WO1996031592A1

WO1996031592A1 - Sustained-solubilization agent, solid toilet deodorizer, solid toilet cleanser, and methods for producing the same

Info

Publication number: WO1996031592A1
Application number: PCT/JP1996/000484
Authority: WO
Inventors: Masao Fukuda; Sakae Nishide
Original assignee: Sanyo Chemical Industries, Ltd.; Environmental Revival Co., Ltd.
Priority date: 1995-04-05
Filing date: 1996-03-01
Publication date: 1996-10-10
Also published as: KR100263871B1; TW325408B; KR19980703272A

Abstract

Solid toilet deodorizer and cleanser which neither swell nor get muddy even in contact with water, can be easily maintained and, further, are excellent in the persistence of the deodorizing effect. A sustained-solubilization agent (A) is produced from an oxyethylene-containing aromatic compound (C) having a melting point of 50 °C or above, optionally together with a water-soluble aliphatic compound (D). The deodorizer is one produced from the above agent (A) and a microbial material (B), and the cleanser is one produced from the above agent (A), a surfactant and a bleaching agent.

Description

Specification damage Slow solubilizer, solid deodorant for toilet, solid detergent for toilet, and manufacturing method

The present invention relates to a solubilizing agent, a solid deodorizing agent for toilet, a solid detergent for toilet, and a method for producing the same. More specifically, the present invention relates to a solubilizing agent having good shape retention and long-lasting deodorizing effect. The present invention relates to an excellent solid deodorizer for toilets, a solid detergent for flush toilets, and an effective production method thereof. Background art

Solid deodorizers for toilets are widely used in daily life for the purpose of keeping the inside of the toilet clean and directly removing the bad smell of urine and such decomposed products by chemical reaction or masking the bad smell. Used. The solid deodorant for toilets can be poured directly into the flush water tank of the flush toilet or placed in the hand wash section above the water storage tank and gradually dissolved or dispersed by running water during flushing. It is used continuously for a period of about a month.

As such a solid deodorizing agent for toilets, a compound in which a deodorizing component, a fragrance component, a coloring component, and the like are blended with a solubilizing agent is generally used. Examples of the solubilizer include high-molecular-weight polyethylene glycol, those obtained by etherifying or esterifying a hydroxyl group at one or both terminals of polyethylene glycol, and ethylene oxide and propylene oxide. High molecular weight polyethylene glycols such as copolymers are known (JP-A-51-37905, JP-A-5-131098, JP-A-57-1799298).

However, each of these solubilizers swells with water and loses shape and retains shape. It has become impossible to use it for men's urinals because it deteriorates and becomes muddy, flows into drains and clogs drain pipes. As a solid air freshener (deodorant) for men's urinals, the sublimable men's toilet ball made of paradichlorobenzene is still used in the 9¾ shape.

Japanese Unexamined Patent Publication (Kokai) No. 2-169920 discloses that urine odor caused by a fast-acting urolith decomposer consisting of a microbial component, a nutrient component, and a fragrance component is completely different from the above-mentioned masking evening deodorant. There has been proposed a method for suppressing the above.

Also, Japanese Patent Application Laid-Open No. 3-4916 discloses a mixed organism, a mixture of bacteria of the genus Bacillus 厲, Streptococcus 卜, Nitrosomonas sp. There has been proposed a male urinal odor prevention molded article which is formed by mixing lactic acid, ammonium chloride, an organic adhesive, and a dye into a porous body. In this porous molded body, microorganisms and nutrients are confined in the pores, that is, the voids, and when water penetrates into the voids, the microorganisms start to grow from dormancy and start to grow, producing enzymes and the like. Bacterial products such as enzymes are discharged from the molded product by running water, and malodor components adhering to the drain pipe of toilet bowls are decomposed to suppress malodor.

However, the urolith decomposer described in Japanese Patent Application Laid-Open No. 2-169902 is excellent in deodorizing properties immediately after spraying the drug, but since the deodorizing effect diminishes with the treatment B, the deodorizing effect is maintained. To do so, it is necessary to spray the disintegrant on the toilet regularly, for example, about once a week. In addition, since this decomposer is an aqueous solution, it can only be stored for a few days at most, since it decomposes under normal room temperature storage, so it is necessary to make a new decomposer every time it is sprayed. The maintenance was very troublesome.

Also, in the molded article of the odor preventing toilet bowl disclosed in JP-A-3-4916, microorganisms in the pores of the porous body take in nutrients after contact with water and rapidly multiply. However, since water-soluble nutrients such as glucose and ammonium chloride are easily discharged from the pores, the nutrients in the porous pores rapidly disappear with the passage of time, and the microorganisms grown in the porous pores conversely die. Therefore, there is a disadvantage that the deodorizing effect rapidly decreases with time.

In order to solve such a problem, even if the solid deodorant is immersed in water, water does not penetrate into the solid deodorant, and the microorganisms inside the solid deodorant remain dormant. By gradually dissolving from the outside, microorganisms that have started their activity due to contact with water are gradually discharged, and can gradually remove the foul odor of the toilet. The emergence of the drug was expected.

In view of the above, an object of the present invention is to provide a solid deodorizing agent for tiles which does not swell and does not become muddy even in contact with water, is easy to maintain, and has excellent deodorizing effect. To provide. Disclosure of the invention

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that the above objects can be achieved by combining a solubilizer having a specific composition with a microbial material, and have reached the present invention. That is, the present invention relates to a method comprising: a force comprising an oxyethylene group-containing aromatic compound (C) having a melting point of 50 or more; or a solubilizer (A) comprising the same and a water-soluble aliphatic compound (D); A toilet solid deodorant comprising the agent (A) and the microbial material (B); and a toilet solid detergent comprising the slow-solubilizing agent (A) and a surfactant.

Hereinafter, the present invention will be described in detail.

The solubilizing agent (A) used in the present invention comprises the above-mentioned aromatic compound (C) having an oxyethylene group having a melting point of 50 ° C. or higher, or a mixture with the water-soluble aliphatic compound (D). Consists of By using (C) and (D) together It is possible to change the dissolution speed of the solid deodorant more widely than (c) alone.

Examples of the aromatic compound (C) having a melting point of 50 ° C. or higher and having a melting point of 50 ° C. or more include, for example, a high-temperature aromatic compound having a hydroxyl group and a hydroxyl or carboxyl group in the molecule. Ethylene oxide (hereinafter, ethylene oxide is abbreviated as "E0"). Specific examples thereof include, for example, E 0 adducts of aromatic monocarboxylic acids such as benzoic acid and salicylic acid (or ethylene glycol ester) (C 1); phthalic acid, isophthalic acid, terephthalic acid, and benzene triglyceride. E0 adducts of aromatic polycarboxylic acids such as carboxylic acids (or ethylene glycol esters) (C 2): C6-20 aromatics such as resorcinol, hydroquinone, bisphenol A and bisphenol F E0 adducts of aromatic divalent phenols (C 3); E0 adducts of aromatic amines such as methylene dianiline; These compounds can be used alone or in combination of two or more.

Among these, the compounds (C 1) and (C 2) are preferable, and the compound (C 2) is more preferable, and particularly preferable, because of good balance between shape retention and dissolution speed. These are bis (2-hydroxystil) isophthalate and bis (2-hydroxysethyl) terephthalate, with bis (2-hydroxystil) terephthalate being the most preferred.

The melting point of the oxyethylene group-containing aromatic compound (C) is usually from 50 to 200 ° C, preferably from 50 to 150 ° C. If the melting point of (C) is less than 50 ° C, the surface of the solid deodorant tends to be sticky, and if it exceeds 200 ° C, a large amount of energy is required for melting, which is uneconomical.

Solubility in 2 0 ° C in the Okishechiren group-containing aromatic compound (C) (/ 1 0 0 g H 2 0) is usually 3 to 0.0 0 0 1, is rather to preferred 1 to 0.0 0 Is one. When the solubility exceeds 3, the dissolution speed becomes faster, The solid deodorant has poor dissolution persistence, and if it is less than 0.0001, the solid deodorant hardly dissolves.

Water-soluble aliphatic compound used in the present invention as the (D), for example, in low volatility (boiling point 1 5 0.C higher), solubility in 2 0 (g / 1 C 0 g H 2 0) Is 30 or more. Specific examples thereof include alkylene glycols having 2 to 6 carbon atoms (D 1), such as ethylene glycol, dipropylene glycol, trimethylene glycol, butylene glycol, 1,6-hexynelen glycol; and glycerin. Polyhydric alcohols (D 2) such as triglycerin, trimethylolpropane, etc .; polypropylene glycol (molecular weight of 250 or less), polyethylene glycol (molecular weight of 300 or less), poly (propylene) —Ethylene) Polyalkylene glycols (D 3) such as glycols (molecular weight of 300,000 or less).

Among the above (D1) to (D3), (D1) and (D2) are preferred in that the solid deodorant has good shape retention, and (D2) is more preferred. Glycerin is most preferred.

If the boiling point of the water-soluble aliphatic compound (D) is lower than 150 ° C., (D) will evaporate over time, and the shape of the solid deodorant will change, for example, due to shrinkage, generation of voids, etc. Easily occur.

When solubility in 2 0 ^e C of the water-soluble aliphatic compound (D) (g / 1 0 0 g HO) is less than 3 0, solid deodorants that an easily swell in contact with water.

The microbial material (B) used in the present invention contains at least one kind of organism such as bacteria, fungi, yeast, etc., and is a powdery substance comprising enzymes, a medium, a carrier, etc., and has a water content of about 5% by weight. The microorganisms in (B) are dormant (inactive) because they are substantially free of water below. Examples of the microorganisms that may be contained in the microorganism material (B) include, for example, Bacillus, Lactobacillus, Streptococcus, and Entero. Enterococcus, Enterobacter, Nitrosomonas, Nitrobacter, Cell mouth Monas, Examples include Pseudomonas, Agrobacterium, Rhizopus, Aspergillus, and yeast. Two or more of these microorganisms can be used in combination. When used in combination, they often coexist and act in the same environment, and often act effectively to decompose organic substances and odorous substances by sharing roles.

Among the above microorganisms, Bacillus, Lactobacillus, Streptococcus, Enterococcus, Nitrosomonas Microorganisms of the genus Nitrobacter, Rhizopus, Aspergillus, and Sacc aromyces have been shown to reduce the fermentative ability of organic odorous components. Preferred in terms of superiority, microorganisms of the genus Bacillus, Lactobacillus, Streptococcus, and Enterococcus are even more preferred. In particular, microorganisms of Bacillus II are most preferred because they have excellent heat resistance and, as described later, have a high survival rate even at a high temperature of 50 to 80 when molding a solid deodorant.

In the present invention, examples of the microorganism species include the following.

(1) Bacillus

Bacillus' Subtilis (IFO (lnstitute for Fermentation Osaka) : Fermentation Research Institute, hereinafter the same) 1 3 7 1 9), Bacillus' Natsuto (IF 03 0 13), Bacillus' Licheniformis (IF 0 1 2 2 0 0), Bacillus' Coagulance ( IF 01 258 3), Bacillus, Maserance (IFO 340), Bacillus 'Megamedia (IF 0 1 2 0 8) Bacillus' Polymixer (IF 0 1 3 0 0 3 ) etc.

(2) Lactobacillus

Lactobacillus casei (IF 0 1 2 5 2 1), Lactobacillus acid filings (IF 0 1 3 9 5 1), Lactobacillus delvuluki (IF 0 3 0 2 0 2), etc. .

(3) Streptococcus

Streptococcus felicalis (IF03971), streptococcus cremolith (IF03427), streptococcus cracked (IFO1207), Stroboccus * salivarius (IFO13956), Strobococcus' thermophilis (IF013957) Trebutococcus bacium (IF012256).

(4) Enterococcus

Enterococcus Fécaris (IF03971 IF03989), Enterococcus' Fashim (IF031228 IF03535).

(5) Enterobacter

Entrance 'factory' aero ginis (IF 0 1 2 0 1 0 IF 0 1 3 5 3 4) etc.

(6) Nitrosomonas

Nitrosomonas' Europaea (IF 0 1 298) etc.

(7) Nurobacter

Nitropacta agiris (IFO 14 297) and the like.

(8) Cellulomonas Cellulomonas 'Hula Vigena (IF03754), Cellulomonas' Viazotea (IF0126680), Cellulomonas 'Cerasea (IF03748) Cellulomonas' Uda (IF033747), Cellulomonas 'Gerida (IF 03 7 4 8) and so on.

(9) Pseudomonas

Pseudomonas 'Putida (IF0116), Pseudomonas' double-reduced sense (IF0126964) and the like.

(10) Agrobacterium

Agrobacterium, Tume van ence (IF03058, [F012667]) and the like.

(11) Rhizopus

Resorts Orizae (IF047 06), Resorts Forolumo Saensis (IF0432), Resorts 'Japonicas (FO4732), Resorts' Delemar (IF047) 4 6) etc.

(12) Aspergillus

Aspergillus' Orizae (IF0301104), Aspergillus' Nigar (IF0311), Aspergillus' Samisa (IFO4388), Aspergillus Soja (IF04391) ), Aspergillus. Terreus (IF 03 12 17).

(13) Saccharomyces

Saccharomyces * cerevisiae (IFOi0217), Saccharomyces' Carlsbergensis (IF0117), etc.

In the present invention, the microorganism material (B) can be produced by a conventionally known method, for example, as follows. That is, an appropriate amount of the above-mentioned microorganisms (one or more), a medium and a carrier are added to water, mixed, and cultured at a temperature of 25 to 50 for 24 to 72 hours. 5% by weight or less It can be manufactured by vacuum drying and powdering below.

Agriculture and marine products such as fishmeal, oily scum, bran, wort and the like and wastes thereof can be used as the above-mentioned medium, and the above-mentioned carriers include calcium carbonate, magnesium carbonate, calcium gayate, silica silicate, zeolite, Inorganic or organic powders such as Ogatazu can be used.

The microbial material (B) thus obtained contains enzymes such as a protease, an amylase, a lactase, a lipase, a hemicellulase, and a cellulase, which are produced by the microorganism in the culture.

In the present invention, in order to further enhance the deodorizing property, an enzyme other than the above may be added to the microorganism material (B), or the same enzyme as described above may be added later.

In the present invention, the content of microorganisms in the microorganism material (B) is usually 5 to 70% by weight, preferably 20 to 60% by weight. If the amount is less than 5% by weight, the deodorizing property of the solid deodorant decreases, and if it exceeds 70% by weight, the production cost of the microbial material (B) increases.

The total viable count of microorganisms contained in 1 g of the above-mentioned microbial material (B) is usually about 10 'to 10' ', but the viable count of each microorganism in (B) is deodorant. From the viewpoint of the above, it is preferable to be in the following range. That is,

(1) belonging to the genus Bacillus ^{(Bacillus subtilis): 1 0 8} 1 0 g

(2) La click Bokuha 'Chinoresu genus ^{(Lactobacillus): 1 0 6 1} 0'. G

(3) S Bok Lev Bok Koh Tsu grounds belonging to the genus ^{(Streptococcus) ·· 1 0 6 1} 0

(4) Entero Koh Tsu dregs厲^{(Enterococcus): 1 0 6 1} 0 9 / g

(5) Enteronokuku ter sp ^{(Enterobacter): 1 0 6 1} 0 9 /

(6) Nitrosomonas: 10 ⁶ 1 0 ⁹ /

(7) Double Bok Robaku data one genus ^{(Ni trobacter): 1 0 6} 1 0 9 / g

(8) Senole α-monas (Cel lulomonas) 2 10 ⁶ 10 ⁹ / g (9) the shoes Pseudomonas厲^{(Pseudomonas): 1 0 6 ~} 1 0 8 / g

(10) § Gros Corynebacterium Riu arm belonging to the genus ^{(Agrobacterium): 1 0 8 ~} 1 0 8

(11) Rhizopus厲^{(Rhizopus): 1 0 6 ~} 1 0 9 / z

(12) Asuperugirusu厲^{(Aspergillus): 1 0 6 ~} 1 0 8 / g

(13) Saccharomyces厲(Saccharomyces): 1 0 ⁶ The amount of their respective of ~ 1 0 ⁸ / g the gradual solubilizing agent in the present invention (A) and the microorganism资材(B) is usually (A) 3 0 To 95 parts by weight, (B) 70 to 50 parts by weight, preferably (A) 40 to 90 parts by weight, and (B) 60 to 10 parts by weight ft. When (A) is less than 30 parts by weight, the solid deodorant tends to swell, and when (A) exceeds 95 parts by weight, the deodorizing property of the solid deodorant becomes small. The amounts of the aromatic compounds (C) and the water-soluble aliphatic compounds (D) containing the oxyethylene at a clear point of 50 ° C or more, which are the constituents of (A), are calculated as the weight of (D) / (C). The ratio is (0Z100) to (70/30), preferably (100 to 90) to (60 to 40).

When the weight ratio of (D) / (C) exceeds 70/30, the solid deodorant becomes easy to dissolve, resulting in poor dissolution stability.

In the present invention, if necessary, known surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used for cleaning toilet toilets. Among these, nonionic surfactants are preferred in that they do not cause damage to the growth of microorganisms. Among them, aliphatic alcohols having 1 to 25 carbon atoms and phenol compounds having 6 to 25 carbon atoms are preferred. A non-ionic surfactant having a molecular weight of 300,000 or less, which is obtained by adding ethylenoxide to an active hydrogen-containing compound such as the above, is more preferable.

The amount of the surfactant used is usually 0.5 to 50% by weight, preferably 1 to 20% by weight based on the total amount of the solubilizer (A) and the microbial material (B). In the present invention, known fragrances, coloring agents, and the like conventionally used in toilet cleaners for toilets and the like can be used as necessary. Use of the above flavors «

It is usually from 0.01 to 10% by weight, preferably from 0.1 to 2% by weight, based on the total amount of (A) and (B). The use S of the above coloring agent is usually 0.01 to 10% by weight, preferably 0.1 to 5 times ft% based on the total weight of (A) and (B).

In the present invention, if necessary, inorganic salts such as sodium sulfate, anhydrous sodium sulfate, potassium sulfate, sodium carbonate, calcium carbonate, calcium phosphate, and boric acid can be used as a bulking agent. The amount of the inorganic salt to be used is generally 10 to 200% by weight S%, preferably 20 to 100% by weight, based on the total amount of (A) and (B).

In the present invention, if necessary, bleaching agents such as sodium persulfate and sodium perborate; fillers such as talc and colloidal silica; chelating agents (metal scavengers); Additives can be used.

Next, the outline of the method for producing the solid deodorant for toilet of the present invention will be described. Method 1

Melt and mix each component except the microbial material (B) exemplified above, adjust the pH to a neutral range of about 4.0 to 8.5 if necessary, cool if necessary, and then cool the microbial material. (B) is added to the molten mixture (temperature: about 50 to 80 ° C) and mixed. Next, the molten mixture is poured into a plastic container or mold, left at room temperature or the like, cooled, and then released to obtain a solid deodorant.

Method 2

Melt and mix each component except the microbial material (B) exemplified above, adjust the pH to a neutral range of about 4.0 to 8.5 if necessary, cool to below the melting point, and then pulverize. And pulverize. Next, the powder of microbial material (B) Powder blend and homogenize, put the powder blend into the mold and heat and press if necessary, or melt-mix the powder blend again and repeat the procedure described in Method 1-1 above. Molding is performed in the same manner to obtain a solid deodorant.

Known methods such as extrusion molding, injection molding, liquid casting, and compression molding (tablet molding) can be applied as a method for molding the solid deodorant for tiles of the present invention. In method 1, the injection molding method and the liquid casting method can be advantageously applied, and in method 2, the extrusion molding method and the compression molding method (tablet molding method) can be advantageously applied.

Further, in the present invention, as a method for producing a solid deodorant for toilet, a method of molding by a liquid casting method according to the procedure of Method 1 is preferable because the production cost is inexpensive. It is more preferable to use a film mold having the above-mentioned cramps to produce it in the following first to fourth steps. Examples of the film-type material include plastics such as polystyrene, polypropylene, and polyvinyl chloride. Injection molding, vacuum molding, etc. can be applied as a method for producing these film molds.

0! It is preferable to manufacture a plastic film with a thickness of ~ 0.5 mm by vacuum molding, because it is inexpensive.

① 1st process: Raw materials are heated and welded to mix.

(2) Second step: Inject the heated and melted raw material mixture into a film-shaped depression having a plurality of depressions.

(3) Third step: The film mold into which the raw material mixture has been injected is 35. Cool to about C or less to solidify the raw material mixture.

④ Fourth step: The solidified product is released from the film mold.

In the present invention, the total viable count of microorganisms in the solid deodorant produced as described above must be maintained at 1 × 10 ⁶ Zg or more. If (B) is less than 1 × 10 ⁶ particles / g, the deodorizing property of the solid deodorant becomes low. It is considered that the solid deodorizer for tiles of the present invention removes the malodor of tiles by the following mechanism. The microbes eluted together with the solubilizer in the running water of the toilet are the organic substances that are odor sources such as urine and urinary stones that adhere to the walls of toilets and drain pipes and adhere to the walls of drain pipes. It decomposes and ferments proteins, proteins, etc. down to sugar and amino acids, and oxidizes ammonia, which is the cause of the bad smell of toilets, generated during the decomposition process into nitric acid (salt) and nitrogen molecules. . Here, the main role of each microorganism is considered as follows. That is, microorganisms such as Bacillus, Pseudomonas, Lactobacillus, Streptococcus II, Resorbes II and Aspergillus III decompose and ferment organic substances as malodorous sources. Are oxidized to nitrite (salt), and 10 cells of Nitrobacter are oxidized to nitric acid (salt), and become odorless.

Since bacteria of Nitromonas and Nitropactor are always present in the drainage pipes of toilets, they do not need to be added to the solid deodorant. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

In the following, parts and% indicate parts by weight and% by weight, respectively.

The evaluation and test methods of the solid deodorant used in the examples and comparative examples are shown.

(1) Melting point

Evaluation was performed using a trace melting point measuring device (manufactured by Yanagimoto Seisakusho).

(2) Ownership time and shape retention

A stainless steel cylindrical basket (diameter: 4 Omm, height: 60 mm) containing a solid deodorizer (approximately 30 g) molded into a cylindrical shape is placed in a 15-liter water tank (water temperature: 25 ° C). The weight of the solid deodorant was measured every 5 days, and the number of days when the weight was less than 5 g was defined as the holding time. In addition, the shape retention (presence of cracks, swelling, etc.) up to the holding time was observed.

The water in the tank was replaced with new water once a day.

(3) Total viable cell count

The measurement was performed by the mixed flat culture method under the following conditions. The unit is Zg.

Medium: Standard agar medium (St andard Method Agar) "Product name: Nissi" (Nippon Pharmaceutical Co., Ltd.)

Incubation temperature 'time: 3 5 X 7 2 hours

(4) Deodorant sensory evaluation

Place a water-permeable plastic case containing one solid deodorant (approximately 30 g) on the pan of a men's urinal with a flush function (50 times in total). After 2 days and 15 A sensory evaluation was conducted daily for urinal odor based on the following four-grade criteria. When the duration of the solid deodorant was reached, the test was continued by replacing it with a new solid deodorant.

<4-step standard>

1: Almost invisible odor

2: Odor perceived by the guy

3: Immediate odor

4: Strong: ¾ 気

(5) Ammonia deodorization

Place 50 g of artificial urine in a 100 cc triangular flask, then add 1 g of solid deodorant powder ground in a mortar, shake the top of the flask with a rubber stopper, and shake for 1 minute. Then, it was left still in an atmosphere of about 25 ° C. Using an ion meter (Ionmeter EA920, manufactured by Orion Research Co., Ltd.), the ammonia concentration after 24 hours was measured to evaluate the ammonia deodorizing property. Next, the abbreviations and compositions of the raw materials used in Examples and Comparative Examples of the present invention are shown.

(1) B H E T bis (2-hydroxyshethyl) terephthalate

(2) B P—E 2 bisphenol A ethylene oxide 2.2 mol additive

(3) P G propylene glycol

(4) GLC glycerin

(5) TMP trimethylolpropane

(6) Microbial material

(i) Bio-material (a)

Carrier comprises about 50% of (庾酸calcium), Bacillus's Microbial Puchirisu (I F01 3 7 1 9) 8 X 1 0 8 Zg, Bacillus' re Kenifu O Lumi scan (I F01 2 2 0 0) 1 X 1 0 ⁹ / &, Enteroko Kkasu 'Hue mosquito re-scan (I F03 9 7 1) 6 X 1 0 8 /. Rizobusu' Orizae (IF 04 7 0 6) 3 xl 0 7 Zg of 4厲, containing seeds Microbial powder materials

(Total viable count: ¹ X 1 0 1 g)

(ii) Biomaterials (b)

Carrier comprises about 50% of (calcium carbonate), Bacillus Zupuchiri scan (IF 0 1 3 7 1 9 ) 5 1 0 9 Roh g, carbonochloridate Chirusu 'Li Kenifu O Honoré mistakes

(IF 0 1 2 2 0 0 ) 1 X 1 0 5 / g, Bacillus ■ Bollywood mixer (IF 03 0 2 0) lxl O. Microbial powder material containing 3厲'species zg (total viable count: 7 X 1 0 ⁹ Zg)

(7) Denatured PEG

Polyethylene glycol (molecular weight: 600,000) was joined with 4.4-difluoromethane diisocitrate to reduce the molecular weight to 500,000. Solubilizer.

(8) Activator 1: 7 mol of ethylene oxide adduct of sorbitan oleate

(9) Activator 2: Pluronic nonionic surfactant (polyoxyalkylene glycol of molecular weight 222,000 with ethylene glycol added to polypropylene glycol of molecular weight 170,000)

(10) SPB: sodium perborate

(1 1) Fragrance: Rose oil

(1 2) Colorant: Food Blue No.1 Aluminum Lake

(13) Artificial urine: 80 g of urea, 32 g of sodium chloride, 1.2 g of calcium chloride, 3.2 g of magnesium sulfate, 1.4 g of 28% aqueous ammonia and tap water 38 88 . 2 g dissolved

(14) Film type: Polystyrene film with a size of 450 × 550 × 0.25 (thickness) mm (including a small amount of silicon oil as a slip improver) manufactured by vacuum molding 5 vertical and 6 horizontal dents (50 mm in diameter, 50 mm in diameter at the bottom of the upper opening, 30 mm in height) with a 50 m 1 disk-shaped volume Examples) Examples 1-4: Comparative Example 1

The components shown in Table 1 were melt-mixed, cooled and solidified, and then pulverized. Next, this fine powder was molded into a cylindrical tablet (about 30 g) with a diameter of 38 mm and a height of 25 mm using a tableting machine, and the above-mentioned performance evaluation was performed. Table 1 shows the obtained results. table 1

Comparative Example 1 is a commercially available solid aromatic detergent

As is evident from Table 1, the solubilizer of the present invention has good shape-retaining properties, and furthermore can widely change the dissolution speed of the solid escaping agent. Examples 5 to 8 and Comparative Example 2

The components shown in Table 2 (excluding biomaterials) were melt-mixed, cooled, solidified, and then pulverized. Next, the fine powder and the biomaterial were uniformly blended in the ratio shown in Table 2 and then, using a tableting machine, a cylindrical tablet with a diameter of 38 mm and a height of 25 mm (about 30 g). ) And performance was evaluated. The results are shown in Table 2. Example 9

55 parts of BHET, 30 parts of GLC, and 15 parts of BP-E2 were heated and mixed to adjust to about 75 parts. To this, 0.3 part of a coloring agent was added and mixed and dissolved at the same temperature. Next, 30 parts of the biomaterial (b) was added and stirred for 30 seconds, and about 30 g of the mixed solution was poured into a 30 ml polypropylene cup. After standing at room temperature for 24 hours, the solid was removed from the tub to remove the solid deodorant, and the same evaluation as in Examples 1 to 5 was performed. Table 2 shows the results.

Two

(Note) Melting point: For solids excluding components of biomaterials, feedstock and colorants

Measurement.

Next, ammonia deodorizing properties were evaluated using the solid deodorants of Examples 5 to 9 and a commercially available solid aromatic detergent (Comparative Example). The results are shown in Table 3. Table 3

Comparative Example 3 is a commercially available solid fragrance detergent c

As is evident from Table 2, in the case of the conventional solid deodorant using the solubilizing agent (Comparative Example 2), the solid deodorant was replaced and the deodorizing property was good for a while, but after the replacement, From around 5 days, the deodorization rapidly decreased. This decrease in deodorization is due to the fact that the entire solid deodorant swells with water and the microorganisms are reactivated, but since the solid deodorant originally has no nutrients, the activity in the solid deodorant is It is presumed that many of the transformed microorganisms died after a while.

In contrast, the solid deodorant of the present invention does not swell even when it comes into contact with water, and water does not penetrate into the solid deodorant, so that the microorganisms inside the solid agent are inactivated (dormant). Remains. Therefore, the outer part (including activated microorganisms) of the solid deodorant that has come into contact with water gradually elutes, and the activated microorganisms are activated and adhere to the toilet bowl, drain port and drain pipe. It breaks down organic matter, takes in nutrients, and grows. Also, even if some of the microorganisms that have landed on the drain pipes are washed away by running water such as washing water, the solid deodorant continuously elutes gradually, and the toilet bowl, drain outlets and drain pipes are discharged. For example, newly activated microorganisms are gradually and continuously supplied in a stable manner, and some activated microorganisms are constantly attached to these surfaces. It is considered to be. Due to such a difference in mechanism, in the case of the solid deodorant of the present invention, the deodorizing property becomes good after about two days, the state is maintained for a long time thereafter, and the deodorizing property is very good before and after the replacement of the solid deodorant. It does not change.

In addition, the solid deodorant of the present invention does not become muddy even when it is in contact with water for a long time, and has much better shape retention than a solid deodorant using a conventional slow-solubilizing agent. Maintenance is easy without clogging the drainpipe. Furthermore, as is clear from Table 3, the solid deodorant of the present invention has extremely excellent deodorizing properties of gammonia, which is a main odor source of toilets. Example 10

Heat and mix (about 70 parts) 70 parts of BHET, 20 parts of GLC, 5 parts of activator 1, and 5 parts of activator 2, then add 2 parts of fragrance and mix. About 40 g of the mixture was poured into a 6 O ml polypropylene cup. After leaving at room temperature for 2 hours, the mold was removed from the wrench to obtain a solid detergent.

Next, the solid detergent was stored in a plastic basket-like plastic case, and placed in the hand-washing section of a household on-tank flush toilet. As a result, the number of flushes of 10 L of tap water in which the weight of the solid detergent is less than 5 g is about 600 times, during which time the solid detergent maintains its fragrance and has no deformation such as swelling. The toilet was not contaminated and had good antifouling properties. Example 1 1

A mixture consisting of 50 parts of BHET, 20 parts of BP-E2, 20 parts of GLC, and 10 parts of SPB, a total of 100 parts, was kneaded with an extruder at about 50 parts. A plate-like solidified product having a thickness of about 30 mm was produced. After about 15 hours, this was cut to obtain a box-shaped solid detergent weighing about 60 g. The solid detergent was evaluated in the same manner as in Example 10. As a result, the number of flashes was about 500, and there was no deformation such as swelling. During the period of use, the toilet of the flush toilet was clean, and the solidifying agent had good cleanliness.

60 parts of BHET, 10 parts of BP-E2, 30 parts of GLC, 1 part of colorant (), 1 part of heating, welding and uniform mixing at about 85 ° C, then bio-material (b) 4 0 parts and 0.2 parts of fragrance were added and mixed for another 30 seconds. Next, the heated and molten mixture was poured into all the recesses of the film mold. After leaving it in a room at about 20 ° C. for about 15 hours and allowing it to cool naturally, the solidified material was removed from the film mold to obtain 30 solid deodorants weighing about 55 g.

This solid deodorant was evaluated in the same manner as in Examples 5 to 9, and found to have a melting point of 60. C, retention time was 30. The solid deodorant did not undergo any deformation such as swelling during the use period, and the shape retention was good.

The results of the sensory evaluation of the deodorizing property were the same as in Example 9, and the level of class 1 was changed from the second day of the test. Industrial applicability

The solid deodorizer for toilets of the present invention is very simple to maintain (eg, once every 1 to 3 months), and only needs to capture the solid deodorant, and is 1 to 3 months long. It has the feature that the deodorizing property does not decrease even if it is used for a period. In addition, the solid deodorizer for toilets of the present invention has the advantage of being environmentally friendly, because it uses microorganisms existing in nature as deodorizing components instead of chemical deodorizing components such as glyoxal. ing. The deodorant of the present invention has excellent shape retention properties and does not swell or become muddy even after prolonged contact with water, so it is used as a solid deodorant for men's toilets, which has been considered technically difficult to date. it can.

Furthermore, since the solubilizer used in this solid deodorant has excellent shape retention as described above, it can be used not only for toilet-related applications but also as a solubilizer in other fields such as sustained-release pesticides. Can also be used, and their practical value is extremely high.

Claims

The scope of the claims

1. A solubilizing agent comprising an aromatic compound (C) having a melting point of at least 50 and comprising an oxyethylene group-containing aromatic compound (C) or the above-mentioned (C) and a water-soluble aliphatic compound (D).

2. The oxyethylene group-containing aromatic compound (C) having a melting point of 50 ° C. or higher is an ethylene oxide adduct of an aromatic polycarboxylic acid or an ethylene glycol ester of an aromatic polycarboxylic acid. 3. The solubilizing agent according to item 1.

3. The solubilizing agent according to claim 2, wherein the polycarboxylic acid is terephthalic acid.

4. The water-soluble aliphatic compound (D) is an alkylene glycol having 2 to 6 carbon atoms and a polyhydric alcohol having 3 or more valences. Item 3. The solubilizing agent according to Item 3.

5. The solubilizing agent according to claim 4, wherein the water-soluble aliphatic compound (D) is glycerin.

6. The weight ratio of the water-soluble aliphatic compound (D) and the oxyethylene group-containing aromatic compound (C) having a melting point of 50 ° C. or more is (0-100) to (70-0). The sustaining agent according to any one of claims 1 to 5, which is 30).

7. A solid deodorizing agent for tilles, comprising the solubilizing agent (A) according to any one of claims 1 to 6, and a microbial material (B).

8. The solid deodorizing agent for a toilet according to claim 7, wherein the weight ratio of the solubilizing agent (A) and the microorganism material (B) is (30Z70) to (95/5). .

9. The solid deodorization for a tray according to claim 7 or 8, wherein the microbial material (B) contains one or more microorganisms selected from the group consisting of bacteria, fungi and yeast. Agent.

10. The solid deodorizer for tillers according to claim 9, wherein the microorganism is a Bacillus bacterium.

1 1. The solid deodorizing agent for toilet according to any one of claims 7 to 10, further comprising at least one selected from the group consisting of a surfactant, a fragrance, and a coloring agent.

1 2. The method for producing a solid deodorizer for toilets according to any one of claims 7 to 11, wherein

A first step of heating and melting and mixing all the raw materials to obtain a raw material mixed liquid; a second step of injecting the raw material mixed liquid into a film-shaped depression having a plurality of depressions; A third step of solidifying the raw material mixture by cooling the film mold in which the raw material mixture has been injected to a temperature below 35, and releasing the solidified material of the raw material mixture liquid from the film mold. A method for producing a solid deodorizer for toilets, comprising four steps.

13. The method for producing a solid deodorant for toilets according to claim 12, wherein the film mold is a plastic film having a thickness of 0.1 to 0.5 mm produced by a vacuum molding method.

1 4. A solid detergent for toilets, comprising the solubilizing agent (A) according to any one of claims 1 to 6, and a surfactant and / or a bleaching agent.

15. The solid detergent for toilets according to claim 14, further comprising at least one of a fragrance and a coloring agent.

1 6. A method for producing a solid detergent for toilet according to claim 14 or 15, wherein

A first step of heating and welding and mixing all the raw materials to obtain a raw material mixed liquid; a second step of injecting the raw material mixed liquid into a film-shaped recess having a plurality of depressions; and injecting the raw material mixed liquid A third step of cooling the formed film mold to a temperature of 5 ° C. or lower to solidify the raw material mixture, and a step of releasing the solidified solid of the raw material mixture from the film mold. A method for producing a solid cleaning agent for toilets, comprising four steps.

17. The production of a solid cleaning agent for a toilet according to claim 16, wherein the film type is produced by vacuum molding a plastic film having a thickness of 0.1 to 0.5 mm. Method.