TW202028449A - Gel detergent composition - Google Patents

Abstract

The purpose of the present invention is to provide a gel detergent composition which is suppressed in decrease of the gel strength over time and is therefore capable of maintaining a stable gel state even though a disinfectant is contained therein. It is found that a gel detergent composition which contains a polyoxyalkylene block polymer represented by general formula (1) and a compound represented by general formula (2) is suppressed in decrease of the gel strength over time and is therefore capable of maintaining a stable gel state.

Description

Gel-like detergent composition

The present invention relates to a gel-like detergent composition for use on hard surfaces such as toilets, glass, windows, doors, and bathroom walls. The gel-like detergent composition includes sterilization However, it can also suppress the decrease in gel strength that occurs over time and stably maintain the gel state.

In the past, various detergent compositions have been used in order to remove dirt on hard surfaces such as toilets in toilets and create a sanitary environment. For example, as a detergent composition for flushing toilets, an on tank designed to dissolve detergent into flush water by being installed in the hand washing part or water storage tank of the flushing toilet is used. ) Or toilet detergent used in tank (in tank). However, in recent years, tankless flushing toilets have become popular, and the detergent composition for toilets used on or in the tank has the disadvantage that it cannot be applied to tankless flushing toilets. Therefore, in recent years, a gel-like detergent composition that is attached to the surface of the bedpan of the toilet for use has been developed. For example, Patent Document 1 reports a case where a gel for toilets containing a polyoxyethylene alkyl ether composed of polyoxyethylene having a degree of polymerization of 13-50 and an alkyl group having 12-18 carbon atoms The detergent adheres to the surface of the bedpan of the toilet, and even if it is in contact with running water, it can maintain the state of being attached to the surface of the bedpan, and in this state, the detergent is continuously released into the running water.

In addition, in the detergent composition used to clean hard surfaces such as toilets in toilets, in order to prevent blackening and other contamination from microorganisms, didecyl dimethyl ammonium chloride is widely used as a disinfectant. And other tetraalkyl ammonium chloride. Moreover, various composition studies have been conducted in the past to try to improve the performance of detergent compositions containing tetraalkylammonium chloride. For example, Patent Document 2 discloses that, in the detergent composition for hard surfaces, the combination of didecyl dimethyl ammonium chloride and a specific polyoxyethylene alkyl ether can improve the cleaning power.

On the other hand, in the gel-like detergent composition used to adhere to hard surfaces such as toilets in toilets, in order to stably adhere to the hard surface and exhibit the desired cleaning effect, it is necessary to adhere to the The hard surface prevents liquefaction or decrease in gel strength to maintain a stable gel state. However, the current state of the art is that the prior art has not sufficiently studied the composition design for maintaining a stable gel state in the gel detergent composition containing the antimicrobial agent. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-57780 [Patent Document 2] Japanese Patent Application Publication No. 2018-95718

[The problem to be solved by the invention] A gel detergent composition prepared with didecyl dimethyl ammonium chloride commonly used in the past as a disinfectant has the disadvantage that the gel strength decreases with time. Therefore, the object of the present invention is to provide a gel-like detergent composition that can suppress the decrease in gel strength generated over time and stably maintain the gel state even though it contains a sterilizing agent.

The inventors of the present invention conducted diligent studies to solve the above-mentioned problems, and found that a polyoxyalkylene block polymer (compound represented by general formula (1)) with a specific structure and a fungicide with a specific structure (general formula) (2) The gel-like detergent composition of the compound shown in) can suppress the decrease in gel strength that occurs over time and stably maintain the gel state. The present invention is based on these insights and has been completed through further repeated studies.

[通式（1）中，j、k、l、m、及n分別表示加成莫耳數。j+n為1以上，k為0以上，l為1以上，m為0以上。A₁ O表示碳數2～4的環氧烷。A₂ O表示碳數為2～4且與A₁ O不同的碳數的環氧烷。A₃ O表示碳數為2～4且與A₂ O不同的碳數的環氧烷。A₁ O、A₂ O及A₃ O的至少一者為環氧乙烷。]及 （B）下述通式（2）所示的化合物

[通式（2）中，R¹ 及R² 相同或不同，且表示碳數6～18的烷基，R³ 及R⁴ 相同或不同，且表示碳數1～4的烷基，R⁵ 表示碳數1～4的烷基、或氫原子。]。 項2. 如項1所述的凝膠狀洗淨劑組成物，其中，所述聚氧伸烷基嵌段聚合物為由下述通式（1a）表示的聚氧伸烷基嵌段聚合物。 [化3]

[通式（1a）中，j、k、l、m、及n分別表示加成莫耳數。j+n為1以上，k為0以上，l為1以上，m為0以上。EO表示環氧乙烷。A₂ O表示碳數3或4的環氧烷。A₃ O表示碳數2～4且與A₂ O不同的碳數的環氧烷。]。 項3. 如項2所述的凝膠狀洗淨劑組成物，其中，在所述聚氧伸烷基嵌段聚合物中，碳數3～4的環氧烷所佔的部分的分子量為1400以上。 項4. 如項1至項3中任一項所述的凝膠狀洗淨劑組成物，其中，所述聚氧伸烷基嵌段聚合物的分子量為4600以上。 項5. 如項1至項4中任一項所述的凝膠狀洗淨劑組成物，其中，所述通式（2）所示的化合物為二癸基二甲基甲基硫酸銨。 項6. 如項1至項5中任一項所述的凝膠狀洗淨劑組成物，其用於沖洗廁所的便器的洗淨。 項7. 一種凝膠狀洗淨劑組成物的凝膠強度的降低抑制方法，抑制所述凝膠狀洗淨劑組成物的經時性的凝膠強度降低，所述方法使所述凝膠狀洗淨劑組成物中含有： （A）下述通式（1）所示的聚氧伸烷基嵌段聚合物， [化4]

[通式（1）中，j、k、l、m、及n分別表示加成莫耳數。j+n為1以上，k為0以上，l為1以上，m為0以上。A₁ O表示碳數2～4的環氧烷。A₂ O表示碳數為2～4且與A₁ O不同的碳數的環氧烷。A₃ O表示碳數為2～4且與A₂ O不同的碳數的環氧烷。A₁ O、A₂ O及A₃ O的至少一者為環氧乙烷。]及 （B）下述通式（2）所示的化合物

[通式（2）中，R¹ 及R² 相同或不同，且表示碳數6～18的烷基，R³ 及R⁴ 相同或不同，且表示碳數1～4的烷基，R⁵ 表示碳數1～4的烷基、或氫原子。]。 [發明的效果]That is, the present invention provides inventions in the aspects disclosed below. Item 1. A gel-like detergent composition, comprising: (A) a polyoxyalkylene block polymer represented by the following general formula (1), [化1]

[In the general formula (1), j, k, l, m, and n represent the number of added moles, respectively. j+n is 1 or more, k is 0 or more, l is 1 or more, and m is 0 or more. A ₁ O represents an alkylene oxide having 2 to 4 carbon atoms. A ₂ O represents an alkylene oxide having a carbon number of 2 to 4 and a carbon number different from A ₁ O. A ₃ O represents an alkylene oxide having a carbon number of 2 to 4 and a carbon number different from A ₂ O. At least one of A ₁ O, A ₂ O, and A ₃ O is ethylene oxide. ] And (B) the compound represented by the following general formula (2)

[In the general formula (2), R ¹ and R ^{2 are the} same or different and represent an alkyl group having 6 to 18 carbons, R ³ and R ^{4 are the} same or different and represent an alkyl group having 1 to 4 carbons, R ⁵ It represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. ]. Item 2. The gel-like detergent composition according to Item 1, wherein the polyoxyalkylene block polymer is a polyoxyalkylene block polymer represented by the following general formula (1a) Things. [化3]

[In the general formula (1a), j, k, l, m, and n represent the number of added moles, respectively. j+n is 1 or more, k is 0 or more, l is 1 or more, and m is 0 or more. EO stands for ethylene oxide. A ₂ O represents an alkylene oxide having 3 or 4 carbon atoms. A ₃ O represents an alkylene oxide having 2 to 4 carbon atoms and a carbon number different from A ₂ O. ]. Item 3. The gel-like detergent composition according to Item 2, wherein in the polyoxyalkylene block polymer, the molecular weight of the part occupied by the alkylene oxide having 3 to 4 carbon atoms is 1400 or more. Item 4. The gel detergent composition according to any one of items 1 to 3, wherein the polyoxyalkylene block polymer has a molecular weight of 4,600 or more. Item 5. The gel-like detergent composition according to any one of Items 1 to 4, wherein the compound represented by the general formula (2) is didecyl dimethyl ammonium methyl sulfate. Item 6. The gel-like detergent composition according to any one of Items 1 to 5, which is used for washing a toilet in a toilet. Item 7. A method for suppressing the decrease in the gel strength of the gel-like detergent composition, which suppresses the decrease in the gel strength over time of the gel-like detergent composition, and the method makes the gel The detergent composition contains: (A) a polyoxyalkylene block polymer represented by the following general formula (1), [formation 4]

[In the general formula (1), j, k, l, m, and n represent the number of added moles, respectively. j+n is 1 or more, k is 0 or more, l is 1 or more, and m is 0 or more. A ₁ O represents an alkylene oxide having 2 to 4 carbon atoms. A ₂ O represents an alkylene oxide having a carbon number of 2 to 4 and a carbon number different from A ₁ O. A ₃ O represents an alkylene oxide having a carbon number of 2 to 4 and a carbon number different from A ₂ O. At least one of A ₁ O, A ₂ O, and A ₃ O is ethylene oxide. ] And (B) the compound represented by the following general formula (2)

[In the general formula (2), R ¹ and R ^{2 are the} same or different and represent an alkyl group having 6 to 18 carbons, R ³ and R ^{4 are the} same or different and represent an alkyl group having 1 to 4 carbons, R ⁵ It represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. ]. [Effects of the invention]

The gel-like detergent composition of the present invention combines a polyoxyalkylene block polymer (block polymer represented by the general formula (1)) containing a specific structure and a sterilizing agent (general The compound represented by the formula (2)) can suppress the decrease in gel strength that occurs over time and stably maintain the gel state.

1. Gel-like detergent composition The gel-like detergent composition of the present invention is characterized by containing (A) a polyoxyalkylene block polymer (block polymer represented by general formula (1)) of a specific structure, and (B) a specific Structure of the sterilant (the compound of general formula (2)). Hereinafter, the gel-like detergent composition of the present invention will be described in detail.

[(A) Polyoxyalkylene block polymer] The gel detergent composition of the present invention contains a polyoxyalkylene block polymer represented by the following general formula (1) (sometimes also expressed as "block polymer represented by general formula (1) "). The combination of a polyoxyalkylene block polymer of such a specific structure and a sterilizing agent of a specific structure described later to form a gel-like detergent composition can provide adhesion to a hard surface at the same time It suppresses the decrease in gel strength caused by time and stably maintains the gel state. In addition, the polyoxyalkylene block polymer exhibits interfacial activity, and therefore, by contacting with running water and being released, it can play a cleaning effect on hard surfaces.

[化6]

In the general formula (1), j, k, l, m, and n respectively represent the number of added moles. j+n is 1 or more, k is 0 or more, l is 1 or more, and m is 0 or more. A ₁ O represents an alkylene oxide having 2 to 4 carbon atoms. A ₂ O represents an alkylene oxide having a carbon number of 2 to 4 and a carbon number different from A ₁ O. A ₃ O represents an alkylene oxide having a carbon number of 2 to 4 and a carbon number different from A ₂ O. At least one of A ₁ O, A ₂ O, and A ₃ O is ethylene oxide.

In the general formula (1), A ₁ O represents an alkylene oxide having a carbon number of 2 to 4, that is, ethylene oxide, propylene oxide, or butylene oxide. From the viewpoint of more effectively suppressing the decrease in gel strength over time, A ₁ O may preferably be ethylene oxide.

In addition, in the general formula (1), j+n represents the total number of addition moles of alkylene oxide (A ₁ O), and j+n may be 1 or more, and either j or n may be used Is 0. From the viewpoint of more effectively suppressing the decrease in gel strength over time, j and n are each preferably 1 or more. In addition, j and n are preferably approximately the same number. The upper limit of j+n is not particularly limited, and for example, 400 can be cited. In addition, from the viewpoint of more effectively suppressing the decrease in gel strength over time, j+n is preferably 30 or more, more preferably 30 to 350, and particularly preferably 70 to 350. More specifically, j is preferably 15 or more, more preferably 15 to 175, particularly preferably 35 to 175, and n is preferably 15 or more, more preferably 15 to 175, and particularly preferably 35 to 175. .

In the general formula (1), A ₂ O represents an alkylene oxide having a carbon number of 2 to 4, that is, ethylene oxide, propylene oxide or butylene oxide. However, A ₂ O becomes an alkylene oxide having a carbon number different from A ₁ O. That is, when A ₁ O is ethylene oxide, A ₂ O is propylene oxide or butylene oxide, and when A ₁ O is propylene oxide, A ₂ O is ethylene oxide or ring For butylene oxide, when A ₁ O is butylene oxide, A ₂ O is ethylene oxide or propylene oxide. From the viewpoint of more effectively suppressing the decrease in gel strength over time, as A ₂ O, propylene oxide or butylene oxide is preferred, and butylene oxide is more preferred.

In addition, in the general formula (1), k and m represent the number of added moles of alkylene oxide (A ₂ O), and each is 0 or more. When k is 0, m is also preferably 0, but from the viewpoint of more effectively suppressing the decrease in gel strength over time, k and m are more preferably 1 or more. In addition, k and m are preferably approximately the same number. The upper limit of k and m is not particularly limited. For example, as the upper limit of k, 30 can be cited, and as the upper limit of m, 30 can be cited. In addition, the upper limit of k+m is not particularly limited, and for example, 60 can be cited. In addition, from the viewpoint of more effectively suppressing the decrease in gel strength over time, k+m is preferably 0-60, more preferably 0-40, and particularly preferably 10-40. More specifically, k is 0-30, preferably 0-20, more preferably 5-20; m is 0-30, preferably 0-20, more preferably 5-20.

In the general formula (1), A ₃ O represents an alkylene oxide having a carbon number of 2 to 4, that is, ethylene oxide, propylene oxide or butylene oxide. However, A ₃ O becomes an alkylene oxide having a carbon number different from that of A ₂ O. That is, if k and m are 0 (when there is no A ₂ O), A ₃ O is ethylene oxide, propylene oxide, or butylene oxide. In addition, when k and/or m are 1 or more, if A ₂ O is ethylene oxide, A ₃ O is propylene oxide or butylene oxide, and if A ₂ O is propylene oxide, then A ₃ O is ethylene oxide or butylene oxide. If A ₂ O is butylene oxide, A ₃ O is ethylene oxide or propylene oxide. From the viewpoint of more effectively suppressing the decrease in gel strength over time, as A ₃ O, propylene oxide or butylene oxide is preferred, and propylene oxide is more preferred.

In addition, in the general formula (1), l represents the number of addition moles of the alkylene oxide (A ₃ O), and is 1 or more. The upper limit of l is not particularly limited, and for example, 60 can be cited. From the viewpoint of more effectively suppressing the decrease in gel strength over time, 1 is 1 to 60, preferably 15 to 60. More specifically, when k and m are 0, l is more preferably 1-60, particularly preferably 15-60, and most preferably 30-60. In addition, when k and m are 1 or more, 1 is more preferably 1-60, particularly preferably 15-60, and most preferably 15-30.

In the general formula (1), at least one of A ₁ O, A ₂ O, and A ₃ O is ethylene oxide. From the viewpoint of more effectively suppressing the decrease in gel strength over time, it is preferable that at least A ₁ O is ethylene oxide. When A ₁ O is ethylene oxide, the block polymer represented by general formula (1) has a structure represented by the following general formula (1a).

[化7]

In the general formula (1a), j, k, l, m, and n are the same as above. EO stands for ethylene oxide. A ₂ O represents an alkylene oxide having 3 or 4 carbon atoms. A ₃ O represents an alkylene oxide having 2 to 4 carbon atoms and a carbon number different from A ₂ O.

In addition, in the block polymer of the general formula (1a), the part (hydrophobic group part: (A ₂ O) _k -(A ₃ O) _l -(A) occupied by alkylene oxide having 3 to 4 carbon atoms The molecular weight of ₂ O) _m ) is within a range that satisfies the conditions of the general formula (1a). From the viewpoint of more effectively suppressing the decrease in gel strength over time, it is preferable to 1400 or more, more preferably 1700 or more, particularly preferably 1700 to 3500.

In addition, with regard to the molecular weight of the block polymer represented by the general formula (1), as long as it is within the range that satisfies the conditions of the general formula (1), the decrease in gel strength caused by time can be more effectively suppressed From the viewpoint of, preferably 4600 or more, more preferably 6500 or more, and particularly preferably 6500-20000.

In the block polymer represented by the general formula (1), from the viewpoint of more effectively suppressing the decrease in gel strength over time, as a preferred specific example, the following general formula (1a- 1) ~ Polyoxyalkylene block polymer represented by general formula (1a-3).

[化8]

In the general formula (1a-1), EO represents ethylene oxide, BO represents butylene oxide, and PO represents propylene oxide. In addition, in the general formula (1a-1), j1, k1, l1, m1, and n1 represent the number of added moles, respectively. j1 and n1 each represent 1 or more, preferably 15 or more, more preferably 15 to 175, and particularly preferably 35 to 175. Preferably, j1 and n1 are approximately the same number. In addition, j1+n1 (the number of added moles of ethylene oxide) is preferably 30 or more, more preferably 30 to 350, and particularly preferably 70 to 350. k1 and m1 each represent 0 or more, preferably 0-30, more preferably 0-20, and particularly preferably 5-20. Preferably, k1 and m1 are approximately the same number. In addition, k1+m1 (the number of addition moles of butylene oxide) is 0 or more, preferably 0-60, more preferably 0-40, and particularly preferably 10-40. l1 represents 1 or more, preferably represents 1-60, more preferably represents 15-60, and particularly preferably represents 15-30.

[化9]

In the general formula (1a-2), EO represents ethylene oxide, and PO represents propylene oxide. In addition, in the general formula (1a-2), j2, l2, and n2 each represent the number of added moles. j2 and n2 each represent 1 or more, preferably 15-150, more preferably 35-150. j2 and n2 are preferably approximately the same number. In addition, j2+n2 (the number of added moles of ethylene oxide) is 2 or more, preferably 30 to 300, and more preferably 70 to 300. l2 represents 1 or more, preferably represents 1-60, more preferably represents 15-60, and particularly preferably represents 30-60.

[化10]

In the general formula (1a-3), EO represents ethylene oxide, and BO represents butylene oxide. In addition, in the general formula (1a-3), j3, l3, and n3 each represent the number of added moles. j3 and n3 each represent 1 or more, preferably 15-150, more preferably 35-150. Preferably, j3 and n3 are approximately the same number. In addition, j3+n3 (the number of added moles of ethylene oxide) is 2 or more, preferably 30 to 300, and more preferably 70 to 300. l3 represents 1 or more, preferably represents 1-50, more preferably represents 20-50.

In the polyoxyalkylene block polymer represented by the general formula (1a-1) to the general formula (1a-3), from the viewpoint of more effectively suppressing the decrease in gel strength caused by time, The polyoxyalkylene block polymers represented by (1a-1) and (1a-2) are preferred, and the polyoxyalkylene block polymers represented by (1a-1) are more preferred.

In the gel detergent composition of the present invention, as the block polymer represented by the general formula (1), polymers of one structure may be used alone, or polymers of two or more structures may be used in combination.

In the gel-like detergent composition of the present invention, the content of the block polymer represented by the general formula (1) can be appropriately set within a range that can form a gel in the presence of water, for example It may be 15% by weight to 70% by weight, preferably 15% by weight to 40% by weight, more preferably 20% by weight to 40% by weight.

[(B) Sterilizer] The gel-like detergent composition of the present invention contains a compound represented by the following general formula (2) as a sterilizing agent. By selecting the compound represented by the following general formula (2) as a sterilizing agent, and combining it with the block polymer represented by the general formula (1), it is possible to provide adhesion to hard surfaces. At the same time, it suppresses the decrease in gel strength that occurs over time and stably maintains the gel state.

[化11]

In the general formula (2), R ¹ and R ^{2 are the} same or different, and represent an alkyl group having 6 to 18 carbon atoms. The alkyl group constituting R ¹ and R ² may be linear or branched, and preferably linear. In addition, as the carbon number of the alkyl group constituting R ¹ and R ² , from the viewpoint of exerting an excellent sterilization effect and having higher safety, preferably 8-16, more preferably 8~ 14, 8-12 is particularly preferred.

In the general formula (2), R ³ and R ^{4 are the} same or different and represent an alkyl group having 1 to 4 carbon atoms. When the carbon number of the alkyl group constituting R ³ and R ⁴ is 3 or 4, the alkyl group may be either linear or branched, and preferably linear. In addition, as the carbon number of the alkyl group constituting R ³ and R ⁴ , from the viewpoint of exerting an excellent sterilization effect and more effectively suppressing the decrease in gel strength over time, preferably 1 to 3, more preferably 1 or 2, particularly preferably 1.

In the general formula (2), R ⁵ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. When the number of carbon atoms of the alkyl group constituting R ⁵ is 3 or 4, the alkyl group may be either linear or branched, and preferably linear. In addition, as R ⁵ , from the viewpoint of exerting an excellent sterilization effect while more effectively suppressing the decrease in gel strength over time, an alkyl group having 1 to 4 carbon atoms is preferred, and more preferred is The alkyl group having 1 to 3 carbon atoms is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

As the compound represented by the general formula (2), specifically, dihexyl dimethyl ammonium methyl sulfate, dioctyl dimethyl ammonium methyl sulfate, didecyl dimethyl ammonium methyl sulfate, Di-dodecyl dimethyl ammonium methyl sulfate, di-tetradecyl dimethyl ammonium methyl sulfate, di-hexadecyl dimethyl ammonium methyl sulfate, di-octadecyl dimethyl ammonium Base methyl ammonium sulfate and so on. Among these, from the viewpoint of exerting an excellent sterilization effect while more effectively suppressing the decrease in gel strength over time, the preferred is didecyl dimethyl ammonium methyl sulfate (in the general formula (1) Compounds in which R ¹ and R ² are decyl groups, R ³ and R ⁴ are methyl groups, and R ⁵ are methyl groups).

In the gel detergent composition of the present invention, the compound represented by the general formula (2) may be a compound of one structure alone, or a combination of two or more structures.

Regarding the content of the compound represented by the general formula (2) in the gel detergent composition of the present invention, it may be appropriately set according to the sterilization action to be imparted, and for example, it may be 0.1% by weight to 40% by weight. It is preferably 0.5% by weight to 25% by weight, more preferably 0.7% by weight to 10% by weight, and particularly preferably 0.7% by weight to 3.5% by weight.

In addition, in the gel-like detergent composition of the present invention, the ratio of the block polymer represented by the general formula (1) to the compound represented by the general formula (2) should be the ratio of the The content may be within a range corresponding to the content. From the viewpoint of more effectively suppressing the decrease in gel strength over time, 100 parts by weight relative to the total amount of the block polymer represented by the general formula (1) can be cited. The total amount of the compound represented by the general formula (2) is 0.5 parts by weight to 150 parts by weight, preferably 2.5 parts by weight to 100 parts by weight, more preferably 3.5 parts by weight to 20 parts by weight.

[(C) Polyoxyalkylene alkyl ether] The gel detergent composition of the present invention preferably contains the block polymer represented by the general formula (1) and the compound represented by the general formula (2), and contains polyoxyalkylene alkyl ether . By further including the polyoxyalkylene alkyl ether, the decrease in gel strength caused by time can be more effectively suppressed. Furthermore, when polyoxyalkylene alkyl ether is contained, the cleaning effect can also be improved.

The type of the oxyalkylene group in the polyoxyalkylene alkyl ether is not particularly limited, and examples include alkylene oxides having 2 to 4 carbon atoms, that is, ethylene oxide, propylene oxide, and butylene oxide. Among these oxyalkylene groups, from the viewpoint of forming a gel state having a moderate gel strength and at the same time more effectively suppressing the decrease in gel strength over time, ethylene oxide is preferred. And propylene oxide, more preferably ethylene oxide. In addition, the polyoxyalkylene alkyl ether may contain oxyalkylene groups of one structure alone, or may contain oxyalkylene groups of two or more structures in combination.

The number of added moles of the oxyalkylene group in the polyoxyalkylene alkyl ether is not particularly limited, and examples thereof include 10-100, preferably 25-75, and more preferably 40-60.

In addition, the carbon number of the alkyl group in the polyoxyalkylene alkyl ether is not particularly limited, and examples thereof include 10-22, preferably 14-20, and more preferably 16-18. In addition, the alkyl group in the polyoxyalkylene alkyl ether may be either linear or branched, preferably linear.

Among the polyoxyalkylene alkyl ethers, it is possible to further form a gel state with moderate gel strength, to have higher transparency, or to further improve the adhesion to a hard surface. Enumerated preferably polyoxyethylene (addition mole number 10-100) alkyl (carbon number 10-22) ether, more preferably polyoxyethylene (addition mole number 40-60) alkyl (carbon number 16 ~ 18) Ether.

As the polyoxyalkylene alkyl ether, the polyoxyalkylene alkyl ether of one structure may be used alone, or the polyoxyalkylene alkyl ether of two or more structures may be used in combination.

In the gel-like detergent composition of the present invention, when polyoxyalkylene alkyl ether is contained, its content is not particularly limited. For example, it can include 1% by weight to 40% by weight, and preferably 2 Weight%-15 weight %, more preferably 3 weight%-7 weight %.

In addition, in the gel-like detergent composition of the present invention, the ratio of the block polymer represented by the general formula (1) to the polyoxyalkylene alkyl ether should be in accordance with the respective components The content of the polyoxyalkylene block polymer may be within a range corresponding to the range. From the viewpoint of more effectively suppressing the decrease in gel strength over time, the polyoxyalkylene block polymer is 100 parts by weight relative to the total amount of the polyoxyalkylene block polymer. The total amount of alkylene alkyl ether is 1 part by weight to 100 parts by weight, preferably 3 parts by weight to 70 parts by weight, more preferably 4 parts by weight to 60 parts by weight.

[(D) Water-soluble inorganic chloride] The gel-like detergent composition of the present invention may further contain a water-soluble inorganic chloride. By including a water-soluble inorganic chloride, it is possible to more effectively suppress the decrease in gel strength generated over time.

Regarding the types of water-soluble inorganic chlorides, there is no particular limitation as long as they can be dissolved in water at about 4°C. Specifically, examples include: chlorides of alkali metals such as sodium chloride and potassium chloride; magnesium chloride, chlorine Divalent metal chlorides such as calcium chloride and barium chloride; ammonium chloride, etc. These water-soluble inorganic chlorides can better possess the viscoelastic properties, and at the same time further improve the appearance with gloss, the effect of suppressing the drawing from the outlet of the container, and the formation of complex shapes on the surface to be attached From the viewpoint of effects, alkali metal chlorides and ammonium chlorides are preferred, and sodium chloride and ammonium chloride are more preferred.

These water-soluble inorganic chlorides may be used alone or in combination of two or more.

As the water-soluble inorganic chloride, it is preferable to use an alkali metal chloride and ammonium chloride in combination. When the alkali metal chloride and ammonium chloride are used in combination in this way, the ratio of these may be, for example, 100 parts by weight relative to the total amount of the alkali metal chloride, and ammonium chloride is 10 parts by weight to 1000 parts by weight. Parts are preferably 20 parts by weight to 200 parts by weight, more preferably 30 parts by weight to 100 parts by weight.

In the gel-like detergent composition of the present invention, when a water-soluble inorganic chloride is contained, its content is not particularly limited. For example, it can be 0.1% by weight to 10% by weight, preferably 0.3% by weight to 5 wt%, more preferably 0.5 wt% to 3 wt%.

In addition, in the gel-like detergent composition of the present invention, the ratio of the block polymer represented by the general formula (1) to the water-soluble inorganic chloride should be comparable to the content of each component. The corresponding range is sufficient. From the viewpoint of more effectively suppressing the decrease in gel strength over time, the water-soluble inorganic chloride can be exemplified relative to 100 parts by weight of the total amount of the polyoxyalkylene block polymer. The total amount is 0.5 parts by weight to 50 parts by weight, preferably 2 parts by weight to 40 parts by weight, more preferably 2.5 parts by weight to 30 parts by weight.

[(E) Water] In order to form a gel form, the gel detergent composition of the present invention preferably contains water.

In the gel-like detergent composition of the present invention, the content of water may be appropriately set within a range capable of forming a gel state, for example, 20% to 80% by weight, preferably 30% by weight. % To 70% by weight, more preferably 40% to 60% by weight.

[(F) Solvents other than water] The gel-like detergent composition of the present invention may contain a solvent other than water as necessary. By containing a solvent other than water in this way, it is possible to impart dispersibility or solubility to other additives such as fragrances.

The type of solvent is not particularly limited. Examples include: glycerol polyoxyethylene adducts (e.g., three ethylene oxides with an addition mole number of 5 to 80, preferably 10 to 40, and more preferably 15 to 30 Glycerol polyoxyethylene adducts ester-bonded with glycerin); monohydric lower alcohols such as ethanol, propanol, butanol; polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, and glycerin.

Among these solvents, glycerol polyoxyethylene adducts can be preferably cited.

These solvents may be used alone or in combination of two or more.

In the gel-like detergent composition of the present invention, when a solvent (other than water) is contained, its content is not particularly limited. For example, it may exceed 0% to 30% by weight, preferably 3% by weight. ~20% by weight, more preferably 5% to 10% by weight.

[(G) Spices] In the gel-like detergent composition of the present invention, in order to impart aroma to the space used, fragrance may be contained as necessary. Regarding the fragrance, a fragrance component that exhibits a desired fragrance may be appropriately selected according to the application of the gel-like detergent composition. Examples of fragrances contained in the gel-like detergent composition of the present invention include natural fragrances, as well as hydrocarbon fragrances, ether fragrances, ester fragrances, alcohol fragrances, aldehyde fragrances, and ketone fragrances. Synthetic spices such as spices.

As natural fragrances, for example, lemon oil, orange oil, bergamot oil, perfume oil, citronella oil, citronella oil, lemongrass oil, rosewood oil (Bois de rose oil), clove oil, eucalyptus oil, incense Tar, lavender oil, sandalwood oil, vetiver oil, geranium oil, labdanum oil, peppermint oil, peppermint oil, rose oil, jasmine oil, litsea cubeba oil, etc. . In addition, examples of hydrocarbon-based fragrances include limonene, α-pinene, camphene, p-cymene, fenchene, and the like. In addition, as ether-based fragrances, for example, tetrahydro-2,4-dimethyl-4-phenylfuran, 1,8-cineole, rose ether, cedarol methyl ether (methyl cedarwood ether ( cedramber)), p-cresol methyl ether, isoamyl phenyl ethyl ether, 4-phenyl-2,4,6-trimethyl-1,3-dioxane, anethole, etc. In addition, as ester fragrances, for example, geranyl acetate, ethyl acetate, ethyl propionate, methyl butyrate, ethyl isobutyrate, ethyl butyrate, butyl acetate, 2-methylbutyl Ethyl acetate, isoamyl acetate, ethyl 2-methylvalerate (manzanate), hexyl acetate, allyl hexanoate, tricyclodecenyl propionate (VERTOPRO; fluorocycloene (Fluorocyclene)), allyl heptanoate, isobornyl acetate, linalyl acetate, citronellyl acetate, 2-tert-butylcyclohexyl acetate, etc. In addition, as alcoholic fragrances, for example, linalool, 3-octanol, 2,6-dimethyl-heptanol, 10-undecenol, geraniol, nerol, citronellol, rose Alcohol, Geraniol, Tetrahydrolinalool, Terpineol, Cedarol, 2,4-Dimethyl-3-cyclohexane-1-methanol, 4-isopropylcyclohexanol, Neroli Alcohol (nerolidol), 9-decenol, cis-3-hexenol, trans-2-hexenol, eugenol, etc. In addition, examples of aldehyde-based fragrances include citronellal, caprylic aldehyde, paraaldehyde, benzaldehyde, aldehyde C-6, aldehyde C-7, aldehyde C-8, aldehyde C-9, and aldehyde C- 10. Triplal, Furorazon, 2-tridecenal, aldehyde C11, etc. In addition, as ketone-based fragrances, for example, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, acetone, methylpentyl ketone, Ethyl amyl ketone, methyl hexyl ketone, methyl nonyl ketone, methyl heptanone, magnonone (koavone), camphor, carvone, menthone, d-purenone, piperonone, fenchone ), geranyl acetone, maltol, ethyl maltol, 2,5-dimethyl-4-hydroxyfuranone, 4-methyl tricyclic [6.2.1.02.7] undecane-5- Ketones (PLICATONE), acetophenone, p-methylacetophenone, benzyl acetone, benzyl ketone, etc.

These fragrances can be used alone as a single-product fragrance, or two or more can be used in combination as a blended fragrance.

In the gel-like detergent composition of the present invention, when fragrance is contained, its content is not particularly limited. For example, it may exceed 0% by weight to 15% by weight, preferably 1% by weight to 12% by weight. , More preferably 3 wt% to 10 wt%.

[Other additives] In the gel detergent composition of the present invention, not only the above-mentioned components are contained, but also a nonionic surfactant (general formula (1)) may be contained in an appropriate amount as needed within a range that does not impair the effects of the present invention. ) Except for block polymers and polyoxyalkylene alkyl ethers), anionic surfactants, cationic surfactants (except for compounds represented by general formula (2)), enzymes, bactericides, chelating agents Mixtures, colorants, pigments, deodorants, emulsifiers, solubilizers, extenders, solubility modifiers, bleaching agents, water repellents, hydrophilic agents, fillers, pH modifiers, thickeners, buffers, Additives such as defoamers.

[Manufacturing method] The gel-like detergent composition of the present invention is produced by mixing a predetermined amount of contained components at room temperature.

[use] The gel-like detergent composition of the present invention is used for cleaning and sterilizing hard surfaces. Specifically, the gel-like detergent composition of the present invention is adhered to a hard surface, and water is brought into contact with the gel-like detergent composition of the present invention adhered to the hard surface, whereby the contained components flow out Into the water, to clean and sterilize the hard surface.

In the gel-like detergent composition of the present invention, as the hard surface to be cleaned, any hard surface that can come into contact with water is sufficient. Examples include toilet bowls, handwashing parts of toilets, glass, windows, Doors, bathroom walls, etc. Among these, a toilet bowl can be preferably cited.

When the gel-like detergent composition of the present invention is used for washing toilet bowls, the gel-like detergent composition of the present invention only needs to adhere to the part that comes into contact with the water supplied as flushing water. can. As such an attachment part, the surface of a potty is preferably mentioned, but in the case of a flush toilet with a hand washing part on the water storage tank, it may also be the receiving tray of the hand washing part (the upper cover surface of the water storage tank). The gel-like detergent composition of the present invention has excellent adhesion to the surface to be adhered even if it adheres to such a site. Therefore, even if flushing water flows or comes into contact with water supplied to a storage tank as flushing water, It can also maintain the attached state.

In order to make the gel-like detergent composition of the present invention adhere to a hard surface, it is only necessary to squeeze or spray the adhered surface from a container containing the gel-like detergent composition of the present invention to eject it.

[container] The gel-like detergent composition of the present invention is housed in extrusion-type containers such as tube containers, bottle containers, and syringe-type containers; spray-type containers such as aerosol containers, etc., and supplied. The extrusion mechanism of the extrusion container is not particularly limited, and it may be any of a manual type or a compression type.

In addition, in the container containing the gel detergent composition of the present invention, the shape of the ejection port through which the gel detergent composition is ejected needs to be designed so that the ejected gel detergent composition can be It is sufficient to form the desired shape on the surface to be attached.

2. Method for inhibiting the decrease in gel strength of the gel-like detergent composition The present invention further provides a method for suppressing the time-dependent decrease in gel strength of the gel-like detergent composition. Specifically, this method is performed by including the block polymer represented by the general formula (1) and the compound represented by the general formula (2) in the gel-like detergent composition.

Regarding the type or content of the block polymer represented by the general formula (1) and the compound represented by the general formula (2) used in this method, and the types of other ingredients that can be formulated in the gel detergent composition Or the content, the object to be cleaned of the gel-like detergent composition, etc. are as described in the section "1. Gel-like detergent composition". [Example]

Hereinafter, examples are given to illustrate the present invention, but the present invention is not limited to these examples.

In addition, the structure, brand name, etc. of the main components used in the following examples, reference examples, and comparative examples are as follows.・Polyoxyalkylene block polymer: structural formula HO-(EO) _j1 -(BO) _k1 -(PO) _l1 -(BO) _m1 -(EO) _n1 -H[j1 and n1 are approximately the same number , K1 and m1 are approximately the same number, the EO additive mole number (j1+n1) is about 330, the BO additive mole number (k1+m1) is about 20, and the PO additive mole number (l1 ) Is about 20, the molecular weight is about 16800, and the molecular weight of the hydrophobic group ((BO) _k1 -(PO) _l1 -(BO) _m1 ) is about 2200] ・Didecyl dimethyl ammonium methyl sulfate: use the trade name "Lipoquad 210-80MSPG" (manufactured by Lion Specialty Chemicals Co., Ltd.).・Didecyldimethylammonium chloride: Use the trade name "Cation DDC-70PG" (manufactured by Sanyo Chemical Co., Ltd.).・Polyoxyethylene alkyl ether: a mixture of polyoxyethylene (addition mol number about 50) cetyl ether and polyoxyethylene (addition mol number about 50) oleyl ether ・Glycerol oxide: addition mol A glycerol polyoxyethylene adduct in which three ethylene oxides of 20 ears are ester-bonded with glycerin, brand name "GE20", manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.・Amphoteric surfactant: Coconut oil fatty acid amidopropyl dimethyl betaine, brand name "AMOGEN CB-H", manufactured by Daiichi Industrial Pharmaceutical Co., Ltd. ・Fragrance A: Peppermint-based fragrance・Fragrance B: soap (soap)-based fragrance and fragrance C: floral (floral)-based fragrance

Reference test example 1 Put the prescribed amount of each component shown in Table 1 into a glass beaker (manufactured by AGC Techno Glass Co., Ltd./capacity 500 ml), and mix the prescribed amount at room temperature to prepare a gel wash Detergent composition (50 g in a container). In addition, the content shown in Table 1 shows the substantial amount of each component other than the solvent contained in the additive (commodity) added. The obtained gel-like detergent composition was stored at 60°C for 5 days. The gel strength of the gel detergent composition immediately after preparation and storage was measured under the following conditions, and the gel strength retention rate was calculated according to the following formula. <Measurement conditions of gel strength> Fill a cylindrical container with a diameter of 3 cm and a height of 6.5 cm with a gel-like detergent composition, and use a rheometer ("SUNRHEOMETERCR-500DX)" (manufactured by Sun Kagaku Co., Ltd.) ), the gel strength was measured under the following conditions. ・Measurement mode: fixed depth measurement (MODE 20) ・Measurement jig: plate with diameter 10 mmΦ and thickness 1 mm ・Entry speed: 60 mm/min ・Entry depth: 40 mm ・Measurement temperature: 25℃

[Number 1] Gel strength maintenance rate (%)={(gel strength after storage)/(gel strength immediately after preparation)}×100

The results are shown in Table 1. As a result, in the gel detergent composition containing polyoxyalkylene block polymer, in the case where didecyldimethylammonium chloride was not included (Reference Example 1), it was not confirmed after storage The gel strength decreased, but in the case where didecyldimethylammonium chloride was included (Comparative Example 1), a decrease in gel strength was confirmed after storage. That is, it was confirmed from this result that the gel-like detergent composition containing didecyldimethylammonium chloride, which is commonly used in the past, as a fungicide, the gel strength is decreased over time, and it cannot be stabilized. To maintain the gel state.

[Table 1] Reference example 1 Comparative example 1 Polyoxyalkylene block polymer 19.5 19.5 Didecyl Dimethyl Ammonium Chloride - 1.9 Polyoxyethylene alkyl ether 5.0 5.0 Amphoteric Surfactant 10.0 10.0 Glycerol oxide 6.5 6.5 Sodium chloride 1.0 1.0 Ammonium Chloride 0.5 0.5 Spice A 7.0 7.0 Denatonium (denatonium) 0.01 0.01 water The remaining part The remaining part Total (weight%) 100.0 100.0 Just after preparation Gel strength (gf) 76 103 After 5 days storage at 60℃ Gel strength (gf) 89 67 Gel strength maintenance rate (%) 117 65

Test example 1 The prescribed amount of each component shown in Table 2 is put into a glass beaker (made by AGC Techno Glass Co., Ltd./capacity 500 ml), and the prescribed amount is mixed at room temperature to prepare a gel wash Detergent composition (50 g in a container). In addition, the content shown in Table 2 shows the substantial amount of each component other than the solvent contained in the additive (commodity) added. The obtained gel-like detergent composition was stored at 60°C for 5 days. The gel strength of the gel-like detergent composition immediately after preparation and storage was measured by the same method as in the case of Reference Test Example 1, and the gel strength retention rate was determined.

[Table 2] Example 1 Comparative example 2 Polyoxyalkylene block polymer 20.0 20.0 Didecyl dimethyl ammonium methyl sulfate 2.4 - Didecyl Dimethyl Ammonium Chloride - 2.4 Sodium chloride 1.0 1.0 Ammonium Chloride 0.5 0.5 Spice A 7.0 7.0 water The remaining part The remaining part Total (weight%) 100.0 100.0 Just after preparation Gel strength (gf) 119 130 After 5 days storage at 60℃ Gel strength (gf) 104 77 Gel strength maintenance rate (%) 87.4 59.2

The results are shown in Table 2. As a result, it was confirmed that in a gel detergent composition containing a polyoxyalkylene block polymer and didecyldimethylammonium methyl sulfate, the decrease in gel strength after storage can be suppressed, thereby It can maintain the gel state stably.

Test example 2 Put the prescribed amount of each component shown in Table 3 into a glass beaker (manufactured by AGC Techno Glass Co., Ltd./capacity 500 ml), and mix the prescribed amount at room temperature to prepare a gel wash Detergent composition (50 g in a container). In addition, the content shown in Table 3 shows the substantial amount of each component other than the solvent contained in the additive (commodity) added. The obtained gel-like detergent composition was stored at 40°C for four months. The gel strength of the gel-like detergent composition immediately after preparation and storage was measured by the same method as in the case of Reference Test Example 1, and the gel strength retention rate was determined.

The results are shown in Table 3. From this result, it was also confirmed that in a gel detergent composition containing a polyoxyalkylene block polymer and didecyldimethylammonium methyl sulfate, the decrease in gel strength after storage can be suppressed .

[table 3] Example 2 Comparative example 3 Polyoxyalkylene block polymer 18.0 18.0 Didecyl dimethyl ammonium methyl sulfate 1.4 - Didecyl Dimethyl Ammonium Chloride - 1.4 Polyoxyethylene alkyl ether 5.0 5.0 Amphoteric Surfactant 3.0 3.0 Glycerol oxide 6.0 6.0 Sodium chloride 1.0 1.0 Ammonium Chloride 0.5 0.5 Spice B 5.0 5.0 water The remaining part The remaining part Total (weight%) 100.0 100.0 Just after preparation Gel strength (gf) 90.7 86.0 After four months of storage at 40℃ Gel strength (gf) 67.3 48.8 Gel strength maintenance rate (%) 74.2 56.7

Test example 3 Put the prescribed amount of each component shown in Table 4 into a glass beaker (manufactured by AGC Techno Glass Co., Ltd./capacity 500 ml), and mix the prescribed amount at room temperature to prepare a gel wash Detergent composition (50 g in a container). In addition, the content shown in Table 4 shows the substantial amount of each component other than the solvent contained in the additive (commodity) added. The obtained gel-like detergent composition was stored under the conditions of four months at 60°C and 40 days at 50°C. The gel strength of the gel detergent composition immediately after preparation and after storage was measured by the same method as in the case of Reference Test Example 1, and the gel strength retention rate was determined.

The results are shown in Table 4. From this result, it was also confirmed that in a gel detergent composition containing a polyoxyalkylene block polymer and didecyldimethylammonium methyl sulfate, the decrease in gel strength after storage can be suppressed .

[Table 4] Example 3 Comparative example 4 Polyoxyalkylene block polymer 19.0 19.0 Didecyl dimethyl ammonium methyl sulfate 1.4 - Didecyl Dimethyl Ammonium Chloride - 1.4 Polyoxyethylene alkyl ether 5.0 5.0 Amphoteric Surfactant 3.0 3.0 Glycerol oxide 6.0 6.0 Sodium chloride 1.0 1.0 Ammonium Chloride 0.5 0.5 Spice C 5.0 5.0 water The remaining part The remaining part Total (weight%) 100.0 100.0 Just after preparation Gel strength (gf) 80.3 86.0 After four months of storage at 40℃ Gel strength (gf) 64.7 58.0 Gel strength maintenance rate (%) 80.6 67.4 After 40 days storage at 50℃ Gel strength (gf) 73.7 65.0 Gel strength maintenance rate (%) 91.8 75.5

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Claims (7)

A gel-like detergent composition, comprising: (A) a polyoxyalkylene block polymer represented by the following general formula (1),

In the general formula (1), j, k, l, m, and n respectively represent the number of addition moles; j+n is 1 or more, k is 0 or more, l is 1 or more, and m is 0 or more; A ₁ O Represents an alkylene oxide having 2 to 4 carbon atoms; A ₂ O represents an alkylene oxide having 2 to 4 carbon atoms and a different carbon number from A ₁ O; A ₃ O represents an alkylene oxide having 2 to 4 carbon atoms and is compatible with A ₂ O Alkylene oxides of different carbon numbers; at least one of A ₁ O, A ₂ O, and A ₃ O is ethylene oxide; and (B) a compound represented by the following general formula (2),

In the general formula (2), R ¹ and R ^{2 are the} same or different and represent an alkyl group having 6 to 18 carbons, R ³ and R ^{4 are the} same or different and represent an alkyl group having 1 to 4 carbons, and R ⁵ represents C1-C4 alkyl group or hydrogen atom. The gel-like detergent composition according to the first item of the patent application, wherein the polyoxyalkylene block polymer is a polyoxyalkylene block represented by the following general formula (1a) polymer,

In the general formula (1a), j, k, l, m, and n respectively represent the number of addition moles; j+n is 1 or more, k is 0 or more, l is 1 or more, and m is 0 or more; EO represents the ring Ethylene oxide; A ₂ O represents an alkylene oxide having a carbon number of 3 or 4; A ₃ O represents an alkylene oxide having a carbon number of 2 to 4 and a carbon number different from A ₂ O. The gel-like detergent composition according to the second item of the patent application, wherein, in the polyoxyalkylene block polymer, the molecular weight of the part of the alkylene oxide having 3 to 4 carbon atoms It is above 1400. The gel-like detergent composition according to any one of items 1 to 3 in the scope of patent application, wherein the molecular weight of the polyoxyalkylene block polymer is 4600 or more. The gel detergent composition according to any one of items 1 to 4 in the scope of the patent application, wherein the compound represented by the general formula (2) is didecyl dimethyl methyl sulfuric acid Ammonium. The gel-like detergent composition as described in any one of items 1 to 5 of the scope of the patent application is used for washing toilets in toilets. A method for inhibiting the decrease in the gel strength of a gel-like detergent composition, which suppresses the decrease in the time-dependent gel strength of the gel-like detergent composition, and the method makes the gel-like detergent composition clean The agent composition contains: (A) a polyoxyalkylene block polymer represented by the following general formula (1),

In the general formula (1), j, k, l, m, and n respectively represent the number of addition moles; j+n is 1 or more, k is 0 or more, l is 1 or more, and m is 0 or more; A ₁ O Represents an alkylene oxide having 2 to 4 carbon atoms; A ₂ O represents an alkylene oxide having 2 to 4 carbon atoms and a different carbon number from A ₁ O; A ₃ O represents an alkylene oxide having 2 to 4 carbon atoms and is compatible with A ₂ O Alkylene oxides of different carbon numbers; at least one of A ₁ O, A ₂ O, and A ₃ O is ethylene oxide; and (B) a compound represented by the following general formula (2),

In the general formula (2), R ¹ and R ^{2 are the} same or different and represent an alkyl group having 6 to 18 carbons, R ³ and R ^{4 are the} same or different and represent an alkyl group having 1 to 4 carbons, and R ⁵ represents An alkyl group having 1 to 4 carbon atoms, or a hydrogen atom.