WO2012173537A1 - Amidon modifié de colorant soluble dans l'eau amélioré dans une composition de projectile de noyau et procédé de fabrication - Google Patents

Amidon modifié de colorant soluble dans l'eau amélioré dans une composition de projectile de noyau et procédé de fabrication Download PDF

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Publication number
WO2012173537A1
WO2012173537A1 PCT/SE2011/050747 SE2011050747W WO2012173537A1 WO 2012173537 A1 WO2012173537 A1 WO 2012173537A1 SE 2011050747 W SE2011050747 W SE 2011050747W WO 2012173537 A1 WO2012173537 A1 WO 2012173537A1
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WO
WIPO (PCT)
Prior art keywords
starch
starches
modified
oil
water soluble
Prior art date
Application number
PCT/SE2011/050747
Other languages
English (en)
Inventor
Tornee PANG
Original Assignee
GLÜCKSAM, Nikolaj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GLÜCKSAM, Nikolaj filed Critical GLÜCKSAM, Nikolaj
Priority to PCT/SE2011/050747 priority Critical patent/WO2012173537A1/fr
Publication of WO2012173537A1 publication Critical patent/WO2012173537A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B12/00—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
    • F42B12/02—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect
    • F42B12/36—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information
    • F42B12/40—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information of target-marking, i.e. impact-indicating type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/18—Oxidised starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/10—Oxidised starch
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B6/00—Projectiles or missiles specially adapted for projection without use of explosive or combustible propellant charge, e.g. for blow guns, bows or crossbows, hand-held spring or air guns
    • F42B6/10—Air gun pellets ; Ammunition for air guns, e.g. propellant-gas containers

Definitions

  • lipophilic carrier used in fills material for preparing prior water soluble dye has been polyethylene glycol as the base for all ingredients.
  • polyethylene glycol has been subject to significant interactions which may have been occurred between the polyethylene glycol based fill material and impact ruptured projectile capsules shell. These interactions may have resulted, for example in substantially brittle surface of the impact ruptured projectile capsules shell which has been subject to an increased risk of shattering whilst being fired from projectile air gun device. Therefore there is a significant storage requirement associated in handling this prior art polyethylene glycol fills based.
  • the main objective in manufacturing cost effective lipophilic carrier for present enhanced water soluble dye is to overcome the setback in the prior art that is caused by its instability with the impact ruptured projectile capsules gelatin shell and within the fill composition.
  • prior art there is a disclosure of the drawbacks of using native starches with vegetables oil or polyethylene glycol based composition in manufacturing impact ruptured projectile capsules fill material.
  • Such drawbacks were highlighted as FIGURE 3 in reduced surface area of the resulting impact ruptured projectile capsules hit because the filler of previous invention is thicker in consistency of other prior art.
  • the use of the impact ruptured projectile capsules of prior art is limited mostly for cold or cool weather since the filler starts to deteriorate when temperature is ranging from 18 to 25 degree Celsius as shown in FIGURE 1.
  • the gelatin shell of the impact ruptured projectile capsules be chemically stable with the water soluble dye enhanced formulation .
  • Fig. 1 is a drawing showing "00” denotes vegetables oil or polyethylene glycol separates badly from “HOH” combination of native starches with vegetables oil or polyethylene glycol, and "HH” denotes native starches completely separated from the later and become solid substance in prior art of dye composition.
  • Fig. 2 is a drawing showing "X” the enhanced composition of modified oxidized starches blended with "0" shortening oil FL30TM and vegetables oil or polyethylene glycol still “intact” indicated by “XOX” chemical binding stability throughout a period of time storage given temperature is ranging from 18 to 35 degrees Celsius.
  • Fig. 3 highlighted in reduced surface area of the resulting impact ruptured projectile capsules hit because the filler of prior art invention is thicker in consistency of other.
  • Fig. 4 is showing present invention of less thickness with less viscosity and free flowing attribution for greater splattering of paint without dipping on target surface upon impact and rupture of the gelatin shell.
  • Fig. 5(A) of microphotograph is showing prior art of native starches granule.
  • Fig. 5(B) of microphotograph is showing present invention of modified oxidized starches granule.
  • Fig. 6(A) of microphotograph is showing present invention of crystal distribution in shortening oil new fluid FL30TM. Crystal of homogeneous size and distribution indicates good fluidity and solubility.
  • Fig. 6(B) of microphotograph is showing the crystal distribution in solid shortening oil indicates poor fluidity and non flexible solubility.
  • impact ruptured projectile capsules is referring to capsules made of gelatin shell is spherical in shape containing a new combination of modified oxidized starches in the present of shortening oil FL30TM blended with vegetables oil or polyethylene glycol, emulsifier agent and dye color, said projectile capsule shell is made of gelatin shell and is subjected to rupture upon hitting on target with a solid or non solid surface or contact.
  • the impact ruptured projectile capsules described herein is not intended to be limited to a spherical in shape within the content of this present invention.
  • target shooting capsules "rupturable capsule”, “paintballs” and “impact ruptured projectile capsule” are used interchangeably.
  • Impact ruptured projectile capsule is a popular sporting activity whereby in one form of this game, players on each teams are supplied with a projectile air gun device and a number of impact ruptured projectile capsule which are spherical in shape of ammunition.
  • Projectile air gun fires these impact ruptured projectile capsule using compressed gas (C02 or N2, etc) as a propellant.
  • compressed gas C02 or N2, etc
  • the projectile capsule shell ruptures to cause enhanced water soluble dye splattering on the target surface providing dramatic visible evidence of the hit, without injuring the player.
  • the impact ruptured projectile capsule shell is made of gelatin, starches, food grade color and other ingredients which are biodegradable.
  • This impact ruptured projectile capsule is used to encapsulate enhanced water soluble dye using rotary die technology as similar to soft capsule method of making.
  • the vegetables oils used in accordance with the present invention can include vegetable oils.
  • Such vegetables oil include, but are not limited to soybean oil, corn oil, sunflower oil, cereal oil, peanut oil, oil palm, coconut oil, shortening oil, olive oil, rapeseed oil, canola oil, pumpkin seed oil, rice oil, safflower oil and the like.
  • Other oleaginous oil include but are not limited to fish oil, walnut oil, almond oil, hemp oil, jojoba oil, oiticica oil, meadowfoam oil, linseed oil, polyethylene glycol, sesame oil, cottonseed oil, mineral oil, castor oil and paraffin oil.
  • shortening oil FL30TM is used but are not limited to a group of blended vegetables oil or polyethylene glycol base aforesaid.
  • the blended shortening oil FL30TM with vegetables oil or polyethylene glycol base can be present in an amount ranging from about 20% to 95% by weight of the total composition.
  • the blended shortening oil FL30TM with vegetables oil or polyethylene glycol base is present in amount ranging from about 45% to about 80% by weight of the total composition.
  • Emulsifying agent is used as a binding agent between two usually non compatible materials.
  • ethoxylated sorbitan esters ethoxylated triglycerides, ethoxylated glyceryl esters, ethoxylated fatty acids, ethoxylated fatty alcohols, ethoxylated fatty acids, polyol esters, beewaxes, lecithin, paraffin waxes and emulsifying waxes.
  • the emulsifying agents aforesaid are used in but are not limited to preservative purpose, protective coating for powders, a solidifier and stabling pharmaceuticals fills material, additive in water based printing oil or cosmetic, detergent agent, viscosity conditioning agent, solubility agent, dispersing agent, leveling agent, wetting agent, antistatic agent, foaming agent, vegetables oil emulsion, foam stabilizer agent, suspension agent, lubricant agent and chemical intermediate agent .
  • the emulsifier can be present in an amount sufficient to provide a stable emulsion in accordance to the storage and usage temperatures.
  • the emulsifier can be added in the composition from 0.01% to about 20% by weight of the total composition. More preferably, the emulsifier is present in an amount ranging from 0.01% to 10% by weight of the total composition.
  • new composition of modified oxidized starches are preferably to use or combination thereof among the following classification but are not limited to physically modified starch, pregelatinization modified starch, enzymatically modified starch, resistant modified starch, dextrin starch (E1400), acid treated starch (E1401), alkaline treated starch (E1402), bleached starch (E1403), oxidized starch (E1404), enzyme-treated starch (E1405) , monostarch phosphate (E1410) , distarch glycerol (E1411), distarch phosphate esterified with sodium trimetaphosphate (E1412), phosphated distarch phosphate (E1413) , acetylated distarch phosphate (E1414), starch acetate esterified with acetic anhydride (E1420), starch acetate esterified with vinyl acetate (E1421), acetylated distarch adip
  • modified oxidized starch is selected or combination thereof among others may be used subject to the binding proportion and will vary subject to the viscosity properties desired.
  • a selected modified oxidized starch or combination thereof among others are used in the composition ranging from 10% to 70% of the total weight composition. More preferably a selected modified oxidized starch or combination thereof among others maybe added into the composition ranging from 20% to 60% of the total weight composition.
  • modified oxidized starch is added into the enhanced composition in the present of shortening oil FL30TM to improve over prior arts of preparing native starches with vegetables oil or polyethylene glycol base impact ruptured projectile capsules fill material.
  • the proportion of mixture between modified oxidized starch and blended shortening oil FL30TM with vegetables oil or polyethylene glycol base are important to determine the viscosity of the final prepared fill material composition.
  • the present invention is intended but is not limited to prepare a less viscosity, free flowing attribution with less thickness for greater splattering of paint without dipping on target surface upon impact and rupture of the gelatin shell as shown in FIGURE 4.
  • New combination composition of modified oxidized starch aforesaid blended chemical binding stability in the present of shortening oil FL30TM with vegetables oil or polyethylene glycol base is due to high binding capacity to produce less viscosity enhanced fill composition according to FIGURE 2.
  • a less viscosity, free flowing attribution with less thickness fill material in this present invention has improved over prior art of making native starches/oil based fill material and produced a non-shifting fill composition encapsulated into impact ruptured projectile capsule.
  • the non-shifting fill composition during flight will increase accuracy in hitting a target upon firing by using projectile air gun device.
  • native starches with vegetables oil or polyethylene glycol fill material for less viscosity solution
  • native starches, other suitable biomass food filler, bioorganic flour and native powder do not have the chemical binding stability caused by retrogradation, syneresis and lower swelling power in free flowing solubility.
  • Native starches, other suitable biomass food filler, bioorganic flour and native powder only act as thickener agent or density agent.
  • modified oxidized starch and shortening oil FL30TM aforesaid present in starches with vegetables oil or starches with polyethylene glycol formulation being acted as high binding capacity, there is tend to observe bad separation between starches and vegetables oil or polyethylene glycol as shown in FIGURE 1 within short period of storage time given temperature ranging about 18 to 35 degree Celsius.
  • modified oxidized starches blended in the present of shortening oil FL30TM with vegetables oil or polyethylene glycol can be explained according to the following mentioned below.
  • the oxidation process leads to a decrease in the amount of phosphorus and linear fraction amylose in the modified oxidized starches.
  • the result of the oxidation process is an increase in the number of carboxylic and carbonyl groups with a clear preference of forming those latter.
  • the modified oxidized starches over catalyst are characterized by lower viscosity in comparison to the native starch, which results from starch deploymerization during the reaction of oxidation.
  • FIGURE 7 (B) it is evident by a big number of the carbonyl groups. Binding stability and solubility prepared from modified oxidized starches, in comparison to thickening made from native starch is many times stronger due to the presence of the carboxylic and carbonyl groups in these modified oxidized starches .
  • acetyl groups interfere with the regrouping of amylose and amylopectin during gelatinization generated more linear segments eases the absorption of higher amount of iodine, reflected in the amylose content which depends on the number of acetyl groups incorporated.
  • These acetyl groups considered increased solubility due to better dispersion of starch in aqueous systems because acetyl groups obstruct chain association. Therefore, the chemical binding stability over retrogradation, syneresis, swelling power and solubility can be resolved using acetylation, oxidization, cross-linked and hydroxypropylation processes in accordance to different type of starches, size and shape of its molecular components and the method of pretreatment.
  • Modified oxidized starches make the starches more hydrophilic (water loving) and aid cross-linking. This makes modified oxidized starch useful in detergent agent that contributed in completely washable dye solubility and is identified non staining paint. Modified oxidized starch bind compatible with blended shortening oil FL30TM and vegetables oil or polyethylene glycol due to binding attribution that do not cause expansion within the fill material during summer season. Unlike prior art of making the same, fill material tends to react expansion when it exposes to heat that caused the impact ruptured projectile capsules out of shape.
  • the modified starches selected from the aforesaid have attributed new improvement in water soluble dye enhanced formulation from the functional classes but are not limited to dye coating, detergent builders, reduce retrogradation and syneresis, increase swelling powder and solubility, paste stabilizer and high capacity in chemical binder with oil for free flowing attribution.
  • Those aforesaid are new attributions being discovered in the new improvement of enhanced water soluble dye composition for preparing impact ruptured projectile capsules fill material.
  • the dye coloring can be present in an amount sufficient to cause the composition with appearance coloration.
  • the FD&C dye can be present in an amount ranging from 0.01% to about 10% by weight of the total composition. Preferably, the FD&C is added in an amount of about 0.05% to 5% by weight of the total composition.
  • a variety of colors can be used as the dye ingredient of the present invention.
  • the liquid dye composition can be colored red, blue, yellow, orange, purple, green, violet, gold and the like. Typically, high visible neon colors are used including
  • the impact ruptured projectile capsule in sporting activity come in the size ranging from 0.40-0.70 caliber, or an approximately of 0.68 caliber.
  • the new improvement composition in enhanced water soluble dye for impact ruptured projectile capsule have significantly contributed by providing an impact ruptured projectile capsules that is efficient to manufacture, low cost, and safe to the environment.
  • an impact ruptured projectile capsule that is formed other than as a purely liquid or purely oil and or purely polyethylene glycol filled in impact ruptured projectile capsule.
  • an impact ruptured projectile capsule formed from available material that may be acquired and processed at low cost.
  • the method based on common general knowledge of an ordinary person for preparing the present invention water soluble dye fill material compositions is mentioned below. A group of blended oils or polyethylene glycol are added to a suitable mixing vessel equipped with a disperser blade. Mixing is initiated and the mixing speed adjusted to the optimum that does not incorporate air into the liquid mixture.
  • a second group of composition is to be added to the mixing vessel together with a well blended mixture of a group of emulsifying agents, modified starches and thickening agents to the said composition.
  • the vegetable oil or polyethylene glycol together with a group of blended mixture is heated to the temperature ranging from 50 degree Celsius to about 90 degree Celsius.
  • the dye or color pigment may be added with or without additional water, where the dye or color pigment is water soluble, it is generally added as an aqueous solution. To ensure the composition is free of solids, the pigment and dye mixtures are passed through, for example, a 200 mesh screen, as they added to the mixture vessel. Mixing of the composition is continued until the color pigment or dye is well blended and uniform.
  • the fill composition is to be cold down to about room temperature before encapsulating within the impact ruptured projectile capsules using the rotary die encapsulation method, a similar process being practiced in soft gel capsules production.
  • the following examples demonstrate certain aspects of the present invention. However, it is to be understood that these examples are for illustrative purpose only and do not purport to be wholly definitive as to conditions and scope of the present invention. It also should be appreciated that when typical reaction conditions, for example, temperature and reaction times which are those specific ranges can be used, though generally less conveniently.
  • Retrogradation consists of two separable processes, gelation of amylose molecules exuded from the granules during gelatinization and recrystallization of amylopectin .
  • Amylose gelation proceeds via formation of left handed double helical chain segments, followed by helix-helix aggregation of B-type structure.
  • Starch in this sample processed into modified oxidized starch showed the lowest % transmittance value (retrogradation rate) than native starches.
  • the presence of acetyl groups interferes with the regrouping of amylose and amylopectin during cooling of the starch molecules that have been subjected to gelatinization . Based on this evident, the generation of more linear segments eases the absorption of higher amount of iodine, reflected in the amylose content which depends on the number of acetyl groups incorporated .
  • acetyl groups considered increased solubility due to better dispersion of starch in aqueous systems because acetyl groups obstruct chain association.
  • Modified oxidized starch presented higher solubility values than common native starches due to different chain length distribution in these starches. Swelling power values of modified oxidized starches may be explained by the introduction of hydrophilic substitution groups, allowing the retention of water molecules because of their ability to form hydrogen bonds. The granule size and supramolecular organization of starch components is an important role in this solubility pattern.
  • native starches have limitation due to shear stress resistance, thermal decomposition, high retrogradation and syneresis, low swelling power and solubility.
  • these shortcomings can be overcome but is not limited to carbonyl and carboxylic groups, acetylation, oxidization, cross-linked, physically modified, enzymatically modified, acid or alkaline treated and hydroxypropylation processes in accordance to different type of starches, size and shape of its molecular components and the method of pretreatment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention porte sur une nouvelle composition combinée utilisant des amidons oxydés modifiés mélangés à une huile de shortening FL30 (marque déposée) et à une huile végétale ou une combinaison d'amidons oxydés modifiés avec une amélioration attribuée à du polyéthylène glycol dans un colorant soluble dans l'eau amélioré pour l'encapsulation dans des capsules de projectile rompues à l'impact. Dans un mode de réalisation préféré de la composition améliorée, l'amélioration précédemment mentionnée par rapport à l'état antérieur de la fabrication d'amidons natifs mélangés à des huiles végétales ou à du polyéthylène glycol est associée à une stabilité de liaison chimique significative en présence de groupes carbonyle et carboxylique, à des processus d'acétylation, de réticulation, de modification physique, de modification enzymatique, de traitement acide ou alcalin et d'hydroxypropylation qui peuvent réduire une rétrogradation et une synérèse, une puissance de gonflement accrue et une propriété de solubilité en écoulement libre pour un plus grand effet d'éclaboussement et une solubilité complètement lavable. La présente invention est utilisée dans les domaines des sports et des loisirs avec un dispositif de tir d'une arme pneumatique à projectile.
PCT/SE2011/050747 2011-06-16 2011-06-16 Amidon modifié de colorant soluble dans l'eau amélioré dans une composition de projectile de noyau et procédé de fabrication WO2012173537A1 (fr)

Priority Applications (1)

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PCT/SE2011/050747 WO2012173537A1 (fr) 2011-06-16 2011-06-16 Amidon modifié de colorant soluble dans l'eau amélioré dans une composition de projectile de noyau et procédé de fabrication

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PCT/SE2011/050747 WO2012173537A1 (fr) 2011-06-16 2011-06-16 Amidon modifié de colorant soluble dans l'eau amélioré dans une composition de projectile de noyau et procédé de fabrication

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108290963A (zh) * 2015-11-26 2018-07-17 卡吉尔公司 稳定化淀粉
US10889753B2 (en) 2016-04-25 2021-01-12 Halliburton Energy Services, Inc. Self-breakable treatment fluids for use in subterranean formation operations

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050025968A1 (en) * 2003-07-28 2005-02-03 Suying Liu Seamless BB paintball
US20070095240A1 (en) * 2005-10-31 2007-05-03 X.O. Industries Inc. Oil and polyethylene glycol fill material for use in paintball shells
US20090260536A1 (en) * 2006-12-19 2009-10-22 Procaps L.P. Paintball and method of manufacture
US20100064927A1 (en) * 2008-09-17 2010-03-18 Aldo Perrone Starch-based paintball fill material
US20110146524A1 (en) * 2009-12-17 2011-06-23 Tornee Pang Modified Starch of Enhanced Water Soluble Dye Composition in Core Projectile and Method of Making

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050025968A1 (en) * 2003-07-28 2005-02-03 Suying Liu Seamless BB paintball
US20070095240A1 (en) * 2005-10-31 2007-05-03 X.O. Industries Inc. Oil and polyethylene glycol fill material for use in paintball shells
US20090260536A1 (en) * 2006-12-19 2009-10-22 Procaps L.P. Paintball and method of manufacture
US20100064927A1 (en) * 2008-09-17 2010-03-18 Aldo Perrone Starch-based paintball fill material
US20110146524A1 (en) * 2009-12-17 2011-06-23 Tornee Pang Modified Starch of Enhanced Water Soluble Dye Composition in Core Projectile and Method of Making

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108290963A (zh) * 2015-11-26 2018-07-17 卡吉尔公司 稳定化淀粉
CN108290963B (zh) * 2015-11-26 2021-09-21 卡吉尔公司 稳定化淀粉
US10889753B2 (en) 2016-04-25 2021-01-12 Halliburton Energy Services, Inc. Self-breakable treatment fluids for use in subterranean formation operations

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