JP7650650B2 - Liquid cleaning composition for hard surfaces - Google Patents

Description

The present invention relates to a liquid cleaning composition for hard surfaces.

Liquid detergent compositions using various surfactants have been proposed for cleaning hard surfaces such as pottery, porcelain, glass, and metal. For example, Patent Document 1 proposes a liquid detergent composition containing, as an essential component, a nonionic surfactant made of a polyoxyalkylene alkylamine having a Gardner dye of 3 or less.

JP 2008-247952 A

As mentioned above, Patent Document 1 describes the use of polyoxyalkylene alkylamines as liquid detergent compositions for hard surfaces, and specifically describes in the examples that excellent cleaning properties can be obtained by using them in combination with an anionic surfactant such as sodium polyoxyethylene alkyl sulfate. However, the liquid detergent composition described in Patent Document 1 has a problem in that it has poor antifouling properties on hard surfaces.

The object of the present invention is to provide a liquid cleaning composition for hard surfaces that has cleaning and stain-resistant properties.

一般式（２）中、Ｒ^２は炭素数８～２４のアルキル基もしくはアルケニル基を表し、Ａ^２ＯおよびＡ^３Ｏはそれぞれ独立に炭素数２～４のオキシアルキレン基を表し、ｍおよびｐはオキシアルキレン基の平均付加モル数を表し、ｍ＋ｐが１０～４０の数である。 The liquid detergent composition for hard surfaces according to an embodiment of the present invention contains a nonionic surfactant (A) represented by the following general formula (1), a nonionic surfactant (B) represented by the following general formula (2), and water, and the mass ratio (A)/(B) of the nonionic surfactant (A) to the nonionic surfactant (B) is 0.5 to 8.0.
R ¹ -O-(A ¹ O) _n -H (1)
In general formula (1), R ¹ represents an alkyl or alkenyl group having 8 to 18 carbon atoms, A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents the average number of moles of oxyalkylene groups added (a number of 6 to 40).

In general formula (2), R ² represents an alkyl group or alkenyl group having 8 to 24 carbon atoms, A ² O and A ³ O each independently represent an oxyalkylene group having 2 to 4 carbon atoms, m and p represent the average number of moles of oxyalkylene groups added, and m+p is a number of 10 to 40.

According to an embodiment of the present invention, by using the above nonionic surfactant (A) and nonionic surfactant (B) in a content ratio (A)/(B) of 0.5 to 8.0, it is possible to achieve both cleaning properties and antifouling properties for hard surfaces.

The liquid cleaning composition for hard surfaces according to this embodiment (hereinafter, sometimes referred to as the "cleaning composition") contains a nonionic surfactant (A), a nonionic surfactant (B), and water.

[Nonionic surfactant (A)]
The nonionic surfactant (A) is a surfactant represented by the following general formula (1).
R ¹ -O-(A ¹ O) _n -H (1)

In formula (1), ^R1 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms. The number of carbon atoms in the alkyl group or alkenyl group is preferably 10 or more and 16 or less.

Examples of the alkyl group having 8 to 18 carbon atoms include linear or branched alkyl groups or cycloalkyl groups, such as n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, n-tetradecyl, isotetradecyl, n-hexadecyl, isohexadecyl, and stearyl. Examples of the alkenyl group having 8 to 18 carbon atoms include linear or branched alkenyl groups or cycloalkenyl groups, such as octenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, and octadecenyl. R ¹ may consist of only one of these alkyl groups or alkenyl groups, or may be a mixture of two or more of them.

In formula (1), A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms. These are derived from alkylene oxides, and examples thereof include an oxyethylene group derived from ethylene oxide, an oxypropylene group derived from propylene oxide, a 1,2-oxybutylene group derived from 1,2-butylene oxide, and a 2,3-oxybutylene group derived from 2,3-butylene oxide.

In formula (1), n represents the average number of moles of oxyalkylene groups added, and is a number in the range of 6 to 40. When the average number of moles added, n, is 6 or more, the cleaning properties are excellent, and when it is 40 or less, the cleaning properties are excellent. The average number of moles added, n, is preferably 10 or more, more preferably 12 or more, and is preferably 35 or less.

In (A ¹ O) _n of formula (1), a plurality of A ¹ O may be the same or different. When they are different, the addition form may be random addition or block addition, and is not particularly limited.

(A ¹ O) _n in formula (1) preferably contains 50 to 100 mass% of oxyethylene groups. That is, the content of oxyethylene groups (EO) in all oxyalkylene groups (AO) in formula (1) (EO/AO) is preferably 50 mass% or more and 100 mass% or less. Thus, (A ¹ O) _n is preferably composed mainly of oxyethylene groups, and may be composed only of oxyethylene groups, but preferably contains other oxyalkylene groups such as oxypropylene groups in order to suppress an increase in viscosity of the cleaning composition. For example, the content of oxyethylene groups in (A ¹ O) _n (EO/AO) may be 60 to 85 mass%, or the content of oxyethylene groups may be 60 to 85 mass% and the content of oxypropylene groups may be 15 to 40 mass%.

[Nonionic surfactant (B)]
The nonionic surfactant (B) is a surfactant represented by the following general formula (2).

In formula (2), ^R2 represents an alkyl group or an alkenyl group having 8 to 24 carbon atoms. The number of carbon atoms in the alkyl group or the alkenyl group is preferably 10 or more, more preferably 12 or more, and is preferably 20 or less, more preferably 18 or less.

Examples of the alkyl group having 8 to 24 carbon atoms include linear or branched alkyl groups or cycloalkyl groups, such as n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, n-tetradecyl, isotetradecyl, n-hexadecyl, isohexadecyl, stearyl, nonadecyl, eicosyl, docosyl, and tetracosyl. Examples of the alkenyl group having 8 to 24 carbon atoms include linear or branched alkenyl groups or cycloalkenyl groups, such as octenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, and docosenyl. ^R2 may consist of only one of these alkyl groups or alkenyl groups, or may be a mixture of two or more of them.

In formula (2), A ² O and A ³ O each independently represent an oxyalkylene group having 2 to 4 carbon atoms. These are derived from alkylene oxides, and examples thereof include an oxyethylene group derived from ethylene oxide, an oxypropylene group derived from propylene oxide, a 1,2-oxybutylene group derived from 1,2-butylene oxide, and a 2,3-oxybutylene group derived from 2,3-butylene oxide.

In formula (2), m and p represent the average number of moles of A ² O and A ³ O added, respectively. There are no particular limitations on m and p as long as the sum of the two, m+p, is 10 to 40, but it is usually preferable that each is 5 or more. When m+p is 10 or more, the antifouling property can be improved. When m+p is 40 or less, the detergency can be improved. It is preferable that m+p is 15 or more, and it is preferable that m+p is 35 or less.

In (A ² O) _m and (A ³ O) _p of formula (2), the plurality of A ² O and A ³ O may be the same or different. When they are different, the addition form may be random addition or block addition, and is not particularly limited.

It is preferable that (A ² O) _m and (A ³ O) _p in formula (2) contain 60 to 100 mass% of oxyethylene groups in total. That is, the content (EO/AO) of oxyethylene groups (EO) in the total oxyalkylene groups (AO) in formula (2) is preferably 60 mass% or more and 100 mass% or less. In this way, it is preferable that (A ² O) _m and (A ³ O) _p are mainly composed of oxyethylene groups, and may be composed only of oxyethylene groups. More preferably, the content (EO/AO) of oxyethylene groups in the total oxyalkylene groups in formula (2) is 75 to 100 mass%, and when an oxyalkylene group other than an oxyethylene group is used, an oxypropylene group is preferable, and for example, the content of oxypropylene groups may be 0 to 25 mass%.

[Cationic surfactant (C)]
The cleaning composition according to the present embodiment preferably further contains a cationic surfactant (C). By using the cationic surfactant (C) in addition to the nonionic surfactants (A) and (B), the antifouling properties can be further improved.

As the cationic surfactant (C), a fatty acid amidoamine such as stearyl dimethylaminopropylamide may be used, but it is preferable to use a quaternary ammonium salt.

The quaternary ammonium salt is not particularly limited, and examples thereof include alkyl trimethyl ammonium halides such as lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, and stearyl trimethyl ammonium chloride, or the corresponding methyl sulfates; dialkyl dimethyl ammonium halides such as didecyl dimethyl ammonium chloride and dioctyl dimethyl ammonium chloride, or the corresponding methyl sulfates; trialkyl benzyl ammonium halides such as lauryl dimethyl benzyl ammonium chloride and tributyl benzyl ammonium chloride, or the corresponding methyl sulfates; and alkyl dimethyl ethyl ammonium ethyl sulfates such as octyl dimethyl ethyl ammonium ethyl sulfate, lauryl dimethyl ethyl ammonium ethyl sulfate, and palmityl dimethyl ethyl ammonium ethyl sulfate. These can be used alone or in combination of two or more.

Among these, it is preferable to use at least one selected from alkyl trimethyl ammonium salts such as alkyl trimethyl ammonium halides and alkyl trimethyl ammonium methyl sulfates, dialkyl dimethyl ammonium salts such as dialkyl dimethyl ammonium halides and dialkyl dimethyl ammonium methyl sulfates, and trialkyl benzyl ammonium salts such as trialkyl benzyl ammonium halides and trialkyl benzyl ammonium methyl sulfates, as the quaternary ammonium salt. More preferably, it is preferable to use at least one selected from the group consisting of alkyl trimethyl ammonium salts and dialkyl dimethyl ammonium salts, and even more preferably, it is preferable to use at least one selected from the group consisting of alkyl trimethyl ammonium halides, alkyl trimethyl ammonium methyl sulfates, dialkyl dimethyl ammonium halides, and dialkyl dimethyl ammonium methyl sulfates. Here, it is preferable that the number of carbon atoms of the alkyl in the alkyl trimethyl ammonium salt is 8 to 24, and it is preferable that the number of carbon atoms of the alkyl in the dialkyl dimethyl ammonium salt is 8 to 24. It is preferable that the number of carbon atoms of the alkyl in the trialkyl benzyl ammonium salt is 1 to 20.

[Cleaning agent composition]
The cleaning composition according to this embodiment has a liquid form in which the nonionic surfactants (A) and (B), and preferably the cationic surfactant (C), are dissolved or dispersed in water. The content of water in the cleaning composition is not particularly limited, but is preferably 10 to 80 mass%, more preferably 20 to 70 mass%, and even more preferably 30 to 60 mass%.

In the cleaning composition, the mass ratio (A)/(B) of the nonionic surfactant (A) to the nonionic surfactant (B) is preferably 0.5 to 8.0. When the mass ratio (A)/(B) is 0.5 or more, cleaning properties can be improved. When the mass ratio (A)/(B) is 8.0 or less, antifouling properties can be improved. The mass ratio (A)/(B) is preferably 0.7 or more, more preferably 1.0 or more. The mass ratio (A)/(B) is preferably 6.0 or less, more preferably 4.0 or less.

The content of the nonionic surfactant (A) in the cleaning composition is not particularly limited, but is preferably 10 to 50 mass%, more preferably 15 to 40 mass%. The content of the nonionic surfactant (B) in the cleaning composition is not particularly limited, but is preferably 1 to 30 mass%, more preferably 3 to 20 mass%.

When cationic surfactant (C) is added, the content of cationic surfactant (C) in the cleaning composition is not particularly limited, but is preferably 5 to 30% by mass, and more preferably 10 to 25% by mass.

The detergent composition may contain anionic surfactants, amphoteric surfactants, and nonionic surfactants other than those described above as surfactants other than those described above, as long as the effects of this embodiment are not impaired. In addition to the above components, the detergent composition may contain various additives that are typically included in liquid detergent compositions for hard surfaces, as long as the effects of this embodiment are not impaired. Examples of such additives include fragrances, chelating agents, builders, organic solvents, pH adjusters, preservatives, colorants, antioxidants, and ultraviolet absorbers.

As the fragrance, a water-soluble fragrance or an oil-soluble fragrance can be used, and the oil-soluble fragrance can be solubilized in water by the nonionic surfactants (A) and (B). In one embodiment, when a fragrance is included, the content of the fragrance in the cleaning composition is not particularly limited, but may be, for example, 0.01 to 20% by mass, or 1 to 10% by mass.

The cleaning composition according to this embodiment can be prepared by adding the nonionic surfactants (A) and (B), the cationic surfactant (C) as a preferred component, water, and other optional components, and stirring and mixing them by a known method.

The cleaning composition according to this embodiment is used to clean hard surfaces. Examples of hard surfaces include inorganic solid surfaces such as pottery, porcelain, glass, enamel, tiles, ceramics, aluminum, and stainless steel. Specifically, the cleaning composition is preferably used to clean hard surfaces in toilets, kitchens, bathrooms, washstands, etc.

The cleaning method using the cleaning composition according to this embodiment is not particularly limited, and examples of possible methods include (1) impregnating a sponge or the like with the cleaning composition, scrubbing the surface to be cleaned with the sponge, and then rinsing with water, (2) spraying or applying the cleaning composition to the surface to be cleaned, and then rinsing with water, or (3) spraying or applying the cleaning composition to the surface to be cleaned, and then scrubbing with a sponge or the like, and then rinsing with water.

In one embodiment, the above-mentioned cleaning agent composition is preferably used as a flush toilet cleaning agent, more preferably stored in a discharge container and used by discharging the flush toilet cleaning agent from the discharge container onto the toilet bowl surface during flushing, and even more preferably used as an on-tank type flush toilet cleaning agent. An on-tank type flush toilet cleaning agent is configured such that the flush toilet cleaning agent stored in a discharge container is placed on the water tank of a flush toilet and the cleaning agent is discharged into the water tank together with flushing water, and by flushing, i.e., by flushing the toilet water, it exerts its cleaning power against human and urine stains on the toilet bowl surface. Furthermore, the cleaning agent composition according to this embodiment can clean the toilet bowl surface and impart antifouling properties to the toilet bowl surface.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.

Details of the surfactants used in the examples and comparative examples are as follows.
[Nonionic surfactant (A)]
・A-1:
A compound represented by the above formula (1) (polyoxyalkylene decyl ether; in formula (1), n = 13, EO/AO = 63 mass%), obtained by randomly adding 9 moles of ethylene oxide and 4 moles of propylene oxide to 1 mole of C10 alcohol (product name: Decanol, manufactured by KH Neochem Co., Ltd.).
・A-2:
A compound represented by the above formula (1) (polyoxyalkylene lauryl ether; in formula (1), n = 17, EO/AO = 78% by mass) obtained by randomly adding 14 moles of ethylene oxide and 3 moles of propylene oxide to 1 mole of C12 alcohol (product name: Kalcol 2098, manufactured by Kao Corporation).
・A-3:
A compound represented by the above formula (1) (polyoxyalkylene tridecyl ether; in formula (1), n = 35, EO/AO = 82 mass%), obtained by randomly adding 30 moles of ethylene oxide and 5 moles of propylene oxide to 1 mole of C13 alcohol (product name: Tridecanol, manufactured by KH Neochem Co., Ltd.).

[Nonionic surfactant (B)]
・B-1:
A compound represented by the above formula (2) (tallow amine ethylene oxide adduct; in formula (2), m+p=25, EO/AO=100% by mass) obtained by adding 25 moles of ethylene oxide to 1 mole of beef tallow amine (product name: Nissan Amine ABT-2, manufactured by NOF Corporation).
・B-2:
A compound represented by the above formula (2) (coconut amine alkylene oxide adduct; in formula (2), m+p=35, EO/AO=82% by mass) was obtained by randomly adding 30 moles of ethylene oxide and 5 moles of propylene oxide to 1 mole of coconut amine (product name: Nissan Amine FB, manufactured by NOF Corporation).
・B-3:
A compound represented by the above formula (2) (laurylamine ethylene oxide adduct; in formula (2), m+p=10, EO/AO=100% by mass) obtained by adding 10 moles of ethylene oxide to 1 mole of laurylamine (product name: Nissan Amine BB, manufactured by NOF Corporation).

[Cationic surfactant (C)]
・C-1:
Didecyldimethylammonium chloride (product name: Catiogen DDM-PG, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
・C-2:
Cetyltrimethylammonium chloride (product name: Catiogen TMP, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

[Anionic surfactant]
D-1:
Sodium polyoxyethylene lauryl ether sulfate (product name: Hitenol 227L, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
[Amphoteric surfactant]
D-2:
Lauryl dimethylamine oxide (product name: Amogene AOL, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

[Other nonionic surfactants]
E-1:
Polyoxyethylene glyceryl isostearate (product name: Noigen GIS-125, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
E-2:
Polyoxyethylene sorbitan monooleate (product name: Solgen TW-80, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
E-3:
Polyoxyethylene polyoxypropylene block polymer (product name: Epane 450, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

The cleaning compositions of Examples 1 to 11 and Comparative Examples 1 to 8 were obtained by mixing the raw materials according to the formulation (mass%) shown in Table 1 below. The formulations in Table 1 are the proportions of solids for the components other than water, and the amount of water is the proportion of water in the entire cleaning composition, including the amount of water contained in the components other than water.

The cleaning properties and antifouling properties of the resulting cleaning compositions of Examples 1 to 11 and Comparative Examples 1 to 8 were evaluated using the following methods.

[Cleaning ability]
20 mg of artificial feces was applied to a glass slide, and the glass slide was immersed in 300 mL of a 1% by mass aqueous solution of the detergent composition for 30 seconds. Next, the glass slide was rinsed with running water at 1 L/min. Thereafter, the artificial feces remaining on the glass slide was photographed with a digital camera, and the area ratio of the residue after washing to the applied area of the artificial feces before washing was measured using the obtained image, and evaluated according to the following criteria.
A: No residue B: Less than 10% residue C: 10% or more residue

[Anti-stain properties]
0.1 g of the detergent composition was diluted 20,000 times with water to obtain 2 L of diluted aqueous solution. A glass plate (10 cm x 10 cm) was immersed in the diluted aqueous solution for 10 seconds, stood at 90° and left at 20°C for 2 hours, and then dried. Next, 10 g of artificial feces was applied to the surface of the glass plate, and then rinsed with running water for 10 seconds. The surface of the glass plate was then visually observed and evaluated according to the following criteria.
A: After rinsing with running water at 1 L/min, no artificial feces remains on the glass plate.
B: After rinsing with running water at 3 L/min, no artificial feces remains on the surface of the glass plate.
C: After rinsing with running water at 3 L/min, artificial feces remains on the surface of the glass plate.

The composition of the artificial stool used to evaluate cleaning and stain resistance was 50% by mass of rice miso, 5% by mass of xanthan gum, 2.3% by mass of oleic acid, and 42.7% by mass of water, which was mixed together and adjusted to pH 7 with sodium hydroxide to be used as the artificial stool.

The results are shown in Table 1. In Comparative Examples 1 and 2, the polyoxyalkylene alkylamine type nonionic surfactant (B) and the cationic surfactant (C) were used in combination, but the polyoxyalkylene alkyl ether type nonionic surfactant (A) was not blended, and therefore the cleaning and antifouling properties were poor. In Comparative Examples 3 and 5, the nonionic surfactants (A) and (B) were used in combination, but the mass ratio (A)/(B) of the two was too large, and therefore the antifouling properties were poor. In Comparative Example 4, the mass ratio (A)/(B) was too small, and therefore the cleaning properties were poor. Comparative Examples 6 to 8 are examples in which the polyoxyalkylene alkylamine type nonionic surfactant (B) was used in combination with other alkylene oxide-added type nonionic surfactants, and therefore the cleaning properties were poor.

In contrast, in Examples 1 to 11, in which nonionic surfactants (A) and (B) were used in combination and the mass ratio (A)/(B) of the two was within the range of 0.5 to 8.0, excellent cleaning properties were achieved as well as antifouling properties. In particular, in Examples 1 to 6 and 9 to 11, in which cationic surfactant (C) was blended in addition to nonionic surfactants (A) and (B), excellent effects were achieved in both cleaning properties and antifouling properties.

Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the gist of the invention. These embodiments and their omissions, substitutions, modifications, etc. are included within the scope and gist of the invention as well as the invention and its equivalents as set forth in the claims.

Claims (5)

A liquid cleaning agent composition for hard surfaces, which is a cleaning agent for flush toilets, comprises a nonionic surfactant (A) represented by the following general formula (1), a nonionic surfactant (B) represented by the following general formula (2), and water, wherein the mass ratio (A)/(B) of the nonionic surfactant (A) to the nonionic surfactant (B) is 0.5 to 8.0:
R ¹ -O-(A ¹ O) _n -H (1)
In general formula (1), R ¹ represents an alkyl or alkenyl group having 8 to 18 carbon atoms, A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents the average number of moles of oxyalkylene groups added (a number of 6 to 40).
In general formula (2), R ² represents an alkyl group or alkenyl group having 8 to 24 carbon atoms, A ² O and A ³ O each independently represent an oxyalkylene group having 2 to 4 carbon atoms, m and p represent the average number of moles of oxyalkylene groups added, and m+p is a number of 10 to 40. The liquid cleaning composition for hard surfaces according to claim 1, further comprising a cationic surfactant (C). The liquid cleaning composition for hard surfaces according to claim 2, wherein the cationic surfactant (C) is a quaternary ammonium salt. The liquid cleaning composition for hard surfaces according to any one of claims 1 to 3 , which is contained in a dispensing container. The liquid detergent composition for hard surfaces according to any one of claims 1 to 4 , which is a detergent for on-tank type flush toilets.