2011-105360 A JP 2008-163292 A

In liquid detergent compositions for automatic dishwashers used in dishwashers, the recommended amount of use is often small, and it is desirable to develop a method for simply putting a small amount into a predetermined place. ing. In particular, liquid detergent products filled with a liquid detergent composition for automatic dishwashers containing surfactants, chelating agents, etc., discharge a predetermined amount even with changes in temperature due to summer and winter seasons. It is hoped that it can be done.
The containers described in Patent Documents 1 and 2 can easily discharge a predetermined amount, but do not describe the quantitativeness with respect to seasonal temperature changes.
In addition, Patent Document 3 describes a liquid detergent for tableware containing a surfactant, a thickener, and a chelating agent, but there is no description regarding quantitativeness with respect to seasonal temperature changes, and There is no description about compatibility with a container that can be easily discharged while measuring a predetermined amount.

  The present invention relates to a liquid detergent article obtained by filling a container that discharges a certain amount of liquid by deforming a container body with a liquid detergent composition for an automatic dishwasher, and is suitable for temperature changes in summer and winter seasons. Regardless, a liquid detergent product that can discharge a certain amount of liquid detergent composition for an automatic dishwasher and does not cause problems such as dripping.

That is, the gist of the present invention is as follows.
[1] Contains an anionic surfactant (a), a cationic surfactant (b), a polysaccharide polymer (c), a metal sequestering agent (d), and water (e) at 20 ° C. Viscosity is 100 mPa · s or more and 4,000 mPa · s or less, and the total mass of the anionic surfactant (a) and the cationic surfactant (b) with respect to the polysaccharide polymer (c) The ratio [[(a) + (b)] / (c)] is 3 or more and 20 or less, and the mass ratio of the anionic surfactant (a) to the cationic surfactant (b) [(A) / (b)] is a liquid detergent article obtained by filling a container with a liquid detergent composition for an automatic dishwasher having 1 or more and 10 or less, and the container deforms the container body. To discharge a predetermined amount of the liquid detergent composition for an automatic dishwasher from the discharge port of the container. Liquid detergent article is a dispensing squeeze container to.
[2] A method for discharging a liquid detergent, wherein a predetermined amount of liquid is discharged by deforming the container body of the liquid detergent article according to [1].
[3] A method for discharging a liquid cleaning agent, wherein a predetermined amount of liquid is discharged by pushing and deforming the container body after the container of the liquid cleaning product article according to [1] is tilted or inverted.

  According to the present invention, the present invention relates to a liquid detergent article obtained by filling a container that discharges a certain amount of liquid by deforming a container body with a liquid detergent composition for an automatic dishwasher, and the summer and winter season temperatures. Provided is a liquid detergent article that can discharge a fixed amount of a liquid detergent composition for an automatic dishwasher regardless of changes and does not cause problems such as dripping.

It is a perspective view of the container main body of a fixed discharge squeeze container. It is sectional drawing of the cap member for fixed amount discharge squeeze containers. It is a cross-sectional perspective view of the cap member for fixed amount discharge squeeze containers.

[Liquid detergent products]
The liquid detergent article of the present invention comprises an anionic surfactant (a), a cationic surfactant (b), a polysaccharide polymer (c), a metal sequestering agent (d), and water (e). And the viscosity at 20 ° C. is 100 mPa · s or more and 4,000 mPa · s or less, and the anionic surfactant (a) and the cationic surfactant (for the polysaccharide polymer (c) ( b) The total mass ratio [[(a) + (b)] / (c)] is 3 or more and 20 or less, and the anionic surfactant with respect to the cationic surfactant (b) A liquid detergent product obtained by filling a container with a liquid detergent composition for an automatic dishwasher having a mass ratio [(a) / (b)] of 1 to 10 in (a), the container being Liquid washing for the automatic dishwasher which is the content liquid from the outlet of the container by deforming the container body The composition is a liquid detergent article is a dispensing squeeze container to a predetermined ejection amount. In the present specification, the “liquid detergent composition for an automatic dishwasher” may be referred to as a “liquid detergent composition”.

<Anionic surfactant (a)>
In the present invention, an anionic surfactant (a) is used for the purpose of imparting cleaning performance to the liquid cleaning composition.
The anionic surfactant (a) is preferably a linear alkylbenzene sulfonate or alkyl sulfate ester salt having an alkyl chain of preferably 10 or more, more preferably 12 or more, and preferably 18 or less. Alkali metals such as alkane sulfonate, polyoxyalkylene alkyl ether sulfate, N-acyl amino acid type surfactant, alkyl or alkenyl ether carboxylate, amino acid type surfactant, alkyl or alkenyl phosphate ester or salt thereof Salt.
Among these, alkane sulfonates having 10 to 18 carbon atoms are preferable, and alkane sulfonates having 12 to 18 carbon atoms are more preferable. A secondary alkane sulfonate is even more preferable.

  The content of the anionic surfactant (a) in the liquid detergent composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, from the viewpoint of blending stability and detergency against composite dirt. More preferably, it is 1.5% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less.

<Cationic surfactant (b)>
In the present invention, a cationic surfactant (b) is used in addition to the anionic surfactant (a). By using an anionic surfactant and a cationic surfactant in combination, the cleaning performance of the liquid detergent composition is improved.
Examples of the cationic surfactant (b) include quaternary ammonium salts and amidoamines. The number of carbon atoms in the alkyl group is preferably 12 or more, and preferably 22 or less, more preferably 18 or less.
Examples of the quaternary ammonium salt include alkyltrimethylammonium chloride such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, dialkyldimethylammonium chloride such as distearyldimethylammonium chloride, alkylbenzyldimethylammonium chloride, and the like. .
Amidoamines include stearic acid dimethylaminoethylamide, stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, palmitic acid dimethylaminoethylamide, palmitic acid dimethylaminopropylamide, myristic acid dimethylaminoethylamide, myristic acid dimethylaminopropyl. Examples include amide, behenic acid dimethylaminoethylamide, and behenic acid dimethylaminopropylamide.
Among these, lauryltrimethylammonium chloride or stearic acid dimethylaminopropylamide is preferable.

  The content of the cationic surfactant (b) in the liquid detergent composition is preferably 0.1% by mass or more, more preferably 0.6% by mass, from the viewpoint of blending stability and detergency against composite dirt. % Or more, more preferably 0.8% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

The mass ratio [(a) / (b)] of the anionic surfactant (a) to the cationic surfactant (b) is 1 or more and 10 or less. When the mass ratio [(a) / (b)] is within the above range, it is possible to improve the cleaning ability while suppressing excessive foaming.
The mass ratio [(a) / (b)] is 1 or more, more preferably 1.2 or more, still more preferably 1.3 or more, from the viewpoint of improving the cleaning ability while suppressing excessive foaming. More preferably, it is 1.4 or more, and is 10 or less, preferably 8 or less, more preferably 7 or less, further preferably 6 or less, still more preferably 5 or less, and still more preferably 4 or less.

<Polysaccharide polymer (c)>
In the present invention, the polysaccharide polymer (c) is used for the purpose of adjusting the viscosity of the liquid detergent composition.
Examples of the polysaccharide polymer (c) include pectin, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, tragacanth gum, carrageenan, locust bean gum, dextrin, dextrin fatty acid ester, xanthan gum, guar gum, sodium alginate, and starch.
In the present invention, among the polysaccharide polymers (c), xanthan gum is preferable from the viewpoints of thickening and storage stability.

The polysaccharide polymer (c) has a viscosity of an aqueous solution of preferably 500 mPa · s or more, more preferably 1,000 mPa · s or more, still more preferably 1,300 mPa · s or more, and preferably 100, 000 mPa · s or less, more preferably 10,000 mPa · s or less, further preferably 5,000 mPa · s or less, and further preferably 2,000 mPa · s or less.
The viscosity of the aqueous solution of the polysaccharide polymer (c) was determined by using an aqueous solution having a polysaccharide polymer concentration of 1.0% by mass and adjusted to pH 7.0 with sodium hydroxide. It means the viscosity measured at 20 ° C. using rotor No. 4, rotation speed 12 r / m).

The total mass ratio of the anionic surfactant (a) and the cationic surfactant (b) to the polysaccharide polymer (c) [[(a) + (b)] / (c)] Is 3 or more and 20 or less. When the mass ratio [[(a) + (b)] / (c)] is within the above range, a certain amount of the liquid detergent composition can be discharged regardless of the temperature change.
The mass ratio [[(a) + (b)] / (c)] is 3 or more, preferably from the viewpoint of being able to discharge a certain amount of the liquid detergent composition regardless of the temperature change. 3.5 or more, more preferably 4 or more, still more preferably 4.3 or more, and 20 or less, preferably 15 or less, more preferably 10 or less, still more preferably 8 or less.

<Metal sequestering agent (d)>
In the present invention, the metal sequestering agent (d) is used for the purpose of improving the cleaning performance.
Examples of sequestering agents include citric acid, malic acid, tartaric acid, succinic acid, methylglycine diacetic acid, glutamic acid diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, 1,3-propanediamine triacetic acid, Polycarboxylic acids such as 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, and hydroxyethylethylenediaminedicarboxymethylglutamic acid Acid, tripolyphosphoric acid, a copolymer of acrylic acid and maleic acid, or a salt thereof can be used.
Among these, citric acid, malic acid, methylglycine diacetic acid, glutamic acid diacetic acid, ethylenediaminetetraacetic acid and tripolyphosphoric acid, copolymers of acrylic acid and maleic acid, or salts thereof are preferred, and citric acid or salts thereof are more preferred. . These metal sequestering agents (d) may be used alone or in combination of two or more.

  The mass ratio [(d) / [(a) + (b)]] of the sequestering agent (d) to the total of the anionic surfactant (a) and the cationic surfactant (b) From the viewpoint of improving performance, it is preferably 1 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and even more preferably 7 It is as follows.

<Water (e)>
As water constituting the liquid detergent composition, tap water, distilled water, or deionized water can be used. Among these, distilled water or deionized water is preferable from the viewpoint of storage stability of the liquid detergent composition.

<Enzyme (f)>
The liquid detergent composition used in the present invention preferably contains the enzyme (f) for the purpose of improving the cleaning performance.
As the enzyme, one or more selected from amylase, protease, lipase, cellulase, esterase, and peroxidase can be used, and a commercially available product can be used. Any enzyme may be appropriately selected in consideration of storage stability with other components.
Among these, amylase which is expected to act on gelatinized starch that is difficult to remove with a surfactant is preferable. A protease is also preferable because it exhibits a remarkable effect on a denatured protein that is difficult to remove with a surfactant or the like. In the present invention, it is most preferable to use amylase and protease in combination.
When the liquid detergent composition contains the enzyme (f), the content of the enzyme (f) is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and further preferably 0.9% by mass. %, And preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and still more preferably 2.5% by mass or less.

<Silicone compound (g)>
In the present invention, a silicone compound (g) may be used for the purpose of suppressing foaming.
The silicone compound (g) is preferably a water-insoluble silicone compound from the viewpoint of suppressing foaming. In the present specification, “water-insoluble” means a property in which the amount dissolved in 1 L of ion-exchanged water at 20 ° C. is 1 g or less.

Specific examples of the silicone compound (g) include straight silicone compounds such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and modified silicones. In the present specification, “modified silicone” refers to polysiloxane having an organic group introduced at the side chain or terminal.
Modified silicones include long chain alkyl modified silicone, alkyl aralkyl modified silicone, alkyl polyether modified silicone, polyether modified silicone, higher alcohol ester modified silicone, higher fatty acid ester modified silicone, fluoroalkyl modified silicone, amino modified silicone, amide modified. One selected from silicone, amino polyether modified silicone, epoxy modified silicone, carboxyl modified silicone, carbinol modified silicone, phenol modified silicone, methacryl modified silicone, oxazoline modified silicone, polyester modified silicone, hydroxy modified silicone, and alkoxy modified silicone The above can be used.
The silicone compound (g) in the present invention may be in any form such as an oil type, an emulsion type, and a compound type, and among these, a compound type that is a mixture with an inorganic compound such as silica. Is preferred.

The weight average molecular weight of the silicone compound (g) is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and preferably 1,000,000 or less, more preferably 800,000 or less. More preferably, it is 600,000 or less.
The viscosity of the silicone compound (g) at 25 ° C. is preferably 100 mPa · s or more, more preferably 200 mPa · s or more, still more preferably 500 mPa · s or more, and preferably 10,000 mPa · s or less. More preferably, it is 5,000 mPa * s or less, More preferably, it is 1,500 mPa * s or less.

  When the liquid detergent composition contains the silicone compound (g), the content of the silicone compound (g) is preferably 0.005% by mass or more, more preferably 0.01% by mass from the viewpoint of suppressing foaming. From the viewpoints of production cost and storage stability, preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more. Is 0.5% by mass or less, more preferably 0.3% by mass or less, and still more preferably 0.2% by mass or less.

<Solvent>
In the present invention, a solvent other than water may be used. Solvents include ethanol, polyethylene glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, phenoxyethanol, phenyl glycol , Phenoxyisopropanol, butyl diglycol (diethylene glycol monobutyl ether), dibutylene glycol, and benzyl alcohol can be used.
These solvents may be used alone or in combination of two or more.
Among these, it is preferable to use at least one selected from ethanol, propylene glycol, phenoxyethanol, butyl diglycol, and benzyl alcohol, and it is preferable to use at least one selected from ethanol, propylene glycol, and benzyl alcohol. Most preferably, glycol is used.
When a solvent is used, the amount of the solvent in the liquid detergent composition is preferably 2% by mass or more, more preferably 3% by mass or more from the viewpoint of improving the stability of the composition, and the liquid detergent composition Is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less.

<Viscosity>
The viscosity at 20 ° C. of the liquid detergent composition is 100 mPa · s or more and 4,000 mPa · s or less. When the viscosity at 20 ° C. of the liquid detergent composition is within the above range, the liquid detergent composition is discharged from the container in a predetermined amount without causing liquid leakage or clogging of the liquid detergent composition. .
The viscosity at 20 ° C. is 100 mPa · s or more, preferably 150 mPa · s or more, more preferably 200 mPa · s or more, from the viewpoint of prevention of liquid leakage or liquid clogging from a specific container containing the liquid detergent composition. More preferably 250 mPa · s or more, still more preferably 300 mPa · s or more, still more preferably 350 mPa · s or more, and 4,000 mPa · s or less, preferably 3,500 mPa · s or less, more preferably 3 2,000 mPa · s or less, more preferably 2,500 mPa · s or less, and still more preferably 2,000 mPa · s or less.
In addition, the viscosity at 20 ° C. of the liquid detergent composition in the present specification means a viscosity measured at 20 ° C. using a Brookfield viscometer (B-type viscometer). The rotor and the number of rotations when performing measurement are appropriately set so as to be close to full scale.

In addition, the ratio of the viscosity at 5 ° C. to the viscosity at 40 ° C. of the liquid cleaning composition [viscosity at 5 ° C./viscosity at 40 ° C.] From the viewpoint of discharge, it is ideally 1, but when it is not 1, it is preferably 0.5 or more, more preferably 0.8 or more, and still more preferably 0.9 or more, and preferably 5 or less, more preferably 3 or less, still more preferably 2 or less, and still more preferably 1.8 or less.
In addition, the viscosity at 5 ° C. and 40 ° C. of the liquid dishwashing composition in this specification means a viscosity measured at 5 ° C. or 40 ° C. using a Brookfield viscometer (B-type viscometer). .

<PH>
The pH at 25 ° C. of the liquid detergent composition used in the present invention is preferably 6 or more and 8 or less, more preferably 7 or more and 8 or less from the viewpoint of blending stability. In addition, pH of the liquid cleaning composition in this invention is the value measured by the method as described in JIS-Z-8802: 1984 "pH measuring method".

  In the present invention, a pH adjuster can be used to adjust the pH value to the above range, specifically, an inorganic alkaline agent selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, The organic alkali agent chosen from an amine compound can be mentioned. As the amine compound, an amine compound represented by the following formula (I) is preferable. An appropriate amount of the pH adjuster is appropriately added to adjust the pH of the liquid detergent composition.

(In the formula, R ⁶¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 2 to 4 carbon atoms, and R ⁶² and R ⁶³ represent a hydrogen atom and 1 carbon atom, respectively. The above represents an alkyl group having 4 or less or a hydroxyalkyl group having 2 to 4 carbon atoms.

Examples of the compound represented by the formula (I) include monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol and the like.
Among these, from the viewpoint of blending stability and cost of the liquid detergent composition, the inorganic alkali agent is preferably a hydroxide such as potassium hydroxide or sodium hydroxide, and the organic alkali agent is preferably monoethanolamine. .

<Other ingredients>
In the present invention, as other cleaning components, polymer components such as polypropylene glycol and water-soluble inorganic salts such as sulfate, sulfite, hydrogen sulfate, hydrochloride and phosphate can be used.
Moreover, the other component which can be used for a normal liquid detergent composition can be mix | blended. For example, stabilizers such as p-cumene sulfonic acid and benzoic acid, preservatives, bleaching agents, bleach activators, enzyme stabilizers such as calcium salts and formic acid, fragrances, antibacterial agents, antifungal agents, dyes, etc. Can be mentioned.
Furthermore, from the viewpoint of improving cleaning performance and preventing foaming, surfactants other than the anionic surfactant (a) and the cationic surfactant (b), that is, a nonionic surfactant, and Amphoteric surface activity may be used.
Nonionic surfactants include, for example, polyoxyalkylene type nonionic surfactants, sucrose fatty acid esters, aliphatic alkanolamides, fatty acid glycerin monoesters, amine oxides, and glycoside type nonionic surfactants (alkyls). 1 or more types selected from glycosides and the like.

<Container>
The liquid detergent article of the present invention is a liquid detergent article obtained by filling a container with the liquid detergent composition. As the container, a quantitative discharge squeeze container that discharges a predetermined amount of the liquid detergent composition as the content liquid from the discharge port of the container by deforming the container main body is used.
Hereinafter, a fixed discharge squeeze container that can be used in the present invention will be described with reference to FIG. A quantitative discharge squeeze container 10 shown in FIG. 1 is a hollow bottle-shaped container made of a synthetic resin, including a container body 11, a mouth part 12, a body part 13, a squeeze operation part 14, and a bottom part 15.
A detachable cap member (not shown), which will be described later, is attached to the mouth part 12 of the container body 11. And the squeeze container 10 can be filled with the said liquid detergent composition as a content liquid.

The squeeze container 10 squeezes (squeezes) the squeeze operation part 14 existing in the body part 13 in the squeeze direction X in a state where the body part 13 of the container body 11 is gripped and tilted or inverted. For example, a predetermined amount of the liquid cleaning composition can be discharged from the discharge port provided in the cap member toward the discharge location.
In this embodiment, the container main body 11 can be manufactured with well-known synthetic resins, such as a polyethylene terephthalate, a polypropylene, a high density polyethylene, a vinyl chloride, for example, and can be formed by blow molding, for example.

  Next, a cap member that can be attached to and detached from the mouth 12 of the container body 11 will be described with reference to FIGS. The cap member 20 in FIGS. 2 and 3 is used by being attached to the mouth-neck portion 12 of the container body 11, and the liquid detergent composition is discharged from the discharge port 24 by squeeze deformation (squeezing deformation) of the squeeze operation unit 14. A liquid flow path for discharging the liquid. In addition, the mouth part 12 and the cap member 20 are detachably mounted via various known screwing means and fitting means.

The cap member 20 has a spiral channel 25 that constitutes at least a part of a liquid channel from the neck 12 of the container body 11 to the discharge port 24. The spiral flow path 25 is formed by a spiral blade 21 provided in a cylindrical lead-out path 26 facing the discharge port 24 of the cap member 20. The spiral blade 21 is a plastic molded product integrally formed with the central shaft member 22.
In this embodiment, the spiral blade 21 is disposed by joining a support rod 23 provided integrally with the lower end portion of the central shaft member 22 to the peripheral edge portion of the lower end opening of the cylindrical lead-out path 26. In addition, it is preferable that the peripheral end surface of the spiral blade 21 is in contact with the inner peripheral surface of the cylindrical lead-out path 26.

The bottom surface portion 25 a of the spiral flow path 25 provided by the spiral blade 21 is a descending slope that continuously inclines from the upper end portion of the spiral blade 21 toward the trunk portion 13 of the container body 11 in the upright state of the squeeze container 10. Form a gradient. Here, the downward gradient is not limited as long as the bottom surface portion 25a of the spiral channel 25 has a downward gradient as a whole, and there may be a horizontal portion in the middle.
In the present embodiment, a form in which the spiral blade 21 makes one round around the central shaft member 22 is adopted, but the spiral blade 21 may have a form of less than one round around the central shaft member 22. It may be in the form of a circumference or more.
According to the cap member 20 of the present embodiment, the bottom surface portion 25a of the spiral flow path 25 has a downward slope in the upright state of the squeeze container 10 as described above, and therefore in a state before the squeeze container 10 is squeezed. , Leakage of liquid contents and dripping can be effectively avoided.

  The present invention is not limited to the above embodiment, and various modifications can be made. For example, the member for forming the spiral flow path provided in at least a part of the liquid flow path from the neck portion of the container body to the discharge port is not limited to the above-described spiral blade, and other various members Can be used.

[Liquid cleaning agent discharge method]
The liquid cleaning agent discharge method of the present invention is a method of discharging a predetermined amount of liquid by tilting or inverting the container of the liquid cleaning article and then deforming it by pushing the container body.
In addition, the liquid detergent discharge method of the present invention is a method of discharging a fixed amount of liquid by deforming the container body of the liquid detergent article filled with the liquid detergent.
According to these methods of the present invention, it is possible to discharge a certain amount of the liquid cleaning composition regardless of the temperature change.

<Examples 1 to 6, Comparative Examples 1 and 2>
A liquid detergent composition was prepared with the composition shown in Tables 1 and 2, and the following evaluation was performed. The evaluation method is as follows. In addition, pH of all the Examples and Comparative Examples was adjusted to 7.5 using monoethanolamine or hydrochloric acid (concentration 1M).
<Measurement method of viscosity>
The liquid detergent compositions prepared in the examples and comparative examples were used as B-type rotational viscometers, No. Viscosities of 5 ° C., 20 ° C., and 40 ° C. were measured using 3 rotors. In addition, the value after rotating for 2 minutes at 30 rpm was set as the measured value.

<Discharge amount>
The amount of discharge was evaluated using the container shown in FIG. 1 equipped with the cap member shown in FIG. Measure the amount of the detergent composition discharged by filling the container with 400 g of the cleaning composition of Examples and Comparative Examples, inverting the container vertically with the discharge part of the container open, and deforming the container. did. This operation was performed five times by each of five measurers, and the average value was taken as the discharge amount of this evaluation. The results are shown in Tables 1 and 2.

<Evaluation of ejectability>
The container shown in FIG. 1 was filled with 400 g of the cleaning compositions of Examples and Comparative Examples in a container equipped with the cap member shown in FIG. 2, and the following various evaluations were performed. The results are shown in Tables 1 and 2.
[Drip]
After the discharge amount was evaluated at 20 ° C., the dripping amount from the discharge portion was evaluated according to the following criteria.
A: When the dripping amount is less than 0.5 g.
B: When the dripping amount is 0.5 g or more and less than 1.0 g.
C: When the dripping amount is 1.0 g or more.

[Quantitative]
After measuring the discharge amount 5 times for each of 5 ° C., 20 ° C. and 40 ° C. by 5 measurers, calculate the average value at each temperature, then calculate the discharge amount error based on the following formula, Evaluation was made according to criteria.
Discharge amount error = [(40 ° C. discharge amount / 20 ° C. discharge amount) − (5 ° C. discharge amount / 20 ° C. discharge amount)] × 100 [%])
A: When the discharge amount error is less than 10%.
B: When the discharge amount error is 10% or more and less than 30%.
C: When the discharge amount error is 30% or more and less than 50%.
D: The discharge amount error is 50% or more, or the discharge itself is difficult.

The compounds used in the examples and comparative examples are as follows.
<Anionic surfactant (a)>
-Anionic surfactant (a-1)
Alkanesulfonic acid salt with 12 to 18 carbon atoms (HOSTAPUR SAS 60, manufactured by Clariant Japan Co., Ltd.)
<Cationic surfactant (b)>
-Cationic surfactant (b-1)
A quaternary ammonium salt having 12 to 14 carbon atoms (Coatamine 24P, lauryltrimethylammonium chloride, manufactured by Kao Corporation)
・ Cationic surfactant (b-2)
Fatty acid dimethylaminopropyl having 12 to 14 carbon atoms (NIKKOL amidoamine MPS, stearic acid dimethylaminopropylamide, manufactured by Nikko Chemicals Co., Ltd.)
<Polysaccharide polymer (c)>
Xanthan gum (Keldent, DSP Gokyo Food & Chemical Co., Ltd.)
Viscosity of 20 ° C. and 1.0 mass% aqueous solution under the above conditions: 1500 mPa · s
<Metal sequestering agent (d)>
Trisodium citrate (purified sodium citrate, manufactured by Fuso Chemical Industry Co., Ltd.)

<Water (e)>
・ Ion exchange water

<Enzyme (f)>
・ Protease (1)
Savinase Ultra 16XL (Novozymes Japan K.K.)
・ Α-Amylase
Termamyl Ultra 300L (manufactured by Novozymes Japan Ltd.)

<Solvent>
・ Propylene glycol (manufactured by Kao Corporation)

<Others>
・ P-cumenesulfonic acid (manufactured by Teika Co., Ltd.)
・ Benzoic acid (Fushimi Pharmaceutical Co., Ltd.)
・ Aroma (made by Kao Corporation)

  As is clear from Tables 1 and 2, according to the liquid detergent product of the present invention, a constant amount of the liquid detergent composition can be ejected regardless of each temperature change, and problems such as dripping do not occur. I understand that.

Claims (6)

Contains an anionic surfactant (a), a cationic surfactant (b), a polysaccharide polymer (c), a metal sequestering agent (d), and water (e), and has a viscosity at 20 ° C. of 100 mPa · S to 4,000 mPa · s,
The total mass ratio of the anionic surfactant (a) and the cationic surfactant (b) to the polysaccharide polymer (c) [[(a) + (b)] / (c)] Is 3 or more and 20 or less,
Liquid detergent composition for automatic dishwashing machine wherein the mass ratio [(a) / (b)] of the anionic surfactant (a) to the cationic surfactant (b) is 1 or more and 10 or less A liquid detergent article filled with a container,
A liquid detergent article, which is a quantitative discharge squeeze container in which a predetermined amount of the liquid detergent composition for an automatic dishwasher as a content liquid is discharged from the discharge port of the container by deforming the container body.   2. The ratio of the viscosity at 5 ° C. to the viscosity at 40 ° C. of the liquid detergent composition for an automatic dishwasher [viscosity at 5 ° C./viscosity at 40 ° C.] is 0.5 or more and 5 or less. Liquid detergent articles.   The mass ratio [(d) / [(a) + (b)]] of the sequestering agent (d) to the total of the anionic surfactant (a) and the cationic surfactant (b) is The liquid detergent article according to claim 1, wherein the liquid detergent article is 1 or more and 15 or less.   The said container is provided with the cap member which has a liquid flow path for discharging the liquid detergent composition for automatic dishwashers, and at least one part of this liquid flow path is helical. 4. The liquid detergent article according to any one of 3.   A method for discharging a liquid detergent, wherein a predetermined amount of liquid is discharged by deforming the container body of the liquid detergent article according to any one of claims 1 to 4.   A method for discharging a liquid cleaning agent, wherein after a container of the liquid cleaning product according to any one of claims 1 to 4 is tilted or inverted, a predetermined amount of liquid is discharged by pressing and deforming the container main body.