JP2001072503A - Low odor volatile mildewproofing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent oxidation of benzyl alcohol as a volatile mildewproofing agent to benzaldehyde or benzyl ether, to reduce strong odor and to prolong the life of a mildewproofing function by a vaporization controller. SOLUTION: Oxidation is prevented by using an antioxidant in an amount of 1 to 5 wt.% based on the weight of benzyl alcohol. Odor is reduced by using an odor-lowering agent in an amount of 3 to 10 wt.% based on the weight of benzyl alcohol. The life of an mildewproofing function is prolonged by formulating or adsorbing a vaporization controller in such a way that the weight ratio of the vaporization controller to a formulated product consisting of benzyl alcohol, the antioxidant and the odor-lowering agent is (1:19) to (2:1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-odor, vaporizing and mildew-proofing agent which exhibits a wide range of functions without coming into contact with an object to be controlled.

[0002]

2. Description of the Related Art Conventional fungicides include methyl parahydroxybenzoate, ethyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, thiabendazole, dehydroacetic acid, dehydroacetic acid. Sodium, benzoic acid, sodium benzoate, sorbic acid, sorbin potassium, calcium propionate, sodium propionate and zinc pyrithione. These fungicides are powders or crystals, slightly odorous or odorless. However, in order to impart a fungicidal function, they must be brought into contact with an antifungal substance. Other powder or crystalline fungicides that emit a strong odor include orthophenylphenol, sodium orthophenylphenol, diphenyl, and the like. It is necessary to contact the antifungal substance.

[0003] Examples of liquid fungicides include low-odor ethylene glycol monophenyl ether (also known as 2-phenoxyethanol) and benzalkonium chloride. These materials also cannot provide a fungicide function unless the fungicide is brought into contact with the fungus-proof material.

[0004] Ethyl alcohol, which occupies 80% of the germicidal disinfectant market, is used as a fungicide by being added to processed foods. However, since the food is contaminated with ethyl alcohol, the flavor of the food is impaired. I was afraid. In order to solve this drawback, virgin pulp sheets were impregnated with edible fatty acids and edible ethanol, and the impregnated sheets were coated with a resin and a film with high gas barrier properties. There are things.
This multilayer structure of the ethyl alcohol-impregnated material is for gradually evaporating ethyl alcohol having high volatility (volatilization). This multilayer structure of ethyl alcohol impregnated material exhibits fungicidal properties when it is completely sealed together with food with a high gas barrier film, but when it is sealed with a low gas barrier film or has a gas barrier property If the film is not completely sealed even if a film having a high degree is used, the fungicide cannot be exhibited.

[0005]

The problems to be solved are that most of the antifungal agents are required to come into contact with the antifungal agent, so that a wide range of antifungal function cannot be expected, and the freshness of food. When used as a preservative, it may give a strong odor or impair the flavor, and there are many substances that are regarded as endocrine disruptors, and their safety is a concern.

[0006]

DISCLOSURE OF THE INVENTION The present invention uses highly safe benzyl alcohol as a volatile antifungal agent, and considers that this volatile antifungal agent changes to benzaldehyde, an aldehyde harmful to the human body, by natural oxidation. In addition to preventing benzyl ether, which has no fungicide function, it is prevented by an antioxidant, and the strong odor of benzyl alcohol is reduced by an odor reducing agent, and the life of the fungicide is extended by a vaporization regulator. It is to plan.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The low odor vaporizing antifungal agent of the present invention comprises L-ascorbic acid stearic acid ester, in order to prevent the loss of antifungal ability due to the natural oxidation of benzyl alcohol.
At least one of the antioxidants consisting of dibutylhydroxytoluene, dl-α-tocopherol, guaiac butter, nordihydroguaiaretic acid and gallic acid is dissolved in benzyl alcohol in an amount of 1 to 5% based on the weight of benzyl alcohol. I just need.

The strong odor of benzyl alcohol can be reduced by using glycerin in an amount of 3 to 10% based on the weight of benzyl alcohol. When butylhydroxyanisole is used as an antioxidant, it is difficult to reduce the odor because the odor of the antioxidant rises.

Surfactants other than glycerin as odor reducing agents include polyoxyethylene octyl phenyl ether (provided that the number of moles of ethylene oxide added is 5 to 12).
Up to moles. ), 1: 1 molar coconut oil fatty acid diethanolamide, 1: 1 molar lauric acid diethanolamide, 1: 2 molar coconut oil fatty acid diethanolamide,
1: 2 molar lauric acid diethanolamide and sodium salt of dioctyl sulfosuccinic acid. These surfactants are present in an amount of 3 to 3% by weight of benzyl alcohol.
When 10% is used, specific odor is reduced. It is preferable that the surfactant is used in combination with glycerin or a plurality of surfactants is used rather than a single product.

To extend the life of the antifungal function, it is conceivable to delay or prevent the natural oxidation of benzyl alcohol with an antioxidant. However, the volatilization of benzyl alcohol cannot be adjusted with an antioxidant, so that the life of the benzyl alcohol should be extended. Can not do. Therefore, in order to adjust the volatilization of benzyl alcohol, a mixture of benzyl alcohol, an antioxidant and an odor reducing agent, a porous carrier and / or an oil absorbing agent as a vaporization adjusting agent are used in a ratio of 19: 1 to 1: 1. : 2 by weight ratio.

The porous carrier includes vermiculite, perlite, shirasu balloon, theolite, sepiolite,
Hill stone, pumice, activated clay, kaolin mineral, hydrotalcite, talc, snowtex, bentonite, smectite, serpentine mineral, anhydrous silica, mica clay mineral, activated carbon, hollow silica, synthetic aluminum silicate and diatomaceous earth . Among these porous carriers, the specific surface area is 30.
The carrier preferably has a pH of 3 to 8 in a 4% aqueous dispersion from the viewpoint of not less than 0 m ² / g and preventing deterioration of benzyl alcohol.

Examples of the oil absorbing agent include cyclodextrin, anhydrous crystalline maltose, hydrated crystalline maltose, polyethylene glycol, paraffin wax, and hydrogenated castor oil. Among these oil absorbing agents, water-insoluble paraffin wax and hardened castor oil have good compatibility with a compound comprising an antifungal agent, an antioxidant and an odor reducing agent. In addition,
Polyethylene glycol having an average molecular weight of 20,000 to 30,000 is also a desirable oil-absorbing agent, but is disadvantageous in that it easily dissolves in water and softens as the temperature rises.

[0013]

EXAMPLES Example 1 A glass mouthpiece having a volume of 500 cc (outside diameter × height = 90 mm × 119 mm) was placed in a glass bottle.
Prepare 6 bottles each containing 1 slice of bread cut into 0 mm, 30 mm in height, and 35 mm in width, and fix both ends with cellophane tape so that the following nonwoven fabric is straddled across the mouth of the bottle. Place the bottle in a polystyrene petri dish (outer diameter 1
(2 cm, height 1.7 cm). The bottle with the lid was placed in a room having an average temperature of 27 ° C., and the occurrence of mold was observed. The non-woven fabric is made of polyester (with a basis weight of 50 g / m2).
² ) The dimensions were 2 cm x 10 cm, and bread was used on the second day after production. Non-woven fabric A: Non-woven fabric only. Non-woven fabric B: 0.2 g of benzaldehyde impregnated in the center of the non-woven fabric and left for 1 hour in a room. Non-woven fabric C: 0.2 g of benzyl ether impregnated in the center of the non-woven fabric and left for 1 hour in a room. Non-woven fabric D: 0.2 g of benzyl alcohol in the center of the non-woven fabric
Impregnated and left in the room for 1 hour. Nonwoven fabric E: 0.2 g of benzyl alcohol containing 1% by weight of L-ascorbic acid stearic acid ester dissolved in the center of the nonwoven fabric, and left in a room for 1 hour. Non-woven fabric F: 0.2 g of benzyl alcohol containing 1% by weight of L-ascorbic acid stearic acid ester and 3% by weight of glycerin dissolved in the center of the non-woven fabric, and
Things left in the room for hours. Non-woven fabric G: A non-woven fabric D impregnated with 0.2 g of a mixture of a benzyl alcohol solution impregnated in a non-woven fabric D and a smectite in a weight ratio of 95: 5, and left in a room for 1 hour. Results Nonwoven fabric A: One sesame seed-sized blue mold was formed at a corner 2 mm above the bottom of the bread after 58 hours, and after 80 hours, the blue mold grew to soybean size. One month later, the mold was white, grey,
About 40% of the bread contains black and gray-colored olive-colored molds in about 40% of bread, and 25% of gray and light-black colored molds containing blue mold on the adjacent side. Reached. Non-woven fabric B: No mold was generated even after one month, and the inside of the bottle had a slight smell of benzaldehyde. Non-woven fabric C: After 89 hours, one spot of sesame seed-sized red mold was generated at the corner of the bread bottom. Non-woven fabric D: No mold was generated even after one month, and the inside of the bottle smelled of benzyl alcohol. Non-woven fabric E: Mold was not generated even after one month, and the inside of the bottle smelled of benzyl alcohol. Non-woven fabric F: Mold was not generated even after one month, and the inside of the bottle only slightly smelled the bread at the time of purchase. Non-woven fabric G: Mold was not generated even after one month, and the inside of the bottle had only a scent of bread at the time of purchase, and was slightly dry and crisp when eaten.

(Example 2) Nonwoven fabric A used in Example 1
Reuse 7 types of non-woven fabrics from ~ G
The same fungicidal test as in Example 1 was performed, except that the polyethylene film bag of μ was used. The dimensions of the polyethylene film bag are 250 mm x 300 mm. The nonwoven fabric was fixed laterally to the center of the inner surface of the polyethylene bag with cellophane tape, blown air with a dryer to inflate the bag, and then tied the mouth of the bag with rubber bands. For bread, use the one that has been moistened by spraying it with water by spraying. Results Non-woven fabric A: Observation after 17 hours produced an odor having a sour taste, 26 hours later produced a rotten odor, and 41 hours later produced red mold and yellow mold. Non-woven fabric B: Observed 17 hours later, exhibited a fermentation odor similar to ethyl alcohol, but became odorous after 26 hours, and developed blue mold 41 hours later. Non-woven fabric C: Observation after 17 hours produced an odor having a sour taste, 26 hours later produced a rotten odor, and 41 hours later produced red mold. Non-woven fabric D: Observation after 17 hours produced an odor exhibiting a slight acidity, 26 hours later produced a rotten odor, and 41 hours later produced blue mold. Non-woven fabric E: Observed 17 hours later, exhibited a slight fermentation odor like ethyl alcohol, 26 hours later exhibited a slightly sour taste, 41 hours later became a mixed odor with strong acidity and rotten odor, and 50 hours later Black mold developed. Non-woven fabric F: No change was observed after 17 hours, 26
After hours, it was slightly sour, but after 41 hours, black mold appeared. Non-woven fabric G: 17 hours, 26 hours, 41 hours, 50 hours
There was no change in any of the observations after hours, and there was no change after 720 hours, and the scent of the bread was still present.

Example 3 The following coating agent was prepared using a benzyl alcohol solution containing 5% by weight of dibutylhydroxytoluene, and had a size of 150 mm × 30.
0.1 g of a coating agent is applied to a 0 mm, 15 μm thick polyethylene film bag with a metal spatula. The application of metal with a spatula is 5 cm below the mouth of the bag, 2 cm wide,
Using a mold to measure the length of 4 cm,
Air-drying was performed for minutes. After air drying, turn the bag upside down and put a preservative-free fish paste kneaded pen (with a thickness of 2 cm,
The bag was swelled by blowing air into the bag with a drier, and then the mouth of the bag was tied with a rubber band. still,
The binder of the coating agent was obtained by dissolving chlorinated polypropylene in 30% by weight toluene, and the anhydrous silica used had a pH of 3.5 when dispersed in 4% water. Coating agent H: binder only. Coating agent I: mixture of 10 g of benzyl alcohol solution and 90 g of binder. Coating agent J: 10 g of 0.5 g of glycerin dissolved in 10 g of benzyl alcohol solution and binder 9
Mixture with 0 g. Coating agent K: a product obtained by dissolving 0.5 g of polyoxyethylene octyl phenyl ether (8 mol of ethylene oxide adduct) in 10 g of benzyl alcohol solution 1
A mixture of 0 g and 90 g of a binder. Coating agent L: 0.2 g of glycerin and polyoxyethylene octyl phenyl ether (8 mol of ethylene oxide adduct) in 10 g of benzyl alcohol solution
A mixture of 10 g obtained by dissolving 0.3 g and 90 g of a binder. Coating agent M: 0.2 g of glycerin and polyoxyethylene octyl phenyl ether (8 mol of ethylene oxide adduct) in 10 g of benzyl alcohol solution
9.5 g in which 0.3 g is dissolved and 0.5 g of anhydrous silica
Of 10 g of a mixture of the above and 90 g of a binder. Results Coating agent H: Observation after 20 hours revealed that the hang pen had a weak odor like ammonia. Coating agent I: The nonwoven fabric had a slight odor of benzyl alcohol, and there was no change in the hang pen after 20 hours of observation. However, after 25 hours, a weak ammonia-like odor was generated and green mold of sesame seeds was formed. Three had occurred. Coating agent J: The nonwoven fabric had a slight benzyl alcohol odor, and there was no change in the hang pen after 20 hours of observation. However, after 25 hours, a weak ammonia-like odor was generated, and sesame seed-sized blue mold was observed. And black mold were generated one by one. Coating agent K: The nonwoven fabric had a slight benzyl alcohol odor, and there was no change in the hang pen after 20 hours of observation. However, after 25 hours, a weak ammonia-like odor was generated, and the sesame seeds were black. One mold had developed. Coating agent L: The non-woven fabric had almost no smell, and there was no change in the hang pen after 20 hours of observation. However, after 25 hours, a weak ammonia-like odor was generated together with a moldy smell, and two black molds of sesame seed size also appeared. Had occurred. Coating agent M: The non-woven fabric has almost no smell, no change in any of the observations after 20 hours and 25 hours, and every 28 hours after 28 hours, but no change in the observation after 260 hours. I didn't. When I ate the hang pen after 260 hours, the surface was slightly dry and felt slightly hard, but the inside was soft and did not lose its flavor.

Example 4 2 g of the following antifungal agent was put into a nonwoven bag, and the mouth of the bag was heat-sealed. Use what is hung for 48 hours. Each of the antifungal agents in the bags is placed in a bag of polyvinyl chloride having a size of 22.5 cm × 15 cm × 3.5 cm, and each bag is placed in a 17 cm space.
Place a 10 m (10 mm) foot with a gap of 1 cm (foot height: 7 mm) and place "open horse mackerel dried overnight" and seal with a vinylidene chloride film for home use. The sealed “opened horse mackerel” is placed in a room with an average temperature of 28 ° C. to perform a freshness maintenance test. The non-woven fabric is polyester 10
At 0%, the basis weight is 90 g / m ² and the bag size is 2 cm
× 3 cm. In addition, "opened horse mackerel dried overnight" (hereinafter abbreviated as "specimen") was used without red eyes. Antifungal agent O: 5 mm pellets of synthetic aluminum silicate having a specific surface area of 320 m ² / g (hereinafter simply referred to as “pellets”). Antifungal agent P: A substance obtained by adsorbing benzyl alcohol to a pellet by half the weight of the pellet. Antifungal agent Q: A product obtained by adsorbing a benzyl alcohol solution containing 3% by weight of dl-α-tocopherol on a pellet to half the weight of the pellet. Antifungal agent R: A benzyl alcohol solution in which 5% by weight of guaiac acid is dissolved is adsorbed to a pellet by half the weight of the pellet. Antifungal S: 100 g of benzyl alcohol solution containing 3% by weight of dl-α-tocopherol, 4 g of 1: 1 molar lauric acid diethanolamide and 2 g of Na salt of dioctyl sulfosuccinic acid are pelletized into pellets. A substance adsorbed by half the weight. Antifungal agent T: A solution in which 100 g of benzyl alcohol in which 5% by weight of guaiac acid is dissolved, 2 g of glycerin, and 4 g of 1: 2 mole coconut oil fatty acid diethanolamide are adsorbed on a pellet in half the weight of the pellet. Antifungal agent U: A benzyl alcohol solution containing 5% by weight of polyethylene glycol having an average molecular weight of 20,000 (hereinafter simply abbreviated as "PEG") is adsorbed to a pellet by half the weight of the pellet. Antifungal agent V: A solution obtained by dissolving 5% by weight of PEG in a benzyl alcohol solution of antifungal agent Q, and adsorbing half of the weight of the pellet on the pellet. Antifungal agent W: A solution obtained by dissolving 5% by weight of PEG in a benzyl alcohol solution of antifungal agent R, and adsorbing half of the weight of the pellet on the pellet. Antifungal agent X: A solution obtained by dissolving 5% by weight of PEG in a solution of antifungal agent S and adsorbing half of the weight of the pellet on the pellet. Antifungal agent Y: A solution obtained by dissolving 5% by weight of PEG in a solution of antifungal agent T and adsorbing half of the weight of the pellet onto pellets. Antifungal agent Z: 100 g of benzyl alcohol solution in which 2% by weight of nordihydroguaiaretic acid and 3% by weight of propyl gallate are dissolved, 2 g of 1: 2 mole lauric diethanolamide and 1: 1 mole coconut fatty acid A solution obtained by dissolving 5% by weight of paraffin wax in a solution of 3 g of diethanolamide and adsorbing half of the pellet weight on the pellet. Results Antifungal agent O: After 8 hours, the eyes of the sample were discolored red, but there was no odor associated with the decrease in freshness. 2
After 4 hours, both the body and the back of the sample were sticky and spoiled, and had a weak amine-like odor. Antifungal agent P: No change was observed in the eyes of the sample after 8 hours, and the inside of the container slightly smelled benzyl alcohol. After 24 hours, there was no change in the sample, but after 32 hours, the eye of the sample had turned red, but no odor was generated. After 48 hours, an amine-like odor was generated due to putrefaction, and a light brown juice had appeared at the bottom of the container. Antifungal agent Q: Same results as antifungal agent P. Antifungal agent R: Same results as antifungal agent P and antifungal agent Q. Antifungal agent S: No change was observed in the eyes of the sample after 8 hours, and only the smell of the sample was found in the container. After 24 hours, there was no change in the sample, but after 32 hours, only the eye of the sample turned red and no odor was generated. After 48 hours, an amine-like odor was generated due to putrefaction, and a light brown juice had appeared at the bottom of the container. Antifungal agent T: Same results as antifungal agent S. Antifungal agent U: After 8 hours, no change was observed in the eyes of the sample, and the inside of the container smelled benzyl alcohol. 2
After 4 hours, there was no change in the sample, but a colorless juice had appeared at the bottom of the container. After 48 hours, there was no change in the sample, and the colorless juice slightly increased. After 168, the eyes of the sample were withered due to the dehydration phenomenon, but did not rot, and smelled of benzyl alcohol. After 168 hours, the sample was baked and eaten, but no change in taste was observed. Antifungal agent V: Same results as antifungal agent U. Antifungal agent W: Same results as antifungal agent U and antifungal agent V. Antifungal agent X: Observation after 8 hours showed no change in the sample, and the inside of the container only smelled the sample. 2
The change in the specimen after 4 hours was that a colorless juice had appeared at the bottom of the container. After 48 hours, no change was observed in the sample, but the colorless juice had increased slightly. After 168 hours, the eyes of the sample were slightly withered, but did not rot and only smelled. After 168 hours, the sample was baked and eaten, but no change in taste was observed. Antifungal agent Y: Same results as antifungal agent X. Antifungal agent Z: No change was observed in the sample after 8 hours of observation, and the sample only smelled. After 24 hours, there was no change in the specimen and no juice was produced. After 168 hours, there was no change in the specimen, but the place where he baked and ate, U ~ X
It tasted fresher and fresher than the one containing the antifungal agent.

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[Procedure amendment]

[Submission date] October 18, 1999 (1999.10.
18)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0002 (conventional technology)

[Correction method] Change

[Correction contents]

(Prior art) Conventional fungicides include methyl parahydroxybenzoate, ethyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, thiabendazole, dehydroacetic acid. , Sodium benzoate, sodium benzoate, sorbic acid, potassium sorbate , calcium propionate, sodium propionate and zinc pyrithione.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) A01N 25/30 A01N 25/30 25/32 25/32

Claims (7)

[Claims] 1. A low-odor vaporizing antifungal agent comprising benzyl alcohol as a vaporizing antifungal agent, which contains an antioxidant, an odor reducing agent and a vaporization controlling agent. 2. An antioxidant comprising L-ascorbic acid stearic acid ester, dibutylhydroxytoluene, dl-
at least one of α-tocopherol, guaiac, nordihydroguaiaretic acid and propyl gallate, the content of which is 1 to the weight of benzyl alcohol;
The low-odor vaporizing fungicide according to claim 1, wherein the amount is from 5% to 5%. 3. The low-odor gaseous antifungal agent according to claim 1, wherein the odor reducing agent is at least one of glycerin and a surfactant, and the content thereof is 3 to 10% based on the weight of benzyl alcohol. 4. The surfactant is polyoxyethylene octyl phenyl ether (provided that the number of moles of ethylene oxide added is from 5 to 12 mol), 1: 1 mol type coconut oil fatty acid diethanolamide, 1: 1 mol type The low-odor gaseous antifungal agent according to claim 3, which is at least one of lauric acid diethanolamide, 1: 2 mol type coconut oil fatty acid diethanolamide, 1: 2 mol type lauric acid diethanolamide, and sodium salt of dioctyl sulfosuccinic acid. . 5. The method according to claim 1, wherein the vaporization modifier is at least one of a porous carrier and an oil absorbing agent, and the content thereof is 1:19 with a composition comprising benzyl alcohol, an antioxidant and an odor reducing agent.
The low-odor gaseous antifungal agent according to claim 1, which has a weight ratio of about 2: 1. 6. A porous carrier comprising vermiculite, perlite, shirasu balloon, zeolite, sepiolite, hillite, pumice, activated clay, kaolin mineral, hydrotalcite, talc, snowtex, bentonite, smectite, serpentine mineral, anhydrous silica 6. The low-odor gaseous antifungal agent according to claim 5, which is at least one selected from the group consisting of mica clay mineral, activated carbon, hollow silica, synthetic aluminum silicate and diatomaceous earth. 7. The low-odor gaseous antifungal agent according to claim 5, wherein the oil absorbing agent is at least one of cyclodextrin, anhydrous crystalline maltose, hydrated crystalline maltose, polyethylene glycol, paraffin wax and hydrogenated castor oil.