JPH08239694A - Cleaning agent for toilet bowl - Google Patents

Abstract

PURPOSE: To obtain a cleaning agent for a toilet bowl, which is excellent in handleability, allows an antibacterial agent to stably dissolve out over a long period of time while hardly influenced by the solubility of the antibacterial agent, and can prevent black and light yellow discoloration, by using a clathrate compound of an antibacterial agent. CONSTITUTION: This cleaning agent contains a clathrate compound consisting of an antibacterial agent and a polymolecular host compound. The polymolecular compound is a compound that forms a crystalline complex (clathrate compound) in such a manner that a plurality of host compound molecules surround one molecule of a guest compound comprising an antibacterial agent. A particularly preferable antibacterial agent serving as the guest compound is 5-chloro-2- methyl-4-isothiazolin-3-one. The content of the clathrate compound is usually 0.1-50wt.% of the total weight. This cleaning agent is used, for example, in the form of a molding containing a surfactant that is solid at ordinary temperature and/or a subliming substance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toilet bowl cleaner, and more specifically, it is installed in a container suspended on the wall of a toilet bowl or a dissolver installed in the middle of a wash water pipe to flush wash water. The present invention relates to a chemical that dissolves a little in each wash water to wash the toilet bowl surface, the trap portion of the toilet bowl, and the drain pipe portion to prevent dirt and traps on the toilet bowl surface and stains and scale from adhering to the drain pipe portion.

[0002]

2. Description of the Related Art A mixture of a surface active agent, a fragrance, a pigment, etc. is placed in a toilet flush water tank, in the upper hand wash section or in a container suspended on the toilet bowl, and a small amount of the chemical is added to the flush water. Many cleaning agents for toilet bowls have been proposed and put into practical use by dissolving them one by one to prevent stains on the toilet bowl surface and coloring the wash water to give a refreshing feeling.

[0003]

A method of storing a drug containing a solid acid as an active ingredient in a dissolver installed in the toilet flush water pipe and dissolving it in the flush water is to clean the toilet bowl surface and the urine of the trap portion and the pipe. It has an excellent feature that it can prevent stones from adhering at the same time, but in some toilets black and pale yellow deposits are generated in the dissolver, the toilet flush water outflow hole part and the trap part, and the dissolver operates. It has been found that there is a drawback that washing water for toilets and toilets interferes.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that an inclusion compound of an antibacterial agent and a multi-molecular host compound is contained in a toilet bowl cleaner for toilet. The present inventors have completed the present invention by discovering that the addition of the antibacterial agent makes it easy to handle, is less susceptible to the solubility of the antibacterial agent, and can stably elute the antibacterial agent for a long period of time to prevent black and pale yellow coloring.

The present invention will be described in detail below. The present invention is a toilet bowl cleaning agent containing an antibacterial agent and an inclusion compound comprising a multimolecular host compound capable of including the antibacterial agent.

(Guest Compound) A compound generally known as an antifungal agent or an antibacterial agent as an antibacterial agent serving as a guest in the present invention, for example, 5-chloro-2-methyl-4.
-Isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-3-n-octyl-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2- Methoxycarbonylbenzimidazole, 2,3,5,6-tetrachloro-4-methanesulfonylpyridine, 2-thiocyanomethybenzothiazole, 2,2-dithio-bis- (pyridine-1-oxide), 3,3. 4,4-tetrahydrothiophene-1,1-dioxide, 4,5-dichloro-1,2
-Dithiolan-3-one, 5-chloro-4-phenyl-
1,2-dithiolan-3-one, N-methylpyrrolidone, phenyl- (2-cyano-2-chlorovinyl) sulfone, methylenebisthiocyanate, 2-bromo-2-
Examples include nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, 2-bromo-4'-hydroxyacetophenone, dibromonitrile pyropionamide, and 2-bromo-2-bromomethylglutarnitrile. I can do things.

Further, natural essential oils are generally known to have a fungicide or antibacterial action, for example, terpene compounds such as cineol, hinokitiol, menthol, terpineol, borneol, nopol, citral, citronellol, citoneral, geraniol. , Linalool, dimethyloctanol and the like can be exemplified.

In particular, 5-chloro-2-methyl-4-isothiazolin-3-one (commercially available as a 10.1 wt% aqueous solution)
Has an excellent antibacterial effect, but its high solubility in water and strong skin irritation make it difficult to handle when added to a toilet bowl cleaner. It is difficult to elute into. However, by using this clathrate compound, it is easy to handle, and the antibacterial agent can be eluted at a stable concentration over a long period of time, and slime generation can be prevented.

(Host Compound) The multi-molecular host compound of the present invention is a crystalline complex (inclusion compound) in which an antibacterial agent serving as a guest is surrounded by a plurality of host compounds per one molecule of the guest compound. Refers to the compound forming

As the multi-molecular host compound of the present invention,
There is no particular limitation as long as it is a compound having the above properties, but the following compounds can be used, for example. (1) 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, 1,1,
2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2
-Tetrakis (3-methoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,
3,3-tetrakis (4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-fluoro-4-)
Hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-chloro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1 , 3,3-Tetrakis (3-methoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethyl-
4-hydroxyphenyl) propane, 1,1,4,4-
Tetrakis (4-hydroxyphenyl) butane, 1,
1,4,4-tetrakis (3-fluoro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3
-Chloro-4-hydroxyphenyl) butane, 1,1,
4,4-tetrakis (3-methyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methoxy-4-hydroxyphenyl) butane, 1,1,4
4-tetrakis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,1,5,5-tetrakis (4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-fluoro-4-) Hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-chloro-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-methyl-4-hydroxyphenyl) pentane, 1,1 , 5,5-Tetrakis (3-methoxy-4-)
Hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3,5-dimethyl-4-hydroxyphenyl)
Tetrakis (hydroxyphenyl) alkanes such as pentane (2) 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol (3) 1,6-bis (2-chlorophenyl) 1, 6-diphenylhexa-2,4-diyne-1,6-diol (4) 1,1,4,4-tetraphenyl-2-butyne-
1,4-diol (5) 2,5-bis (2,4-dimethylphenyl) hydroquinone (6) 1,1-bis (2,4-dimethylphenyl) -2
-Propin-1-ol (7) 1,1,2,2-tetraphenylethane-1,2
-Diol (8) 1,1-bi-2-naphthol (9) 9,10-diphenyl-9,10-dihydroxyanthracene (10) 1,1,6,6-tetra (2,4-dimethylphenyl)- 2,4-hexadiyne-1,6-diol (11) 9,10-bis (4-methylphenyl) -9,
10-Dihydroxyanthracene (12) 1,1-bis (4-hydroxyphenyl) cyclohexane (13) N, N, N ', N'-tetrakis (cyclohexyl)-(1,1'-biphenyl) -2,2' -Dicarboxamide (14) 4,4'-sulfonylbisphenol (15) 4,4'-butylidenebis (3-methyl-6-
tert-butylphenol) (16) 2,2'-methylenebis (4-methyl-6-t)
ert-butylphenol) (17) 4,4′-thiobis (4-chlorophenol) (18) 2,2′-methylenebis (4-chlorophenol) (19) deoxycholic acid (20) cholic acid (21) α, α, α ′, α′-tetraphenyl-1,
1'-biphenyl-2,2-dimethanol

The inclusion compound used in the present invention is usually
It can be easily obtained by reacting the guest organic compound and the host compound with stirring in the presence of water or an organic solvent at room temperature to 100 ° C. for several minutes to several hours.

The inclusion compound of the present invention is used in the form of powder, granules or liquid. In addition, there is no particular limitation on the dosage form of the treating agent for the circulation type toilet containing this as an active ingredient, and powder,
Any dosage form such as granules, tablets and liquids can be selected.

The content of the clathrate compound as an active ingredient in the toilet treating agent is not particularly limited, but is usually 0.1 to 50% by weight, preferably 1 to 20% by weight based on the total weight. Is.

The clathrate compound can be added to the toilet bowl detergent by various known methods, but it is desirable that the inclusion compound be uniformly dispersed in the detergent. For example, in the case where the detergent is manufactured by a manufacturing method in which a heated and melted medicine is filled in a mold such as plastic and cooled and solidified, a method of adding an inclusion compound to the melt and uniformly mixing is exemplified, and a powder mixture. When it is produced by a tableting molding method, a method of adding it to the powder and uniformly mixing it can be exemplified.

In addition, we install solid acid as an active ingredient in the trap part of the urinal for boys and dissolve it little by little in the wash water to prevent scales called urine stones from adhering to the trap part and drain pipe. Proposed a drug (Japanese Patent Laid-Open No. 62-0382)
99) Partly put into practical use, the same chemicals are stored in a dissolver installed in the middle of the toilet flush water drain pipe, and a portion of the wash water is taken into the dissolver to dissolve the chemicals. A method of simultaneously preventing the dirt on the toilet surface and the attachment of urine stones to the trap portion and the drain pipe by returning the urine to the inside of the pipe and allowing the toilet surface to flow down (JP-A-3-200887 and JP-A-3-223386). , Japanese Patent Laid-Open No. 3-224923). It is also an aspect of the present invention to add the inclusion compound to a urinary stone inhibitor containing these solid acids as an active ingredient.

In the present invention, the solid acid is an acidic substance that is solid at room temperature and has a pH of 5 or less in an aqueous solution having a concentration of 1% by weight. For example, succinic acid, adipic acid,
Organic acids such as fumaric acid, benzoic acid, isophthalic acid, orthophthalic acid, terephthalic acid, salicylic acid, maleic acid, methylenesuccinic acid, isocyanuric acid, acidic salts such as sodium hydrogensulfate, potassium hydrogensulfate, ammonium hydrogensulfate, sulfamic acid , Boric acid, 1-prom-3-
Examples include chloro-5,5-dimethylhydantoin, trichloroisocyanur, and the like.

The solid acid of the present invention has a saturated solubility in water of 0.01 g to 50 g / 100 g (20 ° C.),
Preferably, 0.1 g to 30 g / 100 g (20 ° C.) is used.

Particularly preferred solid acids are benzoic acid,
Fumaric acid, adipic acid, orthophthalic acid, succinic acid,
Examples thereof include maleic acid, methylenesuccinic acid, sulfamic acid and the like. These solid acids are used alone or as a mixture of two or more. The solid acid content in the molded product varies depending on the weight of the molded product, the size of the dissolver, the frequency of use of the toilet bowl, etc., but is 20 to 95% by weight, preferably 30 to 70% by weight in the molded product.

In the present invention, the surfactant which is solid at room temperature has a solubility in water of 0.5 g to 20 g / 100 g.
(20 ° C.), preferably 1 g to 10 g / 100 g (2
0 ° C.) and has a melting point of 35 to 100 ° C., preferably 40 to 80 ° C.

Although various kinds of surfactants can be used in the present invention, a copolymer of ethylene oxide-propylene oxide, which is one of the nonionic surfactants, and a mixture of this copolymer and other surfactants. Are particularly preferably used.

Examples of the surfactant to be mixed with the ethylene oxide-propylene oxide copolymer include sorbitan monooleate, dialkyl sulfosuccinate and its salts, and polyoxyethylene nonylphenyl ether surfactant. .

To adjust the dissolution of the toilet bowl cleaner of the present invention, in addition to selecting an appropriate dissolution rate for the clathrate compound or solid acid, a method of adding fine powder such as talc or calcium stearate having a low solubility, or a sublimation method It is carried out by a method of adding a substance or the like.

Particularly, a slurry obtained by adding and mixing solid acid powder and an inclusion compound to a heated melt of paradichlorobenzene which is a sublimable substance and a nonionic surfactant which is solid at room temperature is poured into a mold and solidified by cooling. The shaped bodies thus obtained exhibit excellent dissolution properties.

Various active ingredients can be added to the toilet bowl cleaner of the present invention. For example, various corrosion inhibitors are added for the purpose of preventing corrosion of metal parts such as drainage pipes due to solid acid, and alkylthiourea compounds and triazole compounds are preferably used as the corrosion inhibitors.

Further, various binders can be added for the purpose of improving the moldability of the solid acid, and hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, Na salt of carboxymethyl cellulose and the like are preferably used. These binders are used by adding and mixing in the powder state, and polyethylene glycol (powder) is mixed with an aqueous solution of the binder in a mixture of solid acid and other additives, and then kneaded, and this is extruded by an extruder. It is added by various known methods such as drying after granulation.

In addition, enzymes for the purpose of decomposing organic stains on the toilet bowl surface, various chelating agents for the purpose of preventing inorganic stains, fragrances for the purpose of imparting aroma, and various sterilizations for the purpose of preventing the propagation of germs. An antibacterial agent and a deodorant or the like can be added for the purpose of removing a bad odor.

The toilet bowl cleaner of the present invention is molded by various known methods such as a method of press-molding a mixture of each component, a method of injecting a heated melt or a mixed slurry of a heated melt and a powder into a mold and cooling and solidifying the mixture. To be done.

The toilet bowl cleaning agent of the present invention is mainly used by being stored in a dissolver installed in the middle of the flush water pipe of the toilet bowl. Store in a dissolver installed at the outlet of the wash water in the tank or above the wash water tank, or a dissolver installed in the trap part of the toilet bowl, or use the molded body as it is in each of the above parts. You can also

The toilet bowl cleaner of the present invention contains a solid acid for preventing urinary stones and an inclusion compound in the same molded body, and simultaneously dissolves both components at the time of use. Body and a molded body containing an inclusion compound are separately molded, and both molded bodies are put into a dissolver at the same time for use, and only a molded body containing only a fungicide and a solid acid in the dissolver And a molded article containing an antibacterial agent is put into the trap of the trap-removable urinal.

When a solid acid having a slow solubility or an inclusion compound is used as an active ingredient, the drug is not in the form of a molded product but is directly charged into the dissolver or trap in the form of granules or powder. It can also be used as it is, or a liquid or a readily soluble drug can be filled in a container having a filter or the like at its mouth and placed in a dissolver for use.

When a solid acid having a slow solubility or an inclusion compound is used as an active ingredient, a molded product containing a disintegrant is used.
A method of disintegrating into a powder state in a trap or a dissolver is also preferably adopted. As the disintegrator, calcium salt of carboxymethyl cellulose, boron oxide and the like are preferably used.

[0032]

[Function] A detergent containing a solid acid as an active ingredient is stored in a dissolver installed in the toilet flush water pipe, and when the detergent is dissolved in the wash water, in the dissolver or in the flush water outflow hole portion and trap portion of the toilet bowl. The generated black deposits are the result of research by the present inventors,
It was found that the mold in the air grew with the surfactant in the detergent and the organic components in tap water as nutrient sources, and the slime generated in the trap of the detachable trap urinal is derived from bacteria. It was

The inclusion compound added to the toilet bowl cleaner is
Other components of the detergent dissolve in the wash water and release the antibacterial agent into the wash water, and molds and bacteria grow in the dissolver, the wash water outflow holes and traps of the toilet bowl to form deposits (slime). Prevent from doing.

When the drug containing the clathrate compound is directly put into the trap of the trap removable urinal, the concentration of the antibacterial agent in the trap is reduced during the time when the use of the toilet is stopped for a long time, such as at night or on holidays. Since it becomes significantly higher than usual, it becomes possible to antibacterially or sterilize the propagated bacteria, and the effect becomes particularly remarkable.

The urinary stones that adhere to the traps and drains of the toilet bowl are that the urea in the urine is decomposed into ammonia and carbon dioxide by the action of microorganisms and the pH rises, so that the urine, which is originally weakly acidic, becomes alkaline. The water-soluble calcium component in the urine is bound to carbon dioxide and phosphoric acid to precipitate as a water-insoluble calcium compound and adhere as a scale. Acidic substances suppress the rise in urine pH and prevent the development of urinary stones by its pH-regulating action, but they also inhibit the activity of microorganisms by the addition of antibacterial agents. The stone-preventing effect is higher than the urine-preventing effect as compared with the toilet cleaner containing only acidic substances.

[0036]

EXAMPLES The present invention will be described more specifically by way of examples. However, the scope of the present invention is not limited to the following examples.

Reference Example 1 Sample: CMI (5-chloro-
2-Methyl-4-isothiazolin-3-one) Inclusion Compound Production TEP (1,1,2,2-tetrakis (4-hydroxyphenyl) ethane) 2.51 mmo in 5 ml of methanol
Add 1 (1.0 g) and stir while warming until the TEP is completely dissolved. 20 g (11.4 mmol as CMI) of caisson WT (made by Rohm & Haas) was gradually added dropwise thereto, and the mixture was reacted at 25 ° C. for 1 hour with stirring. Next, this solution was allowed to stand at room temperature for a while, the precipitate was suction-filtered, and the residue was vacuum dried at room temperature to obtain a CMI inclusion compound as a pale yellow powder. TG-DTA measurement and I
As a result of R measurement, it was confirmed that this was an inclusion compound having TEP: CMI = 1: 2 mol.

The analytical values of the antibacterial agent (Caisson WT) used in Reference Example 1 are as follows. CMI (5-
Chloro-2-methyl-4-isothiazolin-3-one): 10.1 wt%, MI (2-methyl-4-isothiazolin-3-one): 3.8 wt%, balance: magnesium chloride + magnesium nitrate + water

Example 1 A mixture of 93% by weight of succinic acid, 1% by weight of the inclusion compound prepared in Reference Example 1, 5% by weight of hydroxypropylcellulose fine powder, and 1% by weight of a triazole type corrosion inhibitor was pressed. Molded, diameter 40mm,
A molded body having a height of 20 mm was obtained. This chemical was put into a dissolver in the middle of the washing water pipe and used.

Example 2 A mixture of 87% by weight of benzoic acid, 10% by weight of the inclusion compound prepared in Reference Example 1, 2% by weight of hydroxypropylcellulose fine powder, and 1% by weight of an alkylthiourea type corrosion inhibitor was added. Press formed, diameter 40
A molded body having a size of 20 mm and a height of 20 mm was obtained. This drug was put into the trap of the urinal with a removable trap.

Example 3 Adipic acid 51% by weight, paradichlorobenzene 25% by weight, nonionic surfactant 1
5% by weight and 5% by weight of polyethylene glycol (solid at room temperature) were heated and mixed at 80 ° C., and 4% by weight of the clathrate compound prepared in Reference Example 1 was added and mixed into the obtained slurry, which was poured into a mold and solidified by cooling. 40 mm x 40 mm x
A 20 mm rectangular parallelepiped shaped body was obtained. This chemical was put into a dissolver in the middle of the washing water pipe and used.

(Comparative Example 1) 5-chloro-2-methyl-4
A molded body to which isothiazolin-3-one was added without being included in the multimolecular host compound was prepared in the same manner as in Example 1.

Comparative Example 2 A molded body containing no inclusion compound was prepared in the same manner as in Example 3.

Comparative Example 3 A molded body containing no inclusion compound was prepared in the same manner as in Example 2.

(Evaluation Test) As described above, Examples 1 to 3 prepared.
Using the agents of Comparative Examples 1 to 3, tests were conducted by the following evaluation methods.

When the cleaning water is flushed into the cleaning water pipe, a part of the cleaning water is taken into the dissolution tank containing the toilet cleaner, and the liquid in which the cleaning agent is dissolved is washed after the cleaning water in the pipe has finished flowing. A dissolver of the type that is supplied into the water pipe and flows into the trap after cleaning the toilet surface is installed in the middle of the flush water pipe of the normal urinal for men's urinals of Examples 1 and 3, The molded bodies of Comparative Examples 1 and 2 were placed in a dissolver. In addition, the molded bodies of Example 2 and Comparative Example 3 were placed in the trap of the trap detachable urinal.

A melter of 5 toilets was charged for each molded product, and a new molded product was charged every month. After using the toilet bowl normally for 3 months, the following items were evaluated. The results are summarized in Table 1. In addition, the test is conducted in the toilet of the building where a lot of adhered substances are generated.When starting the test, the dissolver is replaced with a new one without dirt, and the toilet bowl and trap part use an acidic cleaning agent to remove dirt and urine stones. Was removed and sterilized using sodium hypochlorite solution. -Slime adhesion After three months, the condition of slime adhesion inside the dissolver, toilet flush water outflow hole, and trap was visually observed.・ Urreal stone adhesion The urinary stone adhesion state of the trap portion was visually observed after 3 months.

[0048]

[Table 1]

[0049]

As shown in Table 1, the toilet bowl cleaner of the present invention contains an inclusion compound consisting of an antibacterial agent and a multi-molecular host compound to give an antibacterial agent having high water solubility and skin irritation. Easy handling with strong antibacterial agents,
Furthermore, since the elution concentration of the antibacterial agent from the clathrate compound is relatively constant, even if the concentration is low, it is possible to effectively generate the deposits generated in the wash water outflow hole part and trap part of the dissolver or the toilet bowl. It is an economical and environmentally friendly composition that exhibits excellent effects of preventing urine stones and preventing urinary stones from occurring.

Further, by adding the clathrate compound to the drug, or by adding it as a separate drug into the dissolver or the trap, it is difficult to prevent the occurrence of deposits only with the drug having an acidic substance as an active ingredient. It has an excellent effect of preventing the generation of bacteria-derived deposits generated in the trap portion of the trap-removable urinal and improving the performance of preventing urinary stones.

The present invention relates to an improved toilet bowl cleaner. By using the composition of the present invention, it is possible to significantly reduce the daily cleaning work of the toilet bowl, and it is also possible to prevent the urine stones of the trap and drain pipe that are the cause of clogging and bad odor of the toilet bowl that cannot be handled by normal cleaning. Moreover, troubles such as the occurrence of slime do not occur, and its public health and industrial significance is extremely great.

Claims (5)

[Claims] 1. A toilet bowl cleaning agent comprising an inclusion compound comprising an antibacterial agent and a multimolecular host compound. 2. A toilet bowl cleaning agent, which is a molded article containing an inclusion compound composed of an antibacterial agent and a multimolecular host compound, and a solid acid. 3. A surface active agent and / or a sublimable substance which is solid at room temperature is contained in the composition.
Toilet toilet bowl cleaner described. 4. The antibacterial agent is 5-chloro-2-methyl-4-
The toilet cleaning agent according to claim 1, 2 or 3, which is isothiazolin-3-one. 5. The multimolecular host compound is one or two selected from the group consisting of the following compounds (1) to (25):
The toilet bowl cleaner according to claim 1, 2, 3 or 4, wherein the toilet bowl cleaner comprises one or more kinds. (1) 1,1,2,2-Tetrakis (4-hydroxyphenyl) ethane (2) 1,1,6,6-Tetraphenyl-2,4-hexadiyne-1,6-diol (3) 1,6 -Bis (2-chlorophenyl) 1,6-diphenylhexa-2,4-diyne-1,6-diol (4) 1,1,4,4-tetraphenyl-2-butyne-
1,4-diol (5) 2,5-bis (2,4-dimethylphenyl) hydroquinone (6) 1,1-bis (2,4-dimethylphenyl) -2
-Propin-1-ol (7) 1,1,2,2-tetraphenylethane-1,2
-Diol (8) 1,1-bi-2-naphthol (9) 9,10-diphenyl-9,10-dihydroxyanthracene (10) 1,1,6,6-tetra (2,4-dimethylphenyl)- 2,4-hexadiyne-1,6-diol (11) 9,10-bis (4-methylphenyl) -9,
10-Dihydroxyanthracene (12) 1,1-bis (4-hydroxyphenyl) cyclohexane (13) N, N, N ', N'-tetrakis (cyclohexyl)-(1,1'-biphenyl) -2,2' -Dicarboxamide (14) 4,4'-sulfonylbisphenol (15) 4,4'-butylidenebis (3-methyl-6-
tert-butylphenol) (16) 2,2'-methylenebis (4-methyl-6-t)
ert-butylphenol) (17) 4,4′-thiobis (4-chlorophenol) (18) 2,2′-methylenebis (4-chlorophenol) (19) deoxycholic acid (20) cholic acid (21) α, α, α ′, α′-tetraphenyl-1,
1'-biphenyl-2,2'-dimethanol (22) t-butylhydroquinone (23) 2,5-di-tert-butylhydroquinone (24) Granular corn starch (25) 1,4-diazabicyclo- (2 2,2) -Octane