JPH06271704A - Aqueous easily combustible composition - Google Patents

Abstract

PURPOSE:To obtain an aqueous composition which is odorless and nontoxic, is capable of being ignited and burnt at low temperature to stably vaporize the effective component by mixing a specified combustible binder with an effective component such as an insecticide, a bactericide or a flaming colorant for fireworks. CONSTITUTION:A combustible binder comprising a polysaccharide derivative (A) satisfying the formulas: 0.2<=X<=1.5, 0.4<=Y<=2.7, and X+Y<3 (wherein X is the number of hydrophilic functional groups per repeating unit, and Y is the number of nitric acid groups) is mixed with at least one effective component (B) selected from among an insecticide, a bactericide, a flaming colorant for fireworks, an oxidizing agent for fireworks, a flammable agent for fireworks, paper, a woven fabric, a phosphor, a dielectric, a conductor and a low-melting glass frit in an A/B weight ratio of 1/100 to 300/100.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous flammable composition containing a combustible binder made of a specific polysaccharide derivative and an active ingredient. The combustible binder ignites and burns at a low temperature to save energy. Water-based flammability to generate and volatilize and continuously volatilize the active ingredient, or burn out the active ingredient after use, or to burn itself to form a film consisting of the active ingredient only. More specifically, the present invention relates to a volatile composition, more specifically, a smoke agent in which the active ingredient is an insecticide or a bactericide, an active ingredient is a flame colorant for fireworks, an oxidizing agent,
We provide fireworks as a combustible agent, fireworks balls or burnouts as an active ingredient of paper, textiles, or functional paints in which the active ingredient is at least one of phosphor, dielectric, conductor or low-melting glass frit. To do.

[0002]

2. Description of the Related Art Conventionally, in a flammable composition containing a combustible binder and the above-mentioned active ingredient, its low temperature ignitability,
Nitrocellulose has been widely used as a combustible binder because of its self-combustibility and burnout property.

However, in such flammable compositions containing nitrocellulose, conventional nitrocellulose is insoluble in water, so it is essential to use a water-soluble binder separately or use an organic solvent. However, each of them had the following problems.

For example, smoke agents are those which ignite or burn to stably and volatilize the insecticidal active ingredient or bactericidal active ingredient by heat of decomposition or decomposition heat to kill insects or sterilize. No. 224503, JP-A-61-
As described in JP-A-249907, nitrocellulose has been used by kneading and granulating an aqueous solution of a water-soluble polymer such as carboxymethylcellulose and methylcellulose together with an insecticidal or bactericidal active ingredient as a binder. The binder has a problem that it does not have low-temperature ignitability and self-combustibility and impairs the combustibility of the composition.

For fireworks, "chemistry of fireworks" 1
As described in page 00, Tokai University Press (published in 1980), Nori is used as a binder for flame coloring agents, oxidizing agents, and combustible agents used for preparing stars.
These pastes also have a problem that they do not have low-temperature ignitability and self-combustibility, cause smoke and impair the clarity of fireworks.

[0006] In addition, in the case of fireworks balls and medicine,
Conventionally, papers pasted together with glue or synthetic resin or molded synthetic resin and paper or woven fabric have been used, but these have a problem of being left over after burning and mixing cellulose with nitrocellulose. It has been proposed to make paper by using water-soluble or water-dispersible binders such as starch and synthetic resin latex, but these binders also do not have low-temperature ignitability and self-combustibility and generate a large amount of smoke. There was a problem that

It is possible to use nitrocellulose in place of the water-soluble binder in the above-mentioned smoke agent, fireworks, fireworks jade or shell, but conventional nitrocellulose requires the use of an organic solvent. Therefore, there is a problem in terms of work environment hygiene such as odor and toxicity due to the use of an organic solvent, or a danger of fire, and it is not put into practical use.

In the above-mentioned functional paint, the paste for phosphor, the dielectric, the conductor, or the paste of the low-melting glass frit for adhesion or coating is applied to glass or ceramics and then a binder. The components are removed by heating to form a coating layer or an adhesive layer of phosphor, dielectric, conductor or low melting point glass.
As described in JP-A-7328 and JP-A-4-938, the above-mentioned nitrocellulose has been frequently used as a combustible binder, but it is essential to use an organic solvent, and odor and toxicity due to the use of the organic solvent. There was a problem in terms of work environment hygiene or the risk of fire.

[0009]

For the above reasons, an aqueous flame-retardant containing a water-soluble or water-dispersible combustible binder having low-temperature ignitability and burnout similar to nitrocellulose and an active ingredient. There has been a strong demand for a sex composition.

[0010]

In order to solve the above-mentioned problems, the present inventors have retained the function of a flammable binder that ignites at a low temperature and generates energy like conventional nitrocellulose, and is water-soluble. Focusing on polysaccharide derivatives that are water-soluble or water-dispersible, as a result of intensive studies, a flammable binder and an active ingredient consisting of a polysaccharide derivative containing a specific number of hydrophilic functional groups and nitrate ester groups were identified. It has been found that the aqueous flammable composition contained can achieve the above-mentioned object, and has completed the present invention.

That is, according to the present invention, the number of hydrophilic functional groups X and the number of nitrate ester groups Y per repeating unit are 0.
Aqueous flammability containing a flammable binder made of a polysaccharide derivative (hereinafter abbreviated as a polysaccharide derivative) satisfying 2 ≦ X ≦ 1.5, 0.4 ≦ Y ≦ 2.2, and X + Y <3, and an active ingredient. The present invention relates to a sex composition.

The combustible binder as referred to in the present invention is present in the composition together with the active ingredient and binds the active ingredients to each other or the active ingredient and the carrier or the base material, and
The heat source easily ignites and burns to supply combustion or decomposition energy to the composition. In other words,
The combustible binder can be referred to as a binder that burns to generate energy.

The repeating unit referred to in the present invention means one heterocyclic structure of a monosaccharide constituting a polysaccharide, and a pyranose ring having a simple repeating structure is preferable from the viewpoint of industrial availability and is a typical example. As an example, glucose, mannose,
Xylose and the like.

In the polysaccharide derivative used in the present invention,
In order to obtain a practical solution viscosity, the number of repeating units (degree of polymerization) is preferably 20 to 1000.

The hydrophilic functional group referred to in the present invention is an anionic or cationic functional group specific to polysaccharides or an anionic, cationic or nonionic hydrophilic functional group introduced by chemical modification. .

The polysaccharide-specific anionic functional group referred to in the present invention means an anionic functional group contained in a naturally obtained specific polysaccharide, and examples thereof include a carboxyl group of alginic acid or pectin. The cationic functional group unique to the polysaccharide in the invention means a cationic functional group contained in a naturally obtained specific polysaccharide, and examples thereof include an amino group of chitosan.

The anionic, cationic or nonionic functional group introduced by chemical modification as referred to in the present invention means anionic, cationic or nonionic groups introduced by etherification or esterification of the hydroxyl group contained in the polysaccharide. Refers to a nonionic functional group, examples of anionic functional groups include carboxymethylcellulose, carboxymethylstarch, carboxyethylmolulose, carboxyethylstarch and other carboxyl groups, sulfonylethylcellulose sulfone group, phosphoethylcellulose phospho group and the like. Examples of the cationic functional group include amino groups such as aminoethyl cellulose, and examples of the nonionic functional group include hydroxyethyl cellulose, hydroxyethyl starch, hydroxypropyl cellulose, and hydroxypropyl cellulose. There is a hydroxyalkyl group such as Pirusutachi.

As the polysaccharide derivative containing an anionic hydrophilic functional group as referred to in the present invention, a polysaccharide derivative containing a carboxyl group can be obtained by raw material acquisition and nitric acid esterification with a conventional nitric acid-containing sulfuric acid / nitric acid mixed acid. Preferable from the viewpoint of easiness, specific examples include alginic acid, pectin or nitrate esters such as carboxyalkyl cellulose or carboxyalkyl starch described above.
Carboxymethyl cellulose or nitrate ester of carboxymethyl starch is preferable in terms of cost.

As the polysaccharide derivative containing a cationic hydrophilic functional group of the present invention, a polysaccharide derivative containing an amino group is preferable from the viewpoint of easy availability of raw materials and nitrification, and specific examples thereof are given. For example, there are nitric acid esters such as aminoethyl cellulose, aminoethyl starch and chitosan.

In the polysaccharide derivative used in the present invention, the number of hydrophilic functional groups X and the number of nitrate ester groups Y per repeating unit are 0.2 ≦ X ≦ 1.5 and 0.4 ≦ Y ≦ 2.7. , X
It is in the range of + Y <3.

When X is less than 0.2, solubility or dispersibility in water or a mixture of water and a necessary minimum amount of organic solvent is insufficient, and when X exceeds 1.5, conventional nitrification is used. It is difficult to prepare by nitric acid esterification with sulfuric acid / nitric acid mixed acid for use, and Y is less than 0.4, and the self-combustibility is small and the performance as a combustible binder is insufficient. For example, in smoke agents, it disappears, in fireworks and fireworks jade or in the amount of smoke generated, or for phosphors, dielectrics,
In the case of a conductor paste or a glass frit paste for adhesion or coating, the temperature required for heat removal becomes high, and for those with Y exceeding 2.7, water or a mixture of water and a minimum amount of an organic solvent is necessary. The solubility or dispersibility is insufficient, which is not preferable, and more preferably 1.5 ≦ Y ≦
2.5 and the total amount of X and Y theoretically does not exceed 3.

The polysaccharide derivative used in the present invention contains at least 1% of anionic or cationic hydrophilic functional groups.
Is preferably a neutralized polysaccharide derivative, and more preferably 10% or more is a neutralized polysaccharide derivative. A polysaccharide derivative having a degree of neutralization of 1% or more dissolves or disperses in water or water containing an extremely small amount of an organic solvent, and is therefore preferable in terms of work environment hygiene such as odor and toxicity, and improvement of fire hazard and the like.

In the present invention, the term "neutralized" means that a part or all of the anionic or cationic hydrophilic functional group in the polysaccharide derivative forms a salt with the counterion of the neutralizing agent described below. The degree of neutralization is determined by the equivalent number of anionic or cationic functional groups and counterions in the polysaccharide derivative or a composition containing the same, and for example, the anion in the polysaccharide derivative. The degree of neutralization can be measured by measuring the functional or cationic functional group with an alkali or an acid.

The neutralizing agent used for the polysaccharide derivative having an anionic functional group is at least one compound selected from alkali metal compounds, alkaline earth metal compounds, ammonia, organic amines, hydrazine compounds and the like. The alkali metal compound means a compound of an element of Group A of Group 1 of the Periodic Table, and examples thereof include hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate. , Sodium carbonate, potassium carbonate and the like. The alkaline earth metal compound refers to a compound of an element of Group 1 B of the periodic table, and examples thereof include hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide, magnesium hydrogen carbonate, and carbonate. There are carbonates such as calcium hydrogen and calcium carbonate. The organic amine refers to an organic compound containing one or more primary, secondary or tertiary amino groups in one molecule, and examples thereof include alkylamines such as ethylamine, propylamine and triethylamine. Examples include monoamines, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and other alkylpolyamines, dimethylethanolamine, N-methylpyrrolidone, and triethanolamine. The hydrazine compound is hydrazine, methylhydrazine, ethylhydrazine or derivatives thereof.

Of these, compounds containing one amino group in one molecule, such as alkali metal compounds, ammonina or alkylmonoamines, dimethylethanolamine, N-methylpyrrolidone and triethanolamine, are preferred, and neutralizing agents As a compound other than these basic compounds, for example, an alkaline earth metal compound or an organic amine containing two or more amino groups in one molecule is used, the viscosity becomes extremely high when an aqueous flammable composition is prepared. Or, the polysaccharide derivative may coagulate or precipitate, which is not particularly preferable.

Further, in the above-mentioned functional paint, a compound containing one amino group in one molecule, such as ammonia or alkylmonoamines, dimethylethanolamine, N-methylpyrrolidone, triethanolamine,
Particularly preferable in terms of performance as a burnout agent.

The neutralizing agent used for the polysaccharide derivative having a cationic functional group includes inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, monobasic organic acids such as formic acid, acetic acid and propionic acid, oxalic acid, Examples thereof include dibasic organic acids such as maleic acid and phthalic acid. Of these, hydrochloric acid, nitric acid or monobasic organic acids are preferred, and compounds other than these acidic compounds, such as sulfuric acid, phosphoric acid or dibasic acids are preferred. When a water-soluble organic acid or the like is used, the viscosity becomes extremely high during the preparation of the aqueous flammable composition, or the polysaccharide derivative may coagulate or precipitate, which is not particularly preferable. More preferred are monobasic organic acids that sometimes do not generate irritating combustion gases.

The preparation examples of the polysaccharide derivative of the present invention are shown below.

The polysaccharide derivative of the present invention comprises a repeating unit 1
A raw material having a hydrophilic functional group number X of 0.2 ≦ X ≦ 1.5 per piece is obtained by nitric acid esterification, washing and stabilization by a known method. One example is one anhydrous glucose residue. The number of carboxymethyl ether groups per unit is 0.2 to 1.
5 parts by weight of carboxymethylcellulose 10 to 10 parts by weight
After treatment in 50 parts by weight of sulfuric acid / nitric acid / water mixture, deoxidation,
The polysaccharide derivative of the present invention can be prepared by washing with warm water. If necessary, the molecular weight can be adjusted by further heating as an aqueous slurry in an autoclave.

The active ingredients referred to in the present invention include insecticides, bactericides, flame colorants for fireworks, oxidizing agents for fireworks, combustible agents for fireworks, paper,
It means one or more selected from a woven fabric, a phosphor, a dielectric, a conductor, and a low melting point glass frit.

In the composition of the present invention, the ratio of the combustible binder (A) composed of a polysaccharide derivative and the active ingredient (B) is selected according to the kind of the active ingredient to be used. (A) / (B) is 1/100 to 3 in weight ratio
It is preferably 00/100, and when (A) / (B) is less than 1/100, the ignitability and sustainability of combustion of the composition become insufficient, and when it exceeds 300/100, the active ingredient in the composition Insufficient amount, resulting in inadequate utility as a smoke agent, fireworks, pyrotechnic skin, burnout, or functional paint.

A composition containing a combustible binder composed of the above-mentioned polysaccharide derivative and an insecticide or bactericide as an active ingredient is useful as a smoker, and the insecticide or bactericide is volatilized by heat. Known chemicals can be used for controlling harmful insects and bacteria, and for example, JP-A-59-67201, JP-A-4-224503, JP-A-59-25303, and JP-A-59-25303 can be used. 61-24
Those described in Japanese Patent No. 9907 etc. are used. For example, N- (3 ', 5'-dichlorophenyl) -1,2
-Dimethylcyclopropane-1,2-dicarboximide, tetrachloroisophthalonitrile, S-normal butyl S'paratertiary butylbenzyl N-3-pyridyldithiocarbodiimidate, dichlorvos and the like.

The smoke agent may contain a carrier such as diatomaceous earth and calcium carbonate, a combustion aid such as ammonium nitrate, sodium nitrate and sodium chlorate and / or a combustion temperature adjusting agent such as melamine. Combustion and volatilization of the active ingredient gas are made smoother by using the auxiliary agent, and the use of the combustion temperature control agent can improve the efficiency without decomposition of the active ingredient due to excessive heating.

An example of the method for preparing the smoke agent is as follows.

The polysaccharide derivative of the present invention, an insecticidal or bactericidal active ingredient, and diatomaceous earth, if necessary, are mixed with a blender or a mixer. Then, after adding water containing the neutralizing agent while mixing in a kneader, extruding, molding,
The smoking agent can be prepared by drying.

A composition containing the above-mentioned polysaccharide derivative and a flame colorant for fireworks, an oxidizing agent, and a combustible agent as active ingredients is useful as a fireworks, and as a flame colorant, an oxidizing agent, and a combustible agent,
Known for past fireworks, eg "Fireworks Chemistry" No. 9
The compounds described on page 2 (above) can be used. As an example, as the flame colorant, strontium compounds such as strontium nitrate and strontium oxalate, sodium oxalate,
There are sodium compounds such as ultramarine blue, barium nitrate, barium compounds such as barium carbonate, copper sulfate, copper compounds such as copper carbonate, and the like.As oxidants, potassium chlorate, chlorates such as potassium perchlorate, potassium nitrate, and the like. There are nitrates such as sodium nitrate, and flammable agents include pine pitch,
There are sulfur, rapeseed, Nekoyanagi, chaff, etc.

To give an example of the method for preparing fireworks, the above-mentioned flame colorant, oxidizing agent, rapeseed, Nekoyanagi, and combustible agents other than rice husks are put in a container such as a bowl, gently mixed with a bamboo spatula, and the like. The polysaccharide derivative of the present invention is mixed with water or a dispersion containing water or a minimum necessary organic solvent of the polysaccharide derivative, and this is repeatedly dried by adhering it to the surface of rapeseed or chaff. Fireworks can be prepared.

A composition containing the above-mentioned polysaccharide derivative and paper or textile as an active ingredient is useful as a fireworks ball or a shell, and as the paper or textile, wood pulp paper, refined linter paper, waste paper or A cotton cloth, a synthetic fiber cloth, a non-woven cloth or the like can be used without any particular limitation.

As an example of the method for preparing a fireworks jade or a shell, a paper frame or a woven fabric such as kraft paper as described above is wrapped around a bead frame of a desired size, and then water of the polysaccharide derivative used in the present invention is used. Alternatively, an aqueous solution or dispersion containing the minimum necessary amount of organic solvent is applied with a brush, and newspapers are further laminated and laminated to dry. This operation is repeated until a predetermined thickness is reached, and the fireworks jade of the present invention can be obtained. Further, wood pulp, refined linter, waste paper, etc. are made into a water slurry, and water or a solution containing a minimum amount of the organic solvent of the polysaccharide derivative used in the present invention or an aqueous dispersion or dispersion is added thereto, and then papermaking is performed on the formwork. It can be dried afterwards to prepare fireworks balls or shells.

It is also possible to add nitrocellulose to the slurry in the preparation of the above-mentioned fireworks balls or shells, and the addition of nitrocellulose is preferred because it can further reduce smoke generation.

A composition containing a flammable binder composed of the above-mentioned polysaccharide derivative and one or more of a phosphor, a derivative, a conductor or a low melting point glass frit as an active ingredient is useful as a functional coating material.

As the above-mentioned phosphor, derivative, and conductor,
Known phosphors can be used, but examples of the phosphor include "Kagaku Daiji No. 3, page 300 (Kyoritsu Shuppan;
1981) ”, and examples include calcium halophosphate / tin / manganese compounds, organic fluorescent dyes, zinc sulfide / silver compounds, calcium tungstate, etc., and dielectric materials include Rochelle salt and titanium. There are barium acid, strontium titanate, lead titanate and the like, and the conductors include gold, silver or copper.

The polysaccharide derivative of the present invention and a phosphor, a derivative,
An example of the preparation of a functional coating material containing a conductor or one or more low melting point glass frits is water containing the polysaccharide derivative of the present invention and the above neutralizing agent, and if necessary, a small amount of the above organic compound. In a container equipped with a stirrer, a solvent is mixed to prepare a solution of the polysaccharide derivative, and then the solution is used in a disperser such as a kneader, attritor or sand mill, and the above-mentioned phosphor, derivative, conductor or low The above paste can be prepared by mixing with one or more melting point glass frits.

The above-mentioned composition of the present invention contains water as a main solvent, but it may contain a small amount of an organic solvent if necessary.

The organic solvent used is methanol,
Alcohols such as ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, ethyl acetate,
One or more of esters such as propyl acetate, butyl acetate and ethyl lactate, ether alcohols such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and diethylene glycol monobutyl ether, and dioxane, but the solubility is not impaired. Thus, hydrocarbons such as toluene, xylene, hexane and heptane can be used, and the use of a small amount of an organic solvent lowers the solution viscosity of the combustible binder, facilitates preparation of the composition, and The coatability can be improved.

Hereinafter, the present invention will be described in detail.

[0047]

【Example】

Reference Example 1 (Preparation Example of Polysaccharide Derivative) 40 g of carboxymethyl cellulose (Serogen 5A; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: the number of carboxymethyl ether groups per anhydrous glucose residue = 0.7) was prepared at 5 ° C. 400 ml of an acid mixture consisting of 60% by weight of sulfuric acid, 22% by weight of nitric acid and 19% by weight of water was placed in a 1 L glass beaker, and stirring was continued at 5 ° C. for 60 minutes. The reaction mixture was put into a 5 liter stainless steel container containing 4 liters of water, stirred for 5 minutes and then dispersed with a Buchner funnel to collect the reaction product on the funnel. Furthermore, the reaction product is 800
Transfer to a 1 liter glass beaker containing 96 ml of water at 96 ° C.
After heating for 2 hours at 60 ° C., the reaction product on the funnel was collected by separating with a Buchner funnel, and the reaction product was placed in a 1 l autoclave together with 500 ml of water at 130 ° C.
The reaction product was recovered by treatment with a Buchner funnel for 60 minutes. The reaction product is dried at 80 ° C. for 2 hours,
49 g of nitrate of carboxymethyl cellulose was obtained.

The number of functional groups per anhydrous glucose residue of the product was measured by the following method. Precisely weigh 0.1 g of the dry reaction product, and analyze by elemental analysis for the weight% of nitrogen atoms
Was calculated (N%). Precisely weigh 1g of reaction product,
Put it in a 300 ml Erlenmeyer flask with ground stopper, add 15 ml of 80% methanol, and accurately add 100 ml of N / 10 sodium hydroxide solution, shake at room temperature for 3 hours, add phenolphthalein, and add N / 10 sulfuric acid. Titrated with. The equivalent of carboxymethyl ether group per 1 g of the sample was calculated by the following formula (A equivalent / g).

A = (100-N / 10 sulfuric acid ml) × f × 10000 where f; N / 10 sulfuric acid factor Using the obtained N% and A equivalent / g, the anhydrous glucose residue was calculated according to the following equation. The number of nitrate ester groups and the number of carboxymethyl ether groups per group were calculated.

X = 14 yA / n y = 162n / (14-45n-58 × 14A) where x is the number of carboxymethyl ether groups, y is the number of nitrate ester groups, and n is (N%) / 100. The obtained reaction product has a number of nitrate ester groups per anhydrous glucose residue of 1.
5, the number of carboxymethyl ether groups was 0.7. Reference Example 2 5 g of the polysaccharide derivative obtained in Reference Example 1 and 95 g of water were weighed in a 100 ml UM-sample bottle, and ammonia water was added with stirring to adjust the pH to 8.5. A solution was obtained.

The obtained solution was placed on a glass plate in an amount of about 100 μm.
To obtain a film by drying at 60 ° C. for 1 hour. A thermobalance analyzer (TG /
The test was performed using DTA320; manufactured by Seiko Denshi.
The results are shown in Fig. 1. Table 1 shows the decomposition start temperatures determined from FIG. Reference Example 3 A polysaccharide derivative was tested in the same manner as in Reference Example 2 except that the number of nitrate ester groups per anhydrous glucose residue was 0.5 and the number of carboxymethyl ether groups was 0.7. As a result, a uniform solution was obtained, and the decomposition start temperatures shown in Table 1 were obtained from thermobalance analysis. Reference Example 4 10 g of a polysaccharide derivative having 2.3 nitrate groups and 0.6 carboxymethyl ether groups per anhydrous glucose residue, 10 butyrocellosolve
g, 10 g of water and 200 ml tall beaker,
28% ammonia water 0.2 while stirring with a homomixer
g was added to obtain an aqueous dispersion.

The obtained dispersion was placed on a glass plate for 10 mi.
A coating film having a film thickness of 1 l, dried at 100 ° C for 1 hour, peeled and cut was subjected to thermobalance analysis in the same manner as in Reference Example 2. The decomposition initiation temperatures obtained are shown in Table 1. (Example 1) 37 parts of the polysaccharide derivative prepared in Reference Example 1,
N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide (manufactured by Sumirex Chemical) 30 parts, calcium carbonate 27 parts, melamine 5 parts, 3% ammonia water 5 parts were mixed in a kneader, molded with an Eck pelleter to form pellets having a diameter of 3 mm and a length of 7 mm, and dried at 80 ° C. for 3 hours to prepare an aqueous flammable composition.

In order to examine the usefulness of the composition as a smoke agent, the composition was placed in an aluminum gutter of 1 cm square and 5 cm length, one end was ignited and the combustion state was observed. No flame was observed and smoke continued to evolve. (Example 2) The procedure of Example 1 was repeated, except that only the polysaccharide derivative was changed to the same polysaccharide derivative as used in Reference Example 4. No flame was observed and smoke continued to evolve. (Comparative Example 1) Industrial nitrification cotton HIG1 / 2 (70% pure content;
Asahi Kasei) 52.8 parts, Sumirex 30 parts, calcium carbonate 27 parts, melamine 5 parts, 2% carboxymethylcellulose solution 5 parts were mixed in a kneader, and the following Example 1
Was prepared in the same manner as.

The combustion state was observed in the same manner as in Example 1. Small flames due to granular nitrification cotton were observed intermittently, and the amount of smoke generated fluctuated. (Example 3) 100 g of potassium perchlorate on a wooden bowl,
Pine root pitch 10g, strontium carbonate 35g, and the polysaccharide derivative 8g of Reference Example 4 were put and 1% ammonia water 50
While adding g, the mixture was gently stirred with a bamboo spatula to form granules. The obtained sample was put in the aluminum gutter used in Example 1 and added to one end to observe the combustion state. Burning continued with a bright pink flame. (Comparative Example 2) The same procedure as in Example 3 was carried out except that the polysaccharide derivative was changed to midine powder (steamed sticky rice flour traditionally used in fireworks) and 1% aqueous ammonia was changed to water. .

Although a pink flame was emitted and combustion continued, a large amount of smoke remained. (Example 4) Pulp sheet having a width of 1 cm and a length of 10 cm (P
& G) was immersed in the polysaccharide derivative solution of Reference Example 2 for 10 minutes and dried at 100 ° C for 15 minutes. This was repeated to impregnate 3 g of the polysaccharide derivative per 1 g of pulp sheet. A model of fireball ball or shell was prepared.

One end of the obtained sample was ignited and the combustion state was observed. It burned out without smoke. (Comparative Example 3) With respect to the pulp sheet used in Example 4, the burning state was observed in the same manner as in Example 4, and it was found that the pulp sheet had disappeared and remained unburned. (Example 5) Ammonia water was added to 5 parts of the polysaccharide derivative prepared in Reference Example 1 and 95 parts of water while stirring to adjust the pH to 8.5, and stirring was continued. To prepare a polysaccharide derivative solution. 100 parts by weight of glass frit (LS-0803; manufactured by Nippon Electric Glass Co., Ltd.) was added to the obtained solution and kneaded to prepare a glass frit paste.

This was spread on a glass plate with a spatula, dried with hot air at 100 ° C., pulverized, and subjected to thermobalance analysis in the same manner as in Example 2. The decomposition start temperature is shown in Table 1. (Reference Examples 5 and 6) Carboxymethyl cellulose (Serogen 5A; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and methyl cellulose (made by Matsumoto Yushi Co., Ltd.) were subjected to thermobalance analysis in the same manner as in Reference Example 2. The decomposition start temperature is shown in Table 1. (Comparative Examples 4 and 5) In Example 5, the polysaccharide derivative solution was replaced with a 5% carboxymethylcellulose solution or a methylcellulose solution, and the same procedure was followed. The decomposition start temperature is shown in Table 1.

[0058]

[Table 1]

[0059]

EFFECTS OF THE INVENTION The composition of the present invention is free from problems such as odor and toxicity in working environment or danger of fire, and is ignited at low temperature.
It is a composition with excellent properties that can be burned to volatilize and continuously volatilize the active ingredient, burn out the active ingredient after use, or form a film consisting of only the active ingredient by burning out the binder. is there.

[Brief description of drawings]

FIG. 1 is a thermobalance analysis chart of the polysaccharide derivative obtained in Reference Example 2.

Claims (2)

[Claims] 1. The number of hydrophilic functional groups X and the number of nitrate ester groups Y per repeating unit are 0.2 ≦ X ≦ 1.5,
Combustible binder (A) consisting of a polysaccharide derivative with 0.4 ≦ Y ≦ 2.7 and X + Y <3, and an insecticide, a bactericide, a fireworks flame colorant, a fireworks oxidizer, a fireworks combustible agent, paper , (A) / (B) = 1/100 to 300/100 in a weight ratio of the active ingredient (B) consisting of one or more kinds selected from a woven fabric, a phosphor, a dielectric, a conductor and a low melting point glass frit. A water-based flammable composition characterized by being contained in a ratio of 2. The aqueous flammable composition according to claim 1, wherein the hydrophilic functional group of the polysaccharide derivative is a carboxymethyl ether group.