JP2009084456A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition which is less apt to change in viscosity even when it undergoes seasonal, regional or other changes in temperature and is less apt to change in viscosity even upon contact with water. <P>SOLUTION: The liquid detergent composition comprises (A) a nonionic surfactant which is fluid at 20°C, (B) a nonionic surfactant which is not fluid at 20°C, (C) a polyoxyethylene/polyoxypropylene block polymer and (D) water. The composition contains the components (A) to (C) in the following proportions: the sum of the components (A) and (B) is 7-43 pts.wt. per 100 pts.wt. the liquid detergent composition; the amount of the component (A) is 66-3,500 pts.wt. per 100 pts.wt. the component (B); and the amount of the component (C) is 0.5-22 pts.wt. per 100 pts.wt. the total weight of the liquid detergent composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid cleaning composition comprising a nonionic surfactant having fluidity at 20 ° C., a nonionic surfactant having no fluidity at 20 ° C., and a polyoxyethylene polyoxypropylene block polymer.

  The liquid cleaning composition is usually used by being put in some kind of container and discharged from the discharge hole of the container as necessary. And the stable cleaning effect at the time of every use can be acquired by making the discharge | emission amount from the container of a liquid cleaning composition constant.

  However, the viscosity of such a liquid cleaning composition changes due to a temperature change. For example, the viscosity may change due to a difference in temperature throughout the year. In addition, such a liquid cleaning composition is often used in an environment where water is present in the surroundings, and the liquid cleaning composition inside can also be obtained by intrusion of water into a container in which the liquid cleaning composition is enclosed. Can vary in viscosity. When the viscosity of the liquid cleaning composition changes in this manner, the amount of liquid cleaning composition discharged from the container may change, thereby making it impossible to stably discharge a desired amount of the liquid cleaning composition from the discharge hole. For example, if the viscosity of the liquid cleaning composition becomes too high, the amount discharged every time is extremely reduced, and further, it is not discharged from the discharge hole. Also, if the viscosity of the liquid cleaning composition is too low, the amount of each discharge becomes extremely large, causing unnecessary outflow of the liquid cleaning composition. For this reason, there is a need for a liquid cleaning composition that is less susceptible to changes in temperature and viscosity due to contact with water, and that has highly suppressed non-uniformity in the discharge amount from the discharge holes.

  So far, a prescription for suppressing a change in viscosity of the liquid cleaning composition due to a temperature change has been studied. In Patent Document 1, the viscosity and the viscosity of the liquid cleaning composition are adjusted by adjusting the type and amount of the nonionic surfactant used in the liquid cleaning composition, the amount of water, and the type and amount of a solvent used arbitrarily. It is disclosed that it can be adjusted. For example, in Patent Document 1, when the viscosity of the liquid cleaning composition is too low, the viscosity can be increased by reducing the water content in the liquid cleaning composition, while when the viscosity is too high. It has been disclosed that the viscosity can be lowered by increasing the amount of water or adding alcohol or a solvent.

  However, in the liquid cleaning composition as described in Patent Document 1, since the problem of viscosity change of the liquid cleaning composition due to temperature change is solved by adding water, for example, the liquid cleaning composition described above is used. The problem of viscosity change due to contact between an object and water cannot be solved. From this, it can be judged that the liquid cleaning composition as described in Patent Document 1 cannot suppress the non-uniformity of the discharge amount from the discharge hole.

  The liquid cleaning composition has been applied to various uses so far, and an example of the use is a cleaning agent for flush toilets. Cleaning agents for flush toilets include those that are installed on the hand-washing part of the flush toilet, those that are used by being attached to the toilet rim of the flush toilet, and those that are installed in the tank of the flush toilet. Illustrated. These flush toilets have advantages in use such as easy installation, the ability to easily check the remaining amount of detergent, and the addition of fragrances to add aroma effect. is doing.

  On the other hand, such cleaning agents for flush toilets are susceptible to temperature changes. In addition, when a cleaning agent for a flush toilet is used on the hand wash part of the flush toilet, the water supplied from the wash tank hand wash part is mixed into the container containing the liquid cleaning composition. There is a specific problem of doing. In addition, when a flushing toilet cleaner is used attached to the toilet rim of the flush toilet, there is a peculiar problem that flush water is mixed into the container containing the liquid cleaning composition. There is a point.

For this reason, in the liquid cleaning composition for flush toilets, the viscosity change is likely to occur, and the conventional problem of the liquid cleaning composition described above, that is, the non-uniformity of the discharge amount tends to appear remarkably. The uneven discharge of the liquid cleaning composition in the cleaning of the flush toilet using the flush toilet flushing agent may lose the cleaning effect or cause excessive foaming of flush water. It is strongly desired to solve the problems of the cleaning composition, that is, to highly suppress the non-uniformity of the discharge amount of the liquid cleaning composition.
JP-A-9-279180

  The present invention is suitable for liquid cleaning compositions that are less likely to change in viscosity due to temperature changes due to seasons, regions, etc., and that are less likely to change in viscosity due to contact with moisture, particularly for on-tanks and rim parts of flush toilets. The main objective is to provide a liquid cleaning composition.

As a result of intensive studies by the inventor in view of the above problems, the liquid cleaning composition is (A) a nonionic surfactant having fluidity at 20 ° C, and (B) a nonionic interface having no fluidity at 20 ° C. By containing an activator, (C) polyoxyethylene polyoxypropylene block polymer, and (D) water, and by making each of the above components (A), (B), and (C) a predetermined range amount, It has been found that a liquid cleaning composition can be obtained that is less susceptible to viscosity change even when temperature changes occur or is in contact with moisture, and that can highly suppress non-uniformity in the discharge amount from the discharge holes. . In particular, it has been found that such a liquid cleaning composition is suitable as a cleaning agent for flush toilets. The present invention has been completed as a result of further studies based on the above findings, and is described below.
Item 1. (A) Nonionic surfactant having fluidity at 20 ° C, (B) Nonionic surfactant having no fluidity at 20 ° C, (C) Polyoxyethylene polyoxypropylene block polymer, and (D) Water A liquid cleaning composition containing the components (A) to (C) in the following proportions:
(A) The sum total of a component and (B) component is 7-43 weight part with respect to 100 weight part of liquid cleaning compositions,
The component (A) is 66-3500 parts by weight with respect to 100 parts by weight of the component (B), and the component (C) is 0.5-22 parts by weight with respect to 100 parts by weight of the total amount of the liquid cleaning composition. is there.
Item 2. The component (A) is a nonionic surfactant represented by the following general formula (1) and has fluidity at 20 ° C., and the component (B) has the following general formula (1) Item 2. A liquid cleaning composition according to Item 1, which is a nonionic surfactant represented by formula (1) and has no fluidity at 20 ° C;
RO- (AO) k-H (1)
(In the formula, R represents an aliphatic hydrocarbon group having a content of 8 to 16 carbon atoms of 80% by weight or more, and-(AO) k- represents a single or mixed polymer chain of an alkylene oxide having 2 to 4 carbon atoms. Wherein k represents the average number of moles of alkylene oxide added, and k is in the range of 1-100.)
Item 3. The liquid cleaning composition according to item 1 or 2, wherein the component (C) is represented by the following general formula (2):
H- (EO) m- (PO) n- (EO) 1-OH (2)
(In the formula,-(EO) m- and-(EO) l- represent a homopolymer chain of ethylene oxide, and-(PO) n- represents a homopolymer chain of propylene oxide. M, n, l Represents the average number of added moles of alkylene oxide, n is an integer of 1 to 100, m + 1 is an integer of 1 to 197, and the content of ethylene oxide is 60% by weight or less.
Item 4. The liquid cleaning composition according to any one of Items 1 to 3, further comprising at least one selected from the group consisting of a solubilizer and an amphoteric surfactant.
Item 5. Item 5. The liquid cleaning composition according to any one of Items 1 to 4, which is used for an on-tank of a flush toilet.
Item 6. Item 5. The liquid cleaning composition according to any one of Items 1 to 4, which is used for a rim portion of a flush toilet.

  According to the present invention, it is possible to obtain a liquid cleaning composition that not only hardly causes a change in viscosity due to a temperature change depending on the season or region, but also can highly suppress non-uniformity in the discharge amount from the discharge holes. In addition, according to the present invention, a liquid cleaning composition is obtained that not only hardly changes in viscosity even when in contact with moisture, but also can highly suppress non-uniformity in the discharge amount from the discharge holes. be able to.

  Such a liquid cleaning composition of the present invention can be used, for example, as a liquid cleaning composition for an on-tank of a flush toilet used by being installed on a hand-washing portion of a flush toilet. Moreover, such a liquid cleaning composition of the present invention can be used as, for example, a liquid cleaning composition for a rim portion of a flush toilet that is used by being attached to a rim portion of a toilet bowl of a flush toilet. And when using the liquid cleaning composition of the present invention for an on-tank of a flush toilet, for example, when using the container described in the examples under the conditions described in the examples described later, per 35 ml of the liquid cleaning composition The number of holdings can be adjusted to about 300 to 650 times at 5 ° C. and 25 ° C.

  Thus, according to the present invention, even when a temperature change occurs when the liquid cleaning composition is stored in an arbitrary container having a discharge hole, the stored liquid cleaning composition and water are also present. Even if it contacts, it has the effect that the nonuniformity of the discharge | emission amount of the liquid cleaning composition can be suppressed highly. Further, according to the present invention, even when 30 parts by weight of water is mixed with the liquid cleaning composition of the present invention with respect to 100 parts by weight of the liquid cleaning composition, the discharge amount of the liquid cleaning composition This has the effect of highly suppressing the non-uniformity. Therefore, according to the present invention, when the viscosity becomes too high, it is possible to prevent the liquid cleaning composition from being difficult to be discharged or clogged from the container, and when it becomes too low, the liquid cleaning composition is wasted. It can be prevented from doing too much.

Hereinafter, the liquid cleaning composition of the present invention will be described.

(1) Liquid cleaning composition The liquid cleaning composition of the present invention is non-ionic surfactant having fluidity at 20 ° C (hereinafter also referred to as component (A)), and does not have fluidity at 20 ° C. Nonionic surfactant (hereinafter also referred to as component (B)), polyoxyethylene polyoxypropylene block polymer (hereinafter also referred to as component (C)), and water (hereinafter referred to as component (D)) And (A) component, (B) component, and (C) component are contained at a predetermined ratio.

  The viscosity of the liquid cleaning composition of the present invention is not limited as long as it satisfies the properties as a cleaning agent. For example, when the liquid cleaning composition of the present invention is used in a situation where a change in temperature or contact with water is likely to occur, such as a cleaning agent for an on-tank of a flush toilet or a cleaning agent for a rim portion. Even so, it has the effect of highly suppressing non-uniformity in the discharge amount of the liquid cleaning composition, and the number of times it can be maintained in a desired range. The number of times of holding depends on the size of the discharge hole of the container in which the liquid cleaning composition is accommodated. For example, when the container described in the example is used under the condition described in the example described later, The number of holdings is about 300-650 times at 5 ° C. and 25 ° C. per 35 ml of liquid cleaning composition.

  Here, the cleaning agent for the on-tank of the flush toilet refers to the one installed on the hand-washing part of the flush toilet, and the washing supplied from the container containing the liquid cleaning composition and the washing tank hand-washing part The liquid cleaning composition flows out of the container by contact with water for use, and the water in which the liquid cleaning composition is dissolved is discharged into the toilet bowl. Moreover, the cleaning agent for the rim part of the flush toilet refers to the one used by being attached to the rim part of the toilet of the flush toilet, and the flush water discharged to the container and the toilet containing the liquid cleaning composition. Contact with the liquid, the liquid cleaning composition flows out of the container, and the water infiltrated with the liquid cleaning composition can spread into the toilet bowl. Therefore, in this specification, the water for washing | cleaning refers to the water supplied from the washing tank hand-washing part, and the water for flushing refers to the water discharged | emitted from a toilet bowl.

  In the liquid cleaning composition of the present invention, the non-uniformity of the discharge amount, that is, the variation in the number of times, is selected from the above components (A) to (D) as a blending component of the liquid cleaning composition of the present application, and further used. Correspondingly, it is highly eliminated by blending them at a predetermined ratio. Such non-uniformity in the discharge amount may be caused by various factors, one of which is a change in viscosity of the liquid cleaning composition of the present invention.

  The viscosity of the liquid cleaning composition of the present invention is appropriately changed depending on the application, and is not limited as long as the good number of times according to the application is maintained. The viscosity of the liquid cleaning composition of the present invention is such that when the liquid cleaning composition is contained in a container, the liquid cleaning composition does not unnecessarily flow out from the discharge hole of the container, and the discharge hole of the container is clogged. It is sufficient that the viscosity does not occur and the discharge amount does not become non-uniform beyond the allowable range.

  As described above, the viscosity of the liquid cleaning composition of the present invention is appropriately interpreted according to the use of the liquid cleaning composition, the size of the discharge hole of the container to be stored, etc. However, for example, about 20 to 1500 mPa · s at 5 to 25 ° C. is preferable. In particular, when the liquid cleaning composition of the present invention is used as a cleaning agent for flush toilets such as for on-tanks and rims, it is preferably about 40 to 1200 mPa · s from the viewpoint of the number of possessions. More preferably, the pressure is about 130 to 1000 mPa · s.

  In the present invention, the viscosity is appropriately set in the range of a set temperature of 5 ° C. or 25 ° C. in a B type viscometer (manufactured by Toki Sangyo Co., Ltd .: model number TVB-10 type viscometer). 2. Measured under conditions of stirring conditions of 30 rpm and stirring time of 1 minute.

  The above viscosity range is prepared by appropriately preparing the above components (A) to (D) within a predetermined range, and further appropriately preparing the types of other compounding components added as necessary and these compounding components. Is set as appropriate.

  Hereinafter, each component of the liquid cleaning composition of the present invention will be described.

(2) Nonionic surfactant having fluidity at 20 ° C. (component (A)) and Nonionic surfactant having no fluidity at 20 ° C. (component (B))
The nonionic surfactant having fluidity at 20 ° C. (component (A)) used in the present invention is not limited as long as it is a nonionic surfactant having fluidity at 20 ° C. Here, in this invention, the presence or absence of fluidity | liquidity is evaluated by the external appearance, and in detail according to the liquid confirmation test of the Fire Service Act. As for fluidity, JIS K2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products” can be mentioned as a general test method. That is, the said (A) component points out the nonionic surfactant determined to be liquid in the liquid confirmation test. The nonionic surfactant that does not have fluidity at 20 ° C. (component (B)) used in the present invention is a nonionic surfactant that does not have fluidity at 20 ° C. and is liquid in the liquid confirmation test. It refers to a nonionic surfactant determined to be not.

For example, as a nonionic surfactant, the thing of the structure represented with General formula (1) below is mentioned.
RO- (AO) k-H (1)
In the formula, R represents an aliphatic hydrocarbon group having a content of 8 to 16 carbon atoms of 80% by weight or more, and-(AO) k- represents a single or mixed polymerization chain of an alkylene oxide having 2 to 4 carbon atoms. In formula, k shows the average addition mole number of alkylene oxide, and k is the range of 1-100. The aliphatic hydrocarbon group may be linear or branched. Among these, those having fluidity at 20 ° C. can be distinguished as the above-mentioned component (A), and those having no fluidity at 20 ° C. can be distinguished as the above-mentioned component (B).

  The component (A) that can be used in the present invention is not particularly limited as long as it is represented by the general formula (1) and has fluidity at 20 ° C., but preferably within the above range, R = 10 to 14 , K = 1 to 40, more preferably R = 10 to 12, and k = 3 to 35.

  The component (B) that can be used in the present invention is not particularly limited as long as it is represented by the general formula (1) and does not have fluidity at 20 ° C., but preferably in the above range, R = 10-14, k = 6-100, more preferably R = 10-12, k = 8-60.

  Examples of the nonionic surfactant represented by the general formula (1) include polyoxyalkylene decyl ether having R = 10 and polyoxyalkylene lauryl ether having R = 12. Among these nonionic surfactants, as described above, those having fluidity at 20 ° C. are components (A), and those having no fluidity at 20 ° C. are components (B).

  For example, as the component (A), Neugen XL-50, Neugen XL-60, Neugen XL-6190, Neugen XL-70, Neugen XL-80, Neugen XL-100 sold by Daiichi Kogyo Seiyaku Co., Ltd. Neugen SD-60, Neugen SD-70, Neugen SD-80, DKS NL-50, DKS NL-60, DKS NL-Dash400, DKS NL-Dash403, DKS NL-Dash404, DKS NL-Dash408, Neugen LP-70, Examples include Neugen LP-100, Neugen LP-180, Neugen CL-200, Neugen CL-230 and the like.

  For example, as component (B), Neugen XL-140, Neugen XL-160, Neugen XL-400, Neugen XL-1000F, Neugen SD-110, Neugen SD- sold by Daiichi Kogyo Seiyaku Co., Ltd. 150, Neugen SD-300, Neugen SD-400, DKS NL-80, DKS NL-90, DKS NL-100, DKS NL-110, DKS NL-180, DKS NL-250, DKS NL-450, DKS NL- 600, DKS NL-Dash 410, and the like. These (A) component and (B) component may be used individually by 1 type, respectively, and may be used in combination of 2 or more types, respectively.

  In addition, the blending ratio of the component (A) and the component (B) in the liquid cleaning composition is 7 to 43 in combination with the component (A) and the component (B) with respect to 100 parts by weight of the total amount of the liquid cleaning composition. In particular, when the present invention is used as a cleaning agent for an on-tank / rim part for a flush toilet, it is preferably 10 to 41 parts by weight from the viewpoint of the number of times of holding and cleaning power. More preferably, the content is 20 to 41 parts by weight.

  The blending ratio of the component (A) and the component (B) can be 66 to 3500 parts by weight of the component (A) with respect to 100 parts by weight of the component (B). Is used as a cleaning agent for an on-tank / rim part for a flush toilet, it is preferably 77-3500 parts by weight from the viewpoint of the number of times it is taken.

  By setting the above-mentioned components (A) and (B) to the above-mentioned mixing ratio, a liquid cleaning composition in which the unevenness of the discharge amount is highly eliminated can be obtained.

(3) Polyoxyethylene polyoxypropylene block polymer (component (C))
The polyoxyethylene polyoxypropylene block polymer (component (C)) used in the present invention is not particularly limited. For example, examples of the component (C) include those having a structure represented by the following general formula (2).
H- (EO) m- (PO) n- (EO) 1-OH (2)
Here, in the formula,-(EO) m- and-(EO) 1- are a homopolymer chain of ethylene oxide, and-(PO) n- is a homopolymer chain of propylene oxide. In the formula, m, n, and l represent the average number of added moles of alkylene oxide, n is an integer of 1 to 100, m + 1 is an integer of 1 to 197, and the ethylene oxide content is 60% by weight. It is as follows. Preferably, n is an integer of 20 to 100, m + 1 is an integer of 3 to 197, and the ethylene oxide content is 60% by weight or less. In particular, when the present invention is used as a cleaning agent for an on-tank / rim portion for a flush toilet, preferably n is an integer of 20 to 69, and m + 1 is an integer of 3 to 55 from the viewpoint of the number of times it is taken. And the content of ethylene oxide is 60% by weight or less, and particularly preferably, when n is an integer in the range of 20 to 26, m + 1 is an integer of 8 to 20 and the content of ethylene oxide. When the rate is in the range of 30 to 60% by weight and n is in the range of 26 to 34, m + 1 is an integer of 3 to 27, the ethylene oxide content is in the range of 10 to 60% by weight, and n is 34 to 69. M + 1 is an integer of 9 to 55, and the ethylene oxide content is in the range of 20 to 60% by weight.

  Examples of the polymer represented by the general formula (2) include Epan (registered trademark) sold by Daiichi Kogyo Seiyaku Co., Ltd., and in detail, Epan 410, Epan 420, Epan 450, Epan 540, Examples include Epan 610, Epan 710, Epan 720, Epan 740, Epan 750, and the like. Among these, in particular, when the present invention is used as a cleaning agent for an on-tank / rim part in a flush toilet, from the viewpoint of the stability of the prescription when blending many times, perfume, etc., preferably, Examples include Epan 450, Epan 540, Epan 610, Epan 720, Epan 740, Epan 750, and the like.

Examples of the component (C) include those having a structure represented by the following general formula (3) and those having a tetranic type.
H- (PO) x- (EO) y- (PO) z-OH (3)
In the formula, each of x, y and z is an integer of 1 or more, so long as the thickening effect similar to that of the structure represented by the general formula (2) can be imparted to the liquid cleaning composition. Not limited.

  The said polymer may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content ratio of the component (C) in the liquid cleaning composition is 0.5 to 22 parts by weight with respect to 100 parts by weight of the total amount of the liquid cleaning composition. When used as a cleaning agent, it is preferably from 1 to 21 parts by weight, more preferably from 3 to 15 parts by weight, from the viewpoint of the number of holdings.

  By blending the above component (C) in the liquid cleaning composition at the above ratio, it is possible to obtain a cleaning liquid cleaning composition in which the unevenness of the discharge amount is highly eliminated.

(4) Water (component (D))
In the liquid detergent composition of the present invention, water is used as the base component. That is, in the liquid cleaning composition of the present invention, the remainder other than the components (A) to (C) and other blending components added as necessary is composed of water.

(5) Other ingredients
Solubilizer The liquid cleaning composition of the present invention may contain a solubilizer in addition to the components (A) to (D). By including a solubilizing agent, it is possible to impart good solubility and dispersibility to various blending components. Examples of the solubilizer used in the present invention include propylene glycol, ethylene glycol, ethanol, dipropylene glycol, 2-methoxyethanol, 2-ethoxyethanol and the like. The content rate of the solubilizer in the liquid cleaning composition of this invention is 1-20 weight part with respect to 100 weight part of total amounts of a liquid cleaning composition, Preferably it is 3-10 weight part.

Amphoteric surfactant The liquid cleaning composition of the present invention may further contain an amphoteric surfactant. By including the amphoteric surfactant, the cleaning effect is further enhanced, and a better feeling of use can be imparted by the foaming of the liquid cleaning composition of the present invention during use. The amphoteric surfactant used in the present invention is not particularly limited, and is a betaine-type amphoteric surfactant (coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, lauric acid amidopropyl betaine, 2-alkyl -N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl hydroxysulfobetaine, etc.), amino acid type amphoteric surfactant (sodium β-laurylaminopropionate, sodium lauryldiaminoethylglycine, etc.), amine oxide type ( Decyldimethylamine oxide, lauryldimethylamine oxide, etc.). Preferred are betaine-type amphoteric surfactants and / or amine oxide-type amphoteric surfactants.

The mixing ratio of the amphoteric surfactant in the liquid cleaning composition of the present invention is preferably 1 to 20 parts by weight, more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the total amount of the liquid cleaning composition.
Perfumes Furthermore, the liquid cleaning compositions of the present invention may contain a perfume. By blending such a fragrance into the liquid cleaning composition, an arbitrary fragrance can be imparted. For example, when the liquid cleaning composition of the present invention is used in a toilet, a desired fragrance is provided in the toilet space. Can be granted. A fragrance | flavor may be either a natural fragrance | flavor and a synthetic | combination fragrance | flavor, What is necessary is just to select the fragrance | flavor component which exhibits a desired fragrance suitably according to the use of a liquid cleaning composition.

  For example, as the flavor used in the present invention, lemon oil, orange oil, bergamot oil, ylang ylang oil, patchouli oil, citronella oil, lemongrass oil, boad rose oil, clove oil, eucalyptus oil, cedar oil, lavender oil, Natural fragrances such as sandalwood oil, vetiver oil, geranium oil, labdanum oil, peppermint oil, rose oil, jasmine oil, litz accubeba oil, hydrocarbon-based fragrances (for example, limonene, α-pinene, camphene, p-cymene, phen Chen, etc.), ether-based fragrances (for example, 1,8-cineole, rose oxide, cedrol methyl ether (cedlum bar), p-cresyl methyl ether, isoamyl phenyl ethyl ether, 4-phenyl-2,4,6-trimethyl -1,3-dioxane, anethole, etc.), Tellurium fragrances (eg, ethyl acetate, ethyl propionate, methyl butyrate, ethyl isobutyrate, ethyl butyrate, butyl acetate, ethyl 2-methylbutyrate, isoamyl acetate, ethyl 2-methylpentanoate (manzanate) , Hexyl acetate, allyl hexanoate, tricyclodecenyl propionate (VERTOPRO; fluorocyclene), allyl heptanoate, isobornyl acetate, linalyl acetate, citronellyl acetate, 2-ter-butylcyclohexyl acetate (narcidol) Etc.), alcoholic fragrances (for example, linanol, 3-octanol, 2,6-dimethyl-heptanol, 10-undecenol, geraniol, nerol, citronellol, rosinol, mi Lucenol, tetrahydrolinalol, terpineol, cedrol, 2,4-dimethyl-3-cyclohexane-1-methanol, 4-isopropylcyclohexanol, nerolidol, 9-decenol, cis-3-hexenol, trans-2-hexenol, eugenol, etc. ), Aldehyde-based fragrances (for example, citronellal, para-aldehyde, benzaldehyde, aldehyde C-6, aldehyde C-7, aldehyde C-8, aldehyde C-9, aldehyde C-10, tripral, p-ethyldimethylhydrocinnamic aldehyde) Synthetic fragrances such as (florazone), 2-tridecenal, aldehyde C11, etc.) or blended fragrances blended with these.

  The blending ratio of the fragrance in the liquid cleaning composition of the present invention is preferably 0.001 to 30 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the liquid cleaning composition. In particular, in the case where the present invention is used as a cleaning agent of a type attached to an on-tank / rim for a flush toilet, it is 5 to 30 parts by weight from the viewpoint of giving a sufficient scent.

  In addition to the above components, the liquid cleaning composition of the present invention may further contain other nonionic surfactants, anionic surfactants, and cationic surfactants as needed, and if necessary, these are washed. It can also be used as an ingredient.

  Other nonionic surfactants are nonionic surfactants other than (A), (B) and (C), and include the following.

  Glycerin fatty acid esters (glyceryl monostearate, self-emulsifying glyceryl monostearate, glyceryl monoisostearate, etc.), polyoxyethylene glyceryl fatty acid esters (monostearic acid POE glyceryl, monooleic acid POE glyceryl), polyglycerin fatty acid esters (Diglyceryl monostearate, tetraglyceryl tristearate, decaglyceryl pentastearate, etc.), sorbitan fatty acid esters (such as sorbitan monolaurate, sorbitan sesquistearate, sorbitan monooleate), polyoxyethylene sorbitan fatty acid esters ( Mono palm fatty acid POE sorbitan, tristearic acid POE sorbitan, trioleic acid POE sorbitan, etc.), polyoxyethylene sorbit Fatty acid esters (monolauric acid POE sorbit, tetraoleic acid POE sorbit), polyethylene glycol fatty acid esters (polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, etc.), alkylene glycol mono Fatty acid esters (propylene glycol monolaurate, propylene glycol monomyristate, etc.), alkyl polyhydric alcohol ethers (glycerol monododecyl ether, glycerol monocetyl ether, glycerol monostearyl ether, pentaerythritol monododecyl ether, etc.), poly Oxyethylene alkyl ethers (lauryl ether, POE cetyl ester) Ter, POE stearyl ether, etc.), polyoxyethylene polyoxypropylene alkyl ethers (POE / POP cetyl ether, POE / POP decyl tetradecyl ether, etc.), polyoxyethylene alkyl phenyl ethers (POE nonylphenyl ether, POE octylphenyl) Ether, POE branched octylphenyl ether, etc.), polyoxyethylene alkylamines (POE stearylamine, POE oleylamine, etc.), fatty acid alkanolamides (coconut fatty acid diethanolamide, lauric acid diethanolamide, palm kernel oil fatty acid diethanolamide, etc.) , Acylmethylglucamides (such as methyl glucamide laurate, methyl fatty acid palm glucamide), other acetylene glycol, POE acetylene glycerin Examples thereof include coal, POE lanolin, POE lanolin alcohol, POE castor oil, POE hydrogenated castor oil, POE phytosterol, POE cholestanol, POE nonylphenylformaldehyde condensate, and alkylpolyglucoside.

  The following are mentioned as an anionic surfactant.

  Fatty acid salts (base for soap, sodium laurate, sodium palmitate, coconut soap, etc.); alkyl ether carboxylates (POE lauryl ether carboxylates, POP / POE ether myristates; higher alkyl sulfates, eg lauryl) Sodium sulfate, potassium lauryl sulfate, lauryl sulfate triethanolamine, etc.), alkyl ether sulfate esters (POE lauryl sulfate triethanolamine, POE sodium lauryl sulfate, etc.), N-acylamine salts (lauroyl sarcosine sodium, lauroyl-N-methyl) Β-alanine sodium, monosodium N-lauroylglutamate, disodium N-stearoylglutamate, monosodium N-myristoyl-L-glutamate, N-pa Mitoyl aspartate diethanolamine, etc.), higher fatty acid amide sulfonate (N-myristoyl-N-methyl taurine sodium, palm fatty acid methyl taurine sodium, lauroyl methyl taurine sodium, POE lauryl amide ether sodium sulfonate, etc.), phosphate ester salt (Sodium POE oleyl ether phosphate, POE stearyl ether phosphate, sodium POE lauryl amide ether phosphate, etc.), sulfosuccinate (sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, lauryl Polypropylene glycol sodium sulfosuccinate, etc.) Alkylbenzenesulfonate (sodium linear dodecylbenzenesulfonate) , Linear dodecyl benzene sulfonic acid triethanolamine, linear dodecyl benzene sulfonic acid, etc.), higher fatty acid ester sulfates (sulfated oils such as hydrogenated coconut oil fatty acid sodium glycerin sulfate, funnel oil, α-olefin sulfonates, higher fatty acids Ester sulfonates, secondary alcohol sulfates, etc.) and higher fatty acid alkylolamide sulfates (such as sodium lauroyl monoethanolamide succinate and sodium caseinate). Also, sulfate ester type or sulfonate type surfactants such as alkyl sulfate ester salts, polyoxyethylene alkyl sulfate ester salts, fatty acid amide ether sulfate ester salts, acyl isethionate salts, sulfosuccinate salts; and ether carboxylate salts, fatty acids Carboxylic acid type surfactants such as amide ether carboxylate, N-acyliminodiacetic acid, N-acylamino acid salt and the like can be mentioned.

Examples of the cationic surfactant include the following.
Quaternary ammonium salt surfactant (cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyltrimethylammonium chloride, cetylpyridinium chloride, alkyldimethylbenzylammonium chloride, benzethonium chloride, benzalkonium chloride, etc.), amidoamine salt type cationic Surfactant (diethylaminoethylamide glutamate stearate, lanolin fatty acid diethylaminoethylamide glutamate, etc.), amide guanidine laurate hydrochloride, etc. are mentioned.

  In addition to the above-mentioned components, the liquid cleaning composition of the present invention further includes an enzyme, a bactericidal agent, a chelating agent, a colorant, a pigment, a deodorant, an emulsifying and solubilizing agent for oily components, and an increased amount. Agents, solubility modifiers, bleaches, water repellents, hydrophilic agents, fillers, pH adjusters, thickeners, moldability improvers, lubricants, buffers, clouding agents, antifoaming agents, etc. An appropriate amount of agent can be included.

  Specific examples of the enzyme used in the present invention include protease, lipase, amylase, cellulase, xylanase, and mannase.

Specific examples of the bactericides used in the present invention include quaternary ammonium salts such as alkylbenzyldimethylammonium salts and didecyldimethylammonium salts, heterocyclic compounds such as cetylpyridinium salts and benzoisothiazolines, silver oxide, Examples include silver-containing water-soluble glass, silver compounds such as zeolite supporting silver, and other metal compounds.

  Specific examples of the chelating agent used in the present invention include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine hexa Examples include acetic acid and salts thereof.

  Specific examples of the colorant used in the present invention include blue No. 1, blue No. 2, blue No. 3, blue No. 205, yellow No. 3, yellow No. 4, yellow No. 202 (1), yellow 203. No., Red No. 105, Red No. 106, Red No. 2 and Red No. 3 and the like.

The pigment used in the present invention may be either an organic pigment or an inorganic pigment. Moreover, it does not ask | require the distinction of a white pigment or a colored pigment, What is necessary is just to select suitably according to the color tone provided to a liquid cleaning composition. Specific examples of inorganic pigments include titanium oxide, talc, calcium carbonate, zinc oxide, zinc sulfide, barium sulfate, calcium sulfate and its hydrate, iron oxide, cadmium sulfide, lead chromate, zinc chromate, carbon black, etc. Is exemplified. As organic pigments, red 201, red 202, red 203, red 204, red 205, red 206, red 207, red 208, red 220, red 221, orange 203, orange 204 No., yellow 205, red 404, red 405, yellow 401, blue 404, and the like.
(6) Use of the liquid cleaning composition of the present invention Various uses of the liquid cleaning composition of the present invention can be mentioned. By bringing the liquid cleaning composition into contact with each other, the liquid cleaning composition is derived from the contact portion. The present invention is not limited as long as the anti-smudge effect is exhibited and the cleaning effect is exhibited. For example, examples of the cleaning object of the liquid cleaning composition of the present invention include hard surfaces such as toilets, bathrooms, floors, windows, and walls.

  The liquid cleaning composition of the present invention may be used as it is with respect to the object to be cleaned, but even when used in a state diluted with water (about 1 to 1 million times), a sufficient cleaning effect can be obtained. It is desirable to apply to the object to be cleaned in a state appropriately diluted with water.

  The liquid cleaning composition of the present invention is used by being contained in a container having a discharge hole through which the liquid cleaning composition is discharged.

  As one suitable embodiment of the liquid cleaning composition of this invention, the cleaning agent for flush toilets is mentioned, for example. This flush toilet cleaner can be used as an on-tank liquid cleaning composition that is installed on the hand-washing part of the flush toilet, and is also used by being attached to the rim part of the toilet of the flush toilet It can be used as a liquid cleaning composition for the rim. In conventional on-tank cleaning agents and rim cleaning agents, the amount of liquid cleaning composition discharged from the container is low due to changes in viscosity due to temperature changes and changes in viscosity due to contamination of cleaning water or flushing water. The liquid cleaning composition of the present invention solves the problems of the prior art, although there is a drawback that it tends to be uniform.

  According to the liquid cleaning composition of the present invention, since the non-uniformity of the discharge amount due to temperature change or the like is highly eliminated, when used as a cleaning agent for an on-tank of a flush toilet or a cleaning agent for a rim portion Even so, the temperature of the water flowing together is not limited as long as it is in a normal range, and cold water or hot water can also be used.

For example, when the liquid cleaning composition of the present invention is used as a cleaning agent for a flush toilet on-tank, the liquid cleaning composition of the present invention is enclosed in a container having a desired structure, which is the upper part of the water storage tank in the flush toilet. Located in the hand-washing section. The liquid cleaning composition discharged from the container together with the water supplied to the hand-washing section is caused to flow into the water storage tank and further into the toilet bowl, thereby to the surface of the water storage tank and the toilet bowl with the liquid cleaning composition. The effect of preventing the adhesion of dirt and the cleaning effect are exhibited. The container can be any container according to the place of use, and is not limited. However, when the liquid cleaning composition of the present invention is used as a cleaning agent for a flush toilet tank, a discharge hole as described below is used. The container which has is illustrated.
(7) Container having discharge hole The liquid cleaning composition of the present invention is used in a container having an arbitrary discharge hole. For example, when the liquid cleaning composition of the present invention is used for a flush toilet tank, the liquid cleaning composition can be stored in a container as shown in FIG. FIG. 1 is a front view (a) and a side view (b) of the container. FIG. 2 is an exploded view of the container of FIG. As shown in FIGS. 1 and 2, this container is disposed on a liquid wash composition 1 containing a liquid cleaning composition and having a mouth formed at the lower end thereof, and on the hand-washing portion of a flush toilet that supports the chemical liquid containment 1. A support member 2, an adjustment member 3 attached to the support member 2 and connected to the chemical solution storage unit 1, and a guide member 4 for guiding the liquid cleaning composition from the bottom of the support member 2. A discharge hole 5 is provided at the bottom of the adjustment member 3.

  The said container is arrange | positioned with the guide member 4 below in the hand-washing part of the upper part of the water storage tank in a flush toilet. Then, the liquid cleaning composition guided to the guide member 4 from the discharge hole 5 and the cleaning water supplied to the hand washing section come into contact with each other, so that the liquid cleaning composition is efficiently supplied into the water storage tank. It is configured as follows. At this time, the container may be further provided with a storage part for storing the liquid cleaning composition discharged from the discharge hole 5, and the liquid cleaning composition stored in the storage part and the hand washing part It may be configured such that the liquid cleaning composition is efficiently supplied into the water storage tank by contact with the supplied cleaning water.

  Examples of the container having such a discharge hole include, but are not limited to, containers disclosed in JP-A-2004-300861, JP-A-2006-283539, JP-A-2006-283540, and the like. . Moreover, the chemical | medical solution container arrange | positioned on the said support body may consist of a single chemical | medical solution storage part, and may consist of two or more chemical | medical solution storage parts.

  In addition, when using the liquid cleaning composition of this invention for the rim | limb part of a flush toilet, this liquid cleaning composition can be accommodated in a container as described in Japanese translations of PCT publication No. 2003-517124 etc.

  Hereinafter, the present invention will be described with reference to examples in the case where the liquid cleaning composition of the present invention is used for a flush toilet tank, but the present invention is not limited to these examples.

1. Manufacture of liquid cleaning composition for flush toilet on-tank As the liquid cleaning composition for flush toilet on-tank of the present invention, the following Table 1 (Examples 1 to 10), Table 2 (Examples 11 to 20), Table 3 ( The liquid cleaning composition of this invention whose viscosity in 25 degreeC is about 130-300 was prepared by mixing the mixing | blending component shown in Examples 21-30) in each ratio. Each obtained liquid cleaning composition was each accommodated in the chemical | medical solution supply tool (container) described in FIG. 1 of Unexamined-Japanese-Patent No. 2006-283540. The container is provided with two chemical liquid container sections (chemical liquid storage sections), and a liquid cleaning liquid is stored in one of them. In the chemical solution supply device, the size of one side of the chemical solution container containing the liquid cleaning composition is about 40 ml, and the discharge hole for discharging the liquid cleaning composition is a sector shape having a radius of 0.3 mm and a central angle of 45 degrees. Yes, 35 ml of the liquid cleaning composition was contained in the chemical solution container. In addition, as a comparative example, the liquid cleaning composition was separately prepared by mixing the mixing | blending component shown in following Table 4 in each ratio (comparative examples 1-7). Similarly to the liquid cleaning compositions of Examples 1 to 30, the liquid cleaning compositions of Comparative Examples 1 to 7 were also accommodated in the above-described containers.

2. Performance Evaluation of Liquid Cleaning Composition for Flush Toilet On Tank The following evaluation test was performed using the liquid cleaning composition for flush toilet on tank obtained above (Examples 1 to 30 and Comparative Examples 1 to 7). It was.

[Evaluation test of frequency and viscosity change]
The obtained liquid cleaning composition for a flush toilet on-tank was placed on the hand-washing part of TOTO S721B manufactured by Totoki Equipment Co., Ltd. And the lever of the water storage tank of the domestic flush toilet was operated (flushed) every 90 minutes, and the number of flushes until the liquid cleaning composition in the chemical solution supply tool was exhausted was measured. The flow rate of inflow water supplied from the hand-washing part of the flush tank per flush is 50 mL / second, and the full water time (the time from flushing the water until the tank is full and the running water stops) is set to 60 seconds. However, the amount of flowing water is 3L. Here, the inflow water temperature of 25 ° C. (room temperature: 25 ° C.) assumes the summer use conditions, and the inflow water temperature of 5 ° C. (room temperature: 15 ° C.) assumes the winter use conditions. Measure the viscosity of the liquid cleaning composition at water temperatures of 25 ° C. and 5 ° C., respectively, and also measure the viscosity when 10 to 30 parts by weight of water is mixed with 100 parts by weight of the total amount of the liquid cleaning composition at 5 ° C. did.

3. Evaluation results The obtained results are shown in the following Tables 1 to 3 (Examples 1 to 30) and Table 4 (Comparative Examples 1 to 7). The number of holdings was evaluated according to the criteria shown in Table 5 below.

  In the table, “5 ° C. (100%) viscosity” means the viscosity at 5 ° C. of the liquid cleaning composition in which water corresponding to 0 part by weight is further added to the total amount of the liquid cleaning composition 100 of the present invention. Means.

  In the table, “5 ° C. (90%) viscosity” means the viscosity at 5 ° C. of the liquid cleaning composition in which water corresponding to 10 parts by weight is further added to the total amount of the liquid cleaning composition 100 of the present invention. Means.

  In the table, “5 ° C. (80%) viscosity” means the viscosity at 5 ° C. of the liquid cleaning composition in which water corresponding to 20 parts by weight is further added to the total amount of the liquid cleaning composition 100 of the present invention. Means.

  In the table, “5 ° C. (70%) viscosity” means the viscosity at 5 ° C. of the liquid cleaning composition in which water corresponding to 30 parts by weight is further added to the total amount of the liquid cleaning composition 100 of the present invention. Means.

  From the results of Tables 1 to 4, when all of the (A) component, (B) component, (C) component, and (D) component are not included (Comparative Examples 1 to 6), a suitable number of times is exhibited. It was shown that it is not possible. Further, even when all of the above components (A) to (D) are included, for example, when the total amount of the components (A) and (B) is not within the scope of the present invention ( For example, it has been shown that Comparative Example 7) cannot exhibit a good number of times. On the other hand, when all of the components (A) to (D) are included and the blending amounts of the components (A), (B), and (C) are within the range of the present invention, a good holding frequency is obtained. It was shown that it was exhibited (Examples 1-30). In addition, when all the components (A) to (D) are included and the blending amounts of the components (A), (B), and (C) are within the scope of the present invention, the total amount of the liquid cleaning composition It was also shown that even when water corresponding to 10 to 30 parts by weight was added to 100, the viscosity became too high to cause gelation.

  From the above, it was shown that the liquid cleaning composition for flush toilet on-tank of the present invention can realize a stable reduction of the chemical solution that is hardly affected by temperature change and contact with water.

The example of the container in which the liquid cleaning composition of this invention can be accommodated is shown. The example of the exploded view of the container in which the liquid cleaning composition of this invention can be accommodated is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Chemical solution accommodating part 2 Support body 3 Adjustment member 4 Guide member 5 Ejection hole

Claims (6)

(A) a nonionic surfactant having fluidity at 20 ° C.,
(B) a nonionic surfactant having no fluidity at 20 ° C.,
(C) A liquid cleaning composition containing a polyoxyethylene polyoxypropylene block polymer and (D) water and containing the components (A) to (C) in the following proportions;
(A) The sum total of a component and (B) component is 7-43 weight part with respect to 100 weight part of liquid cleaning compositions,
The component (A) is 66-3500 parts by weight with respect to 100 parts by weight of the component (B), and the component (C) is 0.5-22 parts by weight with respect to 100 parts by weight of the total amount of the liquid cleaning composition. is there. The component (A) is a nonionic surfactant represented by the following general formula (1), and has fluidity at 20 ° C.
The liquid cleaning composition according to claim 1, wherein the component (B) is a nonionic surfactant represented by the following general formula (1) and has no fluidity at 20 ° C .;
RO- (AO) k-H (1)
(In the formula, R represents an aliphatic hydrocarbon group having a content of 8 to 16 carbon atoms of 80% by weight or more, and-(AO) k- represents a single or mixed polymer chain of an alkylene oxide having 2 to 4 carbon atoms. Wherein k represents the average number of moles of alkylene oxide added, and k is an integer in the range of 1-100.) The liquid cleaning composition according to claim 1 or 2, wherein the component (C) is represented by the following general formula (2):
H- (EO) m- (PO) n- (EO) 1-OH (2)
(In the formula,-(EO) m- and-(EO) l- represent a homopolymer chain of ethylene oxide, and-(PO) n- represents a homopolymer chain of propylene oxide. M, n, l Represents the average number of added moles of alkylene oxide, n is an integer of 1 to 100, m + 1 is an integer of 1 to 197, and the content of ethylene oxide is 60% by weight or less. Furthermore, the liquid cleaning composition in any one of Claims 1-3 containing at least 1 selected from the group which consists of a solubilizer and an amphoteric surfactant.   The liquid cleaning composition according to any one of claims 1 to 4, which is used for an on-tank of a flush toilet.   The liquid cleaning composition according to any one of claims 1 to 4, which is used for a rim portion of a flush toilet.

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