JP7138560B2 - Liquid detergent composition for toilet and detergent product for toilet in container - Google Patents

Description

TECHNICAL FIELD The present invention relates to a liquid toilet cleaning composition and a packaged toilet cleaning product.

A toilet bowl is generally cleaned by applying a toilet liquid detergent composition to an object to be cleaned and then rubbing (scrubbing) it with a cleaning brush. When rubbing the object to be cleaned with the cleaning brush, the user bends forward or bends over, which is troublesome and places a heavy physical burden on the user. Also, areas such as the underside of the rim of the toilet bowl are hard to reach areas for the cleaning brush and are difficult to clean.
Accumulation of toilet bowl stains causes strong urinary stone stains. In addition, poor cleaning brush reach reduces cleaning satisfaction. Accumulated dirt may be perceived as an odor.

To address these problems, an antifouling detergent composition containing a specific polysiloxane, a specific surfactant, a metal chelating agent, and water has been proposed (Patent Document 1). According to the invention of Patent Document 1, an improvement in detergency and an improvement in durability of the antifouling effect are achieved.

Japanese Patent Application Laid-Open No. 2004-162041

However, the conventional techniques have not yet provided a satisfactory detergency. When the viscosity of the liquid toilet cleaning composition is increased to lengthen the residence time in areas that are difficult to clean (increase retention), it becomes difficult to discharge the liquid toilet cleaning composition from the discharge container. , it is difficult to apply the liquid detergent composition for toilets to the target area (that is, the ejection property is low).
Accordingly, an object of the present invention is to provide a liquid detergent composition for toilets that has excellent detergency, good retention, and good dischargeability.

［式（ｂ１）中、Ｘは、Ｏ又はＣＨ_２Ｏであり、Ｒ^１は炭素数２又は３のアルキレン基であり、ｍは（Ｒ^１Ｏ）の平均繰り返し数を表す１～６の数であり、Ｒ^２は水素原子又は炭素数１～３のアルキル基である。］
［２］前記（Ｂ）成分／前記（Ｃ）成分で表される質量比が、０．１～３００である、［１］に記載のトイレ用の液体洗浄剤組成物。
［３］前記（Ｃ）成分は、重合度５００～２４００であり、かつ、けん化価８０％以上のポリビニルアルコール系高分子である、［１］又は［２］に記載のトイレ用の液体洗浄剤組成物。
［４］前記（Ｄ）成分の含有量が、８０～９５質量％である、［１］～［３］のいずれかに記載のトイレ用の液体洗浄剤組成物。
［５］［１］～［４］のいずれかに記載のトイレ用の液体洗浄剤組成物と、前記トイレ用の液体洗浄剤組成物を収容している吐出容器とを備える、容器入りトイレ用洗浄剤製品。 The present invention has the following aspects.
[1] (A) component: a surfactant,
(B) component: a compound represented by the following formula (b1);
(C) component: one or more polymers selected from polyvinyl alcohol-based polymers and cellulose-based polymers;
(D) component: water and
contains
The mass ratio represented by the component (A)/component (B) is 0.16 to 50,
A liquid detergent composition for toilets, having a viscosity of 40 mPa·s or less at 25°C.

[In the formula (b1), X is O or CH ₂ O, R ¹ is an alkylene group having 2 or 3 carbon atoms, and m is a number from 1 to 6 representing the average number of repetitions of (R ¹ O) and R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]
[2] The liquid detergent composition for toilets according to [1], wherein the mass ratio represented by component (B)/component (C) is 0.1 to 300.
[3] The liquid detergent for toilets according to [1] or [2], wherein the component (C) is a polyvinyl alcohol polymer having a polymerization degree of 500 to 2400 and a saponification value of 80% or more. Composition.
[4] The liquid detergent composition for toilets according to any one of [1] to [3], wherein the content of component (D) is 80 to 95% by mass.
[5] A container toilet comprising the liquid toilet cleaning composition according to any one of [1] to [4] and a discharge container containing the toilet liquid cleaning composition. cleaning products.

The liquid detergent for textile products of the present invention has excellent detergency, good retention, and good dischargeability.

FIG. 4 is a partial cross-sectional view showing an example of a discharge container;

(Liquid detergent composition for toilet)
The liquid detergent composition for toilets of the present invention (hereinafter sometimes simply referred to as "liquid detergent composition") contains components (A) to (C).

<(A) Component>
(A) Component is a surfactant. A liquid detergent composition exhibits detergency by containing (A) component.
Component (A) may be any surfactant that is commonly used in liquid detergent compositions, such as an amphoteric surfactant (component (a1)), an anionic surfactant (component (a2)), and a nonionic surfactant. (component (a3)), amine oxide surfactants (component (a4)), cationic surfactants, and the like. Among these, the (a1) component is preferable as the (A) component. By using component (a1) in combination with component (B), component (C) and component (D), excellent detergency can be exhibited without rubbing the object to be cleaned after applying the liquid detergent composition. In addition, the liquid detergent composition contains the (a1) component, thereby enhancing wiping properties.

The content of component (A) is preferably 0.5 to 5% by mass, more preferably 0.8 to 4% by mass, and 1 to 2.5% by mass, relative to the total mass of the liquid detergent composition. More preferred. By setting the content of component (A) within the above range, excellent detergency can be exhibited without rubbing the object to be cleaned, and wiping properties can be enhanced.

<<(a1) component>>
The component (a1) is an amphoteric surfactant. The component (a1) is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include betaine-based amphoteric surfactants and amino acid-based amphoteric surfactants. Among these, betaine-based amphoteric surfactants are preferred.
Examples of betaine-based amphoteric surfactants include carbobetaine-based amphoteric surfactants, amidobetaine-based amphoteric surfactants, sulfobetaine-based (hydroxysulfobetaine-based, amidosulfobetaine-based) amphoteric surfactants, and imidazolinium betaine. amphoteric surfactants, phosphobetaine amphoteric surfactants, aminopropionic acid amphoteric surfactants, and the like. Carbobetaine-based amphoteric surfactants and amidobetaine-based amphoteric surfactants are preferred, and amidobetaine-based amphoteric surfactants are more preferred.

(1) Carbobetaine-based amphoteric surfactants include betaine laurate dimethylaminoacetate, betaine myristyldimethylaminoacetate, betaine stearyldimethylaminoacetate, and the like.
(2) Amphoteric surfactants based on amidobetaine include coconut oil fatty acid amidopropylbetaine (cocamidopropylbetaine), lauramidopropylbetaine, isostearamidopropylbetaine and the like.
(3) Examples of sulfobetaine-based amphoteric surfactants include, for example, coconut oil fatty acid dimethylaminohydroxysulfobetaine, lauryldimethylaminohydroxysulfobetaine, laurylhydroxysulfobetaine, coconut oil fatty acid dimethylsulfopropylbetaine, laurylsulfobetaine, stearylsulfo betaine, myristylsulfobetaine and the like.
(4) Examples of imidazolinium betaine amphoteric surfactants include coconut oil alkyl-N-hydroxyethylimidazolinium betaine, coconut oil alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, 2- Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and the like can be mentioned.
(5) Phosphobetaine-based amphoteric surfactants include, for example, lauryl hydroxyphosphobetaine.
(6) Examples of aminopropionic acid-based amphoteric surfactants include sodium laurylaminodipropionate and triethanolamine laurylaminodipropionate.
(7) Amphoteric amino acid surfactants include laurylamino fatty acid salts, stearylamino fatty acid salts, myristylamino fatty acid salts, and the like.

As the component (a1), among the above, lauramidopropyl betaine, lauryldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine are preferable, and from the viewpoint of wiping properties, lauramidopropyl betaine and lauryldimethylaminoacetic acid betaine are particularly preferable. .
Examples of the counter ion of the salt include alkali metal salt ions, ammonium salt ions, and alkanolamine salt ions. Among these, ions of alkali metal salts are preferred, and sodium ions and potassium ions are more preferred.

(a1) Component is commercially available. Examples of commercially available component (a1) include lauramidopropyl betaine “Enagicol L-30B (manufactured by Ipposha Yushi Kogyo Co., Ltd.)” and coconut oil fatty acid amidopropyl betaine “CAB-30 (manufactured by Ipposha Yushi Kogyo Co., Ltd.)”, “TEGO BETAIN CK-OK (manufactured by Degussa)” as coconut oil fatty acid amidopropyl betaine, and “ANHOLEX PB-1 (Miyoshi Oil)” as palm kernel oil fatty acid amidopropyl betaine. Co., Ltd.)”, “Lebon LD-36 (manufactured by Sanyo Chemical Industries Co., Ltd.)” and “Ovazoline LB-SF (manufactured by Toho Chemical Industry Co., Ltd.)”, which are lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid There is "Amphitol 86B" manufactured by Kao Corporation, which is betaine.

The amphoteric surfactant in the surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass.

<<(a2) component>>
Component (a2) is an anionic surfactant. As component (a2), conventionally known anionic surfactants can be used, for example, surfactants (1) to (11) below.
(1) A linear or branched alkylbenzenesulfonate (LAS or ABS) having an alkyl group of 8 to 18 carbon atoms.
(2) alkanesulfonates having 10 to 20 carbon atoms;
(3) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(4) Alkyl sulfates or alkenyl sulfates (AS) having 10 to 20 carbon atoms.
(5) an alkylene oxide having 2 to 4 carbon atoms, or an average of 0.5 to 10 of ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) Alkyl (or alkenyl) ether sulfate (AES) having a straight or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms attached by moles.
(6) an average of 3 to 30 moles of either an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1); Alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added.
(7) any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1), an average of 0.5 to An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 moles.
(8) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(9) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(10) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates.
(11) Higher fatty acid salts (soaps) having 10 to 20 carbon atoms.
Salts constituting the salt include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; monoethanolamine salts (monoethanolammonium), diethanolamine salts (diethanolammonium), and triethanolamine. alkanolamine salts such as salts (triethanolammonium); and ammonium salts, among which sodium salts and potassium salts are preferred.

<<(a3) component>>
The (a3) component is a nonionic surfactant. Component (a3) includes, for example, the following surfactants (1) to (8).
(1) an average of 3 to 30 mol of either an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1); A polyoxyalkylene alkyl ether having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added.
(2) an average of 3 to 30 moles of either an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1); A polyoxyalkylene alkyl (or alkenyl) phenyl ether having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added.
(3) C1-2 alkyl esters of long-chain fatty acids with 10-20 carbon atoms and alkylene oxides with 2-4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9) .9 to 9.9/0.1) added with an average of 3 to 30 moles of fatty acid alkyl ester alkoxylate.
(4) A sorbitan ester of a long-chain fatty acid with 10 to 20 carbon atoms and an alkylene oxide with 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9. 9/0.1) added with an average of 3 to 30 moles of polyoxyalkylene sorbitan fatty acid ester.
(5) A long-chain fatty acid with 10 to 20 carbon atoms and an alkylene oxide with 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0) A polyoxyalkylene fatty acid ester having an average of 3 to 30 moles of .1) added thereto.
(6) Either an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) is added to hydrogenated castor oil, average 3 to 30 mol added.
(7) Esters of long-chain fatty acids having 10 to 20 carbon atoms and glycerin.
(8) Linear or branched alkyl polyglycosides having 10 to 20 carbon atoms.

<<(a4) component>>
Component (a4) is an amine oxide surfactant (semipolar surfactant). Examples of component (a4) include alkylamine oxides such as dodecyldimethylamine oxide, myristyldimethylamine oxide and coconut alkyldimethylamine oxide; amidoamine oxides such as coconut oil fatty acid amidopropylamine oxide and lauramidopropylamine oxide; mentioned. Among them, dodecyldimethylamine oxide (AX) is preferred.

These (A) components are: One type may be used alone, or two or more types may be used in combination.

<(B) Component>
Component (B) is a compound represented by formula (b1). Component (B) is a so-called aromatic glycol ether.

In formula (b1), X is an oxygen atom or a CH ₂ O group, preferably an oxygen atom.
R ¹ is an alkylene group having 2 or 3 carbon atoms, preferably an alkylene group having 2 carbon atoms (ethylene group).
m is a number of 1 to 6, preferably 1 to 3, more preferably 1, representing the average number of repeating (R ¹ O) (ie, the average number of added moles of ethylene oxide or propylene oxide).
R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom.

Component (B) includes, for example, monoethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, monopropylene glycol monophenyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monophenyl ether, mono ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, triethylene glycol monobenzyl ether, monopropylene glycol monobenzyl ether, dipropylene glycol monobenzyl ether, tripropylene glycol monobenzyl ether and the like. Among them, monoethylene glycol monophenyl ether is preferable as the component (B) from the viewpoint of easily increasing detergency.

The content of component (B) is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, relative to the total mass of the liquid detergent composition. If the content of component (B) is at least the above lower limit, the ejection property can be further enhanced. If the content of component (B) is equal to or less than the above upper limit value, retention can be further enhanced.

The total amount of components (A) and (B) (AB total amount) is preferably 0.6 to 10% by mass, preferably 1.3 to 7% by mass, based on the total mass of the liquid detergent composition. more preferred. When the AB total amount is at least the above lower limit, the ejection property and detergency can be further enhanced. When the AB total amount is equal to or less than the above upper limit, the detergency can be further enhanced.

The mass ratio (A/B ratio) represented by component (A)/component (B) is preferably 0.16 to 50, more preferably 0.16 to 25, further preferably 0.9 to 5, and 1 .7 to 5 are particularly preferred. If the A/B ratio is within the above range, the detergency can be further enhanced.

<(C) Component)>
Component (C) is one or more polymers selected from polyvinyl alcohol-based polymers (component (c1)) and cellulose-based polymers (component (c2)). By containing the component (C), the liquid detergent composition can improve retention and dischargeability.
A "polymer" as used herein is a compound having a molecular weight of 1,000 or more. The molecular weight of component (C) is a weight average molecular weight measured by gel permeation chromatography using polyethylene glycol (PEG) as a standard substance.

Component (c1) is prepared by preparing vinyl acetate from ethylene, polymerizing it alone and saponifying it with an alkali to prepare a "homopolymer type" and vinyl acetate, then copolymerizing it with other monomers and saponifying it with an alkali. It means "copolymer type".

Examples of component (c1) include polyvinyl alcohol (PVA), cation-modified polyvinyl alcohol (cation-modified PVA), anion-modified polyvinyl alcohol (anion-modified PVA), and the like.
PVA is an unmodified homopolymer type. Commercially available PVA products include the Gosenol series (GL-03, EG-05, EG-30, EG-40, etc.) manufactured by Nippon Synthetic Chemical Co., Ltd., and the Poval (PVA) series manufactured by Kuraray Co., Ltd. (403, 405, 420, 420H, 424H, 203, 205, 210, 217, 220, 224, 235, 217E, 220E, 224E, etc.) and the like.
The saponification value of PVA is preferably 70% or more, more preferably 75% to 95%, even more preferably 80% to 90%. If the saponification value is at least the above lower limit, the retention and discharge properties can be further enhanced.
As the copolymer type with PVA, anion-modified PVA such as carboxylic acid-modified PVA, undecylenic acid-modified PVA, and sulfonic acid-modified PVA, and cation-modified PVA such as ammonium-modified PVA, sulfonium-modified PVA, and amino group-modified PVA are used. be able to.
Commercial products of the copolymer type include Gohsenex T series (T-350, T-330H, etc.), Gohsenex L series (L-3266, etc.), Gohsenex K series (K-434, etc.) manufactured by Nippon Synthetic Chemical Co., Ltd. , Kuraray Co., Ltd. K polymer series (KL-506, KL-318, KL-118, KM-618, KM-118, etc.), C polymer series (C-506, CM-318, etc.) are exemplified. , can be used without limitation.
The copolymer type saponification value is preferably 70% or more, more preferably 75% to 99%, even more preferably 80% to 99%, from the standpoint of retention. If the saponification value is at least the above lower limit, the retention and discharge properties can be further enhanced. Among the copolymer types, anionically modified polyvinyl alcohol is preferred.

The average degree of polymerization of component (c1) is preferably 500 to 2,400. If the average degree of polymerization is at least the above lower limit, the staying property is further enhanced. If the average degree of polymerization is equal to or less than the above upper limit, the dischargeability is further enhanced.

Component (c1) has a molecular weight of 1,000 or more, preferably 10,000 to 200,000, more preferably 20,000 to 120,000.

Component (c2) is a polymer compound derived from polysaccharide obtained from dietary fiber or cellulose obtained by hydrolyzing cellulose acetate.
Component (c2) includes methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylcellulose, carboxymethylcellulose and the like. Among them, carboxymethyl cellulose and hydroxyethyl cellulose are preferable from the viewpoint of further improving ejection properties.

The average degree of polymerization of component (c2) is preferably 400 to 6,000. If the average degree of polymerization is at least the above lower limit, the staying property is further enhanced. If the average degree of polymerization is equal to or less than the above upper limit, the dischargeability is further enhanced.

The molecular weight of component (c2) is 1,000 or more, preferably 10,000 to 1,500,000, more preferably 500,000 to 1,200,000.

The content of component (C) is preferably 0.01 to 5% by mass, more preferably 0.01 to 2.8% by mass, more preferably 0.05 to 2.0% by mass, relative to the total mass of the liquid detergent composition. 5% by mass is more preferred. (C) If content of a component is more than the said lower limit, retention will be improved more. If the content of the component (C) is equal to or less than the above upper limit, the ejection property can be further enhanced.

The total amount of component (B) and component (C) (total amount of BC) is preferably 0.2 to 7.8% by mass, more preferably 0.2 to 7.0% by mass, based on the total mass of the liquid detergent composition. 5% by mass is more preferred. If the total amount of BC is at least the above lower limit, the detergency can be further enhanced. If the total amount of BC is equal to or less than the above upper limit, the ejection property can be further enhanced.

The mass ratio represented by component (B)/component (C) (B/C ratio) is preferably 0.1 to 300, more preferably 0.2 to 150, further preferably 0.2 to 50, and 2 ~10 is particularly preferred. If the B/C ratio is equal to or higher than the above lower limit, the ejection property can be further enhanced. When B/C is equal to or less than the above upper limit, the retention and discharge properties can be further enhanced.

<(D) Component>
(D) A component is water.
The content of component (D) is preferably 80 to 95% by mass, more preferably 88 to 94% by mass, relative to the total mass of the liquid detergent composition.

<Optional component>
The liquid detergent composition of the present invention can contain, if necessary, components that are usually used in toilet detergent compositions, in addition to the components described above. Such optional ingredients include, for example, bactericides, antiseptics, antifungal agents, chelating agents, pigments, antioxidants, thickeners, ultraviolet absorbers, solubilizers (excluding component (B)). , fragrances, pH adjusters, and the like.

The pH adjuster is not particularly limited, but it is preferable to use an alkaline agent selected from sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and its derivatives, monoethanolamine, diethanolamine, triethanolamine, etc. It is more preferable to use an alkaline agent selected from sodium, potassium hydroxide, monoethanolamine, and triethanolamine, and potassium hydroxide is even more preferable.
One type of pH adjuster may be used, or two or more types may be used in combination.

<Physical properties>
The viscosity of the liquid detergent composition is 40 mPa·s or less, preferably 0.8 to 40 mPa·s, more preferably 0.8 to 25 mPa·s, even more preferably 1 to 25 mPa·s. If the viscosity is at least the above lower limit, the staying property can be further enhanced. If the viscosity is equal to or less than the above upper limit, the ejection property can be further enhanced.

The pH of the liquid detergent composition is, for example, preferably 5-9, more preferably 6-8.

(Toilet cleaning products in containers)
A toilet cleaning product in a container (hereinafter sometimes simply referred to as a "product in a container") comprises the liquid cleaning composition of the present invention and a discharge container containing it.
Examples of the discharge container include an aerosol type discharge container that discharges high-pressure gas, a non-aerosol type discharge container, and the like. Among these, the non-aerosol type discharge container is preferable from the viewpoint of ease of use and environmental impact.

Examples of non-aerosol type discharge containers include spray type, squeeze type and pump type. Among these, the spray type is preferable because it is easy to use. The spray type discharge container includes, for example, an aerosol spray container, a trigger spray container (direct pressure type or pressure accumulation type), a dispenser spray container, and the like. These containers may be manually operated or electrically operated. Examples of the aerosol spray container include those described in JP-A-9-3441 and JP-A-9-58765. When filling an aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc. can be used as the propellant. These propellants may be used alone or in combination of two or more.

Examples of trigger spray containers include those described in JP-A-9-268473 and JP-A-10-76196.
Examples of dispenser spray containers include those described in, for example, JP-A-9-256272.
Examples of the pressure accumulation type trigger spray container include those described in JP-A-2013-154276.
Among them, the trigger spray container is preferable as the discharge container because it is easy to apply the liquid detergent composition to the target.
The trigger spray container includes a direct pressure type and an accumulator type, but the accumulator type is preferable because it is easy to apply the liquid detergent composition to the target and the retention of the liquid detergent composition can be further enhanced. .
A pressure accumulation type trigger spray container is one in which even if the trigger is operated, the contents will not be discharged from the discharge port until the liquid pressure in the cylinder reaches the predetermined liquid pressure, and the liquid pressure in the cylinder will reach the predetermined liquid pressure. It is constructed such that when the pressure is raised above the pressure, the liquid is ejected.
The discharge form may be either foam or mist, but foam is preferred from the viewpoints of easy application of the liquid detergent composition to the target and further enhancement of retention of the liquid detergent composition.

As a container for discharging contents in a foamy form, there is a discharge container for discharging contents in a foamy form by mixing the contents with air. Such dispensing vessels are also referred to as former vessels. The foamer container usually comprises a container body for containing the liquid detergent composition, and an injection nozzle attached to the opening of the container body for foaming and discharging the liquid detergent composition contained in the container body. I have.
As a mechanism in which the injection nozzle foams the detergent composition in the container body, the liquid is introduced from the container body into the foaming tube portion incorporated at the tip of the injection nozzle, and the liquid is applied to the wall of the foaming tube. A mechanism of generating turbulent flow by colliding with each other to promote mixing with air can be mentioned. Another example is a mechanism for arranging a barrier or a mesh in front of the injection nozzle to discharge the liquid in the form of bubbles. Air for generating foam is introduced from outside the container. Conventionally known structures can be applied to the detailed structures of these mechanisms, and are not particularly limited.

An example of a discharge container is shown in FIG.
The discharge container 1 of FIG. 1 is a direct pressure trigger type sprayer. A container body 2 and an injection nozzle 6 provided at an opening of the container body 2 are provided. The injection nozzle 6 is connected to a suction pipe 7 extending vertically inside the container body 2 . A nozzle hole 10 is formed at the tip of the injection nozzle 6 . The injection nozzle 6 is provided with a trigger 3 extending downward from the vicinity of the tip. A piston 4 and a spring 5 are provided inside the injection nozzle 6 . Spring 5 is connected to trigger 3 via piston 4 .
When the content (liquid detergent composition) is to be discharged from the discharge container 1, the trigger 3 is pulled toward the piston 4. As shown in FIG. When the trigger 3 is pulled toward the piston 4, the piston 4 and the spring 5 are actuated to suck up the contents into the injection nozzle 6 through the suction pipe 7. - 特許庁The sucked contents are discharged from the nozzle hole 10 in the form of mist or foam.

(Production method)
A liquid detergent composition is manufactured by a conventionally well-known manufacturing method. For example, a method of adding components (A) to (C) to component (D), which is a solvent, optionally adding optional components, and mixing them.
The obtained liquid detergent composition is accommodated in the container main body of the discharge container, and a spray nozzle is attached to the opening of the container main body to obtain a container-packed product.

(how to use)
As a method of using the liquid detergent composition, a product in a container will be described as an example. A suitable amount of the liquid detergent composition is applied to the toilet bowl from the discharge container, and after a certain period of time has passed, the toilet bowl is rinsed with a flush or the like to perform "rinsing". At this time, since the liquid detergent composition has good ejection properties, it is easy to apply the liquid detergent composition to the target position. In addition, since the liquid detergent composition has excellent detergency and retention properties, it is possible to clean the toilet bowl by rinsing without scrubbing.
A suitable amount of the liquid detergent composition may be applied to the toilet bowl and then "rubbed" by rubbing it with a cleaning brush, or "wiping off" by wiping off with a cloth or paper.

[EXAMPLES] Hereafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
<(A) Component: Surfactant>
· A-1: Lauramidopropyl Betaine, "Enagicol L-30B" manufactured by Lion Corporation.
· A-2: Betaine lauryldimethylaminoacetate, "Lebon LD-36" manufactured by Sanyo Chemical Industries, Ltd.
· A-3: Betaine stearyldimethylaminoacetate, Kao Corporation "Amphitol 86B".
· A-4: 12-16 alkyl polyglucoside (APG), manufactured by Cognis, "PLANTACARE 1200up").
A-5: SAS, sodium secondary alkanesulfonate, manufactured by Clariant Japan Co., Ltd., "HOSTAPUR SAS 30A").
· A-6: AX, n-dodecyldimethylamine oxide, manufactured by Lion Specialty Chemicals Co., Ltd., "Cadenax DM12D-W".

<(B) Component: Compound Represented by Formula (b1)>
· B-1: Ethylene glycol monophenyl ether (phenoxyethanol), manufactured by Nippon Nyukazai Co., Ltd., "phenyl glycol".
· B-2: Diethylene glycol monophenyl ether, manufactured by Nippon Nyukazai Co., Ltd., "Phenyl glycol (2 mol)".
· B-3: Hexaethylene glycol monophenyl ether, Nippon Nyukazai Co., Ltd., "Phenyl glycol (5.5 mol)".
<Component (B'): Comparative product of component (B)>
· B'-1: diethylene glycol monobutyl ether, manufactured by Nippon Nyukazai Co., Ltd., "butyl diglycol".

<(C) component: PVA-based polymer, cellulose-based polymer>
· C-1: Polyvinyl alcohol, "PVA-217" manufactured by Kuraray Co., Ltd., saponification value = 88%, molecular weight = 70,000.
· C-2: Polyvinyl alcohol, "PVA-117" manufactured by Kuraray Co., Ltd., saponification value = 98%, molecular weight = 70,000.
· C-3: Polyvinyl alcohol, manufactured by Kuraray Co., Ltd., "PVA-405", saponification value = 82%, molecular weight = 20,000.
· C-4: Carboxymethyl cellulose, manufactured by Daicel Finechem Co., Ltd., "CMC 1290", molecular weight = 1,000,000.
· C-5: Carboxymethyl cellulose, manufactured by Daicel Finechem Co., Ltd., "FDM", molecular weight = 500,000.
· C-6: cetyl hydroxyethyl cellulose, manufactured by Ashland, "polysurf 67", molecular weight = 1,000,000.
· C-7: Polyvinyl alcohol, Nippon Synthetic Chemical Co., Ltd., "Gohsenex T-330H", saponification value = 99%, molecular weight = 90,000.
<Component (C'): Comparative product of component (C)>
· C'-1: Carboxyvinyl polymer, manufactured by Wako Pure Chemical Industries, Ltd., "Hivis Wako 105".
· C'-2: xanthan gum, manufactured by Sansho Co., Ltd., "KELZAN".
· C'-3: Polyvinylpyrrolidone, manufactured by Nippon Shokubai Co., Ltd., "PVP K-30".

<Optional component>
- Ethanol: Ethyl alcohol, manufactured by Japan Alcohol Sales Co., Ltd., "Synthesis 95".
Perfume: Perfume composition A described in JP-A-2003-183697.
- pH adjuster: sulfuric acid (Kanto Kagaku Co., Ltd.), potassium hydroxide (liquid caustic potash, Asahi Glass Co., Ltd.).

(Evaluation method)
<Detergency>
On a PP (polypropylene) plate of 100 mm×100 mm, 100 μL of urine from 5 adult males was placed and left at room temperature (25° C.) for 24 hours to dry. After drying, the PP plate was tilted at 60°, and the liquid detergent composition was sprayed using a discharge container (TA-FA, manufactured by Yoshino Kogyosho Co., Ltd., foam trigger spray pressure accumulation type). After leaving it for 30 seconds and washing it twice with water, the degree of stain remaining was evaluated by five expert panelists according to the following evaluation criteria. The average value of the evaluation results of the expert panelists was calculated, and 3 to 5 points were regarded as passing.

≪Evaluation Criteria≫
5 points: The dirt is completely removed.
4 points: Almost all stains are removed.
3 points: About half of the dirt is removed.
2 points: Slightly soiled.
1 point: The dirt is not removed at all.

<Retention>
The liquid detergent composition was discharged and applied from a place 10 cm away toward a 50 cm square tile (Mistikiramic manufactured by LIXIL) inclined at 60°. The liquid detergent composition was discharged by one stroke (0.5 g/stroke) using a discharge container (TA-FA, manufactured by Yoshino Kogyosho Co., Ltd., foam trigger spray pressure accumulation type). The falling speed (sec/cm) was calculated from the falling distance and the falling time of the applied foamy liquid detergent composition, and evaluated according to the following evaluation criteria.

≪Evaluation Criteria≫
5 points: 2.0 seconds/cm or more.
4 points: 1.8 or more and less than 2.0 sec/cm.
3 points: 1.5 or more and less than 1.8 sec/cm.
2 points: 1.2 or more and less than 1.5 sec/cm.
1 point: less than 1.2 sec/cm.

<Ejectability>
The liquid detergent composition was discharged and applied from a place 10 cm away from the edge of the toilet. The liquid detergent composition was discharged by one stroke (0.5 g/stroke) using a discharge container (TA-FA, manufactured by Yoshino Kogyosho Co., Ltd., foam trigger spray pressure accumulation type). Five panelists evaluated the easiness of aiming at the time of ejection according to the following evaluation criteria. The average score of the evaluation results was obtained, and 3 to 5 points were regarded as acceptable.

≪Evaluation Criteria≫
5 points: Very easy to aim.
4 points: Fairly easy to aim.
3 points: Fairly easy to aim.
2 points: Slightly difficult to aim.
1 point: Very difficult to aim.

(Examples 1 to 30, Comparative Examples 1 to 7)
500 g of the liquid detergent composition of each example was prepared by the following procedure.
According to the formulations in Tables 1 to 4, (A) component, (B) component (or (B') component), (C) component (or (C') component and a common component are mixed with (D) component, If necessary, a pH adjuster (sulfuric acid or potassium hydroxide) was newly added to adjust the pH to 7.0, thereby obtaining a liquid detergent composition of each example.
The compounding amount in the table is a pure content conversion value. Ingredients whose blending amounts are not listed in the table are not blended. In the table, the "balance" of component (E) is the amount required to bring the total amount of the liquid detergent composition to 100% by mass. In the table, the "appropriate amount" of sulfuric acid is the amount required to adjust the pH of the liquid detergent composition to 7.0.
The obtained liquid detergent composition of each example was evaluated for detergency, retention and dischargeability, and the results are shown in the table.
However, Examples 23-25 and 28-30 are reference examples.

As shown in Tables 1 to 4, Examples 1 to 30 to which the present invention was applied had detergency of 3 points or more, staying property of 3 points or more, and ejection property of 3 points or more.
Comparative Example 1 lacking the component (B) and Comparative Example 2 containing the component (B') in place of the component (B) had a detergency of 1 point. Comparative Example 3 with an A/B ratio of 54 had a detergency of 2 points. Comparative Example 4 with an A/B ratio of 0.1 scored 2 points for detergency and 1 point for retention. Comparative Example 5 containing C'-3 in place of the component (C) scored 2 points for detergency and staying power. Comparative Examples 6 and 7, which contained C'-1 or C'-2 instead of component (C), had ejection properties of 1.5 points or less.
From these results, it was confirmed that the detergency, staying power and dischargeability can be improved by applying the present invention.

Claims (5)

(A) component: a surfactant containing one or more selected from lauramidopropyl betaine and lauryldimethylaminoacetic acid betaine ;
(B) component: a compound represented by the following formula (b1);
(C) component: a polyvinyl alcohol-based polymer ;
(D) component: water and
contains
The mass ratio represented by the component (A)/component (B) is 0.16 to 50,
A liquid detergent composition for toilets, having a viscosity of 40 mPa·s or less at 25°C.

[In the formula (b1) , R ¹ is an alkylene group having 2 or 3 carbon atoms, m is a number of 1 to 6 representing the average number of repetitions of (R ¹ O), and R ² is a hydrogen atom or the number of carbon atoms 1 to 3 alkyl groups. ] The liquid detergent composition for toilets according to claim 1, wherein the mass ratio represented by component (B)/component (C) is 0.1 to 300. The liquid detergent composition for toilets according to claim 1 or 2, wherein the component (C) is a polyvinyl alcohol polymer having a polymerization degree of 500 to 2400 and a saponification value of 80% or more. The liquid detergent composition for toilets according to any one of claims 1 to 3, wherein the content of component (D) is 80 to 95% by mass. A containerized toilet cleaning product comprising the liquid toilet cleaning composition according to any one of claims 1 to 4 and a discharge container containing the toilet liquid cleaning composition. .

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