JP2015230141A - Burnout material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a burnout material that is formed into a versatile burnout container and burnout substrate having combustion performance and burnout performance as well as heat resistance performance and impact resistance performance, while exerting a sufficient water resistance against moisture such as humidity and deposited water.SOLUTION: A burnout material is formed by containing a cellulose nitrate, and an internal sizing agent and/or a wet paper strengthening agent. A burnout container 1 being the burnout material formed as the burnout container 1 is selected from any one of a burnout cartridge being spherical or cylindrical and having powder 4 filled and enclosed therein, a charge container having a cylindrical container body 3 with a lower end closed where the powder is filled and enclosed and a top cover 2 fitted therein and closing the opening, and an outer shell for firework ball wrapped with a ball skin and filled with powder inside.

Description

  TECHNICAL FIELD The present invention relates to a burnout container in which explosives are enclosed and used for bullet shooting / recognition guns and the like, and a burnout material formed on a burnout substrate that has a radio communication bullet shell and the like and is attached with a wireless tag. It is.

  The combustible container used for shell shooting contains a gunpowder, containing a gunpowder, such as a gunpowder and an igniting gun, when shooting a bullet, etc. It is a burnout material used to load the chamber. When a bullet is placed on a combustible container containing the explosive, igniting the igniter causes explosive combustion of the propellant, and the resulting combustion gas pressure causes the bullet to move toward the target. Fired.

  Since the burnout container is always exposed to the outside world, it is first exposed to various external threats such as flames, heat, sparks, static electricity, flash, impact, vibration, impact, moisture, and adhering water. Due to these external factors, the explosives are prone to serious influences such as firing unexpectedly or not igniting in reverse. Therefore, this burn-out container is a sensitivity factor for the ammunition, in other words, an external factor. Therefore, this burnout container has sufficient heat resistance that can withstand flames, heat, sparks, etc. during transportation, storage, or loading, and sufficient shock resistance that can withstand impact, vibration, impact, etc. In addition to sufficient electric resistance that can withstand static electricity, sufficient water resistance that can resist moisture and moisture is required.

  In addition, this burnable container has a combustion performance that can burn at the same burning rate as a gunpowder when firing a gunshot or empty envelope by burning a gunpowder with a gunpowder charge, and a combustion residue in the gunpowder. It is necessary to have both the burn-out performance that does not leave the mark.

  This burnout container contains nitrocellulose as a combustible main component so as to have sufficient combustion performance and burnout performance. Further, the burnout container contains porous cellulosic pulp fibers as a reinforcing auxiliary component in order to have sufficient heat resistance and impact resistance. When this surface is unprotected, the combustible main component and reinforcing auxiliary component have physical properties such as a water absorption swelling action and a water absorption / moisture retention action by capillary action. Susceptible to external factors such as moisture below and attached moisture. A surface-unprotected burnable container comes into contact with moisture or adhering moisture and easily absorbs the moisture. As a result, it becomes damp and difficult to burn, the combustion performance is greatly reduced, and even if ignited, there is an increased risk that combustion residues will be generated in the barrel and cannot be burned out.

  Furthermore, the burnout container will be swollen due to the absorption of its moisture, impact resistance performance will be significantly reduced, and due to its own weight and the weight of the stacking burnout container, its size and shape will easily change and become distorted or crushed. To do. As a result, ammunition is caught in the chamber and becomes difficult to insert as a shell, or when it is assembled with special ammunition that should be fitted with metal or resin assembly parts, it is forced to explode or damaged when loaded. The operability is significantly reduced.

  In order to reduce such adverse effects as much as possible, conventionally, the burnable container is covered with a waterproof sheet so that it does not come into contact with water, or the burnable container is simply water-resistant to impart water resistance to the surface. I was protecting it. For example, as a water resistance imparting processing method, nitrocellulose, fiber pulp, etc., which are the main components of a burnout container, are made into a slurry form in water and manufactured through a papermaking and pressing process. As described, water resistance is applied to the burnout container by a method of applying a film to the container surface or a method of applying a paint such as polyester resin, urethane resin, acrylic resin as described in Patent Document 2. Surface protection that imparts properties is performed.

  Giving water resistance to the burnout container by such surface protection requires film sticking and coating application for each burnout container, which is cumbersome and inefficient in work efficiency. Moreover, even a burnable container with a film attached or paint applied cannot be completely protected by the applied protective film or applied paint if exposed to rainwater for a long time or submerged in bad weather. Moisture is absorbed from the part, and there is a risk of becoming unusable.

  Also, the burnout container is water-absorbing when printed with colored ink for displaying the type of ammunition or when printing the conductive pattern for wireless tag with conductive ink for wireless reception. In order to prevent the ink from bleeding, the type of ink is restricted and lacks versatility.

  Further, a decrease in water resistance due to the influence of moisture and a restriction on the type of ink can be seen in the combustible material molded on the combustible substrate as well as the combustible container.

JP 2006-234297 A JP 2010-78215 A

  The present invention has been made in order to solve the above-mentioned problems. While exhibiting sufficient water resistance against moisture and moisture such as adhering water, not only combustion performance and burnout performance but also heat resistance performance and impact resistance. An object is to provide a burnout material molded into a versatile burnout container or a burnout substrate having performance.

  The burnout material of the present invention made to achieve the above object is formed by containing nitrocellulose, an internally added sizing agent and / or a wet paper strength agent.

  This burnout material may be molded into a burnout container.

  This combustible material is a combustible case in which the combustible container is spherical or cylindrical and filled with explosive inside, and a cylindrical container body in which the lower end is closed and filled with explosive And a medicine container having a top lid that fits and closes the opening thereof, and an outer shell for pyrotechnic balls that is wrapped in a bead and filled with explosives.

  This burnout material may be molded into a burnout substrate.

  In this burnout material, the internal sizing agent is a rosin resin, an alkyl ketene dimer, an alkenyl succinic anhydride, a fatty acid amide, a styrene-maleic acid copolymer, a styrene-acrylic acid copolymer, and / or It contains at least one selected from a copolymer resin which is an olefin-maleic acid copolymer.

  The burnout material is preferably molded containing 0.05 to 2% by weight of the internal sizing agent.

  In this burnout material, the internal sizing agent is more preferably cationic.

  In this burnout material, the wet paper strength agent contains at least one selected from urea-formaldehyde resin, melamine-formaldehyde resin, and epichlorohydrin-modified polyamide polyamine resin.

  It is preferable that this burnout material is molded to contain 0.75 to 3% by weight of the wet paper strength agent.

  The burnout material may be molded including at least one selected from natural or synthetic fibers, binders, and stabilizers.

  In this burnout material, it is more preferable that the natural or synthetic fiber, the binder, and / or the stabilizer are anionic and the internal sizing agent is cationic.

  The burnout material of the present invention is sufficiently molded to contain moisture paper strength agent and internal sizing agent, so that the water resistance is sufficiently improved against moisture such as moisture and adhering water. In addition to burn-out performance, heat resistance and impact resistance can be maintained, and dimensional and shape stability can be improved.

  Combustible materials can be burned, burnt, heat-resistant, and shock-resistant even when exposed to moisture such as rainwater, fog, dew, frost, and condensation during long-term rainfall, heavy rain, and extreme cold. Since the performance is maintained, troublesome processes and measures are not required for transportation and storage.

  Therefore, the burnout material does not deteriorate with moisture, and is not affected by external factors such as moisture and adhesion moisture under any harsh environment such as bad weather such as rainwater and rain and snow in storms and hot and humid. In addition, it can be used stably without being damaged.

  The combustible material formed in the combustible container does not need to be covered with a waterproof sheet or kept in a waterproof tent and is easy to handle. In addition, the burnout container can be smoothly loaded into the gun barrel, and can be completely burned out in the gun barrel by ignition, so that the operability is high and the working efficiency can be improved. Furthermore, even if it is loaded on a firearm or the like under conditions exposed to moisture or moisture, it burns completely without leaving a combustion residue, so continuous shooting can be performed.

  In addition, the combustible material formed on the combustible container or the combustible substrate does not bleed even if various water-soluble inks are used for appropriate water resistance. Therefore, there are few restrictions on the manufacturing method and high versatility.

  In addition, since the burnout material itself exhibits water resistance due to the wet paper strength agent and the internal additive sizing agent, it is not necessary to individually attach a troublesome protective film or apply a protective film. Therefore, the combustible material molded into the combustible container or the combustible substrate can be produced simply, homogeneously and with high quality simply by molding.

It is front sectional drawing which shows one form of the burnout container to which this invention is applied.

  Hereinafter, although the burnout material of the present invention will be described in detail, the scope of the present invention is not limited to these forms. A burnout container 1 which is an embodiment of the burnout material will be described with reference to FIG.

  As shown in FIG. 1, the burnout container 1 is loaded into a gun barrel chamber, and is used as a projectile charge container for firing bullets when firing bullets or empty packages when firing. is there.

  The burnout container 1 has a substantially cylindrical container main body 3 and an upper lid 2 fitted to the upper end of the container main body 3. An explosive 4 serving as a propellant is filled in the inside formed by fitting the upper lid 2 to the container body 3.

  The container body 3 and the upper lid 2 are formed from a slurry having the same composition. The container body 3 and the upper lid 2 are made of nitrocellulose, an internal sizing agent or wet paper strength agent, and if necessary, natural fibers such as cellulose fibers such as kraft pulp or synthetic fibers such as acrylic resin. A slurry containing a fiber exemplified in (1), a binder such as a synthetic resin, and a stabilizer is formed, squeezed, and molded.

  The internally added sizing agent and the wet paper strength agent are components for imparting water resistance and enhancing nitrocellulose and natural or synthetic fibers against moisture during molding of the burnout container 1.

  The internally added sizing agent is for adjusting the liquid permeability so as to prevent bleeding of ink printed on the burnout container 1 and to prevent the ink from being broken when wetted or absorbed. .

As an internal sizing agent,
Rosin that adheres to nitrocellulose and natural or synthetic fibers and is the main component of pine resin, and rosin resin that is a derivative thereof, specifically Hersize L-50, Hersize NES-500, Hersize NES-680, Her Size NES-748, Her Size NES-745, New Size 738 (all made by Harima Kasei Co., Ltd .: trade name), Size Pine N-771, Size Pine N-775, Size Pine N-780, Size Pine N- 795, Size Pine N-788, Size Pine N-811, Size Pine N-817, Size Pine N-830, Size Pine N-880, Size Pine NT-78, Size Pine NT-87 (all Arakawa Chemical Industries Ltd. Made by company: trade name, size pine is a registered trademark);
Alkyl ketene dimer (AKD) which ester bonds with hydroxyl groups of cellulose fibers such as nitrocellulose and natural or synthetic fibers, specifically size pine K-287, size pine K-902, size pine K-903-20, size pine K -934, size pine K-921, size pine K-922E, size pine K-925 (all manufactured by Arakawa Chemical Industries, Ltd .: trade name);
Alkenyl succinic anhydride (ASA), which is ester-bonded to a hydroxyl group of nitrocellulose or natural or synthetic fiber, specifically Hersize AN-300 (manufactured by Harima Kasei Co., Ltd .: trade name), Size Pine SA-864, Size Pine SA -865 (all manufactured by Arakawa Chemical Industries, Ltd .: trade name);
Copolymer resin, specifically styrene-maleic acid copolymer, more specifically, polymeron 385, polymeron 1318 (both manufactured by Arakawa Chemical Industries, Ltd .: trade name, polymeron is a registered trademark), or styrene-acrylic acid Copolymers, more specifically, polymeron 360, polymeron 1301 (both manufactured by Arakawa Chemical Co., Ltd .: trade name), or olefin-maleic acid copolymer, more specifically polymeron 482S, polymeron 1329 (both Arakawa Chemical Industries, Ltd. product name);
Fatty acid amide, more specifically size pine DL-15, size pine DLFA-20 (both manufactured by Arakawa Chemical Industries, Ltd .: trade name);
Is mentioned. The internal sizing agents may be used alone or in combination.

  Among these, the internal sizing agent is preferably cationic.

  When the burnout container 1 contains an internal sizing agent, the internal sizing agent molecules adhere to the surface of nitrocellulose or natural or synthetic fibers, or the internal sizing agent molecules and nitrocellulose or natural or synthetic fibers are attached. As a result of the formation of a hydrophobization due to the ester bond between the hydroxyl group of the sizing agent and the exposure of the hydrophobic group of the internal sizing agent, the water repellency is improved.

  The wet paper strength agent is used to make the burnable container 1 difficult to be torn when wetted or wet.

As a wet paper strength agent,
Urea-formaldehyde resin, also called urea resin, obtained by polymerization reaction of urea and formaldehyde, specifically Eulamin P-1500 (manufactured by Mitsui Chemicals, Inc .: trade name, Eulamin is a registered trademark);
Melamine-formaldehyde resin, which is also referred to as melamine resin, obtained by polycondensation reaction between melamine and formaldehyde, specifically Eulamin P-6300 (trade name, manufactured by Mitsui Chemicals);
Epichlorohydrin modified polyamide polyamine resin modified by reacting epichlorohydrin with the amino group of polyamide polyamine resin to control the cationic property, specifically, Arafix 100, Arafix 251S, Arafix 255, Arafix 255LOX (Both manufactured by Arakawa Chemical Industries, Ltd .: trade name, Arafix is a registered trademark), WS4030 (made by Seiko PMC Co., Ltd .: trade name);
Is mentioned. The above wet paper strength agents may be used alone or in combination.

  When the burnout container 1 contains a wet paper strength agent, the water bonds between fibers such as nitrocellulose and natural or synthetic fibers adhere to the water due to the network self-crosslinking of the resin component of the wet strength paper strength agent. Water-resistant chemical bonds are formed by crosslinking and interaction between the resin component of the wet paper strength agent and cellulose fibers such as nitrocellulose and natural or synthetic fibers. The strength after water absorption can be improved.

  The burnout container 1 may contain only one of the internally added sizing agent and the wet paper strength agent, or may contain both.

  When using only the internal sizing agent among the internal sizing agent and the wet paper strength agent in the burnout container 1, it is preferably contained in an amount of 0.05 to 2.0% by weight. If it is less than this range, the water absorption rate becomes high and water resistance is lacking, and if it exceeds this range, the drying strength becomes too weak. Preferably it is 0.2 to 1.5 weight%, More preferably, it is 0.4 to 1.0 weight%.

  When only the wet paper strength agent is used in the burnout container 1 among the internal sizing agent and the wet paper strength agent, it is preferably contained in an amount of 0.75 to 3.0% by weight. It is said that the wet paper strength agent originally does not exhibit water repellency regardless of the content, but by containing 0.75 to 3.0% by weight a little more, water absorption is sufficiently suppressed and water repellency is achieved. The strength after water absorption can be sufficiently maintained while expressing Although the mechanism is not necessarily clear, it is guessed that it is due to the interaction with the nitrocellulose and binder (synthetic resin) contained in the burnable container 1. If the amount of wet paper strength agent is too small, the strength improvement effect when wet cannot be exhibited and water repellency is not exhibited. If it is too much, the strength when drying is reduced in addition to the strength when wet. It becomes a situation. Preferably it is 0.9 to 2.5 weight%, More preferably, it is 1.0 to 2.0 weight%.

  In the case of containing both the internally added sizing agent and the wet paper strength agent in the burnout container 1, the strength after water absorption can be sufficiently maintained while sufficiently suppressing the water absorption even if the amount thereof is small. The sizing agent and wet paper strength agent are 0.05 to 2.0% by weight: 0.1 to 3.0% by weight, preferably 0.5 to 1.0% by weight: 0.5 to 1.0% by weight. Contained. Thereby, the strength after water absorption can be sufficiently maintained while sufficiently suppressing water absorption. Although the mechanism is not necessarily clear, it is caused to interact with nitrocellulose or a binder (synthetic resin) by intercalating it between the fibers of nitrocellulose or natural or synthetic fibers by being added internally to the burnable container 1. Inferred. When both the internally added sizing agent and the wet paper strength agent are contained in the burnout container 1, it is the same in a smaller amount as compared with the case where either the internal additive size agent or the wet paper strength agent is contained. The above effects can be obtained. Thereby, water absorption is further suppressed and the strength of the burnable container 1 after water absorption is improved.

  The binder is for fixing the cellulose or natural or synthetic fiber, which is a non-adhesive component in the burnable container 1, to enhance the strength.

  Examples of the binder include synthetic resins such as emulsion polymerization styrene butadiene rubber and solution polymerization styrene butadiene rubber.

  In the burnout container 1, the binder is generally contained in an amount of 3.0 to 15.0% by weight, but the strength and flammability required according to the required specifications and applications of the burnout material being molded. The content can be increased or decreased according to.

  The stabilizer is used as a stabilizer for smokeless explosives and suppresses spontaneous ignition of nitrocellulose.

Stabilizers include, for example, ethyl central (ECL); methyldiphenylurea acardite II (AKII); diphemylamine (DPA); 2-nitrodimenylamine (2NO ₂ DPA); AO-80 or ADK STAB AO-50 (both manufactured by ADEKA Corporation: trade name, ADK STAB is a registered trademark); 2,6-di-t-butyl-4-methylphenol (BHT); hydroquinone (HQ), etc. Can be mentioned.

  Stabilizers are added as appropriate according to the required specifications and applications of the burnable material being molded.

  As the nitrocellulose used for molding the burnable container 1 of the present invention, those not in the JIS standard are standardized by the ministries and agencies regarding requirements and test methods, and are defined by the Ministry of Defense Standard (NDS) K-4013C ( Grade I (nitrogen content 12.45-12.75%), Grade II (nitrogen content 13.35% by weight or more) and Grade III (nitrogen content 13.10-13) defined for nitrocellulose ammunition 30% by weight) nitrocellulose can be used. The nitrogen content in the total amount is preferably 12.45 to 14.14% by weight.

  In the burnout container 1, nitrocellulose is generally contained in an amount of 20 to 90% by weight, but is contained in accordance with the required strength and combustibility according to the required specifications and applications of the burnout material being molded. You can increase or decrease the amount.

  The natural or synthetic fiber used for molding the burnable container 1 of the present invention is preferably cellulose, fiber, for example, chemical pulp such as kraft pulp, cellulose acetate, cellulose acetate propionate, cellulose acetate butyl, It may be a fiber made of cellulose such as ethyl cellulose, may be a fiber derived from at least one of a herbaceous plant, a shrub plant, or an oak plant, may be waste paper, or may be an acrylic fiber Fine cellulose fiber may be used. Among these, when more strength of impact resistance is required, it is preferable to use fine cellulose fiber or non-wood pulp.

  Herbaceous plants include kenaf, Asa, flax, abaca, bamboo, cotton, rice, wheat, bamboo shoots, and jute. Shrub plants include mulberry, mitsumata, and ganpi. Conifers and hardwoods.

  Among herbaceous plants, Kenaf is a mallow family, Asa is a hempaceae plant also called hemp, Ama is a flax family plant also called flax, and Abaca is a banana family plant also called manila hemp. The tissue containing the fiber is also collected from the bast portion of the stem. Bamboo is a gramineous plant also called bamboo, and a tissue containing fibers is collected from a dried hollow woody stem. Cotton is a mallow that is also called cotton. Tissues containing fibers are collected from cotton. Rice is a plant belonging to the genus Gramineae, and wheat is a gramineous plant such as wheat, barley, rye, and buckwheat. The stem is dried, and the straw, which is a fiber-containing tissue, is collected. A bamboo shoot is a plant of the family Papaveraceae, and a tissue containing fibers is collected from a pseudostem / leaf sheath. Jute is a lindenaceae plant also called burlap, Indian hemp, or leopard, and a tissue containing fiber is collected from the bast.

  Among the shrub plants, mulberry is a mulberry shrub plant also called moth, mitsumata is a gentian shrub plant also called trigonum, and Gumpi is a gentian shrub plant also called scabbard. Tissue containing is collected.

  The oak plant may be a conifer or a hardwood, but is preferably a raw material for kraft pulp. The obtained fiber may be an unbleached product or an unbleached product, and is preferably an unbleached product.

  Examples of the used paper include corrugated used paper, newspaper used paper, and cut paper, and are made into paper after being processed into a fiber and processed as necessary to remove ink.

  The acrylic fiber is preferably a fiber made of a synthetic polymer mainly composed of acrylonitrile.

  Tissues collected from plants or recovered from waste paper are dried, then torn or unwound, cut as necessary, or chemically pulped, and acrylic fibers are cut appropriately. After that, the fibers have an average diameter of 5 to 40 μm and an average length of 0.5 to 12 mm. You may degrease like absorbent cotton. In particular, a pulp derived from such a plant has a hydroxyl group and is compatible with nitrocellulose having a hydroxyl group. Therefore, even if these are mixed, the familiarity with each other is good, and since the hydroxyl groups are dehydrated and bonded during drying, the molded product can have strong strength. On the other hand, chemical fibers that do not have a hydroxyl group do not conform to nitrocellulose, do not undergo dehydration bonding during drying, and cannot be expected to have strength.

  Micronized cellulose fibers are made of wood, non-wood, pulp made from wood and non-wood, natural fibers such as cotton and hemp, plants such as dietary fiber derived from grains and fruits, seaweed valonia, and chrysanthemum squirts. And / or any raw material selected from bacteria that produce cellulose and the like.

  The refined cellulose fiber is not limited to its production method or defibration method, and a known method can be used, and chemical defibration, physical defibration based on the raw materials, or a complex defibration combining these. It can be obtained with fiber. For example, it is a generally known method, and is obtained by a method in which cellulose is defibrated or refined by grinding or beating using a refiner, a high-pressure homogenizer, a medium stirring mill, a stone mill, a grinder, or the like. be able to. As chemical defibration, for example, a method of oxidizing the cellulose after washing with acid with an N-oxyl compound to defibrate the oxidized cellulose to form nanofibers can be mentioned. Examples of physical defibration include a method of producing a nanofiber precursor by mechanical defibration. For example, in the presence of N-oxyl compound and bromide, iodide or a mixture thereof, powder cellulose is oxidized using an oxidizing agent and wet micronized using pressure using an ultrahigh pressure homogenizer. The method of making it a nanofiber by processing is mentioned. Moreover, the micronized cellulose fiber may be a commercially available product.

  The refined cellulose fiber has an average fiber diameter of 1.5 μm or less, and an aspect ratio obtained by dividing the average fiber length by the average fiber diameter may be 10 or more. For example, cellulose nanofibers, microcellulose fibers , Cellulose nanofiber, microfibrillated cellulose, fine cellulose, cellulose fiber, fine cellulose fiber, and fine fibrous cellulose may be used.

  As refined cellulose fibers, specifically, serish KY-100G, serisch KY-100S, serisch FD-100F, serisch FD-100G, serisch FD-100S, serisch FD-100M, serisch FD-200L, serisch PC-110S ( Any of them may be Daicel Finechem Co., Ltd. (trade name, Selish is a registered trademark) and Binfisu (Sugino Machine Co., Ltd .: trade name, Binfis is a registered trademark).

  The fine cellulose fibers preferably have an average fiber diameter of 4 nm to 1.5 μm, an average fiber length of 40 nm to 1000 μm, and an aspect ratio of 10 to 1000.

  In the burnout container 1, natural or synthetic fibers are generally contained in an amount of 9 to 70% by weight, but according to the required specifications and usage of the burnt-out material being molded, the strength and flammability are required. The content can be increased or decreased.

  The burnout container 1 improves the water resistance and water repellency of the burnout container itself by containing the wet paper strength agent and the internal sizing agent and entering between the fibers of nitrocellulose and natural or synthetic fibers. In addition, the physical strength when wet or after water absorption is enhanced and improved. Therefore, no matter what shape it is molded, it will not be affected by moisture, and will not lose its shape due to improved dimensional and shape stability.

  In addition, the burnout container 1 does not need to change the composition ratio of burnout components such as nitrocellulose and reinforcing components such as natural or synthetic fibers with conventional ready-made products, and can be manufactured using a conventional manufacturing apparatus. It exhibits sufficient impact resistance, combustion performance, and burnout performance.

  In addition, various low-viscosity inks, such as water-soluble inks, which were difficult to use because they penetrated into the burnout container, do not bleed. It is possible to print.

  The burnout container 1 has been shown as an example of a propellant charge container, but may be other chargeable containers, and is wrapped in a burnt cartridge case for a rifle filled with explosives inside or encased in a ball skin. It may be a firework ball outer shell filled with gunpowder.

The shape of the burnout container 1 is not particularly limited, and even if it is a shape that is likely to cause an unpainted portion in the surface treatment, it can be appropriately selected according to the required specifications and applications. For example, a plate shape, a spherical shape, a cylindrical shape, a rectangular tube shape, a cylindrical shape with a wavy outer periphery, or a donut shape having a hollow shape may be used. Even if the burnout container 1 has such a complicated shape, the water resistance is not uneven because it is homogeneous. The burnable container 1 has, for example, a thickness of 0.5 to 4.0 mm and a density of 600 to 1300 kg / m ³ .

  Although the burnout container 1 has been described as the burnout material, a burnout substrate may be used instead of the burnout container or together with the burnout container. The combustible substrate can be produced by molding into a plate shape with the same composition as the combustible container 1, and the shape can be appropriately selected according to the required specifications and applications as with the combustible container 1. Moreover, it is preferable that the thickness of the burnout substrate is 0.1 to 4.0 mm. The burnable substrate may be a burnable material that is affixed, integrally molded or incorporated in the burnout container.

  The burnout material molded on the burnout container 1 or the burnout substrate is printed directly on the surface with colored ink to display the type of shell, or the wireless circuit conductive pattern is printed with conductive ink. It may be done. Such a burn-out material can form a print or a conductive pattern on the surface of an ink, for example, a water-soluble ink by an arbitrary printing method such as inkjet printing without causing the ink to bleed. Once the print or conductive pattern is formed, the ink component is confined or impregnated between fibers in nitrocellulose or natural or synthetic fibers with a wet paper strength agent or internal sizing agent. Does not bleed even when exposed to moisture or moisture. For this reason, the type of ink and the printing or coating method are not particularly limited and are highly versatile.

  The burnout container 1 shown in FIG. 1 is manufactured as follows.

  First, nitrocellulose, an internally added sizing agent, a wet paper strength agent, fibers, a binder, and a stabilizer as necessary are kneaded with water to obtain a slurry. A known manufacturing method, specifically, this slurry is sucked and paper-made, and then pressed against a substantially cylindrical mold for the container body 3 shown in FIG. The container body 3 having a cylindrical shape and having a slightly narrower portion near the lower end is molded. Similarly, the upper lid 2 is molded.

  After filling the molded container body 3 with the explosive 4 and applying an adhesive to the outer periphery in the vicinity of the upper end of the container body 3, the upper lid 2 is fitted to the upper end of the container body 3 to obtain the burnable container 1.

  The burnout container 1 of the present invention is used as follows.

  As shown in FIG. 1, a burnable container 1 and a shell (not shown) are loaded on the breech 6 side of the gun barrel 5 in the chamber, and a closing machine 7 attached to the breech 6 is used. The breech 6 is closed. When a fire tube (not shown) provided in the breech 6 is ignited, combustion of the explosive 4 in the burnable container 1 on the breech 6 side is induced. The part where the burning of the explosive 4 starts burning of the surrounding explosive 4 in sequence very rapidly. As a result, the combustion of the explosive 4 progresses instantaneously as explosive combustion, and the shell is pushed out and fired by the pressure of the combustion gas. The burnout container 1 burns completely without leaving a combustion residue due to its burnout. If necessary, the closure machine 7 is opened after the shell is fired, and the same operation is repeated.

  Hereinafter, an example of preparing a disc-shaped test piece for evaluating the performance of a burnable container to which the present invention is applied will be described as a preparation example, and a disc-shaped test piece for evaluating the performance of a burnable container to which the present invention is not applied will be described. An example of preparing is shown in Comparative Preparation Example. An example in which a burnout container is prototyped is shown in the Examples.

(Preparation Examples 1-33)
As raw materials for the burnout container of the present invention, nitrocellulose ((NDS) K-4013C compliant product), kraft pulp (softwood bleached pulp), non-wood pulp (abaca pulp), refined cellulose fiber (Serish KY-100G, Daicel Finechem) Co., Ltd.), ethyl central (stabilized product based on (NDS) K-4004B), emulsion-polymerized styrene butadiene rubber as a binder, cationic alkyl ketene dimer system as an internal sizing agent (AKD) Sizing agent size pine K-287 (Arakawa Chemical Co., Ltd.) or cationic styrene-acrylic acid copolymer (PS system) sizing agent Polymarlon 360 (Arakawa Chemical Industry Co., Ltd.), wet paper strength WS4030 (an epichlorohydrin modified polyamide polyamine resin as an agent) Using an optical PMC Co., Ltd.). Compositions of nitrocellulose, natural or synthetic fiber (craft pulp, non-wood pulp or fine cellulose fiber), stabilizer, and synthetic resin are constant, and internal sizing agent and wet paper strength agent are shown in Tables 1-6. And a composition ratio were mixed to prepare a slurry suspended in water. The slurry was made into a paper, and a disk-shaped test piece having a diameter of about 145 mm and a density of about 900 kg / m ³ was manufactured by die pressing with a mold.

(Comparative Preparation Example 1)
A disc-shaped test piece of Comparative Preparation Example 1 was prepared in the same manner as Preparation Example 1, except that the internal sizing agent and the wet paper strength enhancer were not added.

(Evaluation of the physical properties)
The physical properties of the disc-shaped test pieces of Preparation Examples 1 to 33 and Comparative Preparation Example 1 were evaluated as follows. The evaluation results are summarized in Tables 1 to 6 below.

(1) Dimensional stability evaluation tests 1 and 2 against moisture
Samples obtained by cutting the disk-shaped test pieces of Preparation Examples 1 to 33 and Comparative Preparation Example 1 into 60 mm × 20 mm were used as samples. First, the sample was placed in a condition of 120 ° C. for 5 minutes and dried, and then the dry mass and the dry thickness were measured under normal temperature and normal humidity. Thereafter, the sample was submerged in water (water temperature 20 ° C., water amount 500 ml), and after 15 minutes, the sample was taken out and the moisture on the surface was wiped off, and the wet mass and wet wall thickness were measured. From the measurement results, the water absorption rates of Preparation Examples 1 to 33 and Comparative Preparation Example 1 and the wall thickness increase rate upon water absorption were calculated as follows.
Water absorption (%) = (wet mass−dry mass) / dry mass × 100
Thickness increase rate (%) = (wet thickness−dry thickness) / dry thickness × 100

(2) Strength evaluation test
(2-1) Strength evaluation test 1 in the dry state
In order to measure the impact resistance performance in a dry state, first, each disk-shaped test piece of Preparation Examples 1 to 33 and Comparative Preparation Example 1 was cut into 75 mm × 12.5 mm to obtain dumbbell samples. Each dumbbell sample was placed in a state of 120 ° C. for 5 minutes to dry, and then subjected to a tensile test in accordance with JIS K6251 at room temperature and humidity to measure the dry strength. Based on the dumbbell sample of Comparative Preparation Example 1, the rate of increase or decrease in dry strength was calculated.

(2-2) Strength evaluation test 2 after water absorption
In order to measure the impact resistance after water absorption, first, each disk-shaped test piece of Preparation Examples 1 to 33 and Comparative Preparation Example 1 was cut into 75 mm × 12.5 mm to obtain a dumbbell sample. Each dumbbell sample piece was placed in a condition of 120 ° C. for 5 minutes to dry, then, under normal temperature and humidity, a tensile test was performed according to JIS K6251 to measure the dry strength. Submerge another dried dumbbell sample in water (water temperature 20 ° C, water volume 500 ml), and after 15 minutes, remove the sample and wipe off the moisture on the surface. Similarly, perform a tensile test and measure the strength after water absorption. did. Based on the dry strength of each dumbbell sample after drying, the rate of decrease in self-strength after water absorption was calculated.

(2-3) Strength evaluation test after water absorption 3
Based on the strength of the dumbbell sample of Comparative Preparation Example 1 after water absorption, the relative strength of each dumbbell sample of Preparation Examples 1 to 33 after water absorption was calculated.

(3) Combustion performance evaluation test A closed bomb calorimeter with a capacity of 100 cc was used to evaluate the combustion performance. Each disk-shaped test piece of Preparation Examples 1-33 and Comparative Preparation Example 1 was loaded at a loading density of 0.2 g / cc, ignited with an igniting agent, and a pressure profile was obtained. From the obtained data, the slope of the pressure profile was calculated and evaluated as a combustion performance result. Based on the reference of Comparative Preparation Example 1, the evaluation was made in two stages, ie, whether the combustion performance was equivalent.

(4) Burnout performance evaluation test About the combustion residue, the burnout performance was evaluated by visually observing the inside of the sealed bomb after the combustion performance evaluation test and confirming the presence or absence of unburned residue.

  As is clear from Tables 1 to 6, the test pieces of Preparation Examples 1 to 33 used for the burnout material of the present invention are increased in water absorption and wall thickness increase rate as compared with the test piece of Comparative Preparation Example 1. The water resistance is improved and the dimensional stability is excellent. In addition, the strength did not decrease so much after water absorption, and both flammability evaluation and burnout evaluation were excellent. As in Preparation Examples 1 to 14, the decrease in dry strength increase / decrease rate was suppressed in the case of using the PS internal additive sizing agent than in the case of using the AKD internal additive sizing agent. Further, as in Preparation Examples 15 to 16, the wet paper strength agent is not supposed to exhibit water repellency regardless of the content, but if it is contained somewhat more as in Preparation Examples 17 to 24, the water absorbency is increased. The strength after water absorption can be sufficiently maintained while sufficiently suppressing the water repellency. When both the internally added sizing agent and the wet paper strength agent are used as in Preparation Examples 27 to 31, the water absorption rate is suppressed and water repellency is exhibited, and the decrease in the strength reduction rate after water absorption is suppressed. Is done. In Preparation Example 5, although the water absorption rate and the dimensional change after water absorption were good, the dry strength tends to decrease. However, as shown in Preparation Examples 32-33, non-wood pulp is used instead of kraft pulp, or refined cellulose fibers are used together with kraft pulp to provide water resistance while maintaining dry strength. Has been.

  As is apparent from Tables 1 to 6, the test pieces of Preparation Examples 1 to 33 used in the burnout container to which the present invention is applied have a wet paper strength agent containing 0.05 to 2.0% by weight of the internal sizing agent. It is not contained, or the wet paper strength agent is 0.75 to 3.00% by weight and does not contain the internal sizing agent, or the internal addition size agent: wet paper strength agent is 0.05 to 2.0% by weight: 0.0. Depending on whether it is contained at 1 to 3.0% by weight, the water absorption rate is suppressed and water repellency is exhibited, and the decrease in the strength reduction rate after water absorption is suppressed.

(Example 1)
Using the slurry prepared when disc-shaped test pieces were prepared in Preparation Examples 1 to 33, the burnout container 1 shown in FIG. This burn-out container 1 exhibited the same physical properties as the disk-shaped test pieces of these preparation examples. In addition, although the burnout board | substrate which has a wireless tag was produced similarly, the physical property similar to the disk-shaped test piece of these preparation examples was shown.

  Since the burnout container of the present invention has sufficient water resistance, it can be used outdoors where it can be exposed to rainwater, and the gunpowder can be safely and easily loaded into a heavy firearm, for shell shooting, for ritual use or Used during training empty bun shooting. This burnout container has sufficient strength even when wet with water, and does not impair operability even in bad weather. In addition, the burnout container burns out completely even when wet, and it is not necessary to clean the inside of the barrel every time after shooting, so it is useful for shooting quickly and continuously.

  1 is a burnable container, 2 is an upper lid, 3 is a container body, 4 is gunpowder, 5 is a barrel, 6 is a breech, and 7 is a closing machine.

Claims (11)

  A burnable material characterized by being formed by containing nitrocellulose and an internal sizing agent and / or wet paper strength agent.   2. The burnout material according to claim 1, wherein the burnout material is molded into a burnout container.   The burnout container has a spherical or cylindrical shape and is filled with a gunpowder and filled with a gunpowder. The burnout material according to claim 2, which is any one selected from a container for a medicine having an upper lid for closing an opening and an outer shell for a firework ball which is wrapped in a ball skin and filled with gunpowder.   2. The burnout material according to claim 1, wherein the burnout material is formed on a burnout substrate having a wireless tag.   The internally added sizing agent is rosin resin, alkyl ketene dimer, alkenyl succinic anhydride, fatty acid amide, styrene-maleic acid copolymer, styrene-acrylic acid copolymer and / or olefin-maleic acid copolymer. The combustible material according to claim 1, comprising at least one selected from a copolymer resin that is a coalescence.   The burnout material according to claim 1, wherein the internal additive sizing agent is molded to contain 0.05 to 2% by weight.   The burnout material according to claim 1, wherein the internally added sizing agent is cationic.   2. The burnout material according to claim 1, wherein the wet paper strength agent includes at least one selected from urea-formaldehyde resin, melamine-formaldehyde resin, and epichlorohydrin-modified polyamide polyamine resin.   The burnout material according to claim 1, wherein the wet paper strength agent is formed to contain 0.75 to 3% by weight.   2. The burnout material according to claim 1, wherein the burnout material is molded to include at least one selected from natural or synthetic fibers, a binder, and a stabilizer.   The burnout material according to claim 8, wherein the natural or synthetic fiber, the binder, and / or the stabilizer is anionic, and the internal sizing agent is cationic.

Images