JP4865929B1 - Burnout container - Google Patents

Abstract

[PROBLEMS] To improve strength of heat resistance and impact resistance while maintaining flammability and burnout as compared with conventional products, excellent in shape stability and dimensional stability, and stably manufactured with high yield. A burnable container is provided.
A burnable container 1 has a cylindrical container body 3 that is closed at the lower end and filled with explosive 4 and an upper lid 2 that is fitted and closed at the upper end to have an average fiber diameter of 1. A fiber component containing a refined cellulose fiber having an aspect ratio obtained by dividing the average fiber length by the average fiber diameter and having a minimum aspect ratio of 10 while being 5 μm, and a nitrocellulose component are molded.
[Selection] Figure 1

Description

  The present invention is used for loading a gun barrel into a chamber while containing a propellant, an ignition agent, etc., when a bullet is shot with a cannon or when an empty envelope is shot with a gun or training. This relates to a burnable container.

  When firing cannonballs like cannons, explosives such as propellants and igniters are sealed in a thin layer of a burnable container, loaded into the gun barrel's chamber, and a bullet placed on top of it. Is done. When this explosive is ignited, it causes explosive combustion, and a bullet is fired by the combustion gas pressure. No bullets are used during air bombardment shooting, but it also causes explosive combustion and produces a bombardment sound.

  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, flashes, bullets, vibrations, and shocks, and fires are unexpectedly caused by these external causes. Susceptible to serious effects. Therefore, this burn-out container becomes a sensitivity factor, in other words, with respect to external factors for the entire propellant. For this reason, this burnout container is strong enough to withstand flames, heat, sparks, etc. during transportation / storage or loading, and with sufficient impact resistance to withstand impact, vibration, impact, etc. 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 combine it with burnout performance that does not leave any residue.

  Such a burnout container is manufactured through a process of papermaking and pressing by making nitrocellulose as a main component, pulp fiber and synthetic resin into a slurry in water.

  In order to improve the strength of the burnout container, for example, in Patent Document 1, a flame retardant nitrocellulose in which a part of a nitrate ester group of nitrocellulose is substituted with an inactive ester group and a reinforcing composition such as an aramid fiber are used. Disclosed is a propellant container made of a mixture with fibers. Further, Patent Document 2 discloses a burnable container formed by including natural fibers derived from a herbaceous plant, a shrub plant, and an oak plant and nitrocellulose.

  The strength of such a burnout container depends on the toughness of the natural fibers and synthetic fibers used for reinforcement. Generally, in a burnable container, there is a trade-off relationship between the strength improvement by these fibers and the burnout performance improvement. Therefore, in order to improve the strength of the burnable container, it is necessary to reduce the content of nitrocellulose as a combustion component and increase the content ratio of these fibers. However, reducing the nitrocellulose content will reduce the burnout performance, and the use of existing natural fibers and reinforcing synthetic fibers alone will improve the strength of the burnout container while maintaining the burnout performance. There are limitations.

  Moreover, it is difficult to improve the strength of the burnout container by using only reinforcing fibers such as synthetic fibers for reinforcement, for example, chemical fibers, instead of pulp fibers such as natural fibers. This is because, firstly, hydrophobic chemical fibers cannot be uniformly dispersed in water, so that it is difficult to produce them stably. Also, in the case of bonding via pulp fibers, hydrogen bonding occurs between the fiber surfaces, so that some strength improvement can be achieved, but generally in the case of bonding via chemical fibers, it depends on the frictional force of the fiber surface. This is because, even if the strength of the chemical fiber alone is somewhat superior, it is difficult to sufficiently improve the strength of the entire burnable container. Furthermore, some chemical fibers exhibit more flame retardancy than pulp fibers, making it difficult to maintain good burnout.

  As another method for improving the strength of the burnout container, there are a method of changing the shape of the burnout container to make it robust and a method of increasing its thickness or increasing the density. For example, Patent Document 3 discloses a drug-filled container comprising a case and a cap, which is formed of a burnable material mainly composed of nitrocellulose, kraft pulp, and synthetic resin, and whose outer periphery is wavy and has improved robustness. It is disclosed. These methods also lead to a decrease in the burnout performance, and due to the reduction in the inner volume of the burnout container, there are disadvantages such as a decrease in the filling rate of the propellant per unit volume and an increase in the weight of the burnout container. .

  In addition, since the combustible container is mainly composed of nitrocellulose or pulp fiber, the burnout container is easily affected by external factors such as temperature and humidity, and its size and shape easily change. In consideration of the assemblability and fitting properties between the burnout containers or other metal or resin members, it is desirable that the dimensional and shape stability with respect to temperature and humidity is improved more than the current situation.

JP 09-89499 A JP 2008-175464 A JP 2005-140458 A

  The present invention has been made to solve the above-mentioned problems, and has improved heat resistance and impact resistance while maintaining flammability and burnout as compared with conventional products, and has shape stability and dimensional stability. An object of the present invention is to provide a burnout container that is excellent in performance and can be stably manufactured with high yield.

  The burnout container according to claim 1, which has been made to achieve the above object, has a cylindrical container body that is closed at the lower end and filled with explosive, and is fitted at the upper end thereof. And an upper lid that covers the fiber, including a finely divided cellulose fiber having an average fiber diameter of 1.5 μm at a maximum and an average fiber length divided by the average fiber diameter to a minimum aspect ratio of 10, and a nitrocellulose component It is characterized by being molded.

  The burnout container according to claim 2 is the one according to claim 1, characterized in that the fiber component is 9 to 70% by weight and the nitrocellulose component is 20 to 90% by weight. To do.

  A burnout container according to a third aspect is the one according to any one of the first to second aspects, wherein the fiber component includes pulp fibers.

  The burnout container according to claim 4 is the one according to any one of claims 1 to 3, wherein the refined cellulose fiber is added in an amount of 0.1 to 100 in 100 parts by weight of the fiber component. It includes a weight part.

  The burnout container according to claim 5 is the one according to claim 3, wherein the pulp fiber is kraft pulp, cellulose acetate, cellulose acetate propionate, cellulose acetate butyl, ethyl cellulose, herbaceous plant. It is at least any one selected from a fiber derived from, a fiber derived from a shrub plant, a fiber derived from an oak plant, waste paper, and an acrylic fiber.

  The combustible container of the present invention improves the strength of the combustible container without impairing the combustibility and the combustibility compared to the conventional combustible container using only nitrocellulose and pulp fibers as fiber components. be able to. Since the specific surface area of the refined cellulose fiber contained in the burnout container is extremely larger than that of the pulp fiber, the number of hydrogen bonds between the fibers at the time of dry molding becomes extremely large, and the strength can be greatly improved. In addition, the refined cellulose fiber has less structural defects that appear in the fiber itself than the pulp fiber, which is a natural material, and thus affects the strength improvement. Since the refined cellulose fiber is mainly composed of the same material constituting the natural fiber, the combustibility and burnout of this burnout container is almost the same as that of the burnout container containing pulp fiber without containing the refined cellulose fiber. It is equivalent.

  In addition, since the thermal expansion coefficient of the refined cellulose fiber is as low as that of quartz glass, this burnable container can improve the dimensional stability with respect to temperature. Furthermore, compared with pulp fibers, finely divided cellulose fibers in a dry state strongly aggregate together and form a denser structure, so that the resistance to dimensional stability against moisture is also improved. Therefore, the dimensional stability with respect to the humidity of the burnout container can also be improved.

  Furthermore, this burnable container can improve manufacturing stability by the improvement of the dispersibility of raw material slurry. As a fiber component, if the inside of the tank is not continuously stirred, the solid content in the slurry will precipitate, and the slurry containing only pulp fibers that have been widely used in the past will not maintain a uniform concentration. The slurry containing can easily continue to uniformly disperse the slurry in the tank without much stirring power. This is considered to be due to the fact that the finely divided cellulose fiber has extremely high dispersibility in water, and contributes to the production stability of the burnout container.

  Moreover, this burnable container has a good yield. When this burnout container contains a synthetic resin and a stabilizer which are raw materials other than the fine cellulose fibers, the synthetic resin and the stabilizer are fixed and collected on the fibers, respectively. Since the specific surface area of the refined cellulose fiber is extremely large, the fixing rate of the synthetic resin is improved, and the finer cellulose fiber has a denser structure between the fibers, so that the collection rate of the stabilizer is also improved. Compared with a burnable container that does not contain finely divided cellulose fibers and uses conventionally used pulp fibers as fiber components, the loss of raw material slurry during the production can be reduced.

It is sectional drawing of the side surface which shows one Example of the burnable container to which this invention is applied.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to FIG. 1, but the scope of the present invention is not limited to these embodiments.

  As shown in FIG. 1, in the burnout container 1, the container body 3 and the upper lid 2 have the same composition, and the average fiber length is divided by the average fiber diameter while keeping the average fiber diameter at most 1.5 μm. It is made by papermaking, pressing, and molding from a slurry containing a fiber component containing finely divided cellulose fibers having an aspect ratio (average fiber length / average fiber diameter) of 10 or more and a nitrocellulose component. .

  When the container main body 3 and the upper lid 2 are formed with the same composition, the burnout container 1 has a simple structure and exhibits sufficient combustibility, burnout, shape stability, and dimensional stability evenly. can do. The burnout container 1 preferably contains 15 to 50% by weight of the fiber component and 45 to 82% by weight of the nitrocellulose component.

  Refined cellulose fibers contained in fiber components are wood, non-wood, pulp made mainly of wood and non-wood, natural fibers such as cotton and hemp, plants such as dietary fiber derived from grains and fruits, and seaweed valonia , Derived from any raw material selected from chordate squirts, and / or bacteria that produce cellulose.

  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, it is described in JP 2009-243014 A, and the oxidized cellulose is defibrated by oxidizing the cellulose raw material washed after acid treatment with an N-oxyl compound. The method of making into nanofibers is mentioned. Examples of physical defibration are described in Japanese Patent Application Laid-Open No. 2008-024788, and include a method of producing a nanofiber precursor by mechanically defibration. The complex fibrillation is described in, for example, JP-A-2009-263651, and oxidizes powdered cellulose using an oxidizing agent in the presence of an N-oxyl compound and bromide, iodide or a mixture thereof. And a method of forming nanofibers by wet atomization with pressure using an ultra-high pressure homogenizer. Moreover, the micronized cellulose fiber may be a commercially available product.

  The finely divided cellulose fiber may have an average fiber diameter of 1.5 μm or less and an aspect ratio of 10 or more. For example, cellulose nanofiber, fine cellulose fiber, cellulose nanofiber, microfibrillated cellulose, fine cellulose, cellulose It may be referred to as fiber, fine cellulose fiber, or fine fibrous cellulose.

  Specifically, as a refined cellulose fiber, serish: KY-100G, KY-100S, FD-100F, FD-100G, FD-100S, FD-100M, FD-200L, PC-110S (all are Daicel Finechem Co., Ltd.) Product name).

  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 addition to these fine cellulose fibers, pulp fibers may be contained as a fiber component. When pulp fibers are contained, it is preferable that 0.1 to 100 parts by weight of fine cellulose fibers are contained in 100 parts by weight of the fiber component.

  The pulp fiber contained in the fiber component is preferably a chemical pulp such as kraft pulp, but may be a fiber made of cellulose such as cellulose acetate, cellulose acetate propionate, cellulose acetate butyl, or ethyl cellulose. Further, it may be a fiber derived from at least one of a herbaceous plant, a shrub plant, and an oak plant, may be waste paper, or may be an acrylic fiber.

  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 3 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.

  As the nitrocellulose component contained in the burnable container 1 of the present invention, the Ministry of Defense Standard (NDS) K-4013C (standardized by the ministries and agencies regarding the requirements and test methods that are not in JIS standards) 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 shells 30% by weight) nitrocellulose can be used. The nitrogen content in the total amount is preferably 12.45 to 14.14% by weight.

  Moreover, the container main body 3 and the upper lid 2 of the burnable container 1 are made of general-purpose additives such as a binder resin, if necessary, in addition to the fiber component containing fine cellulose fiber and pulp fiber and the nitrocellulose component. A synthetic resin, a stabilizer, or a fixing agent may be contained.

  Their content is 0 to 10% by weight, and among the additives, for example, binder resin, stabilizer and fixing agent are (6 to 12) :( 0.5 to 2.0) :( weight ratio). 0.1 to 1.0) is preferable.

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

Specific examples of the stabilizer include ethyl central (ECL), acardite (AKII), diphemylamine (DPA), 2-nitrodimenylamine (2NO ₂ DPA), phenolic antioxidant ADK STAB AO-80, Examples include AO-50 (all manufactured by Asahi Denka Kogyo Co., Ltd .; trade name), 2,6-di-t-butyl-4-methylphenol (BHT), hydroquinone (HQ), and the like.

  Specific examples of the fixing agent include inorganic flocculants (for example, sulfuric acid bands) and organic flocculants (for example, polymer flocculants).

  The shape of the burnout container is not particularly limited as long as it is a cylindrical shape, and may be a cylindrical shape, a rectangular tube shape, a cylindrical shape with a wavy outer periphery, or a hollow donut shape.

  The burnout container to which the present invention is applied is manufactured as follows.

  A slurry is obtained with finely divided cellulose fibers, nitrocellulose, and, if necessary, pulp fibers and additives such as synthetic resins, stabilizers, and fixing agents. After the slurry is made by suction, the slurry is pressed against a substantially cylindrical mold for the container body 3 shown in FIG. 1 and is pressed and dehydrated and solidified while being heated. The collected container body 3 is molded. Similarly, the upper lid 2 fitted to the upper end of the container body 3 is molded. After filling the 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 to which the present invention is applied 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 is burntable and thus burns completely without leaving a combustion residue. Therefore, the wall inside the gun barrel and its chamber is not contaminated and is kept clean. After the shell is fired, the closing machine is opened and the same operation is repeated.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

(Preparation Examples and Comparative Preparation Examples)
Nitrocellulose, refined cellulose fiber (manufactured by Daicel Finechem Co., Ltd .; trade name “Serisch KY-100G”), kraft pulp (softwood bleached pulp), synthetic resin, stabilizer and fixing agent Were mixed at a component ratio shown in Table 1 below to prepare a slurry suspended in water. From this slurry, a rough cylinder is prepared by a suction papermaking method, the coarse cylinder is placed in a male mold heated to 125 ° C., and the shape is φ145 mm in the form of a disk with a diameter of 145 mm and a density of about 900 kg / was molded burn out of the container is squeezed product of m ^3.

  In addition, for comparison, a conventional burnout container was obtained as a comparative preparation example except that it did not contain fine cellulose fibers.

(Evaluation of the physical properties)
Using the burnable containers obtained in the Preparation Examples and Comparative Preparation Examples, the physical properties were evaluated as follows. The evaluation results are shown in Table 1 below.

(1) Strength evaluation test In order to measure the impact resistance performance, a tensile test was performed in accordance with JIS K6251 to confirm the strength.

(2) Combustion performance evaluation test For the combustion performance, a sealed bomb with a volume of 100 cc was used, a loading density was loaded at 0.2 g / cc, ignition was performed 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 combustion performance.

(3) 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.

(4) Dimensional stability evaluation test with respect to temperature The sample shape is 15 × 15 mm. First, after adjusting the temperature and humidity for 3 hours under conditions of a temperature of 25 ° C. and a humidity of 60%, the thickness of each sample was measured. Next, after adjusting the temperature and humidity for 3 hours under conditions of a temperature of 65 ° C. and a humidity of 60%, the thickness of each sample was measured, and the reduction rate of the thickness with respect to the temperature of 25 ° C. was obtained.

(5) Dimensional stability evaluation test against moisture The sample shape is 15 × 15 mm. First, the thickness was measured under conditions of a temperature of 25 ° C. and a humidity of 60%. Then, the sample was picked with tweezers and submerged in water (water temperature 25 ° C., water amount 500 ml). After 3 minutes, the sample was taken out and the thickness was measured. From each measurement result, the rate of increase in wall thickness in a water-containing situation was obtained.

  In Table 1, the dispersion stability of the slurry is the time from when stirring is stopped until the solid content is completely precipitated.

  From Table 1, it became clear that the burnout container using the refined cellulose fiber increases the strength without impairing its combustibility and burnout as compared with the conventional product. In addition, the conditions which showed the especially outstanding intensity | strength were the preparation examples 2 whose abundance ratio of refined cellulose fiber and pulp fiber is an equal weight ratio.

  Regarding the dimensional stability against temperature and moisture, it was found that the dimensional stability was improved as the abundance of fine cellulose fibers was increased.

  Regarding the manufacturability, it has been found that the dispersion stability of the slurry becomes better as the abundance of finely divided cellulose fibers increases.

  The burnable container of the present invention is used for safely and simply loading gunpowder with a gunpowder in a heavy firearm, and for shell shooting or for air wrapping for ritual or training.

  The burnout container has sufficient strength so that it can be stacked and stored, transported, or stacked and loaded on the barrel to shoot heavy bullets. Further, the burnout container is completely burned out, and it is not necessary to clean the inside of the gun barrel every time after shooting, so that 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 (5)

  A cylindrical container body that is closed at the lower end and filled with explosive and an upper lid that fits and closes the upper end is divided by the average fiber diameter while the average fiber diameter is 1.5 μm at the maximum. A combustible container characterized by being molded including a fiber component containing finely divided cellulose fibers having a minimum aspect ratio of 10 and a nitrocellulose component.   The burnout container according to claim 1, wherein the fiber component is 9 to 70% by weight and the nitrocellulose component is 20 to 90% by weight.   The burnout container according to claim 1, wherein the fiber component includes pulp fiber.   The burnable container according to any one of claims 1 to 3, wherein 0.1 to 100 parts by weight of the refined cellulose fiber is contained in 100 parts by weight of the fiber component.   The pulp fibers are kraft pulp, cellulose acetate, cellulose acetate propionate, cellulose acetate butyl, ethyl cellulose, fibers derived from herbaceous plants, fibers derived from shrub plants, fibers derived from oak plants, waste paper, and acrylic fibers The burnable container according to claim 3, wherein the container is at least one selected.

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