JPS63126801A - Beltlike material for heating and vaporization - Google Patents

Abstract

PURPOSE:To obtain a beltlike material for heating and vaporization useful for insect killing, sterilizing, deodorizing, aroma providing, etc., by transferring a beltlike material impregnated with a chemical and a specific compound as an antioxidant, successively heating the beltlike material by a heating element directly and vaporizing the chemical under heating. CONSTITUTION:A beltlike material impregnated or provided with a chemical such as insecticide and at least one compound such as 2,2'-methylenebis(4-ethyl-6- t-butylphenol), etc., as antioxidant not actually vaporizing at a heating tempera ture is transferred and the beltlike material is directly or indirectly heated by a heating element to heat and vaporize the chemical. Thermal decomposition and polymerization of the chemical during heating and formation of resinous substances due to the thermal decomposition, etc., are suppressed and effective and stable vaporizing effects can be continued for a long period. Since the antioxidant is slightly liquefied, the beltlike material hardly becomes a wet state, members such as beltlike material guide, etc., in the circumference of a device for heating and evaporation is slightly contaminated and the beltlike material has excellent stability with time during preservation.

Description

[Detailed Description of the Invention] [Industrial Application] The present invention relates to a belt-shaped body for heating transpiration, and more specifically,
For the purposes of insecticidal, sterilizing, deodorizing, fragrance, etc., a method in which a strip impregnated with and holding a corresponding drug is transferred, and the strip is successively heated directly or indirectly with a heating element to heat and evaporate the drug. This invention relates to a band-shaped body used in a device.

[Conventional technology]

A strip (tape) impregnated with a chemical that evaporates when heated.
Methods and devices have been known for a long time, in which the drug is transferred continuously or intermittently and then heated directly or indirectly as it passes through a heating element to evaporate the drug.
No. 073, Jitko No. 40-19950, Jitko No. 42-5
No. 017, Jitko No. 48-26931, Jitko No. 49-3
No. 1670, Utility Model Publication No. 51-51884, Utility Model Application No. 1988-
No. 7772, Utility Model No. 61-11204, etc.).

An example of a basic configuration of such a heating evaporation method is shown in the drawings. In the figure, reference numeral 1 denotes a band-shaped body impregnated with and holding a heat-volatile chemical, which is wound around and held by a feed roll 2, and driven by a drive roll connected to a motor for 40 rotations. The strip 1 is held between the strip 1 and the vinyl roll 5 and transferred at a predetermined speed, and then wound onto the take-up roll 6. However, when the strip 1 passes through a heating element 3 such as a heater, it is heated and the drug is evaporated. Ru.

The belt-shaped body used in such a heating evaporation method is as follows:
Generally, a tape made of paper, cloth, nonwoven fabric, etc. impregnated with a drug solution is used.

For example, Japanese Patent Publication No. 55-43727, Utility Model Publication No. 51-
No. 51884 discloses that a large impregnable paper tape is immersed in a solution in which the insecticidal ingredient Binanon is dissolved in alcohol, and then the tape is dried to obtain a treated tape, and the treated tape is run at a running speed of 2 to 30 cr. It is described that the material is transported at a very low speed of 180° C./hr and heated by a heating element heated to around 180° C. to volatilize it.

[Problem that the invention seeks to solve]

In the case of a strip impregnated with only a drug as described above, there are problems in that the stability of the drug over time is poor and the thermal stability during heating is extremely poor. In addition, during heat evaporation, high boiling point substances generated by thermal decomposition of the drug and high boiling point substances contained in the solvent produce resin compounds, which adhere to the surface of the heating element, resulting in a decrease in thermal conductivity. However, this leads to a decrease in the volatilization rate, leading to a problem in that the effective volatilization rate of the chemical is significantly lowered.

In order to improve the thermal stability of a drug when it is heated, it is generally considered to add an antioxidant.

For example, in Japanese Patent Application Laid-open No. 57-203002, a drug is dissolved in kerosene, alcohol, etc., and when used, it is 1 to +00 /
A.
A method of heating and evaporating at a heating temperature of 200° C. is described, but it is also described that an antioxidant such as BET, BHA, etc. can be added to the drug solution as necessary.

However, EHT and BHA are approximately 70°C and 60°C, respectively.
It has the property of being liquefied at ℃ and highly volatile, and the agent coated and impregnated on the strip will liquefy and volatilize before reaching the heating part, and the expected effect of adding antioxidant will not be achieved. The effect cannot be expected. In particular, the lower the transfer speed, the longer the preheating time using radiant heat or the like before heating, during which time BHT and BHA will volatilize, and the thermal decomposition of the active pharmaceutical ingredient will become more pronounced during heating. Furthermore, B
The viscosity of the chemical solution is low in the liquefaction temperature range of HT and BHA.
When the surface of the strip is wet, there is a problem in that the surrounding contact surfaces (particularly the surface of the heating element and the guide of the strip) are easily contaminated.

Therefore, the purpose of the present invention is to solve the above problems and
It has excellent stability over time with no deterioration during storage, and virtually no thermal deterioration or thermal decomposition or polymerization of the drug during heat use, ensuring that sufficient drugs remain effective over long periods of time. An object of the present invention is to provide a heating evaporation belt-like body that can evaporate.

A further object of the present invention is to provide a heating evaporation strip that is less likely to become wet near the heating element and has less risk of contaminating contact surfaces such as the heating element surface and the strip guide.

[Means for solving problems]

The band-shaped body for heating evaporation of the present invention is a band-shaped body used in a method in which a band-shaped body impregnated with and holding a drug is transferred, and the band-shaped body is sequentially heated directly or indirectly with a heating element to heat and transpire the drug. , along with the drug, 2.2'-methylenebis(4-ethyl-6-t-butylphenol), 212'methylenebis(4-methyl-6-t-butylphenol), 4
．． 4'-methylenebis(2-methyl-6--butylphenol), 4,4'-butylizo/bis(3-methyl-
6-t-butylphenol), 414'-thiobis(3
-methyl-6-<-butylphenol), 4,4'-methylenebis(2゜6-di-t-butylphenol), stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propio* -), l, 3,5-trimethyl-2,4,6-tris(3,5-di-t-1thyl-
4-hydroxybenzyl)benzene, 1,1,3-tris(2-methyl-5-t-,-7thyl-4-hydroxyphenyl)butane, tetrakis[methylene(3,5-di-t-butyl-4- It is characterized by being impregnated with at least one compound selected from the group consisting of methane (hydroxycinnamate) that does not substantially volatilize at heating temperatures, and thus contains a specific antioxidant. The above-mentioned object is achieved by coating and impregnating the strip with a drug.

[Operation and mode of the invention]

A typical example of an antioxidant is 3,5-di-t--)'
Chi-4-hydroxytoluene (EHT) and 3-t-
Butyl-4-hydroxyanisole (BHA) is known, but these antioxidants quickly volatilize at heating temperatures of 100°C or higher in the heat evaporation method, and cannot exhibit antioxidant effects. . Therefore, when such an antioxidant is added to a chemical solution and used by coating and impregnating a band-shaped body with it, the chemical becomes resinous, deposits accumulate on the surface of the heating element, and the thermal conductivity decreases. This leads to a decrease in the volatilization rate of the chemical, making it impossible to obtain a high effective volatilization rate over the long term.

On the other hand, according to the research conducted by the present inventors, when the above-mentioned specific compound, that is, an antioxidant that does not substantially volatilize at the heating temperature used, is applied and impregnated into a strip together with a drug, the above-mentioned There are no problems, and thermal decomposition, polymerization, or resin formation due to oxidation of the drug during heating is suppressed.
It has been found that there is almost no significant accumulation of deposits on the surface of the heating element, and that chemical volatilization can be maintained stably at a high effective volatilization rate over a long period of time.

The compound to be applied and impregnated with the drug on the strip according to the present invention is an antioxidant that does not substantially volatilize at the heating temperature used, and the following compounds can be used. In addition, an abbreviation was added to each compound as a reference number of the compound used in the Example mentioned later.

0 stearyl-β-(3,5-di-butyl-4-
Hydroxyphenyl) propionate (hereinafter abbreviated as compound A) 02-2'-methylene-bis(4-methyl-6-t-butylphenol) (hereinafter abbreviated as compound B) 02.2'-methylene-bis(4 -ethyl-6-t-butylphenol) (hereinafter abbreviated as compound C) 04.4'-methylene-bis(2-methyl-6--butylphenol) (hereinafter abbreviated as compound C) 04.4 '-methylene-bis(2,6-di-t-butylphenol) (hereinafter abbreviated as compound E) 04.4'-butylidene-bis(3-methyl-6''''t
-butylphenol) (hereinafter abbreviated as compound F) 04.4'-thiobis(3-methyl-6-6-butylphenol) (hereinafter abbreviated as compound G) 0 1.3.5-trimethyl-2,4 ,6-tris(3
, 5-di-t-butyl-4-hydroxybenzyl)benzene (hereinafter abbreviated as compound H) 0 1 , l , 3-tris-(2-methyl-5-1-butyl-4-hydroxyphenyl)butane ( Hereinafter, it will be abbreviated as compound I. Tetrakis[methylene (3,5-di-t-butyl-4-hydroxycinnamate)]methane (hereinafter abbreviated as compound I) These compounds may be used alone or in combination. It is also possible to use a combination of the above.The amount used is preferably 1 to 50% by weight of the amount of the drug.If the amount added is too small, problems such as prevention of thermal deterioration during the production of strips and heat use may occur. It is difficult to obtain the effect of adding antioxidant.

In addition, dilaurylthiodipropione (DLTp) and distearylthiodipropione (DSTp) are used as antioxidants commonly called peroxide decomposers.
Similarly, they can be used in combination with the antioxidant in the present invention.

This decomposes peroxides, such as adhesive substances, during heating use, and allows for stable volatilization over a long period of time.

The strip of the present invention is impregnated and retained with various insecticides, bactericides, deodorants, perfumes, etc. together with the above-mentioned specific compounds for the purpose of insecticidal, sterilizing, deodorizing, fragrance, etc.

When the purpose is to kill insects, various conventionally used volatile insecticides can be used, including pyrethroid insecticides, carmate insecticides, organophosphorus insecticides, etc. be able to. Generally, pyrethroid insecticides are preferably used because of their high safety.
For example, the following insecticides:

03-allyl-2-methylcyclopent-2-ene-4
-on-1-yl di-cis/trans-chrysannamer) (generic name allethrin; trade name pinamine; manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as pA) 03-allyl-2-methylcyclopent-2-ene-4
-O-1-yl d -cis/trans-chrysanthemate (trade name Pinamine Forte: manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as pB) Od-3-allyl-2-methylcyclopent-2-ene- 4-on-1-yl d-trans-chrysanthemate (trade name Exlin: manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as PC) 03-allyl-2-methylcyclopent-2-en-4-one-1 -yl d-) u/sucrysanthemate (-some names paioallethrin, hereinafter abbreviated as pD) 02-Methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl chrysanthemate (hereinafter pE
) OA'-(3t4*5*6-titrahydrophthalimide)
-Methyl dl -cis/trans-chrysantemate (-several phthalthrines; trade name neopinamine; manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as PF) 05-benzyl-3-furylmethyl d-cis/trans-chrysante Mart (-Sumethrin: Product name: Lithrone Forte: Manufactured by Sumitomo Chemical Co., Ltd., hereinafter referred to as pG
o 3-phenoxybenzyl 2,2-dimethy” -3
-(2' s 2' -dichloro)vinylcyclopropane carboxylate (-Several names Vermetri/: Trade name Exmin: Manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as PI) o 3-phenoxybenzyl d-cis/) 2 /suchrysanthemate (-several names Phenotri/:Product name Sumitrin: Manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as pJ) 0 α-cyanophenoxybenzyl isopropyl #-4
-ri ao phenylacet f-) (-Several names Fuenvalerate: Trade name Sumicidine, manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as PK) ○ (S)-α-cyano-3-phenoxybendi# (IRt )-3-(12-tsuk00
(vinyl)-2,2-dimethylcycloprono(carpoxylate (-several names) ipermethrin f, hereinafter abbreviated as pL) o <R,S)-α-cyano-3-phenoxybenzyl (IN, l5) -cis/trans-3-(2,2-
dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (-some names cypermethrin, hereinafter p i
abbreviated as W) 0 α-cyano-3-phenoxybenzyl d-cis/transucrysa/temate (-several ifenoF phosphorus, hereinafter abbreviated as pN) o 1-ethynyl-2-methyl-2-pentele cis/trans-chrysannamer) (-several names hehathrin, hereinafter abbreviated as PO) 03-allyl-2-methyl-cyclopentane 2-
En-4-on-1-yl-2,2,3゜3-tetramethylcyclopropanecarboxylate (-several names telarethrin, hereinafter abbreviated as PP) 01-ethynyl-2-methyl-2-benteny”2+2+
3+3-tetramethylcyclopropanecarboxylate (hereinafter abbreviated as PQ) 01-ethynyl-2-methyl-
2-Pentenyl 2,2-dimethyl-3-(2,2-dictetravinyl)cyclopropane-1-carboxylate (hereinafter abbreviated as PR) 0 ((pentafluorophenyl)-methyl]-IR
,3R-3-<2,2-dictetraloethynyl)-2,2-
Dimethyl-cyclopropane carboxylate (-several 7
Enfluthrin, hereinafter abbreviated as ps) 0 (Si2-me9- to-4-; Irki'/-3-(2-
(7'rovinyl) cyclopent-2-enyl (IR) ~ cis, trans chrysanthemer) (hereinafter abbreviated as PT) For the purpose of insect repellent/repellent effect, diethyl toluanide, dimethyl phthalate, dibutyl phthalate, Retsupar 11 Tetrahuman tetrafurfural derivatives such as (manufactured by Yoshitomi Pharmaceutical Co., Ltd., registered trademark), isocincomero/rn esters such as Retsupar 333 (manufactured by Yoshitomi Pharmaceutical Co., Ltd., registered trademark m>), octanediol (2-ethyl-1,3-hexanediol) , 2-butyl-2-ethyl-1゜3-propa/
Repellents such as diols and di-hexamethylene carboxide can be used.Similarly, when used for fragrance purposes, various natural and artificial fragrances can be used, such as animal and vegetable fragrances. Natural fragrances such as hydrocarbons, alcohols, phenols, aldehydes, ketones, lacto/oxides, artificial fragrances such as esters, etc. These can be used alone or in combination of two or more. You can also. Furthermore, depending on the purpose, deodorants such as borneol and camphor, or chemicals such as bactericides can be used as long as they are volatilized by heating.

In addition, other additives such as pigments, dyes, or extenders such as paraffins, esters, and glycols may be blended as necessary within a range that does not impair the properties.

The strip can be made of any material that can withstand the heating temperature used, such as pulp, linter, rayon, etc.
It is a tape-like material or a string-like material made of hemp, synthetic paper, nonwoven fabric, paper, etc., and its width and thickness can be arbitrarily designed depending on the purpose of use.

As a treatment method for impregnating and retaining the drug and the specific compound into the strip, various conventionally known methods can be adopted. A specific compound is injected into a strip that is pre-impregnated with and holds a chemical, or it is dissolved in a solvent such as alcohol or hydrocarbons, the strip is dipped in this, or the strip is coated, and the solvent is added as necessary. Any method can be used, such as removing by drying. Furthermore, the amount of drug impregnated and retained in the strip can be set within an appropriate range depending on the purpose of use.

The heating evaporation strip of the present invention can be used in various conventional heating evaporation devices, but generally the running speed is 1 to 20.
It is preferable to use the heating element at a temperature of 80 to 180 DEG C., and any heating method can be used such as a heating resistor (chromium wire, etc.), PRC, infrared heating, ceramic heater, etc.

〔Example〕

The present invention will be specifically described below with reference to Examples.

Example 1.2 and Comparative Examples 1 to 4 A solution of each prescription drug shown in Table 1 dissolved in an appropriate amount of hexane was applied to a strip having a width of 10 mm, a thickness of Q, lss, and a length of 360 m1. After that, hexane was removed by drying to prepare various drug-impregnated strips. This was moved at a speed of 30"/Ar in close contact with a heating element having a 15 x 20 m heat sink and set at 160 °C. The volatilization rate of the chemical was determined.The results are shown in Table 1.
It is also shown in .

Note that the volatilization rate was determined as follows.

Amount of drug charged per unit time: Amount of drug charged into a traveling strip within a unit time.

Amount of chemical volatilization per unit time: The volatilized vapor is continuously trapped in a silica gel-filled column for a certain period of time, extracted with chloroform, and quantitatively analyzed using a reduced-diameter gas chromatograph.The sum of the values thus obtained is calculated as the total volatilization time. O divided by Table 1 As is clear from the results shown in Table 1 above, there is no significant difference between those containing the volatile antioxidant BHT and those not containing it. Compared to these, those containing an antioxidant that does not substantially volatilize according to the present invention showed an extremely high volatilization rate of 90% or more.

Examples 3 to 22 Same as Example 1 above, except that the prescription drugs shown in Table 2 were used.
A drug-impregnated strip was prepared in the same manner as above, and the volatilization rate was measured in the same manner. The results are also shown in Table-2.

Table 2 As is clear from the results shown in Table 2 above, when the strip prepared according to the present invention is heated and evaporated, an extremely high volatilization rate can be obtained.

Examples 23 and 24 and Comparative Examples 5 to 8 A strip having a width of 5-1, a thickness of 0.2 mm, and a length of 20 fl. A drug-impregnated strip was prepared.

This was moved at a speed of 50 r in close contact with a heating element having a heat sink of 7 x 20 cm and set at 150°C, and the state of dirt on the surface of the heating element after use was examined. The results are also shown in Table-3.

Table 3 As shown in Table 3 above, when a strip containing substantially non-volatile antioxidant was used according to the present invention, no deposits were observed on the surface of the heating element, but volatile antioxidant When a strip containing the agent BHA or a strip containing no antioxidant is used, blackish brown deposits are observed on the surface of the heating element. It is estimated to be.

〔Effect of the invention〕

As mentioned above, the belt-shaped body for heating evaporation of the present invention.

Because it contains and retains a specific antioxidant that does not substantially volatilize at the heating temperature used, the antioxidant works effectively during heating, suppressing the thermal decomposition and polymerization of the drug and the formation of resin compounds based on it. However, there is almost no adhesion of the resin compound to the surface of the heating element, and an effective and stable volatilization effect can be maintained over a long period of time, resulting in an extremely high effective volatilization rate. In addition, since the antioxidant used in the present invention is difficult to liquefy, it will not liquefy or volatilize near the heating element due to preheating, and therefore the strip will not be in a wet state. The surrounding parts of the heating element are less likely to be contaminated. Therefore, maintenance is easy and the usability is also good. Furthermore, it has excellent stability over time during storage.

[Brief explanation of the drawing]

The drawing is an explanatory diagram showing a basic example of a heating evaporation method using a drug-impregnated strip. DESCRIPTION OF SYMBOLS 1... Band-shaped body, 2... Payout roll, 3... Heating element, 6... Winding roll.

Claims (1)

[Scope of Claims] A belt-shaped body used in a method in which a belt-shaped body impregnated with and holding a drug is transferred, and the belt-shaped body is successively heated directly or indirectly with a heating element to heat and evaporate the drug, which includes: 2,2'
-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-
butylphenol), 4,4'-methylenebis(2-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-methylenebis(2,6-di-t-
butylphenol), stearyl-β-(3,5-di-
t-Butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,
5-di-t-butyl-4-hydroxybenzyl)benzene, 1,1,3-tris(2-methyl-5-t-butyl-4-hydroxyphenyl)butane, tetrakis[methylene(3,5-di- (t-butyl-4-hydroxycinnamate)] A belt-like material for heating evaporation impregnated with and retaining at least one compound selected from the group consisting of methane that does not substantially volatilize at heating temperature.