JPS6148802B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention protects articles that are damaged by microorganisms and insects.
The present invention relates to a composition used for the purpose of protecting from such harm and preserving it for a long period of time. Furthermore, the above-mentioned microorganisms refer to bacteria, molds, yeasts, and the like. The present inventors first proposed an invention for improving the patent (Patent No. 1046326) relating to a food preservation method using an ethanol adsorbent owned by the present applicant, namely, the above-mentioned general formula (wherein R is individually hydrogen). atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an OR′ group) or a preservative composition prepared by adding water and/or an acid to the proviso) Although the invention was invented and a patent application was filed (name preservation composition of the invention filed on July 20, 1982), there was a problem that the effect was somewhat inferior in the case of articles with extremely high moisture content. On the other hand, the inventors of the present invention invented a food preservation method that simultaneously generates ethanol and carbon dioxide gas, and filed a patent application (Japanese Patent Application No. 56-9296).
It was confirmed that the storage period was much longer than the method of Patent No. 1046326, which uses ethanol alone. It was also felt that this effect was particularly pronounced for foods with a high water content, but this was not yet clear. However, in this method and many other methods, solid carbonate and solid acid are used as carbon dioxide gas generators, so the generation of carbon dioxide gas is very slow and lacks smoothness due to the reaction between solids. was. The inventors of the present invention have conducted extensive research to solve these drawbacks, and have found that the present composition comprising the compound represented by the general formula and a carbonate or bicarbonate of an alkali or alkaline earth metal can be used in combination with alcohols. Alternatively, by actively and smoothly generating carbon dioxide gas together with phenols (hereinafter both are simply referred to as alcohols) through a liquid-solid reaction, it is possible to improve the moisture content (in fact, equilibrium-related humidity) of goods, especially the moisture content (actually, as will be explained in detail later, equilibrium-related humidity). They discovered that this method is extremely effective even for items with extremely high costs, leading to the completion of the present invention. The present invention relates to the general formula This is a preservative composition comprising one or more of the compounds represented by the formula and carbonate or bicarbonate of an alkali or alkaline earth metal. The composition of the present invention has a mechanism of action which will be detailed later.
Alcohol vapor and carbon dioxide corresponding to R′OH are smoothly generated, and the synergistic effect of these two types of gases significantly suppresses or prevents the breeding activities of small animals such as the aforementioned microorganisms and insects. It is very effective for preserving. It should be noted that a carrier carrying water can be used in the composition of the present invention, and in this case, the same article preservation effect as that of the composition of the present invention can be obtained. The composition of the present invention is in a state in which a solid component of carbonate or bicarbonate of an alkali or alkaline earth metal is suspended in a liquid compound in the form of a slurry,
The degree of difficulty in industrial handling is much more difficult than that of the preservation composition for which the present applicant applied for a patent on July 20, 1980, which was completely liquid.
This is significantly easier than the powder used in Japanese Patent Publication No. 1046326 (Japanese Patent Publication No. 55-2273), and it is considerably easier than the composition used in the Examples of Japanese Patent Application No. 56-9296. The reason for this is that these solids are not adsorbents that emphasize adsorption performance with a large specific surface area, but the solid components are mainly carbonates or bicarbonates of alkali or alkaline earth metals that have an extremely small specific surface area. . The next feature of the composition of the present invention is that it generates carbon dioxide gas through a liquid-solid reaction, as is clear from the mechanism of action described in detail later. Uncertainty, irregularity and slowness are completely eliminated. Furthermore, while organic acids such as tartaric acid and citric acid, which have a small dissociation constant, are generally used as solid acids, the composition of the present invention uses halogenated acids, which have a much larger dissociation constant, as will be detailed later. Since hydrogen acid is generated by reaction with water and this liquid strong acid reacts with carbonic acid or carbonates, the generation of carbon dioxide gas is fast, reliable and smooth. Another feature of the compositions of the present invention is that, as detailed below, the mixture of the compounds of the compositions of the present invention and the carbonate or bicarbonate of an alkali or alkaline earth metal does not undergo any chemical changes unless water is added. Therefore, it does not have the disadvantage of releasing alcohol or carbon dioxide gas during mixing operations or packaging operations into small containers, and can be easily handled industrially. When this is further packaged with a moisture-containing article to be stored in a small container made of a material with high water vapor permeability, at least a portion of the container is made of a material with high water vapor permeability. When it permeates and comes into contact with the composition, a reaction to release alcohol and carbon dioxide gas occurs immediately, exerting a preservative effect. Moreover, the more moisture there is in the article to be stored, the more moisture it generates, and therefore the more water vapor that will penetrate into the small container containing the composition, the more active the reaction will be. Since it releases a larger amount of alcohol and carbon dioxide gas, it has properties suitable for preserving such items with a high moisture content, and this can be said to be an extremely excellent feature in practical terms. The gist of the present invention will be explained in detail below. The present invention is based on the general formula This is a preservative composition effective for preserving articles susceptible to damage by microorganisms or insects, which is composed of one or more compounds represented by the following formula and carbonate or bicarbonate of an alkali or alkaline earth metal. The compounds used in the present invention are as described above, but to give the most general example, the metal atom M is silicon or titanium, at least one R is a halogen atom, and the remainder are hydrogen atoms, halogen atoms, etc. from an atom or a monovalent hydrocarbon group such as methyl, ethyl, propyl, vinyl, benzyl or phenyl, R' is methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl, hexyl, hexenyl, The compound is a compound in which Y is selected from a monovalent hydrocarbon group such as isoprenyl, cyclohexyl, benzyl, phenyl or cresyl, and a divalent hydrocarbon group such as methylene or phenylene. These compounds are easily available industrially as described below. The industrial manufacturing method of the above-mentioned compound will be briefly explained. The halides, especially the chlorides, of the metal M shown in the general formula are generally known as silicon tetrachloride and titanium tetrachloride, but to these metal halides, alcohols having the above-mentioned R' and an amount equal to or less than the halogen are added. As a result, the esterification reaction (1) occurs very easily, and the corresponding metal acid ester can be obtained. This applies when n=O and R is OR' in addition to halogen in the general formula. On the other hand, it is known that the Grignard reagent RMgX, which has a monovalent hydrocarbon corresponding to R, can be easily obtained by reacting RX with metal magnesium. It is also well known industrially that organometallic bonds can be produced by M _-
It is well known that organometallic halogenides with remaining metal halogen bonds can be obtained, but if the above-mentioned alcohols are added to the organometallic halogenide in an amount equal to or less than the mole of the remaining halogen and reacted,
A corresponding substance is obtained when n=O, R of the compound is a monovalent hydrocarbon group or OR' in addition to a halogen atom. It is also possible to obtain an organometallic halide by directly reacting an organic halide RX having a monovalent hydrocarbon group corresponding to R with the metal of the compound using copper, zinc, etc. as a catalyst (called the direct method). In particular, when is silicon, it is carried out on a large scale industrially and is known as organohalogenosilanes. Needless to say, the same substance can be obtained. In the direct method, a considerable amount of organic hydride metal halides in which hydrogen atoms are bonded to metal atoms is also produced as a side reaction, and by reacting this with R′OH in an amount equal to or less than the equimolar amount to the halogen, the compound is In addition to a halogen atom, n=O, R is a hydrogen atom, a monovalent hydrocarbon group, and
A compound corresponding to OR' can be obtained. It is also known that hydrogenated metal halide can be easily obtained by reacting metal M with hydrogen halide, but by using this as a raw material and reacting with R′OH in an amount equal to or less than the halogen, n of the formula Compounds in which =O and R correspond to a hydrogen atom and OR' in addition to a halogen atom are obtained. In addition, in the direct method, high boiling point products among the reaction products include compounds in which Y in the formula is a divalent hydrocarbon group such as methylene or phenylene, m is 1, and n is a positive integer from 1 to 10; It is also known that compounds in which n is zero and n is a positive integer from 1 to 10 are included, and the amount increases as the reaction temperature in the direct method increases. (However, in the formula, R individually represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 10 carbon atoms, M
is a silicon or titanium atom, Y is a divalent hydrocarbon group having 1 to 7 carbon atoms, and m is 0 or 1.
, n is a positive integer from 1 to 10, and at least one of R is a halogen atom. ) If the halogen of the compound is reacted with an equivalent mole or less of the alcohol R'OH, in the formula, n = 1 to 10, and R is a hydrogen atom or a monovalent group with 1 to 10 carbon atoms individually in addition to the halogen atom. hydrocarbon group or
A compound in which the OR' group, Y=a divalent hydrocarbon group having 1 to 7 carbon atoms, and m=0 or 1 can be easily obtained. Therefore, there is no industrial problem in producing the composition of the present invention. Next, the mechanism of action of the composition of the present invention will be explained in detail. In the compound represented by the general formula, the OR' group bonded to the metal atom M is easily hydrolyzed to produce an alcohol called R'OH, which has the effect of significantly inhibiting the activity and reproduction of the aforementioned living organisms. do. The reaction formula is as follows. This reaction progresses easily at around room temperature due to contact between the compound and water or steam, but the higher the water concentration and temperature, the faster the reaction occurs. This property is extremely effective under high temperature and high humidity conditions, which is a feature that perfectly matches the purpose of the present invention. On the other hand, the halogen atom bonded to the metal atom M also reacts with water very easily to produce hydrogen halide as shown in the following formula. The HX generated in this way reacts with carbonates or bicarbonates of alkali or alkaline earth metals, which are other components of the composition, and synergistically with the alcohols mentioned above, significantly inhibits the activity and reproduction of living organisms. Generates carbon dioxide gas, which has a suppressive effect. For example, HX+AHCO ₃ →AX+H ₂ O+CO ₂ ...(5) 2HX+A'CO ₃ →A'X ₂ +H ₂ O+CO ₂ ...(6) (where A and A' each represent an alkali or alkaline earth metal atom). In addition, generated using equations (3) and (4),

[Formula] is subsequently dehydrated and condensed to form a metal oxide inorganic polymer. The associated significant volume reduction makes it convenient to dispose of the composition of the invention after its use, and this feature adds to the practical advantages of the composition of the invention. This dehydration condensation reaction is shown by the following formula. Therefore, the effect of the composition as a whole is (3),
Equations (4), (5), (6)′, and (7) can be summarized as follows. From formula (3), x・M−OR′+x・H ₂ O=xM−OH+xR′OH
...(3') From formula (4) y・M−X+y・H ₂ O=y・M−OH+yHX
...(4') Representing equations (5) and (6) with equation (5), yHX + yNaHCO ₃ = yNaX + yH ₂ O + yCO ₂
...(5') From formula (7), xM-OH+y・M-OH =x+y/2M-O-M+x+y/2H ₂ O...(7'
) By adding these equations together, we get x・M−OR′+y・M−X+(x+y)H ₂ O +yNaHCO ₃ =(x+y/2)M−O−M+ yCO ₂ +xR′OH+yNaX+(y+x+y/2 ) H ₂ O (8) (x and y each indicate the number of moles). In equation (8), when x = y, that is, M−X and MOR' are equimolar, the H ₂ O term is eliminated, and the reaction as shown in equation (8') below occurs as if water were not present. It seems that M−OR′+M−X+NaHCO ₃ →1/2M−O−M+CO ₂ +R′OH+NaX
...(8′) Actually, in an anhydrous state, such a reaction occurs at least
At temperatures below 100°C, it is not observed at all. If x in equation (8) is smaller than y, that is, M−X is M−
If it is stoichiometrically larger than OR', the reaction will appear to proceed even in the absence of water, but the reaction will not proceed at all without water. On the other hand, if a small amount of water is present stoichiometrically, this reaction of generating R'OH and carbon dioxide proceeds smoothly, which results in the above-mentioned characteristics being exhibited. Next, the mode of using the composition of the present invention will be explained in detail. Articles to be protected from being harmed by the above-mentioned organisms are usually stored in a completely or almost closed container, and at this time, the composition of the present invention is stored together with the product and no emanation from the composition occurs. The two types of vapors, alcohol and carbon dioxide gas, are used to suppress or prevent the activities of the aforementioned organisms attached to the article. In practice, an appropriate amount of the composition of the present invention commensurate with the storage capacity of the article to be protected is stored in a small container at least partially made of a material that is easily permeable to alcohol and carbon dioxide. It is very expedient to place the item together with the item to be protected in a separate container. Materials that are easily permeable to alcohols and carbon dioxide gas may be any known material such as paper, plastic film with micropores in it, metal foil with micropores in it, or a lamination of these materials. can be selected. In addition, as a method for exhibiting the unique functions of the composition of the present invention, when preserving articles with a particularly high moisture content, the composition represented by the general formula of the present invention may be used in a material at least partially having high moisture permeability. Moderately moisture-sensitive polymers (polymer whose gas permeability is low when the water content of the polymer is low, but whose gas permeability increases exponentially when the water content of the polymer increases due to an increase in environmental humidity, etc.) Specifically, if it is stored in a small container made of polyvinyl alcohol, methyl cellulose, polyethylene oxide with an ultra-high degree of polymerization, etc., and then packaged with the stored item, the water vapor generated from the item will be absorbed. It penetrates into the small container through a highly moisture-permeable material and comes into contact with the composition, where the aforementioned reactions of the composition occur for the first time, alcohol and carbon dioxide gas are generated, and these gases enter the small container. It is also possible to easily carry out a method in which the liquid permeates through the highly permeable part of the liquid and fills the product packaging container, thereby suppressing or preventing the activities of the above-mentioned living organisms inside the container. Next, examples of the present invention will be given. Example 1 Anhydrous ethyl alcohol in 166 g of silicon tetrachloride
95 g was added gradually over 60 minutes with vigorous stirring. During this time, the reaction system was cooled from the outside so that the temperature did not exceed 30°C. After adding ethyl alcohol, stir at 30°C for 15 minutes, then gradually raise the temperature to 40°C, and stir for about 1 hour while gradually blowing nitrogen gas to completely drive out the hydrogen chloride produced. I accomplished it. The weight of the obtained product was 186g.
Most of it was dichlorodiethoxysilane, and a small amount of monochlorotriethoxysilane and trichloromonoethoxysilane were also contained, but they were used in the following experiment without being particularly separated. That is, the dichlorodiethoxysilane obtained above was placed in a pouch made of polyvinyl alcohol film (20 microns thick) containing about 8% glycerin as a plasticizer.
0.9 g and dry sodium bicarbonate 0.9 g sealed, the dichlorodiethoxysilane 0.9
g and 0.7 g of dry potassium carbonate and sealed, and 0.9 g of the dichlorodiethoxysilane.
50 bags each were filled and sealed with 0.5 g of dried calcium carbonate. Separately, 100 g of light anhydrous silicic acid and 200 g of anhydrous ethanol were uniformly mixed and adsorbed, and 0.7 g each of the powder was filled into a small bag made of Japanese paper laminated with a perforated polyethylene film. The ethyl alcohol content of this product is approximately equal to 0.9 g of the aforementioned dichlorodiethoxysilane. Also, soda bicarbonate and potassium bitartrate powder each in the same Japanese paper-polyethylene laminate bag.
A version filled with 0.3g was also prepared. We selected white bread as a food with a very high equilibrium humidity of 94%, and put 100 g of a piece of bread into a polypropylene bag. Prepare 5 pieces each containing 1 bag of the same and 1 bag of each, heat seal them, and leave them in a room at 25° to 23°C to determine the number of days until mold grows on the surface of the bread. What I observed was as follows. In the case of only white bread In the case of 3 to 6 days in the case In the case of 16 to 20 days in the case In the case of 17 to 21 days in the case In the case of 16 to 19 days in the case of 8 to 18 days As a result, the composition of the present invention, and It was found that the case in which ethanol is generated is much more effective than the case in which the solid state generates carbon dioxide gas through each reaction, with much less variation.
This is thought to be because there is considerable variation in solid-solid reactions in the static state. Example 2 190 g of titanium tetrachloride was stirred vigorously while being cooled to 5°C, and 120 g of propyl alcohol was added to it.
g was gradually added dropwise over 30 minutes, and then heated to room temperature (23
After heating the mixture to 40°C for 30 minutes and stirring for another 30 minutes, hydrogen chloride was removed by gradually passing in nitrogen gas to obtain 235 g of a product consisting essentially of dichlorodipropoxytitanium. In place of 0.9 g of dichlorodiethoxysilane in Example 1, 1.2 g of this substance was used, and in place of 100 g of bread, the equilibrium relative humidity was 98
An experiment similar to that in the example was conducted using an even higher hanpen. In other words, one piece of commercially available hanpen (approximately 70
g) was used in place of 100 g of bread to check for mold and slimy appearance on the surface. As a result, the number of days until mold and slime appeared was as follows.

[Table] In this case as well, the case in which the composition of the present invention was added was the best. Example 3 A mixed alcohol of 50 g of trans-2-hexenol and 150 g of cis-3-hexenol was reacted with 208 g of monophenyltrichlorosilane under the same conditions as the reaction conditions of silicon tetrachloride and ethanol in Example 1. 330 g of monophenyl monochloro dihexenyloxysilane was obtained. To this was added 200 g of dichlorodiethoxysilane obtained in the same manner as in Example 1 and mixed uniformly, and 180 g of dry calcium carbonate was added and stirred to form a slurry. 20 g of this was placed in 10 wide-mouthed polyethylene bottles each having an internal volume of 50 c.c., and the mouths were covered with Japanese paper.
To 5 of these bottles, 3.5 g of diatomaceous earth carrying 25% water by weight was added per bottle. These jars contain about green asparagus
We placed them in styrene foam boxes containing 800g each and left them at room temperature (25℃) to observe their freshness.
The following results were obtained.

[Table] When the bottle is placed This proves that the composition of the present invention is also effective in preserving the freshness of fresh vegetables.

Claims (1)

[Claims] 1. General formula (However, in the formula, at least one R is a halogen atom, and the rest are individually hydrogen atoms, halogen atoms,
R' is a monovalent hydrocarbon group having 1 to 10 carbon atoms or OR' group, R' is a monovalent hydrocarbon group having 1 to 8 carbon atoms, M is a silicon or titanium atom, and Y is a monovalent hydrocarbon group having 1 to 8 carbon atoms. 7 divalent hydrocarbon group, m is 0
or 1, n is 0 or a positive integer of 10 or less) and carbonic acid or bicarbonate of an alkali or alkaline earth metal. Preservative composition effective for preserving sensitive items.