JP5037247B2 - Solid cleaning agent for toilet - Google Patents

Description

  The present invention relates to a solid cleaning agent for flush toilets, and further relates to a cleaning agent that is installed on a lid of a low tank type flush toilet and dissolves in the wash water to enhance the cleaning effect of the toilet bowl.

  The solid cleaning agent for flush toilets is a so-called in-tank type that sinks and soaks in the wash water in the wash tank, and gradually dissolves by the inflowing water installed on the tank lid. There are two types of so-called on-tank types. Both types are designed to exhibit a toilet bowl cleaning, antifouling effect, and aroma imparting effect continuously for an appropriate period of time by an active ingredient such as a surfactant or a fragrance that gradually dissolves.

  Conventionally, many proposals have been made for the formulation design for such purpose. The basic performance is that the active ingredient gradually dissolves in water to exert its cleaning effect and antifouling effect. Select and combine functional substances such as surfactants, excipients, slow solubilizers, and perfumes. Many are seen. For example, an automatic fragrance cleaning agent for flush toilets using a propylene oxide-ethylene oxide copolymer as a binding retention agent and urea or an inorganic alkali metal salt as a dissolution rate regulator (Patent Document 1), a polyoxyethylene compound and an organic isocyanate compound Automatic fragrance cleaning composition for flush toilets using a water-soluble solid urethane compound obtained by reacting water (Patent Document 2), a specific substitution of a terminal hydroxyl group of a polymer of ethylene glycol or propylene glycol or a copolymer thereof Solid detergent for flush toilets (Patent Document 3) containing a compound protected by a group as a main component (Patent Document 3), water-stored flush toilet composition containing polyoxyethylene fatty acid ester (Patent Document 4), polyoxyethylene distea Reservoir flush toilet containing water and oxidized wax Of non-ionic surfactants such as a detergent composition (Patent Document 5) and a solid detergent for flush toilets (Patent Document 6) using an ester of a water-soluble polyvalent hydroxy compound and a polycarboxylic acid Has been. In addition, as a method for increasing the sustainability of active ingredients in the application of water-soluble polymers, the fragrance for flush toilets using polyalkylene glycol, higher alcohol and higher alcohol ethylene oxide adduct, benzaldehyde and sorbitol condensate, or polyethylene oxide. Cleaning composition (Patent Document 7), automatic fragrance cleaning agent for flush toilets using a copolymer of a hydrophilic monomer, a poorly soluble or insoluble monomer in water and, if necessary, another monomer For example, a slow solubilizing agent (Patent Document 8) is disclosed. The purpose of formulating with these nonionic surfactants and water-soluble polymers is to improve the shape retention and the sustainability of active ingredients such as fragrances, and have the disadvantages of weak detergency. Yes.

  In order to remedy such drawbacks, many attempts have been made to achieve continuous imparting of high detergency and antifouling properties using an anionic surfactant having excellent detergency. For example, fatty acid alkali metal salt, nonionic surfactant, on-tank solid detergent for toilet using carboxymethylcellulose alkali metal salt (Patent Document 9), N-acyl taurine salt or N-acyl amino acid salt and nonionic surfactant Flush toilet on-tank solid detergent (Patent Document 10), alkyl sulfate ester salt, flush toilet on-tank solid detergent (Patent Document 11), α-sulfo fatty acid ester salt Solid detergent for flush toilet on tank using nonionic surfactant (Patent Document 12), α-olefin sulfonate, Use of solid detergent for flush toilet on tank using nonionic surfactant (patent) Document 13) is disclosed. Furthermore, a solid cleaning agent for toilets containing an anionic surfactant and a nonionic surfactant as a surfactant, and containing a high molecular weight polyethylene oxide to suppress partial collapse of the cleaning agent (Patent Document 14) Etc. are disclosed. However, in all of these, the solubility of the anionic surfactant alone is greatly affected by the water temperature, the shape retention is poor at a high temperature and the solubility is too high, and the solubility is lowered at a low temperature. There is a disadvantage that dissolution cannot be obtained. In order to solve these problems, a combination with a high-melting point nonionic surfactant or a water-soluble polymer has been proposed, but it is still insufficient.

JP-A-51-039705 JP-A-55-1331098 JP-A-58-025398 JP 59-024797 JP 60-127400 A JP 2001-234190 A JP-A-53-058507 JP-A 63-317597 Japanese Patent Laid-Open No. 11-092796 JP 2000-273383 A JP 2000-273484 A JP 2000-273486 A JP 2000-273487 A Japanese Patent Laying-Open No. 2005-023176

  The object of the present invention is to use a solid detergent for flush toilets that uses an anionic surfactant as a main agent, and is substantially less soluble in water temperature and has almost constant solubility at both low and high temperatures. Provides a solid cleaning agent for toilets that has uniform solubility and excellent durability throughout the period, and can control the solubility even when a high concentration of anionic surfactant is blended, and has a high cleaning effect It is to be.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a solid detergent for toilets that contains a specific anionic surfactant and fatty acid sodium does not depend on the water temperature during flushing, However, it has been found that it exhibits substantially constant solubility even at high temperatures, has uniform solubility and excellent durability throughout the period of use, and has an excellent cleaning effect, and has thus completed the present invention.

That is, the present invention has the following general formula:
_R1COO-R2-SO 3 M
(Wherein R1 is an alkyl group having 7 to 21 carbon atoms, R2 is an alkylene group having 2 to 3 carbon atoms , and M is an alkali metal)
The solid detergent for toilets which contains the anionic surfactant represented by these, and the C12-C18 fatty acid sodium by the weight ratio of 8: 2 to 3: 7 is provided.

  The present invention also provides the above-mentioned toilet solid cleaning agent, wherein the total content of the anionic surfactant and the fatty acid sodium is 45 to 95% by weight.

  Moreover, this invention provides the said solid cleaning agent for toilets whose anionic surfactant is coconut oil fatty-acid ethyl ester sodium sulfonate.

  The present invention further provides the solid toilet cleaner, wherein the fatty acid sodium is sodium oleate.

  The solid detergent for toilets of the present invention uses a palm oil fatty acid alkyl ester sulfonate alkali metal salt and fatty acid sodium as a main surfactant in a specific ratio, so that the solubility is hardly affected by the water temperature during flushing, and the period of use Through the process, uniform solubility, excellent durability, and high cleaning power can be obtained.

The toilet solid cleaning agent of the present invention has the following formula:
_R1COO-R2-SO 3 M
(Wherein R1 is an alkyl group having 7 to 21 carbon atoms, R2 is an alkylene group having 2 to 3 carbon atoms , and M is an alkali metal)
And a fatty acid sodium having 12 to 18 carbon atoms in a weight ratio of 8: 2 to 3: 7.

  As the alkali metal salt of the anionic surfactant represented by the above general formula, a sodium salt is suitable. Specific examples of the anionic surfactant represented by the general formula include coconut oil fatty acid ethyl ester sodium sulfonate, which is a sodium salt of a condensate of coconut oil fatty acid and isethionic acid. Moreover, sodium oleate is suitable as the fatty acid sodium.

The weight ratio of the anionic surfactant represented by the general formula of the present invention to sodium fatty acid is preferably 8: 2 to 3: 7, more preferably 7: 3 to 5: 5, and from this range If the amount of the anionic surfactant increases, the solubility at low water temperatures deteriorates, and the concentration of the surfactant dissolved in the flushed water is low because the solid detergent for toilets cracks during use. Insufficient detergency.
Moreover, when the ratio of sodium fatty acid increases, the solubility when the water temperature is high becomes high and the sustainability is lacking.

  The total amount of the anionic surfactant and the fatty acid sodium is preferably 45% to 95% by weight, more preferably 60% to 80% by weight, based on the total weight of the solid detergent for toilets. Yes, if the total amount of anionic surfactant and fatty acid sodium is less than this range, the resulting solid detergent may not be able to exert its cleaning effect sufficiently, or the blending ratio of excipients such as inorganic salts It tends to become more difficult to solidify.

  In a toilet solid detergent containing a conventional anionic surfactant, the solubility of the anionic surfactant is essentially dependent on the temperature, that is, the temperature at which the solubility rapidly increases as the temperature increases ( There is a problem that the solubility changes greatly at the boundary of this temperature. This means that, for example, if the temperature of the flashing water is different between summer and winter, the solubility is greatly changed accordingly. In order to solve such a problem, a combination with a high-melting point nonionic surfactant or a water-soluble polymer was necessary. According to the combination of the anionic surfactant of the present invention and fatty acid sodium in a specific ratio, no special high melting point nonionic surfactant or water-soluble polymer is required, and it is substantially independent of the water temperature. A solid toilet cleaning agent having almost constant solubility is obtained.

  It can be used in combination with other anionic surfactants and nonionic surfactants as long as the effects of the present invention are not impaired. The anionic surfactant is not particularly limited. For example, alkyl sulfate ester, polyoxyethylene alkyl ether sulfate ester, alkylbenzene sulfonic acid, α-olefin sulfonic acid, alkane sulfonic acid, α-sulfo fatty acid methyl ester, higher alcohol sulfone. Examples include, but are not limited to, fatty acid esters and alkali metal salts of acylated amino acids.

  Specific examples of the nonionic surfactant include, for example, ethylene oxide adducts of higher alcohols, ethylene oxide adducts of fatty acids, fatty acid esters of polyhydric alcohols and ethylene oxide adducts thereof, sorbitan fatty acid esters and ethylene oxides thereof. Examples include adducts, ethylene oxide adducts of hydrogenated castor oil, polyglycerin fatty acid esters, fatty acid alkanolamides and ethylene oxide adducts thereof, polyoxyethylene polyoxypropylene block copolymers, and the like. Absent.

  In addition, fatty acids, higher alcohols, and the like are used as components for adjusting the hardness and mass of a solid cleaning agent for toilets, solid physical properties such as fluidity during extrusion, manufacturing suitability, and the like. The alkyl chain length of the fatty acid or higher alcohol is preferably 12-18.

  In addition to anionic surfactants, nonionic surfactants, fatty acids, and higher alcohols, components that are commonly used in toilet solid cleaning agents should be used as components used in the toilet cleaning agents of the present invention. Can do. For example, polyethylene oxide, metal salts of carboxymethylcellulose, water-soluble polymers such as dextrin and starch, chelating agents, glycol solvents, sodium sulfate used as extenders, inorganic salts such as sodium chloride, pigments, bactericides, and fragrances A deodorant and the like are used as appropriate. In particular, the fragrance can be specifically exemplified as follows, but is not particularly limited, and a wide range of natural and synthetic fragrances can be used. Specifically, the hydrocarbons include, for example, osymene, α-pinene, β-pinene, camphene, myrcene, dihydromyrcene, limonene, terpinolene, α-ferrandrene, p-cymene, β-caryophyllene, β- Examples include farnesene, bisabolen, cedrene, valencene, tyuopsen, and longifolene.

  Examples of alcohols include linalool, geraniol, nerol, citronellol, myrcenol, lavandulol, mugor, tetrahydrolinalol, hydroxycitronellol, dihydromyrcenol, tetrahydromyrcenol, 3,6-dimethyl-3-octanol, ethyl Linalool, terpineol, dihydroterpineol, l-menthol, carveol, perilla alcohol, 4-tuanol, myrtenol, α-fenalkyl alcohol, farnesol, nerolidol, cedrenol, cis-3-hexenol, 1-undecanol, 2-undecanol, 1-dodecanol, prenol, 10-undecenol, 2,4-dimethyl-3-cyclohexene-1-methanol, pt-butylcyclohexanol Sander roll (Givaudan trade name), Bakudanoru (IFF trade name), may be mentioned phenyl ethyl alcohol, hydro Toro Pas alcohol, anise alcohol, 3-phenylpropyl alcohol, cinnamic alcohol, and amyl cinnamic alcohol.

  Examples of aldehydes include citral, geranial, neral, citronellal, hydroxycitronellal, α-methylenecitronellal, mirutenal, citronellyloxyacetaldehyde, 3,7-dimethyloctanal, acetaldehyde, n-hexanal, n- Heptanal, n-octanal, n-nonanal, 2-methyloctanal, n-decanal, undecanal, 2-methyldecanal, dodecanal, tetradecanal, cis-3-hexenal, trans-2-hexenal, 2,6 -Dimethyl-5-heptenal, cis-4-decenal, trans-2-decenal, 10-undecenal, trans-2-undecenal, trans-2-dodecenal, 3-dodecenal, 2,4-hexadien 2,4-decadienal, 2,4-dodecadienal, cyclocitral, dimethyltetrahydrobenzaldehyde, citral dimethyl acetal, citral diethyl acetal, citral propylene glycol acetal, citronellal cyclomonoglycol acetal, acetaldehyde ethyl linalyl acetal, hydroxycitro Neral dimethyl acetal, octanal dimethyl acetal, nonanal diethyl acetal, decanal dimethyl acetal, decanal diethyl acetal, 2-methylundecanal dimethyl acetal, benzaldehyde, p-isopropylphenylacetaldehyde, p-isopropyl hydratropal aldehyde, cyclamen Aldehyde, phenylpropyl aldehyde, Namic aldehyde, anisaldehyde, p-methylphenoxyacetaldehyde, benzaldehyde diethyl acetal, amylcinnamic aldehyde diethyl acetal, heliotropin dimethyl acetal, acetaldehyde ethylphenylethyl acetal, acetaldehyde 2-phenyl-2,4-pentanediol acetal, phenylacetaldehyde Examples thereof include dimethyl acetal.

  Examples of the ketones include camphor, menthone, piperithenone, geranylacetone, acetyl cedrene, nootkatone, yonon, methyl ionone, allyl ionone, iron, damascon, damasenone, isodamascon, 2-pentanone, 3-hexanone, 2-heptanone, 3- Heptanone, 4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 2-undecanone, 2-tridecanone, methylheptenone, dimethyloctenone, methylenetetramethylheptanone, 2,3-hexadione, 2- Cyclopentylcyclopentanone, ethyl maltol, 2,5-dimethyl-4-hydroxyfuranone, p-methylacetophenone, p-methoxyacetophenone, benzylideneacetone, raspberry ketone, methylnaphthy Ketone, benzophenone, 2,5-dimethyl-4-hydroxy-3 (2H) -furanone, 3-hydroxy-4,5-dimethyl-2 (5H) -furanone, homofuronal (trade name of Givaudan), maltol, ethyl maltol 4,7-dihydro-2-isopentyl-2-methyl-1,3-dioxepin, ethyl acetoacetate ethylene glycol ketal, and the like.

  Examples of the esters include ethyl formate, propyl formate, octyl formate, linalyl formate, citronellyl formate, geranyl formate, neryl formate, terpinyl formate, ethyl acetate, isopropyl acetate, cis-3-hexenyl acetate, trans-2-hexenyl acetate , Octyl acetate, Nonyl acetate, Decyl acetate, Dodecyl acetate, Dimethylundecadienyl acetate, Osimenyl acetate, Milcenyl acetate, Dihydromyrcenyl acetate, Linalyl acetate, Citronellyl acetate, Geranyl acetate, Neryl acetate, Tetrahydromugol acetate, Labanjuryl acetate , Nerolidol acetate, dihydrocuminyl acetate, terpinyl acetate, citryl acetate, nopyr acetate, dihydroterpinyl acetate, 3-pentenyltetrahydropyranyl acetate, miraldyl acetate, 2,4-dimethyl-3-cycloacetate Xenyl methyl, decenyl propionate, linalyl propionate, geranyl propionate, neryl propionate, terpinyl propionate, tricyclodecenyl propionate, styryl propionate, octyl butyrate, neryl butyrate, cinnamyl butyrate, ethyl isobutyrate, isopropyl isobutyrate Cis-3-hexenyl isobutyrate, phenylethyl isovalerate, methyl 3-hydroxyhexanoate, methyl benzoate, geranyl benzoate, linalyl benzoate, methyl cinnamate, ethyl cinnamate, linalyl cinnamate, methyl phenylacetate, Ethyl phenylacetate, eugenyl phenylacetate, geranyl phenylacetate, citronellyl phenylacetate, menthyl phenylacetate, amyl salicylate, linalyl hexanoate, citronellyl hexanoate, linalyl octanoate, Gerika acid isoprenyl, methyl geranic acid, ethyl geranic acid, methyl Shikurogeran acid, ethyl acetoacetate, 2-hexyl ethyl acetoacetate, benzyl ethyl acetoacetate, 2-ethyl allyl butyrate, 3-hydroxybutyrate, and the like.

  Examples of the phenols include thymol, carvacrol, β-naphthol isobutyl ether, anethole, β-naphthol methyl ether, β-naphthol ethyl ether, guaiacol, cresol, veratrol, hydroquinone dimethyl ether, 2,6-dimethoxyphenol, 4- Examples thereof include ethyl guaiacol, eugenol, isoeugenol, ethylisoeugenol, and tert-butylhydroquinone dimethyl ether.

Examples of the ethers include decyl vinyl ether, α-terpinyl methyl ether, isoproxen (trade name of IFF), 2,2-dimethyl-5- (1-methyl-1-propenyl) -tetrahydrofuran, rose furan, 1,4-cineole, nerol oxide, 2,2,6-trimethyl-6-vinyltetrahydropyran, methyl hexyl ether, oxime epoxide, limonene oxide, rubofix (trade name of Firmenich), caryophyllene oxide, linalool oxide, 5- Examples include isopropenyl-2-methyl-2-vinyltetrahydrofuran, theaspirane, and rose oxide.

  Examples of lactones include γ-undecalactone, δ-dodecalactone, γ-hexalactone, γ-nonalactone, γ-decalactone, γ-dodecalactone, jasmine lactone, methyl γ-decalactone, jasmolactone, propylene. Examples thereof include denphthalide, δ-hexalactone, δ-2-decenolactone, ε-dodecalactone, dihydrocoumarin, and coumarin.

  Examples of the acids include benzoic acid, phenylacetic acid, phenylpropionic acid, cinnamic acid, phthalic acid, abietic acid, vanillic acid, pyrogallol and the like.

  Synthetic musks include, for example, muscone, cyclopentadecanone, 5-cyclohexadecene-1-one, cyclopentadecanolide, ambletlide, cyclohexadecanolide, musk umbret, 6-acetylhexamethylindane, Examples thereof include 6-acetylhexatetralin and galaxolide (product name of IFF).

  Natural flavors include, for example, Avies, Ambret Seed, Angelica, Anise, Almoase, Basil, Bay, Bergamot, Birch, Boa de Rose, Calams, Camphor, Cananga, Caraway, Cardamom, Cassia, Cedarwood , Camomil, Citronella, Costas, Cumin, Dill, Elemi, Eucalyptus, Galvanum, Geranium, Ginger, Grapefruit, Guaiac, Gardenia, Cypress, Hawsho, Hyacinth, Jasmine, Junipa Berry, Labdanum, Lavandin, Lavender, Lemon, Lemongrass, Lime, Linaroe, Mimosa, Mint, Oak Moss, Orange Flower, Iris, Patchouli, Palmarosa, Peppermint, Rose, Clary Sage, Sandals, Tuberose, Vetiver Violets, such as essential oils, such as Iran, Iran can be mentioned.

  In addition, it is described in Perfume Chemical Directory, 1, 2, 3 [Osamu Okuda Publishing, Yodogawa Shoten Publishing], Perfume and flavor Chemicals, 1, 2 [By Steffen Arctander], Synthetic Perfume [Motoichi Motoichi Kagaku Kogyo Nikkan Publishing]. Perfume compounds.

  The solid detergent for toilets of the present invention can be easily produced by extrusion molding, press molding, tableting, or the like. For example, the blended ingredients in a powder state are blended with a powder blender such as a V blender, and then the liquid ingredients are added and kneaded sufficiently with a kneader or roll, then extruded with an extruder or pressed with a mold. Can be molded.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Examples 1-4 and Comparative Examples 1-3
A solid cleaning agent was prepared using the formulation shown in Table 1 as a constituent used in Examples and Comparative Examples, and the solubility of the solid cleaning agent for toilets was tested. However, the compounding amount in Table 1 means% by weight.
[Preparation of toilet cleaner]
As an anionic surfactant of the present invention, coconut oil fatty acid ethyl ester sodium sulfonate (manufactured by Clariant Japan Co., Ltd .; Hostapon SCI85G) and as another general anionic surfactant, sodium lauryl sulfate (manufactured by Kao Corporation) Emul 10 powder) was used. Moreover, it prepared using PEO (PEO; Sumitomo Seika Co., Ltd. product) as high molecular weight polyethylene oxide. About other components, what was easily obtained as a general industrial product was used. Specifically, each component shown in Table 1 is mixed well, kneaded with a roll, about 5 g of the mixture is put into a tableting die having an inner diameter of about 30 mm, a punch is inserted, and press molding is performed at about 100 Kgf. A solid toilet cleaner was prepared.

[Evaluation of temperature dependence of solubility]
Take 1 liter of water in a 1 liter beaker, and set a stainless steel sieve having a diameter of 10 cm and 60 mesh on the top of the beaker so that the wire mesh portion is submerged. The toilet was washed with a solid detergent, and the whole water was gently stirred with a magnetic stirrer, and the time until the detergent was completely dissolved was measured. The temperature of water was measured under two conditions of 10 ° C. and 30 ° C., and the temperature dependence of the product made by dissolution was evaluated according to the following criteria.
○: Dissolution time of 10 ° C. ÷ dissolution time of 30 ° C. is less than 2.
X: Dissolution time of 10 ° C. ÷ dissolution time of 30 ° C. is 2 or more.

[Practical test]
For Examples 2 and 3 and Comparative Examples 1 and 3, each compounding component was kneaded with a roller, extruded, and cut into a cylindrical shape having a diameter of 20 mm and a weight of about 25 g to prepare a sample. These samples were placed in a container for on-tank cleaning agent ("Bluelet Okada" shell container manufactured by Kobayashi Pharmaceutical Co., Ltd.) and placed in the hand-washing part of a low tank in a household toilet for practical testing. A counter that can measure the number of lever operations was installed in the low tank of the household toilet, and the amount of water supplied to the hand-washing section was set at 4.5 liters per time. The water temperature was not particularly controlled, and the water temperature was measured and recorded periodically. The water temperature ranged from 20 ° C to 25 ° C during the experiment. The number of flushes until the solid detergent for the toilet was completely melted was evaluated according to the following criteria.

×: 500 times or more ○: 200 to 500 times XX: 200 times or less

SCI: Sodium palm oil fatty acid ethyl ester sulfonate AS: Sodium lauryl sulfate PEO: Polyethylene oxide (average molecular weight: 4.5 million)
EDTA-2Na: Ethylenediaminetetraacetic acid disodium fragrance: Lemon (Hasegawa fragrance)
Dye: Blue No. 1 [Evaluation result]
Table 1 shows the evaluation results. Coconut oil fatty acid ethyl ester Sodium sulfonate and sodium oleate have a significant effect on the temperature dependence of the solubility of the solid detergent for toilets. As shown in Examples 1 to 4, palm oil fatty acid ethyl ester When the blending ratio of sodium ester sulfonate and sodium oleate was in the range of 8: 2 to 3: 7, the results showed low temperature dependence. As shown in Comparative Examples 1 and 2, when the proportion of sodium coconut oil fatty acid ethyl ester sulfonate is larger than this range, the solubility at low temperatures is lowered, resulting in high temperature dependence. On the other hand, as shown in Comparative Example 3, when the proportion of sodium oleate is larger than this range, the solubility increases at both low and high temperatures and the temperature dependence decreases, but the sustainability is remarkable in practical tests. It will be lower.

  From the above results, in the solid cleaning agent for toilets, the use of coconut oil fatty acid ethyl ester sodium sulfonate and sodium oleate in a specific ratio as the main active agent substantially changes the solubility with respect to the change in temperature. It has been found that it is possible to impart a small amount of uniform solubility and excellent properties.

Claims (4)

The following general formula
_R1COO-R2-SO 3 M
(Wherein R1 is an alkyl group having 7 to 21 carbon atoms, R2 is an alkylene group having 2 to 3 carbon atoms , and M is an alkali metal)
The solid detergent for toilets which contains the anionic surfactant represented by these, and a C12-C18 fatty acid sodium by the weight ratio of 8: 2 to 3: 7.   The solid cleaning agent for toilets according to claim 1, wherein the total content of the anionic surfactant and the fatty acid sodium is 45 to 95% by weight.   The solid detergent for toilets according to claim 1 or 2, wherein the anionic surfactant is sodium coconut oil fatty acid ethyl ester sulfonate.   Fatty acid sodium is sodium oleate, The solid cleaning agent for toilets of any one of Claims 1-3.